JP2015014012A - Epoxy compound composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To heighten fire retardant of a resin molding without deteriorating heat resistance and high-temperature reliability.SOLUTION: A resin composition comprises: an epoxy compound composition comprising at least two kinds of epoxy compounds having a phosphazene ring and an epoxy group which are produced by the reaction of a polyfunctional glycidyl compound, such as glycidyl ether of bisphenol A, with a hydroxy group-containing cyclic phosphazene compound such as a cyclic phosphazene compound in which an aryloxy group and a hydroxyaryloxy group are mixed and substituted; and at least one kind of resin component selected from the group consisting of a thermoplastic resin and a thermosetting resin. The resin composition is excellent in heat resistance, high-temperature reliability and flame retardancy, and can form a resin molding having properties inherent to the resin component. The resin molding can be used as a sealing agent for an electronic component, such as an LSI, and a substrate.

Description

  The present invention relates to a composition, particularly a composition of an epoxy compound.

  In the fields of industrial and consumer equipment and electrical products, synthetic resins have advantages over other materials in terms of processability, chemical resistance, weather resistance, electrical properties and mechanical strength. It has been used extensively because of its use, and its usage is increasing. However, since synthetic resins have the property of being easily combusted, they are required to be provided with flame retardancy, and in recent years, the required performance is gradually increasing. For this reason, resin compositions used for encapsulants and substrates for electronic components such as LSIs, such as epoxy resin compositions, are flame retardant and contain halogen-containing compounds, halogen-containing compounds and antimony oxide, etc. A mixture with an antimony compound is added as a general flame retardant. However, a resin composition containing such a flame retardant may generate a halogen-based gas that may cause environmental pollution during combustion or molding. In addition, the halogen-based gas may hinder the electrical characteristics and mechanical characteristics of the electronic component. Therefore, recently, as flame retardants for synthetic resins, non-halogen-based flame retardants that do not easily generate halogen-based gases during combustion or molding, for example, metal hydrates such as aluminum hydroxide and magnesium hydroxide are difficult. Phosphorous flame retardants such as flame retardants, phosphoric acid esters, condensed phosphoric acid esters, phosphoric acid amides, ammonium polyphosphates, and phosphazenes are widely used.

Among these, metal hydrate flame retardants exhibit a flame retardant effect because the endothermic reaction of dehydration pyrolysis and the accompanying water release occur in a temperature range that overlaps the thermal decomposition and combustion start temperature of the synthetic resin. However, in order to enhance the effect, it is necessary to add a large amount to the resin composition. For this reason, the molded article of the resin composition containing this type of flame retardant has a drawback that the mechanical strength is impaired. On the other hand, among phosphoric flame retardants, phosphoric acid ester and condensed phosphoric acid ester types have a plastic effect, so if they are added in a large amount to the resin composition in order to increase flame retardancy, resin molded products There are disadvantages such as a decrease in mechanical strength. In addition, phosphate ester-based, phosphate amide-based, and ammonium polyphosphate-based materials are easily hydrolyzed. Therefore, in materials for manufacturing resin molded products that require mechanical and electrical long-term reliability. It is practically difficult to use. For these, flame retardants phosphazene has a small plasticizing effect and hydrolysis resistance as compared with other phosphorus-based flame retardant, it is possible to increase the addition amount to the resin composition, Patent Documents 1 to 5 below As described in the above, they are frequently used as effective flame retardants for synthetic resins. However, if the amount of the phosphazene-based flame retardant added to the resin composition is increased, the reliability of the resin molded product at high temperatures may be impaired. Specifically, in the case of a thermoplastic resin-based resin composition, the phosphazene-based flame retardant is likely to bleed out (elution) from the resin molded body at a high temperature, and the thermosetting resin-based resin composition. In this case, deformation such as blistering occurs in the resin molded product at a high temperature, and when the resin molded product is used in the electric / electronic field such as a laminated substrate, a short circuit due to deformation may occur.

Therefore, flame retardants phosphazene, the resin molded article of reliability at elevated temperature has been considered improvement in order to increase (high temperature reliability), Patent Document 6 to 10 below as an example, reactive A phosphazene-based flame retardant having a group and an epoxy resin composition or a polyimide resin composition using the same are disclosed. This type of phosphazene-based flame retardant is unlikely to impair the high temperature reliability of the resin molded product even when added in a large amount to the resin composition. It is not sufficient in terms of the essential effect required for it, which is difficult to increase effectively, and it may impair the heat resistance of the resin molded product (mainly evaluated by the glass transition temperature).

On the other hand, in the epoxy resin composition, improvements to enhance the heat resistance, mechanical properties (toughness) and high temperature reliability (which can be improved by increasing water resistance) of resin molded products are being studied. The following Patent Documents 11 to 14 disclose flame retardant epoxy resin compositions having an oxazolidone ring. This flame-retardant epoxy resin composition can realize a resin molded product that has almost achieved the required heat resistance and mechanical properties (toughness) and high-temperature reliability (water resistance). The product has insufficient flame retardancy. However, in order to increase the flame retardancy of the resin molded product, the flame retardant epoxy resin composition is not suitable for phosphoric ester, condensed phosphate ester, phosphaphenanthrene, phosphazene or polyphenylene ether. When a flame retardant or a flame retardant aid is added, the resin molded product has a defect in either heat resistance or high temperature reliability.

JP 2000-103939 A JP 2004-83671 A JP 2004-210849 A JP 2005-8835 A JP 2005-248134 A Japanese Patent Laid-Open No. 6-247989 JP-A-10-259292 JP 2003-302751 A JP 2003-342339 A JP 2004-143465 A JP-A-8-127635 JP 2002-308965 A JP 2003-119253 A WO2006 / 001445

  An object of the present invention is to increase the flame retardancy of a resin molded article without impairing heat resistance and high temperature reliability.

  As a result of repeated studies to solve the above-mentioned problems, the present inventors have achieved excellent heat resistance (high glass transition) when an epoxy compound having a phosphazene ring and an epoxy group at the same time is used in a resin molding material. Temperature) and high temperature reliability (water resistance), and at the same time, found to be excellent in flame retardancy.

  The present invention relates to an epoxy compound composition, and this epoxy compound composition comprises an epoxy compound having a phosphazene ring and an epoxy group, which is obtained by a reaction between a polyfunctional glycidyl compound and a hydroxy group-containing cyclic phosphazene compound. Contains at least two types.

  The polyfunctional glycidyl compound used here is at least one selected from the group consisting of glycidyl ethers, glycidyl esters, glycidyl amines, aliphatic epoxides and alicyclic epoxides, for example. The hydroxy group-containing cyclic phosphazene compound is represented by the following formula (1).

In the formula (1), n represents an integer of 1 to 6, A represents a group selected from the group consisting of the following A1, A2, and A3 groups, and at least one is an A3 group.
A1 group: an alkoxy group having 1 to 8 carbon atoms which may be substituted with at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group and an aryl group.
A2 group: an aryloxy group having 6 to 20 carbon atoms which may be substituted with at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group and an aryl group.
A3 group: a group selected from the group consisting of a hydroxyaryloxy group represented by the following formula (2) and a hydroxyphenyl-substituted phenyloxy group represented by the following formula (3).

  In formula (2), Y represents biphenylene.

In the formula (3), Z represents O, S, SO ₂ , CH ₂ , CHCH ₃ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ , C (CH ₃ ) CH ₂ CH ₃ or CO.

  The cyclic phosphazene compound having a hydroxy group represented by the formula (1) is preferably one in which 1 to (2n + 2) of (2n + 4) A are A3 groups. Moreover, n of Formula (1) is preferably 1 or 2. Alternatively, the cyclic phosphazene compound having a hydroxy group of the formula (1) preferably includes two or more types having different n in the formula (1).

  The epoxy compound composition of the present invention includes at least two types of epoxy compounds having a specific structure, that is, epoxy compounds having a phosphazene ring and an epoxy group at the same time. When it is cured or mixed with a resin material to cure this mixture, a resin molded article having excellent heat resistance and high temperature reliability and flame retardancy can be produced.

  The composition for resin moldings of the present invention includes the epoxy compound composition of the present invention and at least one resin component selected from the group consisting of thermoplastic resins and thermosetting resins. This composition for resin moldings is excellent in heat resistance and high temperature reliability as well as flame retardancy, and can form a resin molding having characteristics obtained from other resin components.

  The resin molded body of the present invention is obtained by curing the epoxy compound composition of the present invention, or obtained by curing the composition for resin molded body of the present invention. This resin molding is excellent in heat resistance and high temperature reliability as well as flame retardancy.

  The electronic component of the present invention uses the resin molded body of the present invention. This electronic component is excellent in flame resistance as well as heat resistance and high temperature reliability.

  Other objects and advantages of the present invention are mentioned in the detailed description below.

Epoxy Compound Composition The epoxy compound composition of the present invention contains at least two types of compounds having a phosphazene ring and an epoxy group, that is, an epoxy compound having a phosphazene ring and an epoxy group at the same time. In the epoxy compound contained in the composition, the epoxy group is usually contained as a glycidyl group. In addition, the epoxy compound contained in the composition may be a low molecular compound or a high molecular compound.

  In the epoxy compound composition of the present invention, the epoxy equivalent is 200 to 10,000 g / eq. Is preferred, 250-2,000 g / eq. Is more preferable. Epoxy equivalent is 200 g / eq. If it is less than the range, it may be difficult to obtain a resin molded article having high temperature reliability (water resistance). Conversely, 10,000 g / eq. If it exceeds 1, it becomes difficult to obtain a resin molded article having good heat resistance and flame retardancy.

  Here, the epoxy equivalent of an epoxy compound composition can be calculated | required by the method prescribed | regulated in JISK-7236 "how to obtain | require the epoxy equivalent of an epoxy resin".

  The epoxy compound contained in the epoxy compound composition of the present invention has an average functional number of epoxy groups per molecule of 1 or more, but the average functional number is preferably 1.2-5, and 1.2-3. More preferred. When this average functional number is less than 1.2, it may be difficult to obtain a resin molded article having good heat resistance. Conversely, when it exceeds 5, a resin molded article having good heat resistance can be obtained, but the high temperature reliability of the resin molded article may be lowered.

Method for Producing Epoxy Compound Composition The epoxy compound composition of the present invention is usually produced by reacting a polyfunctional glycidyl compound with a cyclic phosphazene compound having a hydroxy group, that is, a hydroxy group-containing cyclic phosphazene compound. Can do. In this reaction, a part of the glycidyl group of the polyfunctional glycidyl compound reacts with the hydroxy group of the hydroxy group-containing cyclic phosphazene compound to bond both compounds, and the phosphazene ring derived from the hydroxy group-containing cyclic phosphazene compound and the polyfunctional It becomes an epoxy compound having an epoxy group derived from a soluble glycidyl compound. And since a hydroxyl-group containing phosphazene compound is a mixture of the multiple types of thing from which a structure differs normally, the epoxy compound composition containing two or more types of the said epoxy compounds is obtained by the above reactions.

  The polyfunctional glycidyl compound used in this production method is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule, but preferred are glycidyl ethers, glycidyl esters, Examples thereof include glycidylamines, aliphatic epoxides, alicyclic epoxides, and triglycidyl isocyanurate.

Examples of glycidyl ethers include phenol glycidyl ethers, novolac polyglycidyl ethers, and alkyl glycidyl ethers. Examples of phenol glycidyl ethers include bisphenol-A, bisphenol-F, bisphenol-AD, bisphenol-S, tetramethylbisphenol-A, tetramethylbisphenol-F, tetramethylbisphenol-AD, tetramethylbisphenol-S, Examples thereof include compounds obtained by glycidylation of dihydric phenols such as biphenol and dihydroxynaphthalene. 1,1,1-tris (4-hydroxyphenyl) methane, 1,1,1- (4-hydroxyphenyl) ethane And glycidylation of tris (glycidyloxyphenyl) alkanes such as 4,4- (1- {4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl} ethylidene) bisphenol and aminophenol A compound can also be mentioned. Examples of the polyglycidyl ethers of novolak include compounds obtained by glycidylating novolak such as phenol novolak, orthocresol novolak, biphenyl novolak, bisphenol-A novolak, and naphthol novolak. Examples of alkyl glycidyl ethers include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerin polyglycidyl ether, and neopentyl glycol diglycidyl ether.
Examples of glycidyl esters include diglycidyl ester of hexahydrophthalic acid and diglycidyl ester of dimer acid. Examples of glycidylamines include tetraglycidyldiaminodiphenylmethane, triglycidyl-para-aminophenol, and triglycidyl-meta-aminophenol. Examples of the aliphatic epoxides include epoxidized polybutadiene and epoxidized soybean oil. Examples of the alicyclic epoxides include 3,4-epoxy-6-methylcyclohexyl carboxylate and 3,4-epoxycyclohexyl carboxylate.

  Of the polyfunctional glycidyl compounds, preferred are glycidyl ethers. In particular, glycidyl ethers of divalent phenols are preferable, and glycidyl ether of bisphenol-A or glycidyl ether of bisphenol-F is particularly preferable. Two or more polyfunctional glycidyl compounds may be used in combination.

  The epoxy equivalent of the polyfunctional glycidyl compound is 260 g / eq. The following is preferred. In particular, 160 to 220 g / eq. Is preferred, 170-200 g / eq. Is more preferable. The epoxy equivalent of the polyfunctional glycidyl compound is 260 g / eq. If it exceeds 1, the epoxy compound composition of the present invention may have a high melt viscosity and low fluidity, making it difficult to handle. In addition, the alcoholic hydroxy group of the polyfunctional glycidyl compound is 1.0 eq. / Kg or less is preferable. In particular, 0.05 to 0.7 eq. / Kg is preferred, 0.1 to 0.5 eq. / Kg is more preferable. When the alcoholic hydroxy group of the polyfunctional glycidyl compound is excessive, the reaction stability may be lowered during the production of the epoxy compound composition of the present invention.

  On the other hand, the hydroxy group-containing cyclic phosphazene compound used in this production method is represented, for example, by the following formula (1).

  In the formula (1), n represents an integer of 1 to 6, preferably an integer of 1 to 4, particularly preferably 1 or 2. That is, particularly preferred as the hydroxy group-containing cyclic phosphazene compound represented by the formula (1) is cyclotriphosphazene (trimer) having a hydroxy group with n being 1 and cyclotetraphosphazene having a hydroxy group with n being 2 ( Tetramer). The hydroxy group-containing cyclic phosphazene compound may be a mixture of two or more different n.

  In Formula (1), A represents a group selected from the group consisting of the following A1, A2, and A3 groups. However, at least one of A is an A3 group.

[A1 group]
An alkoxy group having 1 to 8 carbon atoms; This alkoxy group may be substituted with at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group.
Examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy, and n-hexyloxy. Group, n-heptyloxy group, n-octyloxy group, ethenyloxy group, 1-propenyloxy group, 2-propenyloxy group, isopropenyloxy group, 3-butenyloxy group, 2-methyl-2-propenyloxy group, 4 -Pentenyloxy group, 2-hexenyloxy group, 1-propyl-2-butenyloxy group, 5-octenyloxy group, benzyloxy group, 2-phenylethoxy group and the like can be mentioned. Of these, a methoxy group, an ethoxy group, an n-propoxy group, a 2-propenyloxy group, and a benzyloxy group are preferable, and an ethoxy group and an n-propoxy group are particularly preferable.

[Group A2]
An aryloxy group having 6 to 20 carbon atoms; This aryloxy group may be substituted with at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group.

  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, ethenylphenoxy group, 1-propenylphenoxy group, 2-propenylphenoxy group, isopropenylphenoxy group, 1-butenylphenoxy group, sec-butenylphenoxy group, 1-pentenylphenoxy group, 1-hexenylphenoxy group, Nirufenokishi group, naphthyloxy group, and an anthryl group and phenanthryloxy groups and the like. Of these, phenoxy group, methylphenoxy group, dimethylphenoxy group, diethylphenoxy group, 2-propenylphenoxy group, phenylphenoxy group and naphthyloxy group are preferable, and phenoxy group, methylphenoxy group, dimethylphenoxy group and naphthyloxy group are particularly preferable. preferable.

[Group A3]
Selected from the group consisting of a hydroxyaryloxy group represented by the following formula (2), a hydroxyphenyl-substituted phenyloxy group represented by the following formula (3), and a hydroxy-substituted phenyloxy group represented by the following formula (4) Group.

In formula (2), Y represents phenylene, biphenylene or naphthylene.
Specific examples of the hydroxyaryloxy group represented by the formula (2) include a 2-hydroxylphenyloxy group, a 3-hydroxylphenyloxy group, a 4-hydroxylphenyloxy group, and a 3′-hydroxylphenyl-4-phenyloxy group. 4'-hydroxylphenyl-4-phenyloxy group, 4-hydroxylnaphthyl-1-oxy group, 5-hydroxylnaphthyl-1-oxy group and 6-hydroxylnaphthyl-2-oxy group.

In the formula (3), Z represents O, S, SO ₂ , CH ₂ , CHCH ₃ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ , C (CH ₃ ) CH ₂ CH ₃ or CO. Accordingly, the hydroxyphenyl-substituted phenyloxy group represented by the formula (3) is specifically 4′-hydroxyphenyloxy-4-phenyloxy group, 4′-hydroxyphenylthio-4-phenyloxy group, 4 ′ -Hydroxyphenylsulfonyl-4-phenyloxy group, 4'-hydroxybenzyl-4-phenyloxy group, 4'-hydroxyphenylethylidene-4-phenyloxy group, 4'-hydroxyphenylisopropylidene-4-phenyloxy group, 4'-hydroxyphenylhexafluoroisopropylidene-4-phenyloxy group, 4'-hydroxyphenyl (1'-methylpropylidene) -4-phenyloxy group and 4'-hydroxybenzoyl-4-phenyloxy group.

In formula (4), E ^{1 to} E ⁵ are groups in which at least one is a hydroxy group and at least one is selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group, and the remainder is a hydrogen atom. is there.

  Examples of the hydroxy group-substituted phenyloxy group represented by the formula (4) include 2-hydroxy-3-methyl-phenyloxy group, 2-hydroxy-4-methyl-phenyloxy group, and 2-hydroxy-5-methyl-phenyl. Oxy group, 2-hydroxy-6-methyl-phenyloxy group, 2-methyl-3-hydroxy-phenyloxy group, 3-hydroxy-4-methyl-phenyloxy group, 3-hydroxy-5-methyl-phenyloxy group 3-hydroxy-6-methyl-phenyloxy group, 2-methyl-4-hydroxy-phenyloxy group, 3-methyl-4-hydroxy-phenyloxy group, 2-hydroxy-3,4-dimethyl-phenyloxy group 2-hydroxy-3,5-dimethyl-phenyloxy group, 2-hydroxy-3,6-dimethyl-pheny Oxy group, 2-hydroxy-4,5-dimethyl-phenyloxy group, 2-hydroxy-4,6-dimethyl-phenyloxy group, 2-hydroxy-5,6-dimethyl-phenyloxy group, 3-hydroxy-2 , 4-Dimethyl-phenyloxy group, 3-hydroxy-2,5-dimethyl-phenyloxy group, 3-hydroxy-2,6-dimethyl-phenyloxy group, 3-hydroxy-4,5-dimethyl-phenyloxy group 3-hydroxy-4,6-dimethyl-phenyloxy group, 3-hydroxy-5,6-dimethyl-phenyloxy group, 4-hydroxy-2,3-dimethyl-phenyloxy group, 4-hydroxy-2,5 -Dimethyl-phenyloxy group, 4-hydroxy-2,6-dimethyl-phenyloxy group, 4-hydroxy-3,5-dimethyl -Phenyloxy group, 4-hydroxy-3,6-dimethyl-phenyloxy group, 2-hydroxy-3,4,5-trimethyl-phenyloxy group, 2-hydroxy-3,4,6-trimethyl-phenyloxy group 2-hydroxy-3,5,6-trimethyl-phenyloxy group, 2-hydroxy-4,5,6-trimethyl-phenyloxy group, 2,4,5-trimethyl-3-hydroxy-phenyloxy group, 2 , 5,6-trimethyl-3-hydroxy-phenyloxy group, 3-hydroxy-4,5,6-trimethyl-phenyloxy group, 2,3,5-trimethyl-4-hydroxy-phenyloxy group, 2,3 , 6-trimethyl-4-hydroxy-phenyloxy group, 2-hydroxy-3,4,5,6-tetramethyl-phenyloxy group, 3-hydride Roxy-2,4,5,6-tetramethyl-phenyloxy group, 4-hydroxy-2,3,5,6-tetramethyl-phenyloxy group, 2,3-dihydroxy-4-methyl-phenyloxy group, 2,3-dihydroxy-5-methyl-phenyloxy group, 2,3-dihydroxy-6-methyl-phenyloxy group, 2,4-dihydroxy-3-methyl-phenyloxy group, 2,4-dihydroxy-5- Methyl-phenyloxy group, 2,4-dihydroxy-6-methyl-phenyloxy group, 2,5-dihydroxy-3-methyl-phenyloxy group, 2,5-dihydroxy-4-methyl-phenyloxy group, 2, 5-dihydroxy-6-methyl-phenyloxy group, 2,6-dihydroxy-3-methyl-phenyloxy group, 2,6-dihydroxy-4- Til-phenyloxy group, 2,6-dihydroxy-5-methyl-phenyloxy group, 2-hydroxy-3-ethyl-phenyloxy group, 2-hydroxy-4-ethyl-phenyloxy group, 2-hydroxy-5- Ethyl-phenyloxy group, 2-hydroxy-6-ethyl-phenyloxy group, 2-ethyl-3-hydroxy-phenyloxy group, 3-hydroxy-4-ethyl-phenyloxy group, 3-hydroxy-5-ethyl- Phenyloxy group, 3-hydroxy-6-ethyl-phenyloxy group, 2-ethyl-4-hydroxy-phenyloxy group, 3-ethyl-4-hydroxy-phenyloxy group, 2-hydroxy-3-allyl-phenyloxy Group, 2-hydroxy-4-allyl-phenyloxy group, 2-hydroxy-5-allyl-phenyl Xyl group, 2-hydroxy-6-allyl-phenyloxy group, 2-allyl-3-hydroxy-phenyloxy group, 3-hydroxy-4-allyl-phenyloxy group, 3-hydroxy-5-allyl-phenyloxy group 3-hydroxy-6-allyl-phenyloxy group, 2-allyl-4-hydroxy-phenyloxy group, 3-allyl-4-hydroxy-phenyloxy group, 2-hydroxy-3-phenyl-phenyloxy group, 2 -Hydroxy-4-phenyl-phenyloxy group, 2-hydroxy-5-phenyl-phenyloxy group, 2-hydroxy-6-phenyl-phenyloxy group, 2-phenyl-3-hydroxy-phenyloxy group, 3-hydroxy -4-phenyl-phenyloxy group, 3-hydroxy-5-phenyl-phenyloxy group, 3-hydroxy-6-phenyl-phenyloxy group, 2-phenyl-4-hydroxy-phenyloxy group, 3-phenyl-4-hydroxy-phenyloxy group, 2-methyl-3-ethyl-4-hydroxy-phenyloxy Group, 2-methyl-4-hydroxy-5-ethyl-phenyloxy group, 2-methyl-4-hydroxy-6-ethyl-phenyloxy group, 2-ethyl-3-methyl-4-hydroxy-phenyloxy group, 2-ethyl-4-hydroxy-5-methyl-phenyloxy group and 2-ethyl-4-hydroxy-6-methyl-phenyloxy group.

  Of these, 2-hydroxy-3-methyl-phenyloxy group, 2-hydroxy-4-methyl-phenyloxy group, 2-hydroxy-5-methyl-phenyloxy group, 2-hydroxy-6-methyl are preferable. -Phenyloxy group, 2-methyl-3-hydroxy-phenyloxy group, 3-hydroxy-4-methyl-phenyloxy group, 3-hydroxy-5-methyl-phenyloxy group, 3-hydroxy-6-methyl-phenyl Oxy group, 2-methyl-4-hydroxy-phenyloxy group, 3-methyl-4-hydroxy-phenyloxy group, 3-hydroxy-2,4-dimethyl-phenyloxy group, 3-hydroxy-2,5-dimethyl -Phenyloxy group, 3-hydroxy-4,5-dimethyl-phenyloxy group, 3-hydroxy-4,6- Methyl-phenyloxy group, 3-hydroxy-5,6-dimethyl-phenyloxy group, 4-hydroxy-2,3-dimethyl-phenyloxy group, 4-hydroxy-2,5-dimethyl-phenyloxy group, 4- Hydroxy-3,5-dimethyl-phenyloxy group, 4-hydroxy-3,6-dimethyl-phenyloxy group, 3-hydroxy-4-ethyl-phenyloxy group, 3-hydroxy-5-ethyl-phenyloxy group, 3-ethyl-4-hydroxy-phenyloxy group, 2-allyl-3-hydroxy-phenyloxy group, 3-hydroxy-4-allyl-phenyloxy group, 3-hydroxy-5-allyl-phenyloxy group, 3- Hydroxy-6-allyl-phenyloxy group, 2-allyl-4-hydroxy-phenyloxy group, 3-allyl 4-hydroxy-phenyloxy group, 2-phenyl-3-hydroxy-phenyloxy group, 3-hydroxy-4-phenyl-phenyloxy group, 3-hydroxy-5-phenyl-phenyloxy group, 3-hydroxy-6- A phenyl-phenyloxy group, a 2-phenyl-4-hydroxy-phenyloxy group and a 3-phenyl-4-hydroxy-phenyloxy group.

  In particular, 2-methyl-3-hydroxy-phenyloxy group, 3-hydroxy-4-methyl-phenyloxy group, 3-hydroxy-5-methyl-phenyloxy group, 3-hydroxy-6-methyl-phenyloxy group, 2-methyl-4-hydroxy-phenyloxy group, 3-methyl-4-hydroxy-phenyloxy group, 4-hydroxy-3,5-dimethyl-phenyloxy group, 3-hydroxy-4-ethyl-phenyloxy group, A 3-hydroxy-5-ethyl-phenyloxy group and a 3-ethyl-4-hydroxy-phenyloxy group are preferred.

  In formula (1), A includes (2n + 4) A, and at least one of them is an A3 group. Therefore, the hydroxy group-containing cyclic phosphazene compound represented by the formula (1) used in the present invention can be roughly classified into the following forms.

[Form 1]
All (2n + 4) A's are A3 groups. In this case, all of A may be the same A3 group, or two or more A3 groups may be used.

  Specific examples of the cyclic phosphazene compound having a hydroxy group in such a form include a cyclotriphosphazene compound having a hydroxy group in which n is 1 in formula (1), and a hydroxy group in which n is 2 in formula (1). A cyclotetraphosphazene compound having a hydroxy group in which n in formula (1) is 3 and a cyclohexaphosphazene compound having a hydroxy group in which n is 4 in formula (1), all of A 4-hydroxyphenyloxy group, 4′-hydroxyphenyl-4-phenyloxy group, 4-hydroxylnaphthyl-1-oxy group, 5-hydroxylnaphthyl-1-oxy group, 6-hydroxylnaphthyl-2-oxy group 4′-hydroxyphenyloxy-4-phenyloxy group, 4′-hydroxyphenyl Nylthio-4-phenyloxy group, 4′-hydroxyphenylsulfonyl-4-phenyloxy group, 4′-hydroxyphenylisopropylidene-4-phenyloxy group, 2-methyl-3-hydroxy-phenyloxy group, 3-hydroxy -4-methyl-phenyloxy group, 3-hydroxy-5-methyl-phenyloxy group, 3-hydroxy-6-methyl-phenyloxy group, 2-methyl-4-hydroxy-phenyloxy group, 3-methyl-4 -Hydroxy-phenyloxy group, 4-hydroxy-3,5-dimethyl-phenyloxy group, 3-hydroxy-4-ethyl-phenyloxy group, 3-hydroxy-5-ethyl-phenyloxy group and 3-ethyl-4 A kind of A3 group selected from the group of A3 groups consisting of -hydroxy-phenyloxy groups All things shall and A is two or more A3 groups selected from the A3 group group and can be exemplified any mixture thereof.

[Form 2]
A part (that is, at least one) of the (2n + 4) A is an A3 group, and the other A is a group selected from the A1 group and the A2 group. In this case, A other than the A3 group may all be the same A1 group or A2 group, or two or more kinds of A1 groups or A2 groups or one kind or two or more kinds of A1 groups and A2 groups may be It may be in a mixed state.

  Preferred as the hydroxy group-containing cyclic phosphazene compound of this form is one in which 1 to (2n + 2) out of (2n + 4) A are A3 groups. In particular, a cyclotriphosphazene compound having a hydroxy group in which n is 1 in formula (1), a cyclotetraphosphazene compound having a hydroxy group in which n is 2 in formula (1), and n in formula (1) is 3. A cyclopentaphosphazene compound having a hydroxy group and a cyclohexaphosphazene compound having a hydroxy group in which n in formula (1) is 4, wherein 1 to (2n + 2) of (2n + 4) A are A3 groups And any mixtures thereof are preferred. When using this kind of hydroxy group-containing cyclic phosphazene compound, compared to the case of using other hydroxy group-containing cyclic phosphazene compounds, the resin molded product is superior in heat resistance (particularly high glass transition temperature) and high temperature reliability. This is advantageous in that it can be realized.

  Whether 1 to (2n + 2) of (2n + 4) A are A3 groups can be confirmed by TOF-MS analysis of a hydroxy group-containing cyclic phosphazene compound or an intermediate in its production process. it can.

  Specific examples of the hydroxy group-containing cyclic phosphazene compound having such a form include a cyclotriphosphazene compound having a hydroxy group in which n is 1 in the formula (1), and a hydroxy group in which n is 2 in the formula (1). A cyclotetraphosphazene compound, a cyclopentaphosphazene compound having a hydroxy group in which n in formula (1) is 3 or a cyclohexaphosphazene compound having a hydroxy group in which n is 4 in formula (1), wherein A is A3 A combination of a 4-hydroxyphenyloxy group as a group and an n-propoxy group as an A1, a combination of a 4-hydroxyphenyloxy group as an A3 group and a phenoxy group as an A2, a group of A3 A combination of a 4-hydroxyphenyloxy group and a methylphenoxy group that is A2 group, 4 that is A3 group -A combination of hydroxyphenyl-4-phenyloxy group and n-propoxy group which is A1 group, a combination of 4'-hydroxyphenyl-4-phenyloxy group which is A3 group and phenoxy group which is A2 group A combination of a 4′-hydroxyphenyl-4-phenyloxy group that is an A3 group and a methylphenoxy group that is an A2 group, an n that is a 4-hydroxylnaphthyl-1-oxy group that is an A3 group, and an A1 group -In combination with propoxy group, in combination with 4-hydroxynaphthyl-1-oxy group which is A3 group and phenoxy group which is A2 group, 4-hydroxylnaphthyl-1-oxy group which is A3 group and A2 In combination with a methylphenoxy group which is a group, 5-hydroxylnaphthyl-1-oxy group which is an A3 group and n-pro which is an A1 group In combination with a xy group, in combination with a 5-hydroxylnaphthyl-1-oxy group as an A3 group and a phenoxy group as an A2 group, a 5-hydroxylnaphthyl-1-oxy group and an A2 group as an A3 group In combination with a methylphenoxy group that is A4, in combination with 4'-hydroxyphenylsulfonyl-4-phenyloxy group that is A3 group and n-propoxy group that is A1 group, 4'-hydroxy that is A3 group Combination of phenylsulfonyl-4-phenyloxy group and phenoxy group which is A2 group, combination of 4'-hydroxyphenylsulfonyl-4-phenyloxy group which is A3 group and methylphenoxy group which is A2 group 4′-hydroxyphenylisopropylidene-4-phenyloxy group which is A3 group and n-propoxy which is A1 group In combination with a group, 4'-hydroxyphenylisopropylidene-4-phenyloxy group as an A3 group and a phenoxy group as an A2 group, 4'-hydroxyphenylisopropylidene-4 as an A3 group A combination of a phenyloxy group and a methylphenoxy group which is an A2 group, a combination of a 2-methyl-3-hydroxy-phenyloxy group which is an A3 group and an n-propoxy group which is an A1 group, an A3 group A combination of 2-methyl-3-hydroxy-phenyloxy group which is A2 group and a phenoxy group which is A2 group, 2-methyl-3-hydroxy-phenyloxy group which is A3 group and methylphenoxy group which is A2 group A combination of 3-hydroxy-4-methyl-phenyloxy group which is A3 group and n-propoxy group which is A1 group A combination of 3-hydroxy-4-methyl-phenyloxy group which is A3 group and phenoxy group which is A2 group, 3-hydroxy-4-methyl-phenyloxy group which is A3 group and A2 group A combination with a certain methylphenoxy group, a combination of a 3-hydroxy-5-methyl-phenyloxy group which is an A3 group with an n-propoxy group which is an A1 group, a 3-hydroxy-5 which is an A3 group Combination of methyl-phenyloxy group and phenoxy group which is A2 group, combination of 3-hydroxy-5-methyl-phenyloxy group which is A3 group and methylphenoxy group which is A2 group, Combination of certain 3-hydroxy-6-methyl-phenyloxy group and n-propoxy group which is A1 group, 3-hydroxy-6-methyl which is A3 group A combination of a phenyloxy group and a phenoxy group which is an A2 group, a combination of a 3-hydroxy-6-methyl-phenyloxy group which is an A3 group and a methylphenoxy group which is an A2 group, an A3 group Combination of 2-methyl-4-hydroxy-phenyloxy group and n-propoxy group which is A1 group, 2-methyl-4-hydroxy-phenyloxy group which is A3 group and phenoxy group which is A2 group Combination, A3 group 2-methyl-4-hydroxy-phenyloxy group and A2 group methylphenoxy group, A3 group 3-methyl-4-hydroxy-phenyloxy group and A1 In combination with an n-propoxy group which is a group, a 3-methyl-4-hydroxy-phenyloxy group which is an A3 group and a phenoxy group which is an A2 group A combination of 3-methyl-4-hydroxy-phenyloxy group which is A3 group and methylphenoxy group which is A2 group, 4-hydroxy-3,5-dimethyl-phenyloxy which is A3 group A combination of a group with an n-propoxy group which is an A1 group, a combination of a 4-hydroxy-3,5-dimethyl-phenyloxy group which is an A3 group and a phenoxy group which is an A2 group, an A3 group Combination of 4-hydroxy-3,5-dimethyl-phenyloxy group and methylphenoxy group which is A2 group, 3-hydroxy-4-ethyl-phenyloxy group which is A3 group and n-propoxy which is A1 group A combination with a group, a combination of a 3-hydroxy-4-ethyl-phenyloxy group which is an A3 group and a phenoxy group which is an A2 group, an A3 group A combination of a hydroxy-4-ethyl-phenyloxy group and a methylphenoxy group that is an A2 group, a 3-hydroxy-5-ethyl-phenyloxy group that is an A3 group, and an n-propoxy group that is an A1 group Combination, A3 group 3-hydroxy-5-ethyl-phenyloxy group and A2 group phenoxy group, A3 group 3-hydroxy-5-ethyl-phenyloxy group and A2 group In combination with a methylphenoxy group which is A3, 3-ethyl-4-hydroxy-phenyloxy group which is an A3 group and an n-propoxy group which is an A1 group, 3-ethyl-4 which is an A3 group -Hydroxy-phenyloxy group in combination with A2 group phenoxy group and A3 group 3-ethyl-4-hydroxy-phenyloxy If well as those of the combination of methylphenoxy group is A2 groups may be mentioned any mixture thereof.

  Of these, a cyclotriphosphazene compound having a hydroxy group in which n is 1 in formula (1), a cyclotetraphosphazene compound having a hydroxy group in which n is 2 in formula (1), and n in formula (1) being 3. A cyclopentaphosphazene compound having a certain hydroxy group, and a cyclohexaphosphazene compound having a hydroxy group in which n in formula (1) is 4, wherein A is a 4-hydroxyphenyloxy group that is an A3 group and an A2 group A combination with a phenoxy group, a combination of a 4′-hydroxyphenyl-4-phenyloxy group which is an A3 group and a phenoxy group which is an A2 group, a 4-hydroxylnaphthyl-1-oxy group which is an A3 group and In combination with a phenoxy group that is an A2 group, a 5-hydroxylnaphthyl-1-oxy group that is an A3 group, and a fluorine that is an A2 group A combination with a nonoxy group, a combination of 4'-hydroxyphenylsulfonyl-4-phenyloxy group which is an A3 group and a phenoxy group which is an A2 group, 4'-hydroxyphenylsulfonyl-4- which is an A3 group Combination of phenyloxy group and methylphenoxy group which is A2 group, combination of 4'-hydroxyphenylisopropylidene-4-phenyloxy group which is A3 group and phenoxy group which is A2 group, Combination of 4′-hydroxyphenylisopropylidene-4-phenyloxy group and methylphenoxy group which is A2 group, 3-hydroxy-4-methyl-phenyloxy group which is A3 group and phenoxy group which is A2 group In combination with the A3 group 3-hydroxy-4-methyl-phenyloxy group and the A2 group In combination with a methylphenoxy group, A3 group 3-hydroxy-5-methyl-phenyloxy group in combination with an A2 group phenoxy group, A3 group 3-hydroxy-5-methyl- Combination of phenyloxy group and methylphenoxy group which is A2 group, combination of 2-methyl-4-hydroxy-phenyloxy group which is A3 group and phenoxy group which is A2 group, 2 which is A3 group -A combination of a methyl-4-hydroxy-phenyloxy group and a methylphenoxy group which is an A2 group, a combination of a 3-methyl-4-hydroxy-phenyloxy group which is an A3 group and a phenoxy group which is an A2 group A combination of 3-methyl-4-hydroxy-phenyloxy group which is A3 group and methylphenoxy group which is A2 group, A3 group 4-hydroxy-3,5-dimethyl-phenyloxy group and A2 group phenoxy group, A3 group 4-hydroxy-3,5-dimethyl-phenyloxy group and A2 group methyl Combination with phenoxy group, combination of 3-ethyl-4-hydroxy-phenyloxy group which is A3 group and phenoxy group which is A2 group, and 3-ethyl-4-hydroxy-phenyloxy which is A3 group Preferred are combinations of the groups with the methylphenoxy group which is the A2 group and any mixtures thereof.

  In particular, a cyclotriphosphazene compound having a hydroxy group in which n in formula (1) is 1 or a cyclotetraphosphazene compound having a hydroxy group in which n is 2 in formula (1), wherein A is an A3 group Combination of 4-hydroxyphenyloxy group and phenoxy group which is A2 group, combination of 4'-hydroxyphenyl-4-phenyloxy group which is A3 group and phenoxy group which is A2 group, A combination of a certain 5-hydroxylnaphthyl-1-oxy group and a phenoxy group that is an A2 group, a combination of a 4′-hydroxyphenylsulfonyl-4-phenyloxy group that is an A3 group and a phenoxy group that is an A2 group 4'-hydroxyphenylsulfonyl-4-phenyloxy group which is A3 group and methylphenoxy group which is A2 group A combination of 4'-hydroxyphenylisopropylidene-4-phenyloxy group as the A3 group and a phenoxy group as the A2 group, a 3-hydroxy-4-methyl-phenyloxy group as the A3 group In combination with a phenoxy group which is A2 group, a combination of 3-hydroxy-4-methyl-phenyloxy group which is A3 group and methylphenoxy group which is A2 group, 3-hydroxy- which is A3 group A combination of a 5-methyl-phenyloxy group and a phenoxy group which is an A2 group, a combination of a 3-hydroxy-5-methyl-phenyloxy group which is an A3 group and a methylphenoxy group which is an A2 group, A3 A combination of a 2-methyl-4-hydroxy-phenyloxy group as a group and a phenoxy group as an A2 group, a 2-methyl group as an A3 group Combination of ru-4-hydroxy-phenyloxy group and methylphenoxy group which is A2 group, combination of 3-methyl-4-hydroxyphenyloxy group which is A3 group and phenoxy group which is A2 group A combination of 3-methyl-4-hydroxy-phenyloxy group as A3 group and methylphenoxy group as A2 group, 4-hydroxy-3,5-dimethyl-phenyloxy group as A3 group and A2 group In combination with a phenoxy group which is A3, 4-hydroxy-3,5-dimethyl-phenyloxy group which is an A3 group and a methylphenoxy group which is an A2 group, 3-ethyl-4 which is an A3 group -A combination of hydroxy-phenyloxy group and phenoxy group which is A2 group and 3-ethyl-4-hydroxy-phenyloxy which is A3 group A combination of a cis group and a methylphenoxy group which is an A2 group, and any mixture thereof are preferred.

  As the hydroxy group-containing cyclic phosphazene compound, those having a glycidyl group in addition to the hydroxy group can also be used. Examples of such a compound include a cyclotriphosphazene compound having a hydroxy group in which n is 1 in the formula (1) or a cyclotetraphosphazene compound having a hydroxy group in which n is 2 in the formula (1), All of A are 4-hydroxyphenyloxy group, 4′-hydroxyphenyl-4-phenyloxy group, 4-hydroxynaphthyl-1-oxy group, 5-hydroxylnaphthyl-1-oxy group, 6-hydroxylnaphthyl-2 -Oxy group, 4'-hydroxyphenyloxy-4-phenyloxy group, 4'-hydroxyphenylthio-4-phenyloxy group, 4'-hydroxyphenylsulfonyl-4-phenyloxy group, 4'-hydroxyphenylisopropylidene -4-phenyloxy group, 2-methyl-3-hydroxy-phenyl Xoxy group, 3-hydroxy-4-methyl-phenyloxy group, 3-hydroxy-5-methyl-phenyloxy group, 3-hydroxy-6-methyl-phenyloxy group, 2-methyl-4-hydroxy-phenyloxy group 3-methyl-4-hydroxy-phenyloxy group, 4-hydroxy-3,5-dimethyl-phenyloxy group, 3-hydroxy-4-ethyl-phenyloxy group, 3-hydroxy-5-ethyl-phenyloxy group And A is a kind of A3 group selected from the A3 group consisting of 3-ethyl-4-hydroxy-phenyloxy groups, and all of A are two or more A3 groups selected from the A3 group A combination of a 4-hydroxyphenyloxy group that is an A3 group and a phenoxy group that is an A2 group; A combination of a loxyphenyl-4-phenyloxy group and a phenoxy group that is an A2 group, a combination of a 5-hydroxylnaphthyl-1-oxy group that is an A3 group and a phenoxy group that is an A2 group, A is a combination of a 4′-hydroxyphenylsulfonyl-4-phenyloxy group which is an A3 group and a phenoxy group which is an A2 group, and 4′-hydroxyphenylsulfonyl-4-phenyloxy where A is an A3 group A combination of a group and a methylphenoxy group which is an A2 group, A is a combination of a 4′-hydroxyphenylisopropylidene-4-phenyloxy group which is an A3 group and a phenoxy group which is an A2 group, A combination of a 3-hydroxy-4-methyl-phenyloxy group that is an A3 group and a phenoxy group that is an A2 group, and A is an A3 group A combination of a certain 3-hydroxy-4-methyl-phenyloxy group and a methylphenoxy group that is an A2 group, and a phenoxy in which A is a 3-hydroxy-5-methyl-phenyloxy group that is an A3 group and an A2 group In combination with a group, A in combination with a 3-hydroxy-5-methyl-phenyloxy group which is an A3 group and a methylphenoxy group which is an A2 group, 2-methyl- in which A is an A3 group Combination of 4-hydroxy-phenyloxy group and phenoxy group which is A2 group, A is combination of 2-methyl-4-hydroxy-phenyloxy group which is A3 group and methylphenoxy group which is A2 group A combination of a 3-methyl-4-hydroxy-phenyloxy group which is an A3 group and a phenoxy group which is an A2 group, and 3-methyl wherein A is an A3 group A combination of a -4-hydroxy-phenyloxy group and a methylphenoxy group that is an A2 group, and A is a 4-hydroxy-3,5-dimethyl-phenyloxy group that is an A3 group and a phenoxy group that is an A2 group; A combination of 4-hydroxy-3,5-dimethyl-phenyloxy group, which is an A3 group, and a methylphenoxy group, which is an A2 group, and 3-ethyl-, wherein A is an A3 group A combination of a 4-hydroxy-phenyloxy group and a phenoxy group which is an A2 group, and a combination of a 3-ethyl-4-hydroxy-phenyloxy group where A is an A3 group and a methylphenoxy group which is an A2 group A mixture of the same or different hydroxy group-containing cyclic phosphazene compounds selected from the group consisting of combinations, wherein the hydroxy group contained in the mixture In some organic cyclic phosphazene compounds include those in which the hydroxy group is converted into a glycidyl group.

  The hydroxy group-containing cyclic phosphazene compound having a hydroxyaryloxy group represented by the formula (2) as the A3 group and the hydroxy group-containing cyclic phosphazene compound having a hydroxyphenyl-substituted phenyloxy group represented by the formula (3) as the A3 group are as follows: It can manufacture with reference to the method described in the literature 15-19.

Reference 15
JP 58-219190 A
Reference 16
JP 2007-153747 A
Reference 17
PHOSPHORUS-NITROGEN COMPOUNDS, H.P. R. By ALLCOCK, published in 1972, ACADEMI PRES
Reference 18
Alessandro Medici, et. al. , Macromolecules, Vol. 25, no. 10, p. 2569 (1992)
Reference 19
PHOSPHAZENES, A WORLDWIDE INSIGHT, M.C. GLERIA, R.A. DE JAEGER, 2004, NOVA SCIENCE PUBLISHERS INC. Company

On the other hand, a hydroxy group-containing cyclic phosphazene compound having a hydroxy group-substituted phenyloxy group represented by formula (4) as the A3 group (hereinafter sometimes referred to as “formula (4) substituent-containing cyclic phosphazene compound”) It can manufacture by such a method.
First, a cyclic phosphonitrile dihalide represented by the following formula (5) is prepared.

In the formula (5), n represents an integer of 3 to 8. X represents a halogen atom, preferably a fluorine atom or a chlorine atom. Incidentally, the cyclic phosphonitrile dihalide prepared here may be a mixture of several kinds having different n.
The production method of such a cyclic phosphonitrile dihalide and others are described in various documents, for example, the following documents 20 and 21.

Reference 20
PHOSPHORUS-NITROGEN COMPOUNDS, H.P. R. By ALLCOCK, published in 1972, ACADEMI PRES
Reference 21
PHOSPHAZENES, A WORLDWIDE INSIGHT, M.C. GLERIA, R.M. DE JAEGER, 2004, NOVA SCIENCE PUBLISHERS INC. Company

  As described in these documents, the cyclic phosphonitrile dihalide represented by the formula (5) is usually composed of a cyclic phosphonitrile dihalide having a degree of polymerization of about 3 to 8 and a chain phosphonitrile dihalide. Obtained as a mixture. For this reason, the cyclic phosphonitrile dihalide represented by the formula (5) removes the chain phosphonitrile dihalide by utilizing the difference in solubility in the solvent from the mixture as described in the above-mentioned documents. Or the cyclic phosphonitrile dihalide must be obtained from the mixture by distillation or recrystallization.

  Preferred examples of the cyclic phosphonitrile dihalide used in this production method include hexafluorocyclotriphosphazene (where n is 3), octafluorocyclotetraphosphazene (where n is 4), decafluorocyclopentaphosphazene (n 5), dodecafluorocyclohexaphosphazene (where n is 6), a mixture of hexafluorocyclotriphosphazene and octafluorocyclotetraphosphazene, a mixture of cyclic phosphonitrile difluorides where n is 3 to 8, hexachlorocyclo Triphosphazene (n is 3), octachlorocyclotetraphosphazene (n is 4), decachlorocyclopentaphosphazene (n is 5), dodecachlorocyclohexaphosphazene (n is 6), hexac B is a cyclotriphosphazene and mixtures cyclic phosphonate nitrile dichloride mixtures and n is 3 to 8 of the octa-chloro cyclotetrasiloxane phosphazene like. Of these, hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, a mixture of hexachlorocyclotriphosphazene and octachlorocyclotetraphosphazene, and a mixture of cyclic phosphonitrile dichloride having n of 3 to 8 are more preferable, hexachlorocyclotriphosphazene, hexachloro Particular preference is given to mixtures of cyclotriphosphazene and octachlorocyclotetraphosphazene and mixtures of cyclic phosphonitrile dichlorides with n of 3 to 8.

  Moreover, the following compound B1, compound B2, and compound B3 are prepared as a compound made to react with the above-mentioned cyclic phosphonitrile dihalide.

[Compound B1]
Alcohols having 1 to 8 carbon atoms.
These alcohols may be substituted with at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group.
Examples of such alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol, n-hexanol, n-heptanol, and n-octanol. , Vinyl alcohol, 1-propen-1-ol, 2-propen-1-ol (allyl alcohol), 1-methyl-1-ethen-1-ol, 3-buten-1-ol, 2-methyl-2- Examples include propen-1-ol, 4-penten-1-ol, 2-hexen-1-ol, 2-hepten-4-ol, 5-octen-1-ol, benzyl alcohol, and phenethyl alcohol. Among these, methanol, ethanol, n-propanol, allyl alcohol and benzyl alcohol are preferable, and ethanol and n-propanol are particularly preferable.

[Compound B2]
Phenols having 6 to 20 carbon atoms.
These phenols may be substituted with at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group.
Examples of such phenols include phenol, cresol, dimethylphenol, ethylphenol, ethylmethylphenol, diethylphenol, n-propylphenol, isopropylphenol, isopropylmethylphenol, isopropylethylphenol, diisopropylphenol, n-butylphenol, sec-butylphenol, tert-butylphenol, n-pentylphenol, n-hexylphenol, vinylphenol, 1-propenylphenol, 2-propenylphenol, isopropenylphenol, 1-butenylphenol, sec-butenylphenol, 1-pentenyl Phenol, 1-hexenylphenol, phenylphenol, naphthol, anthranol and phenanthate Mention may be made of the Nord and the like. Among these, phenol, cresol, dimethylphenol, diethylphenol, 2-propenylphenol, phenylphenol and naphthol are preferable, and phenol, cresol, dimethylphenol and naphthol are particularly preferable.

[Compound B3]
Acyl group-substituted phenols represented by the following formula (6).

In Formula (6), at least one of L ^{1 to} L ⁵ is an acyl group, and at least one is a group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group, and the remainder is a hydrogen atom. is there.

  The acyl group is not limited in type, for example, formyl group, acetyl group, propionyl group, butyryl group, isobutyryl group, valeryl group, isovaleryl group, pivaloyl group, lauroyl group, myristoyl group, stearoyl group, oxalyl group Succinyl group, acryloyl group, methacryloyl group, benzoyl group, phthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, furoyl group, thenoyl group, nicotinoyl group and anisoyl group. However, since compound B3 is easily available and the synthesis operation for producing the formula (4) substituent-containing cyclic phosphazene compound can be easily carried out, a compound having an acetyl group as an acyl group is used. Is preferred.

  Examples of the acetyl group-substituted phenols used as the compound B3 include 2-methyl-3-acetylphenol, 3-acetyl-4-methylphenol, 3-acetyl-5-methylphenol, and 3-acetyl-6-methylphenol. 2-methyl-4-acetylphenol, 3-methyl-4-acetylphenol, 4-acetyl-3,5-dimethylphenol, 3-acetyl-4-ethylphenol, 3-acetyl-5-ethylphenol and 3- Examples thereof include ethyl-4-acetylphenol. Of these, 3-acetyl-4-methylphenol, 3-acetyl-5-methylphenol, 2-methyl-4-acetylphenol, 3-methyl-4-acetylphenol, 4-acetyl-3,5-dimethylphenol and 3-ethyl-4-acetylphenol is preferred, especially 3-acetyl-4-methylphenol, 2-methyl-4-acetylphenol, 3-methyl-4-acetylphenol and 4-acetyl-3,5-dimethylphenol. preferable.

  In the production method of the formula (4) substituent-containing cyclic phosphazene compound, the cyclic phosphonitrile dihalide is reacted by reacting the cyclic phosphonitrile dihalide represented by the above formula (3) with the above-mentioned compounds B1 to B3. All halogen atoms are substituted with a group selected from the group consisting of the following G1, G2, and G3 groups so that at least one is substituted with the following G3 group to produce a cyclic phosphonitrile substituted product (Step 1). ).

[G1 group]
An alkoxy group having 1 to 8 carbon atoms, which may be substituted with at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group.
This group is substituted with a halogen atom by the compound B1, and corresponds to the A1 group described above.

[G2 group]
An aryloxy group having 6 to 20 carbon atoms, which may be substituted with at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group.
This group is substituted with a halogen atom by the compound B2, and corresponds to the A2 group described above.

[G3 group]
A group selected from the group consisting of acyl group-substituted phenyloxy groups represented by the following formula (7).

This group is substituted with a halogen atom by the compound B3.
In Formula (7), at least one of L ^{1 to} L ⁵ is an acyl group and at least one is at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group, and the rest It is a hydrogen atom.

  In this production process, according to the type of the formula (4) substituent-containing cyclic phosphazene compound to be produced, that is, when the formula (4) substituent-containing cyclic phosphazene compound according to the above-described form 1 is produced, the above-mentioned form According to the formula (4) substituent-containing cyclic phosphazene compound according to 2, the compounds B1 to B3 are appropriately selected and used. Specifically, it is as follows.

[In the case of producing the formula (4) substituent-containing cyclic phosphazene compound of Form 1]
In this case, the cyclic phosphonitrile dihalide is reacted with the compound B3, and all the halogen atoms (hereinafter sometimes referred to as active halogen atoms) of the cyclic phosphonitrile dihalide are substituted with the G3 group derived from the compound B3. The compound B3 used here is one or more of the acyl group-substituted phenols described above. As a method of reacting the cyclic phosphonitrile dihalide with the compound B3 and substituting all the active halogen atoms of the cyclic phosphonitrile dihalide with the G3 group, any of the following methods can be employed.

<Method Aa>
A cyclic phosphonitrile dihalide is reacted with an alkali metal salt of compound B3.
In the case of this method, the amount of the alkali metal salt of compound B3 is usually preferably set to 1.0 to 2.0 equivalents of the amount of active halogen atom of cyclic phosphonitrile dihalide, and 1.05 to 1 More preferably, it is set to 3 equivalents. When the amount used is less than 1.0 equivalent, part of the active halogen atom remains, and the resulting epoxy compound composition using the formula (4) substituent-containing cyclic phosphazene compound does not exhibit the required effect. there is a possibility. On the other hand, if the amount used exceeds 2.0 equivalents, it may be difficult to separate and purify the reaction product, which is uneconomical.

<Method Ab>
Cyclic phosphonitrile dihalide and compound B3 are reacted in the presence of a base capable of capturing hydrogen halide.
In the case of this method, the amount of compound B3 used is preferably set to 1.0 to 2.0 equivalents, preferably 1.05 to 1.3 equivalents, of the amount of the active halogen atom of the cyclic phosphonitrile dihalide. Is more preferable. When the amount used is less than 1.0 equivalent, part of the active halogen atom remains, and the resulting epoxy compound composition using the formula (4) substituent-containing cyclic phosphazene compound does not exhibit the required effect. there is a possibility. On the other hand, if the amount used exceeds 2.0 equivalents, it may be difficult to separate and purify the reaction product, which is uneconomical. The amount of the base used is preferably set to 1.1 to 2.1 equivalents, more preferably 1.1 to 1.4 equivalents, of the amount of active halogen atoms in the cyclic phosphonitrile dihalide. . When the amount used is less than 1.1 equivalents, some of the active halogen atoms remain, and the epoxy compound composition using the formula (4) substituted hydroxy group-containing cyclic phosphazene compound may not exhibit the required effect. There is sex. On the other hand, if the amount used exceeds 2.1 equivalents, it may be difficult to separate and purify the reaction product, which is uneconomical.

[In the case of producing the formula (4) substituent-containing cyclic phosphazene compound of Form 2]
In this case, at least one of compound B3 and at least one compound of compound B1 and compound B2 are reacted with cyclic phosphonitrile dihalide, and a part of the active halogen atoms of cyclic phosphonitrile dihalide is reacted. Is substituted with the G3 group derived from the compound B3, and all of the remaining active halogen atoms are replaced with at least one group selected from the G1 group derived from the compound B1 and the G2 group derived from the compound B2. As a method for this, any of the following methods can be adopted.

<Method Ba>
The cyclic phosphonitrile dihalide is reacted with a mixture of an alkali metal salt of compound B3 and an alkali metal salt of at least one of compound B1 and compound B2 to replace all active halogen atoms. In the said mixture, the ratio of the alkali metal salt of compound B3 can be suitably set according to the kind of formula (4) substituent containing cyclic phosphazene compound to manufacture.
In the case of this method, the amount of the above mixture used is preferably set to 1.0 to 2.0 equivalents of the amount of active halogen atoms of the cyclic phosphonitrile dihalide, and is set to 1.05 to 1.3 equivalents. More preferably. When the amount used is less than 1.0 equivalent, part of the active halogen atom remains, and the resulting epoxy compound composition using the formula (4) substituent-containing cyclic phosphazene compound does not exhibit the required effect. there is a possibility. On the other hand, if the amount used exceeds 2.0 equivalents, it may be difficult to separate and purify the reaction product, which is uneconomical.

<Method B-b>
A cyclic phosphonitrile dihalide is reacted with a mixture of compound B3 and at least one of compound B1 and compound B2 in the presence of a base capable of capturing hydrogen halide, and all of the active halogen atoms are reacted. Replace. In the said mixture, the ratio of compound B3 can be suitably set according to the kind of formula (4) substituent containing cyclic phosphazene compound to manufacture.
In the case of this method, the amount of the above mixture used is preferably set to 1.0 to 2.0 equivalents of the amount of active halogen atoms of the cyclic phosphonitrile dihalide, and is set to 1.05 to 1.3 equivalents. More preferably. When the amount used is less than 1.0 equivalent, part of the active halogen atom remains, and the resulting epoxy compound composition using the formula (4) substituent-containing cyclic phosphazene compound does not exhibit the required effect. there is a possibility. On the other hand, if the amount used exceeds 2.0 equivalents, it may be difficult to separate and purify the reaction product, which is uneconomical. The amount of the base used is preferably set to 1.1 to 2.1 equivalents, more preferably 1.1 to 1.4 equivalents, of the amount of active halogen atoms in the cyclic phosphonitrile dihalide. . If the amount used is less than 1.1 equivalents, a part of the active halogen atoms may remain and the epoxy compound composition using the formula (4) substituent-containing cyclic phosphazene compound may not exhibit the required effect. is there. On the other hand, if the amount used exceeds 2.1 equivalents, it may be difficult to separate and purify the reaction product, which is uneconomical.

<Method Bc>
First, compound B3 is reacted with cyclic phosphonitrile dihalide to obtain a partially substituted product in which a part of the active halogen atom of cyclic phosphonitrile dihalide is substituted with G3 group derived from compound B3 (first step). Next, at least one of compound B1 and compound B2 is reacted with the obtained partially substituted product, and all of the remaining active halogen atoms are converted to G1 group derived from compound B1 and G2 derived from compound B2. Substitution with at least one of the groups (second step).
The first step of this method may be carried out by reacting an alkali metal salt of compound B3 with a cyclic phosphonitrile dihalide, or the compound B3 can capture hydrogen halide with respect to the cyclic phosphonitrile dihalide. The reaction may be carried out in the presence of a simple base. Further, the second step may be carried out by reacting the partially substituted product obtained in the first step with an alkali metal salt of at least one of the compounds B1 and B2, or in the first step. The obtained partially substituted product may be reacted with at least one of compound B1 and compound B2 in the presence of a base capable of capturing hydrogen halide.

<Method Bd>
First, at least one of compound B1 and compound B2 is reacted with cyclic phosphonitrile dihalide, and a part of the active halogen atom of cyclic phosphonitrile dihalide is converted to G1 group derived from compound B1 and compound B2. A partially substituted product substituted with at least one of the derived G2 groups is obtained (first step). Next, compound B3 is reacted with the obtained partially substituted product, and all remaining active halogen atoms are substituted with G3 groups derived from compound B3 (second step).
The first step of this method may be carried out by reacting cyclic phosphonitrile dihalide with an alkali metal salt of at least one of compound B1 and compound B2, or for cyclic phosphonitrile dihalide. Alternatively, at least one of compound B1 and compound B2 may be reacted in the presence of a base capable of capturing hydrogen halide. In addition, the second step may be carried out by reacting the alkali metal salt of compound B3 with the partial substituent obtained in the first step, or compound B3 with respect to the partial substituent obtained in the first step. May be reacted in the presence of a base capable of capturing hydrogen halide.

  In general, the alkali metal salt used in each of the above methods is preferably a lithium salt, a sodium salt, a potassium salt, or a cesium salt. In particular, sodium salt and potassium salt are preferable. Such an alkali metal salt is a dehydrogenation reaction between the compounds B1 to B3 and metal lithium, metal sodium or metal potassium, or the compounds B1 to B3 and lithium hydroxide, sodium hydroxide, potassium hydroxide or the like. It can be obtained by a dehydration reaction from a mixture with an alkali metal hydroxide.

  In addition, the base capable of capturing hydrogen halide used in each of the above-mentioned methods is not particularly limited. For example, trimethylamine, triethylamine, diisopropylethylamine, dimethylaniline, diethylaniline, diisopropylaniline, pyridine, 4 -Aliphatic or aromatic amines such as dimethylaminopyridine, 4-diethylaminopyridine and 4-diisopropylaminopyridine, alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate, and sodium hydroxide, water It is preferable to use alkali metal hydroxides such as potassium oxide and lithium hydroxide. In particular, it is preferable to use an alkali metal hydroxide such as triethylamine, pyridine, or sodium hydroxide.

  The reaction of the above-mentioned cyclic phosphonitrile dihalide and the compounds B1 to B3 can be carried out without solvent for any of the above-mentioned methods, and can also be carried out using a solvent. When a solvent is used, the type of the solvent is not particularly limited as long as it does not adversely affect the reaction. Usually, diethyl ether, tetrahydrofuran (THF), 1,4-dioxane, 1,2- Ethers such as dimethoxyethane, butyl methyl ether, diisopropyl ether, 1,2-diethoxyethane and diphenyl ether, aromatic hydrocarbons such as benzene, toluene, chlorobenzene, nitrobenzene, xylene, ethylbenzene and isopropylbenzene, chloroform and methylene chloride Halogenated hydrocarbons such as pentane, hexane, cyclohexane, heptane, octane, nonane, undecane and dodecane, etc., heterocyclic aromatic hydrocarbons such as pyridine, tertiary amines and cyanide Conversion Is preferably used an organic solvent -based like. Of these, ether-based organic solvents having an ether bond in the molecule and high solubility of the compounds B1 to B3 and their alkali metal salts, and aromatic hydrocarbon-based organic solvents that are easily separated from water It is particularly preferable to use

The reaction temperature at the time of reacting the above-mentioned cyclic phosphonitrile dihalide and the compounds B1 to B3 can be set as appropriate depending on any of the above-mentioned methods or considering the thermal stability of the reaction product. . However, when the reaction is carried out using a solvent, it is usually preferable to set the reaction temperature in a temperature range from −20 ° C. to the boiling point of the solvent. On the other hand, when carrying out the reaction without solvent, the reaction temperature is usually preferably set in the range of 40 to 200 ° C.
In addition, as the formula (4) substituent-containing cyclic phosphazene compound according to the above-described form 2, in particular, 1 to (2n + 2) of (2n + 4) A in the formula (1) is A3. In this case, it is preferable to adopt the above-mentioned method Bc or Method Bd.

  Here, when the method Bc is employed, first, an ether solvent solution or an aromatic hydrocarbon solvent solution of cyclic phosphonitrile dihalide is prepared. Then, an ether solvent solution or an aromatic hydrocarbon solvent solution of an alkali metal salt of compound B3 or an ether solvent solution or an aromatic hydrocarbon of compound B3 and a base capable of trapping hydrogen halide is added to this solvent solution. The system solvent solution is usually added at a temperature of −20 to 50 ° C. over 3 to 24 hours, and is allowed to react in the same temperature range for 1 to 24 hours. A partially substituted product substituted with a G3 group derived from compound B3 is produced. Next, an ether solvent solution or an aromatic solvent of an alkali metal salt of at least one compound selected from the compound B1 and the compound B2 is added to the ether solvent solution or aromatic hydrocarbon solvent solution of the partially substituted product obtained. A hydrocarbon solvent solution or an ether solvent solution or an aromatic hydrocarbon solvent solution of at least one compound selected from Compound B1 and Compound B2 and a base capable of trapping hydrogen halide is usually used at 0 to 50 ° C. And the reaction is carried out at a temperature from 0 ° C. to the boiling point of the solvent, and all of the remaining active halogen atoms are G1 group derived from Compound B1 and G2 group derived from Compound B2 Substitution with at least one of

  On the other hand, when adopting Method Bd, first, an ether solvent solution or an aromatic hydrocarbon solvent solution of cyclic phosphonitrile dihalide is prepared. Then, with respect to this solvent solution, at least one selected from an ether solvent solution or an aromatic hydrocarbon solvent solution of an alkali metal salt of at least one compound selected from Compound B1 and Compound B2 or from Compound B1 and Compound B2 An ether solvent solution or an aromatic hydrocarbon solvent solution of one compound and a base capable of capturing hydrogen halide is usually added at a temperature of −20 to 50 ° C. over 3 to 24 hours. A partially substituted product obtained by reacting for 1 to 24 hours in a range and substituting a part of the active halogen atom of the cyclic phosphonitrile dihalide with at least one of G1 group derived from Compound B1 and G2 group derived from Compound B2 To manufacture. Next, the ether solvent solution or aromatic hydrocarbon solvent solution of the partially substituted product thus obtained is subjected to halogenation with an ether solvent solution or aromatic hydrocarbon solvent solution of compound B3 or compound B3. An ether solvent solution or an aromatic hydrocarbon solvent solution with a base capable of capturing hydrogen is usually added at a temperature of 0 to 50 ° C. over 3 to 24 hours, and from 0 ° C. to the boiling point of the solvent. Reaction at temperature replaces all remaining active halogen atoms with G3 groups derived from compound B3.

Next, the cyclic phosphonitrile substitution product obtained in the above-mentioned step 1, that is, the acyl group-containing cyclic phosphonitrile substitution product is oxidized to produce an acyloxy group-containing cyclic phosphonitrile substitution product (step 2). More specifically, the acyl group-containing cyclic phosphonitrile substitution product is oxidized to produce an acyloxy group-containing cyclic phosphonitrile substitution product.
The method for oxidizing the acyl group-containing cyclic phosphonitrile substitution product is not particularly limited as long as it is a method capable of obtaining the acyloxy group-containing cyclic phosphonitrile substitution product, but it is usually preferable to use the Buyer-Billiger oxidation method. The oxidizing agent that can be used in the Buyer-Billiger oxidation for the oxidation of the acyl group-containing cyclic phosphonitrile substituent is not particularly limited, and various known peroxides. Specifically, inorganic peroxides, organic peroxides, hydrogen peroxide, urea peroxide, transition metal peroxo complexes and the group consisting of organic acids, inorganic acids, Lewis acids, organic peracids, inorganic peracids and dioxiranes And a mixture of at least one selected from the group and a peroxo compound. These oxidizing agents can also be used by mixing as appropriate. A buyer-biller monooxygenase (oxygenase) can also be used.

  Examples of inorganic peroxides include ammonium peroxide, alkali metal peroxide, ammonium persulfate, alkali metal persulfate, ammonium perborate, alkali metal perborate, ammonium percarbonate, alkali metal percarbonate, Mention may be made of mixtures of alkaline earth metal peroxides, zinc peroxides and any combination of these compounds. A preferred alkali metal peroxide is sodium peroxide.

  Examples of organic peroxides include tert-butyl hydroperoxide, cumene hydroperoxide, menthyl hydroperoxide, 1-methylcyclohexane hydroperoxide and mixtures of any combination of these compounds.

  Examples of transition metal peroxo complexes include peroxo complexes of the transition metals iron, manganese, vanadium or molybdenum and mixtures of any combination of these peroxo complexes. This peroxo complex may contain two or more transition metals.

  An example of a mixture of an inorganic acid and a peroxo compound can include a mixture of sulfuric acid and potassium peroxodisulfate, and an example of a mixture of a Lewis acid and a peroxo compound includes boron trifluoride and peroxidation. Mention may be made of mixtures with hydrogen.

  Examples of organic peracids include performic acid, peracetic acid, trifluoroperacetic acid, perbenzoic acid, m-chloroperbenzoic acid, magnesium monoperphthalate, and mixtures of any combination thereof.

  Examples of inorganic peracids include persulfuric acid, percarbonate, permonophosphoric acid, and mixtures thereof.

  The oxidant described above may be used in a pure form or a mixture of various oxidants, but is preferably used in a pure form.

  The required amount of the oxidizing agent used in this step, particularly the equivalent amount of the oxidizing agent to the acyl group of the acyl group-containing cyclic phosphonitrile substituent, depends on the reactivity of the acyl group-containing cyclic phosphonitrile substituent with the oxidizing agent. In general, the equivalent of the oxidizing agent to the acetyl group of the acyl group-containing cyclic phosphonitrile substituted product is preferably set in the range of 1 to 10, more preferably in the range of 1.05 to 1.5, It is particularly preferable to set it in the range of 1.1 to 1.3.

  This step may be performed without a solvent or may be performed using a solvent. When a solvent is used, the type of the solvent is not particularly limited as long as it does not adversely affect the reaction. For example, a halogenated hydrocarbon compound (for example, dichloromethane, chloroform, 1,2-dichloroethane) is used. Or 1,1,2,2-tetrachloroethane), paraffinic compounds (eg, hexane, pentane or ligroin), ether compounds (eg, diethyl ether), acid amide compounds (eg, N, N-dimethylformamide) Nitrile compounds (eg acetonitrile), carbon disulfide, nitroaliphatic compounds (eg nitromethane) or nitroaromatic compounds (eg nitrobenzene) or mixtures of these solvents can be used. Among these, it is preferable to use a halogenated hydrocarbon-based compound.

  Next, the acyloxy group-containing cyclic phosphonitrile substitution product obtained in Step 2 is deacylated to convert the acyloxy group into a hydroxy group (Step 3). Thereby, the objective formula (4) substituent-containing cyclic phosphazene compound is obtained.

  The deacylation in this step may be performed without a solvent or may be performed using a solvent. When a solvent is used, the type of the solvent is not particularly limited as long as it does not adversely affect the reaction, but the same solvents that can be used in Step 2 can be usually used.

  The deacylation in this step is preferably carried out under acidic or alkaline conditions or using an enzyme. These deacylation methods are known, and the conditions can be appropriately set based on the known methods. For example, in the case of deacylation by hydrolysis under acidic or alkaline conditions, an acid (for example, a mineral acid or an organic acid) or an alkali (for example, a mineral acid or an organic acid) or the like in an organic solvent (for example, ethanol, THF or dioxane). , Using an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or an alkali metal carbonate such as potassium carbonate). On the other hand, in the case of deacylation by hydrolysis using an enzyme, an esterolytic enzyme (for example, esterase or lipase) in a mixed solution of an organic solvent (for example, ethanol or dimethyl sulfoxide) and water. ) At 0 to 50 ° C. At this time, a buffer solution may be present in a mixed solution of an organic solvent and water.

  Step 3 can be carried out by isolating the acyloxy group-containing cyclic phosphonitrile substitution product obtained in Step 2 from the reaction solution and applying it to the reaction solution, but the acyloxy group-containing cyclic phosphonitrile obtained in Step 2 can be used. It can also carry out by applying as it is with respect to the reaction liquid containing a nitrile substitution product.

  As a method for isolating the acyloxy group-containing cyclic phosphonitrile substituted product obtained in Step 2 from the reaction solution and a method for isolating the formula (4) substituent-containing cyclic phosphazene compound obtained in Step 3 from the reaction solution. In general, conventional separation methods such as filtration, solvent extraction, column chromatography, and recrystallization can be employed. In addition, the acyloxy group-containing cyclic phosphonitrile substituent obtained in step 2 and the formula (4) substituent-containing cyclic phosphazene compound obtained in step 3 can be purified by the same method.

  The reaction conditions in Steps 2 and 3 are as follows: the type of acyl group-containing cyclic phosphonitrile to be oxidized in Step 2, the type and amount of the oxidizing agent, the presence or absence of the reaction solvent, and the desired formula (4) substituent-containing cyclic phosphazene It can be appropriately selected from a wide range according to the physical properties and use of the compound.

  Incidentally, the oxidation of the acyl group-containing cyclic phosphonitrile substitution product in Step 2 and the hydrolysis of the acyloxy group-containing cyclic phosphonitrile substitution product in Step 3 refer to various literatures, particularly the methods described in the following literatures 22 to 24. Can be implemented.

Reference 22
HASSALL, C.I. H. Author, IN: ADAMS, R.D. (ED.), ORGANIC REACTIONS, WELY, NEW YORK, 1957, VOL. 9, 73-106.
Reference 23
KROW, G.K. R. Written by IN: PAQUETTE, L. A. (ED.), ORGANIC REACTIONS, WELY, NEW YORK, 1993, VOL. 43, 251-798.
Reference 24
KYTE, B.M. G. , ROUVIERE, P.M. , CHENG, Q. , STEWART, J.M. D. , J .; ORG. CHEM. , 2004, VOL. 69 (1), 12-17.

  The formula (4) substituent-containing cyclic phosphazene compound can be produced by the production method described above, but can also be produced by other methods. For example, it can also be produced by removing a protecting group from a substituted cyclic phosphazene compound having a predetermined structure having a site that becomes a hydroxy group by removing the protecting group. More specifically, a compound corresponding to a compound in which the hydroxy group of the formula (4) substituent-containing cyclic phosphazene compound is protected by a protecting group is synthesized, and the protecting group is removed from this compound to remove the target formula 4) A substituent-containing cyclic phosphazene compound can also be produced.

  Here, examples of the protective group for the hydroxy group include a methyl group, a methoxymethyl group, a methylthiomethyl group, a 2-methoxyethoxymethyl group, a tetrahydropyranyl group, a tetrahydrothiopyranyl group, a 4-methoxytetrahydropyranyl group, 4-methoxytetrahydrothiopyranyl group, tetrahydrofuranyl group, tetrahydrofuranyl group, 1-ethoxyethyl group, tert-butyl group, allyl group, benzyl group, o-nitrobenzyl group, triphenylmethyl group, trimethylsilyl group, Examples thereof include a tert-butyldimethylsilyl group, a tert-butyldiphenylsilyl group, a tribenzylsilyl group, and a triisopropylsilyl group. Of these protecting groups, methyl group, methoxymethyl group, tetrahydropyranyl group, 4-methoxytetrahydropyranyl group, tert-butyl group, allyl group, benzyl group and tert-butyldimethylsilyl group are preferred, methyl group, A methoxymethyl group, a tert-butyl group, an allyl group and a benzyl group are particularly preferred.

  Methods for removing these protecting groups are described in many known literatures, and can be selected from various deprotecting reactions depending on the type of protecting group, the stability of the protecting group, and the like. For example, when the protecting group is a methyl group, the cyclic phosphonitrile substituent is preferably reacted with boron trifluoride, trimethylsilane iodide or pyridine hydrochloride. When the protecting group is a tert-butyl group, the cyclic phosphonitrile substituent is preferably reacted with trifluoroacetic acid, hydrogen bromide or trimethylsilane iodide. Furthermore, when the protecting group is a benzyl group, the cyclic phosphonitrile substituent is reacted with hydrogen / Pd-C, metallic sodium / ammonia, trimethylsilane iodide, lithium aluminum hydride, boron tribromide or boron trifluoride. Is preferred.

  The desired cyclic phosphazene compound having the formula (4) substituent group obtained by such elimination of the protecting group is removed from the reaction system by a usual separation and purification method such as filtration, solvent extraction, column chromatography and recrystallization. It can be isolated and purified.

  In the hydroxy group-containing cyclic phosphazene compound, the hydroxyl group equivalent (mass g of the cyclic phosphazene compound containing 1 equivalent of hydroxyl group) is 100 to 5,000 g / eq. Is preferred, 130-1,000 g / eq. Is more preferable. Hydroxyl equivalent weight is 100 g / eq. If it is less than the range, it may be difficult to obtain a resin molded article having high temperature reliability (water resistance). Conversely, 5,000 g / eq. If it exceeds 1, it may be difficult to obtain a resin molded article having good heat resistance (glass transition temperature).

  In the reaction of the polyfunctional glycidyl compound and the cyclic phosphazene compound having a hydroxy group, the amount of the hydroxy group-containing cyclic phosphazene compound used is usually such that the hydroxy group is an epoxy group in the polyfunctional glycidyl compound. It is preferably set to be 10 to 60 equivalent%, and more preferably set to be 15 to 50 equivalent%. If it is less than 10 equivalent%, it may be difficult to obtain a resin molded article having good flame retardancy. On the other hand, when the amount exceeds 60 equivalent%, the epoxy compound composition has a large epoxy equivalent and a high melt viscosity, so that the fluidity is lowered and the handling may be difficult.

  Incidentally, the epoxy equivalent in the epoxy compound composition of the present invention can be set to the above-mentioned preferable range by adjusting the amount of the polyfunctional glycidyl compound and the hydroxy group-containing cyclic phosphazene compound in the above range. .

  Since the reaction between the polyfunctional glycidyl compound and the hydroxy group-containing cyclic phosphazene compound is slow in itself, it is necessary to react at a high temperature, and as a result, it becomes difficult to control the reaction. It is preferable to use it. By using a catalyst, the epoxy group of the polyfunctional glycidyl compound and the hydroxy group of the hydroxy group-containing cyclic phosphazene compound can be reacted quickly at a relatively low temperature, making it easier to control the reaction. The epoxy compound composition can be easily produced.

  The catalysts used here are, for example, quaternary ammonium salts, quaternary phosphonium salts and mixtures thereof. Examples of quaternary ammonium salts include tetramethylammonium chloride, tetraethylammonium bromide, tetrabutylammonium bromide, tetrabutylammonium chloride, trioctylmethylammonium chloride, and benzyltriethylammonium chloride. Two or more of these may be used in combination. Examples of quaternary phosphonium salts include tetraphenylphosphonium chloride, tetrabutylphosphonium chloride, and trioctylethylphosphonium bromide. Two or more of these may be used in combination. The catalyst may be a combination of a quaternary ammonium salt and a quaternary phosphonium salt.

  In general, the catalyst is preferably used in the range of 0.01 to 10% by weight of the polyfunctional glycidyl compound, and more preferably in the range of 0.1 to 5% by weight.

  In the reaction of the polyfunctional glycidyl compound and the hydroxy group-containing cyclic phosphazene compound, a compound having another hydroxy group other than the hydroxy group-containing cyclic phosphazene compound can be used in combination. By using such other compounds having a hydroxy group, the heat resistance (glass transition temperature) and flame retardancy of the resin molded body described later can be adjusted.

  Examples of other compounds having a hydroxy group include bisphenol-A, bisphenol-F, bisphenol-AD, bisphenol-S, tetramethylbisphenol-A, tetramethylbisphenol-F, tetramethylbisphenol-AD, tetramethylbisphenol- S, dihydric phenols such as biphenol and dihydroxynaphthalene, 1,1,1-tris (4-hydroxyphenyl) methane, 1,1,1- (4-hydroxyphenyl) ethane and 4,4- [1- [ And tris (hydroxyphenyl) alkanes such as 4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol. Two or more of these compounds having a hydroxy group can be used in combination.

  When using the other compound which has a hydroxyl group, it is preferable to set the usage-amount to 300 equivalent% or less with respect to a hydroxy group containing cyclic phosphazene compound, and it is more preferable to set to 100 equivalent% or less. When this amount used exceeds 300 equivalent%, it may be difficult to obtain a resin molded article having good flame retardancy.

  The reaction of the polyfunctional glycidyl compound and the hydroxy group-containing cyclic phosphazene compound can be carried out without a solvent or in the presence of a suitable solvent. When a catalyst is used during the reaction, the catalyst can be diluted with an appropriate solvent and used in the former case. Solvents used here are toluene, xylene, methyl cellosolve acetate, tetrahydrofuran (THF), methyl ethyl ketone, methyl isobutyl ketone, N, N-dimethylformamide, N, N-diethylformamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide and A solvent containing no active hydrogen such as N, N-dimethylacetamide is preferred.

  Moreover, it is preferable to set reaction temperature to 80-220 degreeC normally, and it is more preferable to set to 100-200 degreeC. When the reaction temperature is outside this temperature range, the activity of the catalyst is difficult to increase, so that there is a possibility that the reaction becomes slow or the control of the reaction becomes difficult.

  In the reaction of the polyfunctional glycidyl compound and the hydroxy group-containing cyclic phosphazene compound, the polyfunctional glycidyl compound is heated and blown with dry air or nitrogen to remove moisture in the polyfunctional glycidyl compound as much as possible, and then contain the hydroxy group A cyclic phosphazene compound and a catalyst are preferably added. The introduction of the hydroxy group-containing cyclic phosphazene compound and the catalyst may be carried out all at once, but in order to effectively control the progress of the reaction, each separately or simultaneously, divided into several times (ie, intermittently). ) Or continuously gradually. When continuously charging, the charging time is preferably set to 1 to 10 hours, more preferably 2 to 5 hours.

  The above-described reaction is preferably controlled so that 10 to 60 equivalent%, preferably 15 to 50 equivalent%, of the epoxy group in the polyfunctional glycidyl compound reacts with the hydroxy group-containing cyclic phosphazene compound. When less than 10 equivalent% of the epoxy group reacts, it may be difficult to obtain a resin molded article having both high heat resistance and flame retardancy from the resulting epoxy compound composition. On the other hand, if it exceeds 60 equivalent%, it may be difficult to form a resin molded product having satisfactory high temperature reliability using the resulting epoxy compound composition. The proportion of the epoxy group in the polyfunctional glycidyl compound that is involved in the reaction with the hydroxy group of the hydroxy group-containing cyclic phosphazene compound is usually determined by instrumental analysis such as infrared spectroscopy or nuclear magnetic resonance spectroscopy. It can be confirmed by a method or the like.

Use of Epoxy Compound Composition The epoxy compound composition of the present invention can be used as a material for producing a resin molded product. Here, the epoxy compound composition of the present invention can form a resin molded body by curing it alone in a desired shape, but in order to impart desired properties to the resin molded body, A resin molded body can also be formed by mixing with a resin component and curing. Hereinafter, the epoxy compound composition of the present invention and a composition obtained by mixing the composition and another epoxy resin may be collectively referred to as a “resin molded body composition”.

  Resin components that can be mixed with the epoxy compound composition are various thermoplastic resins and thermosetting resins. These resin components may be natural or synthetic. Usable thermoplastic resins include, for example, graft reaction or copolymerization of polyphenylene ether, reactive functional groups such as carboxyl group, epoxy group, amino group, hydroxyl group, and anhydrous dicarboxyl group on part or all of polyphenylene ether. Examples thereof include modified polyphenylene ether, aliphatic polyamide and aromatic polyamide introduced by the above method. Examples of the thermosetting resin include polyurethane, phenol resin, epoxy resin, maleimide resin, cyanate ester resin, maleimide-cyanate ester resin, benzoxazine resin, polybenzimidazole, polyimide resin, polycarbodiimide resin, and the like. An epoxy resin etc. can be mentioned. These various resin components can also use 2 or more types together as needed.

  In the composition for a resin molded body prepared by mixing the epoxy compound composition of the present invention with other resin components, the amount of the epoxy compound composition of the present invention depends on the type of resin component to be mixed and its use (resin molding). It can be suitably set according to various conditions such as body use), but it is usually preferable to set it to 0.1 to 200 parts by weight with respect to 100 parts by weight of the other resin component in terms of solid content, The amount is more preferably set to 0.5 to 100 parts by weight, and further preferably set to 1 to 50 parts by weight. When the usage-amount of the epoxy compound composition of this invention is less than 0.1 weight part, the resin molded object formed using the composition for resin molded objects may not show sufficient flame retardance. On the other hand, when the amount exceeds 200 parts by weight, it may be difficult to obtain characteristics that can be expected from the mixed resin component in the obtained resin molded body.

  In order to cure the resin molded body composition, a curing agent or a curing accelerator can be used. The hardening | curing agent which can be used here can be selected according to the hardening form of the composition for resin moldings.

  For example, in the case of a cured form using an epoxy group, the curing agent includes fats such as ethylenediamine, triethylenepentamine, tetraethylenepentamine, diethylaminopropylamine, hexamethylenediamine, dimer acid-modified ethylenediamine, and N-ethylaminopiperazine. Group amines, metaphenylenediamine, paraphenylenediamine, 2- (dimethylaminomethyl) phenol, 3,3′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylmethane, 4 Aromatic amines such as 4,4'-diaminodiphenol ether, mercaptans such as mercaptopropionic acid esters and terminal mercapto compounds of epoxy resins, bisphenol-A, bisphenol-F, bisphenol-AD, bis Enol-S, tetramethylbisphenol-A, tetramethylbisphenol-F, tetramethylbisphenol-AD, tetramethylbisphenol-S, tetrabromobisphenol-A, tetrachlorobisphenol-A, tetrafluorobisphenol-A and 4,4- Bisphenols such as (1- (4- (1- (4-hydroxyphenyl) -1-methylethyl) phenyl) ethylidene) bisphenol, phenol novolac, cresol novolac, bisphenol-A novolac, brominated phenol novolac and brominated bisphenol -A phenolic resins such as novolak, biphenol, dihydroxynaphthalene, 1,1,1-tris (4-hydroxyphenyl) methane, phosphazene compounds having a hydroxyl group Acid anhydrides such as polyazeline acid anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyl hymic anhydride, phthalic anhydride, trimellitic anhydride and pyromellitic anhydride, 2- Imidazoles such as methylimidazole, 2-ethyl-4-methylimidazole and 2-phenylimidazole, hydrazines such as adipic acid dihydrazide, dimethylbenzylamine and 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) ), Etc., Lewis acids such as boron trifluoride and their salts, triphenylphosphine compounds and dicyandiamide. Two or more of these may be used in combination.

  In the case of a cured form using a crosslinkable group incorporated by modification of an epoxy group or a secondary hydroxy group generated by modification, a melamine resin, a polyisocyanate compound, a blocked isocyanate compound, or the like is used as a curing agent. Examples of the melamine resin include hexamethoxymethylol melamine, methyl butylated melamine, butylated melamine and the like. Examples of the polyisocyanate compound include tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate (HDI), 2,2,4 (or 2,4,4) -trimethyl-1,6-diisocyanatohexane, lysine diisocyanate. , Isophorone diisocyanate, 1,3-bis (isocyanatomethyl) -cyclohexane, 4,4′-dicyclohexylmethane diisocyanate, tetramethylxylene diisocyanate, tolylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, Diisocyanates such as tolidine diisocyanate, xylylene diisocyanate and norbornane diisocyanate and their derivatives Polyisocyanates to be.

  Examples of the polyisocyanate derived from diisocyanate include isocyanurate type polyisocyanate, burette type polyisocyanate, urethane type polyisocyanate, and allophanate type polyisocyanate. Two or more of these polyisocyanate compounds may be used in combination. As the blocked isocyanate compound, for example, a compound obtained by blocking the above-described diisocyanate or polyisocyanate compound with a blocking agent is used. Examples of the blocking agent for preparing the blocked isocyanate compound include alcohols, phenols, oximes, lactams, and active methylenes. Two or more of these blocking agents may be used in combination.

  Furthermore, in the case of a cured form using a reaction between an epoxy group and a cyanate group, a cyanate ester compound can be used as a curing agent. Examples of cyanate ester compounds include those obtained by the reaction of 2,2-bis (4-cyanatophenyl) propane, 1,1-bis (4-cyanatophenyl) butane, novolac resin and cyanogen halide, and Mention may be made of phosphazene compounds having a cyanato group. Two or more cyanate ester compounds may be used in combination.

  Although the usage-amount of a hardening | curing agent is not specifically limited, Usually, it is preferable to set to 0.1 to 90 weight% with respect to the composition for resin moldings, and set to 0.1 to 50 weight% More preferably.

  Moreover, an epoxy compound can also be used as a hardening | curing agent. The epoxy resin usable in this case is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule. For example, glycidyl ethers, glycidyl esters, glycidyl amines, aliphatic Mention may be made of epoxides and cycloaliphatic epoxides and triglycidyl isocyanurate.

  Examples of glycidyl ethers include phenol glycidyl ethers, novolac polyglycidyl ethers, and alkyl glycidyl ethers. Specific examples of phenol glycidyl ethers include, for example, bisphenol-A, bisphenol-F, bisphenol-AD, bisphenol-S, tetramethylbisphenol-A, tetramethylbisphenol-F, tetramethylbisphenol-AD, tetramethylbisphenol. Examples include compounds obtained by glycidylation of dihydric phenols such as -S, biphenol and dihydroxynaphthalene, but 1,1,1-tris (4-hydroxyphenyl) methane, 1,1,1- (4-hydroxy Phenyl) ethane and tris (glycidyloxyphenyl) alkanes such as 4,4- [1- [4- [1- (4-hydroxyphenyl) -1-methylethyl] phenyl] ethylidene] bisphenol and aminophenols are glycidyl. Turned into Things can also be mentioned. Examples of the polyglycidyl ethers of novolak include compounds obtained by glycidylating novolak such as phenol novolak, orthocresol novolak, biphenyl novolak, bisphenol-A novolak, and naphthol novolak. Examples of alkyl glycidyl ethers include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, trimethylolpropane polyglycidyl ether, glycerin polyglycidyl ether, and neopentyl glycol diglycidyl ether.

  Examples of glycidyl esters include diglycidyl ester of hexahydrophthalic acid and diglycidyl ester of dimer acid. Examples of glycidylamines include tetraglycidyldiaminodiphenylmethane, triglycidyl-para-aminophenol, and triglycidyl-meta-aminophenol. Examples of the aliphatic epoxides include epoxidized polybutadiene and epoxidized soybean oil. Examples of the alicyclic epoxides include 3,4-epoxy-6-methylcyclohexyl carboxylate and 3,4-epoxycyclohexyl carboxylate.

  Two or more of these epoxy compounds can be used in combination.

  As the curing accelerator, for example, an imidazole compound, an organic phosphorus compound (phosphine), a tertiary amine, a quaternary ammonium salt, an aminotriazole, and a metal catalyst such as tin or zinc are used. . Further, it is also possible to use an imidazole compound having a potential by masking a secondary amino group with acrylonitrile, isocyanate, melamine or acrylate. Examples of the imidazole compound used here include imidazole, 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 1-benzyl-2-methylimidazole, and 2-heptadecyl. Examples include imidazole, 4,5-diphenylimidazole, 2-methylimidazoline, 2-ethyl-4-methylimidazoline, 2-undecylimidazoline, and 2-phenyl-4-methylimidazoline. Two or more kinds of curing accelerators may be used in combination.

  Although the usage-amount of a hardening accelerator is not specifically limited, Usually, it is preferable to set to 0.01-5 weight part with respect to 100 weight part of the composition for resin moldings. When the amount used is less than 0.01 parts by weight, it is difficult to obtain the effect of using a curing accelerator, and conversely, when it exceeds 5 parts by weight, the composition for a resin molded body to which a curing accelerator is added is stored. Sexuality may deteriorate.

  The composition for resin moldings may be blended with a known reactive diluent as required. The reactive diluent that can be used is not particularly limited, but examples thereof include aliphatic alkyl glycidyl ethers such as butyl glycidyl ether, 2-ethylhexyl glycidyl ether, and allyl glycidyl ether, glycidyl methacrylate, and glycidyl tertiary carboxylate. Examples include alkyl glycidyl esters such as esters, styrene oxide, and aromatic alkyl glycidyl ethers such as phenyl glycidyl ether, cresyl glycidyl ether, para-s-butylphenyl glycidyl ether, and nonylphenyl glycidyl ether. Two or more of these reactive diluents may be used in combination.

  Moreover, the composition for resin moldings may contain a solvent as needed. Usable solvents are, for example, hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirits and naphtha, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, n-butyl acetate and propylene glycol monomethyl. Esters such as ether acetate, alcohols such as methanol, ethanol, isopropanol, n-butanol, ethylene glycol monoethyl ether, butyl cellosolve and butyl carbitol, amides such as N, N-dimethylformamide and N, N-dimethylacetamide In addition, it is water or the like, and can be appropriately selected and used according to the purpose and application. Two or more kinds of solvents can be used in combination.

  The composition for resin moldings contains various fillers and additives that are commonly used in materials for the production of resin moldings, within a range that does not impair the intended physical properties, depending on the type and application of the resin component. You can also.

  Usable fillers are various known ones, for example, clay, clay, kaolin, bentonite, alumina silicate such as feldspar and mica, magnesium silicate such as talc and talc, calcium silicate (walastite) ), Silicates such as pumice powder, natural silica, calcined silica, synthetic silica, amorphous silica, white carbon, aerosil, silica sand, quartz powder and diatomaceous earth, silicic acid or silicic acid, alumina, titanium oxide, Metal oxides such as magnesium oxide, molybdenum oxide and zinc oxide, carbonates such as calcium carbonate, barium carbonate and magnesium carbonate, sulfates such as barium sulfate and magnesium sulfate, titanates such as potassium titanate and barium titanate, Calcium hydroxide, aluminum hydroxide, magnesium hydroxide Hydroxides such as carbon black and graphite, zinc compounds such as zinc borate and zinc molybdate, inorganic or organic balloons such as glass balloons, shirasu balloons and phenol balloons, glass fibers, glass cloth and glass Glasses such as fine powders, and alumina silica fibers, alumina fibers, aramid fibers, boron fibers, carbon fibers, polyvinyl alcohol fibers, polyester fibers, polytetrafluoroethylene fibers, liquid crystal fibers, and PBO (polyparaphenylene benzbisoxazole) Examples thereof include fibers such as fibers. Two or more kinds of fillers can be used in combination.

  Further, usable additives include hindered amine-based, benzotriazole-based and benzophenone-based ultraviolet absorbers, hindered phenol-based, phosphorus-based, sulfur-based and hydrazide-based antioxidants, phosphate esters, condensed phosphorus, and the like. Phosphoric acid esters, phosphoric acid amides, phosphoric acid amide esters, phosphorous compounds such as ammonium phosphate and red phosphorus, nitrogen compounds such as melamine, melamine cyanurate, melam, melem, melon and succinoguanamine, silicone compounds, bromine compounds and chlorine Flame retardants such as paraffins, flame retardant aids such as antimony trioxide, coupling agents such as silanes and titanium, dyes, pigments, colorants, leveling agents, rheology control agents, pigment dispersants, polymerization inhibitors, Examples of repellency inhibitor, antifoaming agent, mold release agent, antistatic agent, etc. . Two or more additives can be used in combination.

  A cured product obtained by curing the composition for a resin molded body, that is, a resin molded body is substantially composed of a polymer having a phosphazene ring derived from the epoxy compound composition of the present invention, and therefore has high heat resistance (high glass Excellent transition temperature) and high temperature reliability (water resistance), and at the same time excellent flame retardancy. For this reason, the composition for resin moldings can be widely used as a material for producing resin moldings used in various fields.

  For example, the composition for a resin molding is a material such as a powder paint, an electrodeposition paint, a paint such as a PCM (pre-coated metal) paint, an adhesive, a sealing material, a molding material, a composite material, a laminate, and a sealing material. Is preferably used. In particular, the resin molding composition is suitable as a material for manufacturing electrical and electronic parts, and a semiconductor sealing material or circuit board (particularly a metal-clad laminate, printed wiring) formed using this composition. Substrate for board, adhesive for printed wiring board, adhesive sheet for printed wiring board, insulating circuit protective film for printed wiring board, conductive paste for printed wiring board, sealing agent for multilayer printed wiring board, interlayer insulating material, insulation Electronic components using a conductive adhesive material, a circuit protective agent, a coverlay film, a cover ink, etc.) are excellent in heat resistance, mechanical properties, high temperature reliability and flame retardancy, and can be expected to operate stably.

  As a resin component to be mixed with the epoxy compound composition of the present invention when the composition for a resin molding is used as a material for electrical and electronic fields, particularly as a sealant or substrate for electronic parts such as LSI, an epoxy resin It is preferable to select a cyanate ester resin, a polyimide resin or a modified polyphenylene ether resin.

EXAMPLES The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited by these. In the following, “unit” in “unit mol” means the smallest structural unit of the cyclic phosphazene compound, for example, (PNA ₂ ) for the general formula (1). In the following, unless otherwise specified, “%” and “parts” mean “% by weight” and “parts by weight”, respectively.

The cyclic phosphazene compounds obtained in the following synthesis examples and the epoxy compound compositions obtained in the examples, etc. are measured with ¹ H-NMR spectrum and ³¹ P-NMR spectrum, CHNP elemental analysis, IR spectrum measurement, alkali It was identified based on the results of analysis of elemental chlorine (residual chlorine) by potentiometric titration using silver nitrate after melting, analysis of elemental phosphorus by ICP-AES after microwave wet decomposition, and TOF-MS analysis. Further, the hydroxyl equivalent of the cyclic phosphazene compound having a hydroxy group is defined in JIS K 0070-1992 “Testing methods for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponified product of chemical products”. The hydroxyl value (mgKOH / g) was measured according to the neutralization titration method of the hydroxyl value measuring method, and the value was converted into the hydroxyl equivalent (g / eq.).

  Moreover, the epoxy equivalent of the composition obtained in the Example and the comparative example is the mass of the composition containing 1 equivalent of epoxy groups according to the method specified in JIS K-7236 “How to determine the epoxy equivalent of epoxy resin”. g (g / eq.) was measured.

Synthesis Example 1 (Production of hydroxy group-containing cyclic phosphazene compound according to Form 2)
[Step 1: Process for producing substituted cyclotriphosphazene]
In a 5-liter reactor equipped with a stirrer, thermometer, reflux condenser, water separator and nitrogen inlet tube, 3,550 mL of toluene, 591 g (6.2 mol) of 98% phenol and 549 g of 44% aqueous NaOH solution were added. Prepared. This was heated under reflux in a nitrogen atmosphere, and water in the reactor was removed by azeotropic dehydration (recovered water: about 470 mL), and then concentrated under normal pressure (distilled toluene: 1,056 g) to obtain a sodium salt of phenol. Prepared. This slurry solution was cooled to 25 ° C., and 1,400 g of tetrahydrofuran (THF) was charged to obtain a uniform solution.

  On the other hand, a toluene solution of hexachlorocyclotriphosphazene [700 g (6.0 unit mol) of hexachlorocyclotriphosphazene, 3,516 g of toluene] in a 10-liter reactor equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube. Was charged. And the sodium salt solution of the said phenol was dripped over 6 hours at 5 degreeC under stirring, and stirring reaction was performed at 25 degreeC for 2 hours, and the phenoxy partially substituted chlorocyclotriphosphazene was obtained.

  Subsequently, in a 20 liter reactor equipped with a stirrer, a thermometer, a reflux condenser, a water separation receiver and a nitrogen introduction tube, toluene 6,600 mL, 99% p-methoxyphenol 978 g (7.8 mol), 470 g of 85% KOH and 560 mL of water were charged. This was heated under reflux in a nitrogen atmosphere, water in the reactor was removed by azeotropic dehydration (recovered water: about 760 mL), and then concentrated at atmospheric pressure (distilled toluene: 1,577 g) to give potassium methoxyphenol Was prepared. The phenoxy partially substituted chlorocyclotriphosphazene was added to the reaction solution, concentrated under normal pressure (distilled toluene: 3,223 g), and stirred for 12 hours under reflux (110 ° C.). After completion of the reaction, 3,000 mL of 2% NaOH aqueous solution was added to dissolve the contents, and then the organic layer was separated using a separatory funnel. The organic layer was washed with 5% NaOH aqueous solution, further washed with water, adjusted to pH 4 with hydrochloric acid, and the toluene layer was separated and concentrated to obtain 1,532 g of a pale yellow product (yield). : 97%) was obtained. The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
—CH ₃ 3.8 (9H), phenyl C—H 6.6 to 6.7 (6H), 6.8 to 6.9 (6H), 6.9 to 7.0 (6H), 7.1 ~ 7.3 (9H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 10.5
◎ TOF-MS (m / z)
755,785,815
◎ Residual chlorine analysis:
<0.01%

From the above analysis results, the products obtained in this step are [N ₃ P ₃ (OC ₆ H ₄ OCH ₃ ) ₂ (OC ₆ H ₅ ) ₄ ], [N ₃ P ₃ (OC ₆ H ₄ OCH). ₃ ) ₃ (OC ₆ H ₅ ) ₃ ] and [N ₃ P ₃ (OC ₆ H ₄ OCH ₃ ) ₄ (OC ₆ H ₅ ) ₂ ], the average composition of which is [NP (OC ₆ H ₄ it was confirmed that _{OCH 3) 1.01 (OC 6 H} 5) 0.99] _3.

[Step 2: Deprotecting group step]
In a 5-liter reactor equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube, 1,422 g (5.4 unit mol) of the above product, 1,200 mL of toluene and 510 g (6.4 mol) of pyridine were added. Prepared. After bubbling 300 g (8.2 mol) of HCl gas into this, it was heated and concentrated (distilled toluene: 1,373 g), and stirred at 200 ° C. for 8 hours. After completion of the reaction, the mixture was cooled, 4,000 mL of methyl isobutyl ketone (MIBK) and 2,000 mL of 1M hydrochloric acid were added to dissolve the contents, and then the organic layer was separated with a separatory funnel. The organic layer was washed with 1M hydrochloric acid and then with water, and after adjusting the pH to 6 with an aqueous NaOH solution, liquid separation was performed, and the organic layer was further washed with water and concentrated to obtain a glassy product 1, 319 g (yield: 98%) was obtained. The analysis result of this product was as follows.

¹ H-NMR spectrum (in heavy acetone, δ, ppm):
Phenyl C—H 6.6 to 7.3 (27H), —OH 8.3 to 8.4 (3H)
◎ ³¹ P-NMR spectrum (in heavy acetone, δ, ppm):
Trimer (P = N) ₃ 10.7
◎ Hydroxyl equivalent:
244 g / eq. (Theoretical value 245 g / eq.)
From the above analysis results, the products obtained in this step are [N ₃ P ₃ (OC ₆ H ₄ OH) ₂ (OC ₆ H ₅ ) ₄ ], [N ₃ P ₃ (OC ₆ H ₄ OH)]. ₃ (OC ₆ H ₅ ) ₃ ] and [N ₃ P ₃ (OC ₆ H ₄ OH) ₄ (OC ₆ H ₅ ) ₂ ], the average composition of which is [NP (OC ₆ H ₄ OH) _{1 .01} (OC ₆ H ₅ ) _0.99 ] ₃ .

Synthesis Example 2 (Production of hydroxy group-containing cyclic phosphazene compound according to Form 2)
[Step 1: Production of substituted cyclotriphosphazene]
41.7 g (0.50 mol) of 48% NaOH aqueous solution, 1,200 mL of toluene and 4′-benzyl in a 3 liter flask equipped with a stirrer, thermometer, reflux condenser, water separator and nitrogen inlet tube 170.2 g (0.50 mol) of oxyphenylsulfonyl-4-phenol was charged. This was stirred and heated in a nitrogen atmosphere, and water in the flask was removed by azeotropic dehydration (recovered water: about 30 mL) to prepare a sodium salt of 4′-benzyloxyphenylsulfonyl-4-phenol. The slurry solution was cooled to 20 ° C., and 600 mL of THF was charged to make a uniform solution.

  On the other hand, in a 1 liter flask equipped with a stirrer, a thermometer, a reflux condenser, a water separation receiver and a nitrogen introduction tube, 87.7 g (0.75 mol) of 48% aqueous KOH solution, 550 mL of toluene and 70.6 g of phenol (0.75 mol) was charged. This was stirred and heated in a nitrogen atmosphere, and water in the flask was removed by azeotropic dehydration (recovered water: about 58 mL) to prepare a potassium potassium salt. The slurry solution was cooled to 20 ° C., and 200 mL of THF was charged to make a uniform solution.

  Next, a THF solution of hexachlorocyclotriphosphazene [58.0 g (0.50 unit mol), THF 300 mL] of hexachlorocyclotriphosphazene was placed in a 5-liter flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube. Prepared. The above 4'-benzyloxyphenylsulfonyl-4-phenol sodium salt solution was added dropwise thereto at 5 ° C. over 6 hours with stirring, and the stirring reaction was carried out at 25 ° C. for 4 hours. Subsequently, the potassium salt solution of phenol was added dropwise to the reaction solution at 25 ° C. over 1 hour with stirring, and the stirring reaction was performed under reflux (103 ° C.) for 2 hours. After completion of the reaction, the reaction solution was concentrated to about 1,000 mL, and after adding 200 mL of toluene and 400 mL of water to dissolve the contents, the organic layer was separated using a separatory funnel. This organic layer was washed twice with 5% NaOH aqueous solution, neutralized with 2% sulfuric acid, further washed with water three times, and then toluene was distilled off. As a result, 201.1 g (yield) : 87%) was obtained. This product did not show a clear melting point due to the glassy solid. The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
-CH ₂ - 5.1 (2H), phenyl C-H 6.7~7.0 (4H), 7.0~7.2 (5H), 7.3~7.4 (5H), 7. 6-7.9 (4H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.3
◎ CHNP elemental analysis:
Theoretical value C: 62.9%, H: 4.2%, N: 3.0%, P: 6.7%
Measured value C: 62.9%, H: 4.2%, N: 3.1%, P: 6.9%
◎ Residual chlorine analysis:
<0.01%
◎ TOF-MS (m / z):
1187, 1434, 1680

From the above analysis results, the product obtained in this step is [N ₃ P ₃ (OC ₆ H ₄ —SO ₂ —C ₆ H ₄ OCH ₂ C ₆ H ₅ ) ₂ (OC ₆ H ₅ ) ₄ ]. _{, [N 3 P 3 (OC} 6 H 4 -SO 2 -C 6 H 4 OCH 2 C 6 H 5) 3 (OC 6 H 5) 3] and _{[N 3 P 3 (OC 6} H 4 -SO 2 - C ₆ H ₄ OCH ₂ C ₆ H ₅ ) ₄ (OC ₆ H ₅ ) ₂ ], the average composition of which is [NP (OC ₆ H ₄ —SO ₂ —C ₆ H ₄ OCH ₂ C ₆ H ₅ ) _0.95 (OC ₆ H ₅ ) _1.05 ] ₃ .

[Step 2: Deprotecting group step]
In a 2 liter flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, 139.5 g (0.30 unit mol) of the product obtained in Step 1 and 800 mL of toluene were charged, and under a nitrogen atmosphere. Boron tribromide (26.9 mL, 0.29 mol) was added dropwise at 5-10 ° C. over 4 hours, and then aged with stirring at 25-30 ° C. for 12 hours. After the reaction, the reaction solution was added to 800 mL of water, and the organic layer was separated using a separatory funnel. When this organic layer was washed 3 times with water and then toluene was distilled off, 105.9 g (yield: 93%) of a brown solid product was obtained. This product did not show a clear melting point due to the glassy solid. The analysis result of this product was as follows.

¹ H-NMR spectrum (in heavy acetone, δ, ppm):
Phenyl C—H 6.8 to 7.3 (9H), 7.7 to 7.9 (4H), —OH 9.5 (1H)
◎ ³¹ P-NMR spectrum (in heavy acetone, δ, ppm):
Trimer (P = N) ₃ 9.6
◎ CHNP elemental analysis:
Theoretical value C: 56.0%, H: 3.4%, N: 3.7%, P: 8.2%
Measured value C: 55.7%, H: 3.7%, N: 3.8%, P: 8.4%
◎ Hydroxyl equivalent:
378 g / eq. (Theoretical value 380 g / eq.)

From the above analysis results, the products obtained in this step are [N ₃ P ₃ (OC ₆ H ₄ —SO ₂ —C ₆ H ₄ OH) ₂ (OC ₆ H ₅ ) ₄ ], [N ₃ P ₃ (OC ₆ H ₄ —SO ₂ —C ₆ H ₄ OH) ₃ (OC ₆ H ₅ ) ₃ ] and [N ₃ P ₃ (OC ₆ H ₄ —SO ₂ —C ₆ H ₄ OH) ₄ (OC ₆ a mixture of H _{5) 2],} confirmed that the average composition _{[NP (OC 6 H 4 -SO} 2 -C 6 H 4 OH) 0.95 (OC 6 H 5) 1.05] which is ₃ did.

Synthesis Example 3 (Production of hydroxy group-containing cyclic phosphazene compound according to Form 1)
[Step 1: Production of substituted cyclophosphazene]
152.0 g (1.30 mol) of 48% aqueous KOH solution, 2,000 mL of toluene and 4′-benzyl in a 3 liter flask equipped with a stirrer, thermometer, reflux condenser, water separator and nitrogen inlet 442.5 g (1.30 mol) of oxyphenylsulfonyl-4-phenol was charged. This was stirred and heated in a nitrogen atmosphere, and water in the flask was removed by azeotropic dehydration (recovered water: about 102 mL) to prepare a potassium salt of 4′-benzyloxyphenylsulfonyl-4-phenol. The slurry solution was cooled to 20 ° C. and charged with 400 mL of THF to obtain a uniform solution.

  Next, in a 5-liter flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen introduction tube, a THF solution of chlorophosphazene [hexachlorocyclotriphosphazene 52.2 g (0.45 unit mol), octachlorocyclotetraphosphazene]. 5.8 g (0.05 unit mol), THF 300 mL], and the potassium salt solution of 4′-benzyloxyphenylsulfonyl-4-phenol was added dropwise with stirring at 25 ° C. over 1 hour, and then refluxed (86 ° C. ) And stirred for 8 hours to carry out the reaction. After completion of the reaction, the reaction solution was concentrated to about 1,500 mL, 500 mL of toluene and 1,000 mL of water were added to dissolve the contents, and then the organic layer was separated using a separatory funnel. This organic layer was washed twice with 5% NaOH aqueous solution, neutralized with 2% sulfuric acid, further washed three times with water, and then toluene was distilled off. As a result, 314.8 g of a white solid product (yield: 87 %)was gotten. The melting point (melting peak temperature) of this product was 149 ° C. The analysis result of this product was as follows.

¹ H-NMR spectrum (in heavy acetone, δ, ppm):
-CH ₂ - 5.0 (4H), phenyl C-H 6.8~7.9 (26H)
◎ ³¹ P-NMR spectrum (in heavy acetone, δ, ppm):
Trimer (P = N) ₃ 9.5, Tetramer (P = N) ₄ -12.4
◎ CHNP elemental analysis:
Theoretical value C: 63.1%, H: 4.2%, N: 1.9%, P: 4.3%
Measured value C: 62.8%, H: 4.4%, N: 2.1%, P: 4.2%
◎ Residual chlorine analysis:
<0.01%

From the above analysis results, the products obtained in this step are [NP (OC ₆ H ₄ —SO ₂ —C ₆ H ₄ OCH ₂ C ₆ H ₅ ) ₂ ] ₃ and [NP (OC ₆ H ₄ − it was confirmed that _{SO 2 -C 6 H 4 OCH 2} C 6 H 5) 2] is a mixture of _4.

[Step 2: Deprotecting group step]
217.1 g (0.30 unit mol) of the product obtained in Step 1 and 800 mL of acetic acid were charged in a 2 liter flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, and the mixture was charged under nitrogen atmosphere. 323.6 g (1.20 mol) of a% hydrobromic acid / acetic acid solution was added dropwise at 5 to 10 ° C. over 2 hours, and the mixture was stirred and aged at 50 ° C. for 8 hours. After completion of the reaction, the reaction solution is concentrated to distill off excess hydrobromic acid and acetic acid. After adding 700 mL of methyl isobutyl ketone and 600 mL of water to the residue and dissolving, the organic layer is separated with a separatory funnel. Was separated. When this organic layer was washed with water three times and methyl isobutyl ketone was distilled off, 145.1 g (yield: 89%) of a white solid product was obtained. This product did not show a clear melting point due to the glassy solid. The analysis result of this product was as follows.

¹ H-NMR spectrum (in heavy acetone, δ, ppm):
Phenyl C—H 6.8 to 7.9 (16H), —OH 9.5 (2H)
◎ ³¹ P-NMR spectrum (in heavy acetone, δ, ppm):
Trimer (P = N) ₃ 9.5, Tetramer (P = N) ₄ -12.4
◎ CHNP elemental analysis:
Theoretical value C: 53.0%, H: 3.3%, N: 2.6%, P: 5.7%
Measured value C: 52.8%, H: 3.6%, N: 2.5%, P: 5.6%
◎ Hydroxyl equivalent:
274 g / eq. (Theoretical value 272 g / eq.)

From the above analysis results, the product obtained in this _{step, [NP (OC 6 H 4} -SO 2 -C 6 H 4 OH) 2] 3 and _{[NP (OC 6 H 4 -SO} 2 -C 6 H ₄ OH) ₂ ] ₄ was confirmed.

Synthesis Example 4 (Production of hydroxy group-containing cyclic phosphazene compound according to Form 2)
[Step 1: Production of substituted cyclotriphosphazene]
In a 1 liter flask equipped with a stirrer, thermometer, reflux condenser, water separator and nitrogen inlet tube, 41.7 g (0.50 mol) of 48% NaOH aqueous solution, 250 mL of toluene and 47.1 g of phenol (0 .50 mol) was charged. This was stirred and heated under a nitrogen atmosphere, and water in the flask was removed by azeotropic dehydration (recovered water: about 29 mL) to prepare a sodium salt of phenol. The slurry solution was cooled to 20 ° C., and 200 mL of THF was charged to make a uniform solution.

  On the other hand, in a 3 liter flask equipped with a stirrer, thermometer, reflux condenser, water separator and nitrogen inlet tube, 87.7 g (0.75 mol) of 48% aqueous KOH solution, 1,500 mL of toluene and 4 ′ -238.8 g (0.75 mol) of benzyloxyphenylisopropylidene-4-phenol was charged. This was stirred and heated in a nitrogen atmosphere, and water in the flask was removed by azeotropic dehydration (recovered water: about 59 mL) to prepare a potassium salt of 4'-benzyloxyphenylisopropylidene-4-phenol. The slurry solution was cooled to 20 ° C., and 500 mL of THF was charged to make a uniform solution.

  Next, a THF solution of hexachlorocyclotriphosphazene [58.0 g (0.50 unit mol), THF 500 mL] of hexachlorocyclotriphosphazene was placed in a 5-liter flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube. The sodium salt solution of the phenol was added dropwise at 5 ° C. over 6 hours with stirring, and the stirring reaction was carried out at 25 ° C. for 2 hours. Subsequently, the potassium salt solution of 4′-benzyloxyphenylisopropylidene-4-phenol was added dropwise to the reaction solution over 1 hour at 25 ° C. with stirring, and the stirring reaction was performed under reflux (85 ° C.) for 14 hours. went. After completion of the reaction, the reaction solution was concentrated to about 1,000 mL, 500 mL of toluene and 1,000 mL of water were added to dissolve the contents, and then the organic layer was separated using a separatory funnel. The organic layer was washed twice with 5% aqueous NaOH solution, neutralized with 2% sulfuric acid, further washed three times with water, and then toluene was distilled off. As a result, 221.9 g of a brown solid product (yield: 96) was obtained. %)was gotten. This product did not show a clear melting point due to the glassy solid. The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
_{-CH 3 1.6 (6H), -} CH 2 - 5.0 (2H), phenyl CH 6.8~6.9 (5H), 7.0~7.1 ( 8H), 7.2 ~ 7.4 (5H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.9
◎ CHNP elemental analysis:
Theoretical value C: 74.0%, H: 5.8%, N: 3.0%, P: 6.7%
Measured value C: 74.2%, H: 5.8%, N: 2.9%, P: 6.6%
◎ Residual chlorine analysis:
<0.01%
◎ TOF-MS (m / z):
1143, 1368, 1592

From the above analysis results, product obtained in this _{step, [N 3 P 3 (OC} 6 H 4 -C (CH 3) 2 -C 6 H 4 OCH 2 C 6 H 5) 2 (OC 6 H _{5) 4], [N 3} P 3 (OC 6 H 4 -C (CH 3) 2 -C 6 H 4 OCH 2 C 6 H 5) 3 (OC 6 H 5) 3] and _{[N 3 P 3} ( OC ₆ H ₄ —C (CH ₃ ) ₂ —C ₆ H ₄ OCH ₂ C ₆ H ₅ ) ₄ (OC ₆ H ₅ ) ₂ ], the average composition of which is [NP (OC ₆ H ₄ —C (CH ₃ ) ₂ —C ₆ H ₄ OCH ₂ C ₆ H ₅ ) _1.03 (OC ₆ H ₅ ) _0.97 ] ₃ was confirmed.

[Step 2: Deprotecting group step]
138.7 g (0.30 unit mol) of the product obtained in step 1 in a 3 liter flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet, Pd / C (trade name of Degussa) “E 101 NE / W”: 10% Pd) 3.8 g and 2,500 mL of methanol were charged, and the mixture was stirred and reacted at 50 ° C. for 5 hours in a hydrogen atmosphere. After completion of the reaction, the reaction solution was filtered to remove Pd / C, and the filtrate was concentrated to distill off methanol. Then, 1,000 mL of methyl isobutyl ketone and 700 mL of water were added to the residue and dissolved, and the organic layer was separated using a separatory funnel. This organic layer was washed three times with water, and methyl isobutyl ketone was distilled off to obtain 96.4 g (yield: 87%) of a brown solid product. This product did not show a clear melting point due to the glassy solid. The analysis result of this product was as follows.

¹ H-NMR spectrum (in heavy acetone, δ, ppm):
—CH ₃ 1.7 (6H), phenyl C—H 6.8 to 6.9 (4H), 6.9 to 7.2 (5H), 7.2 to 7.3 (4H)
◎ ³¹ P-NMR spectrum (in heavy acetone, δ, ppm):
Trimer (P = N) ₃ 10.0
◎ CHNP elemental analysis:
Theoretical value C: 69.2%, H: 5.5%, N: 3.8%, P: 8.4%
Measured value C: 69.3%, H: 5.3%, N: 3.8%, P: 8.3%
◎ Hydroxyl equivalent:
371 g / eq. (Theoretical value: 369 g / eq.)

From the above analysis results, the product obtained in this step was [NP (OC ₆ H ₄ —C (CH ₃ ) ₂ —C ₆ H ₄ OH) _1.03 (OC ₆ H ₅ ) _0.97 ]. ₃ was confirmed.

Synthesis Example 5 (Production of hydroxy group-containing cyclic phosphazene compound according to Form 2)
[Step 1: Production of acetyl group-containing cyclic phosphazene compound by method Bc above]
A 5-liter 4-neck flask equipped with a thermometer, stirrer, condenser and dropping funnel was charged with hexachlorocyclotriphosphazene (173.8 g, 1.50 unit mol) under a nitrogen stream, and toluene (2,000 mL). To dissolve. A solution of sodium 4-acetyl-3-methylphenoxide (215.1 g, 1.25 mol) in THF (450 mL) was added dropwise thereto over 5 hours, and the mixture was stirred at 25 ° C. for 24 hours. This reaction solution was added to a toluene (1,250 g) suspension of sodium phenoxide (140.5 g, 2.65 mol) prepared in advance, and then refluxed at 110 ° C. for 3 hours. The reaction mixture was cooled to room temperature, 5% aqueous sodium hydroxide solution (500 mL) was added, and the mixture was transferred to a separatory funnel. After separating the aqueous layer, the toluene layer was washed with 5% aqueous sodium hydroxide solution (500 mL), neutralized with dilute nitric acid, and washed with water. The toluene layer was concentrated under reduced pressure to obtain 418.8 g (yield: 98.7%) of the product. The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.4 (6H), 2.5 (6H), 6.7 to 7.5 (26H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.2 to 10.3
◎ Residual chlorine analysis:
<0.01%

From the above analysis results, the products obtained in this step are [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) COCH ₃ ) (OC ₆ H ₅ ) ₅ ], [N ₃ P ₃ (OC ₆ H). ₃ (CH ₃ ) COCH ₃ ) ₂ (OC ₆ H ₅ ) ₄ ] and [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) COCH ₃ ) ₃ (OC ₆ H ₅ ) ₃ ] average composition was confirmed to be a cyclic phosphazene compound of _{[N 3 P 3 (OC 6} H 3 (CH 3) COCH 3) 2.0 (OC 6 H 5) 4.0].

[Step 2: Buyer-Billiger oxidation step]
Into a 1-liter four-necked flask equipped with a thermometer, stirrer and dropping funnel, the compound obtained in Step 1 (187.8 g, 0.70 unit mol), trifluoroacetic anhydride (100 mL) and dichloromethane ( 200 mL) was added, 60% hydrogen peroxide (48.7 g, 0.86 mol) was added dropwise at an internal temperature of 0 ° C. or lower, and the mixture was stirred at an internal temperature of 25 ° C. for 3 hours. After confirming the completion of the reaction, the reaction mixture was transferred to a separatory funnel, washed with 20% aqueous sodium hydrogen sulfite solution, saturated aqueous sodium bicarbonate solution and saturated brine, dried and concentrated to 193.3 g (yield 98.98). 9%) of a brown oily product. The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.2 (6H), 2.4 (6H), 6.8 to 7.3 (26H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.5 to 10.4

From the above analysis results, the products obtained in this step are [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OCOCH ₃ ) (OC ₆ H ₅ ) ₅ ], [N ₃ P ₃ (OC ₆ H). ₃ (CH ₃ ) OCOCH ₃ ) ₂ (OC ₆ H ₅ ) ₄ ] and [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OCOCH ₃ ) ₃ (OC ₆ H ₅ ) ₃ ] It was confirmed that the average composition was [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OCOCH ₃ ) _2.0 (OC ₆ H ₅ ) _4.0 ].

[Step 3: Deacetylation step]
Into a 1-liter four-necked flask equipped with a thermometer and a stirrer, the compound obtained in Step 2 (167.5 g, 0.60 unit mol), methanol (100 mL) and 48% aqueous sodium hydroxide solution (70.9 g) were added. , 0.86 mol), and stirred at room temperature for 4 hours. After confirming the completion of the reaction, methanol was distilled off and the concentrated residue obtained was dissolved by adding deionized water (900 mL) and adjusted to pH 6 with 30% nitric acid. This solution was transferred to a separating funnel and extracted with methyl isobutyl ketone (MIBK), and then the MIBK layer was washed twice with deionized water. The MIBK layer was dried and then concentrated to obtain 140.5 g (yield 93.2%) of the product. The analysis result of this product was as follows.

¹ H-NMR spectrum (in heavy acetone, δ, ppm):
2.1 (6H), 6.5-7.3 (26H)
◎ ³¹ P-NMR spectrum (in heavy acetone, δ, ppm):
Trimer (P = N) ₃ 9.1 to 10.3
◎ CHNP elemental analysis:
Theoretical value C: 60.6%, H: 4.6%, N: 5.6%, P: 12.3%
Measured value C: 60.5%, H: 4.5%, N: 5.7%, P: 12.5%
◎ TOF-MS (m / z):
724, 754, 784
◎ Residual chlorine analysis:
<0.01%
◎ Hydroxyl equivalent:
375 g / eq. (Theoretical value 377 g / eq.)

From the above analysis results, this product is obtained from [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OH) (OC ₆ H ₅ ) ₅ ], [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ )]. OH) ₂ (OC ₆ H ₅ ) ₄ ] and [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OH) ₃ (OC ₆ H ₅ ) ₃ ], the average composition of which is [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OH) _2.0 (OC ₆ H ₅ ) _4.0 ].

Synthesis Example 6 (Production of hydroxy group-containing cyclic phosphazene compound according to Form 2)
[Step 1: Production of acetyl group-containing cyclic phosphazene compound by method Bc above]
Under a nitrogen stream, sodium hydride (76.0 g, 3.17 mol) was charged into a 3 liter four-necked flask equipped with a thermometer, stirrer, condenser, and dropping funnel, and hexachlorocyclotriphosphazene (173.8 g). , 1.50 unit mol) in THF (700 mL) was added. While maintaining this at 0 ° C., a solution of 2-methyl-4-acetylphenol (150.2 g, 1.0 mol) in THF (200 mL) was added dropwise over 1 hour, followed by stirring for 1 hour. A solution of phenol (207.0 g, 2.2 mol) in THF (200 mL) was added dropwise to this reaction solution over 1 hour, and then refluxed at 70 ° C. for 6 hours. The reaction mixture was cooled to room temperature, toluene (1,000 mL) and 5% aqueous sodium hydroxide solution (500 mL) were added, and the mixture was transferred to a separatory funnel. After separating the aqueous layer, the toluene layer was washed with 5% aqueous sodium hydroxide solution (500 mL). After neutralizing the toluene layer with dilute nitric acid, the aqueous layer was separated. The toluene layer was washed with deionized water and concentrated under reduced pressure to obtain 312.3 g (yield: 77.5%) of the product. The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.08 (6H), 2.52 (6H), 6.9-7.8 (26H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.1-9.6
◎ Residual chlorine analysis:
<0.01%

From the above analysis results, the _{product, [N 3 P 3 (OC} 6 H 3 (CH 3) COCH 3) (OC 6 H 5) 5], [N 3 P 3 (OC 6 H 3 (CH 3 ) COCH ₃ ) ₂ (OC ₆ H ₅ ) ₄ ] and [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) COCH ₃ ) ₃ (OC ₆ H ₅ ) ₃ ] with an average composition of [ N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) COCH ₃ ) _2.0 (OC ₆ H ₅ ) _4.0 ] was confirmed to be a cyclic phosphazene compound.

[Step 2: Buyer-Billiger oxidation step]
A 1 liter four-necked flask equipped with a thermometer, stirrer, reflux condenser and dropping funnel was charged with the compound obtained in Step 1 (188.0 g, 0.70 unit mol) and acetonitrile (300 mL), An acetonitrile solution (350 mL, 0.70 mol) of 2M superphosphoric acid prepared in advance at an internal temperature of 0 ° C. or lower was added dropwise. After stirring at 25 ° C. for 2 hours, toluene (500 mL) was added, transferred to a separatory funnel, washed in this order with a saturated aqueous sodium thiosulfate solution, a saturated aqueous sodium bicarbonate solution, and saturated brine, dried and concentrated. 184.5 g (94.4% yield) of a brown oily product was obtained. The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.2 (6H), 2.3 (6H), 6.8 to 7.3 (26H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.6 to 10.3

From the above analysis results, the _{product, [N 3 P 3 (OC} 6 H 3 (CH 3) OCOCH 3) (OC 6 H 5) 5], [N 3 P 3 (OC 6 H 3 (CH 3 ) OCOCH ₃ ) ₂ (OC ₆ H ₅ ) ₄ ] and [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OCOCH ₃ ) ₃ (OC ₆ H ₅ ) ₃ ] with an average composition of [ N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OCOCH ₃ ) _2.0 (OC ₆ H ₅ ) _4.0 ] was confirmed to be a cyclic phosphazene compound.

[Step 3: Deacetylation step]
Into a 1-liter four-necked flask equipped with a thermometer and a stirrer, the compound obtained in Step 2 (167.5 g, 0.60 unit mol), methanol (200 mL) and potassium carbonate (55.3 g, 0.40 mol) were added. ) And stirred at 25 ° C. for 3 hours. After distilling off the solvent, water (300 mL) was added to the concentrated residue and transferred to a separatory funnel. After extracting the product from the aqueous layer with MIBK, the MIBK layer was washed twice with deionized water. The MIBK layer was dried and concentrated to obtain 149.1 g (yield 98.9%) of the product. The analysis result of this product was as follows.

¹ H-NMR spectrum (in heavy acetone, δ, ppm):
2.0 (6H), 6.4 to 7.4 (26H)
◎ ³¹ P-NMR spectrum (in heavy acetone, δ, ppm):
Trimer (P = N) ₃ 9.0-11.5
◎ CHNP elemental analysis:
Theoretical value C: 60.6%, H: 4.6%, N: 5.6%, P: 12.3%
Measured value C: 60.7%, H: 4.5%, N: 5.6%, P: 12.4%
◎ TOF-MS (m / z):
724, 754, 784
◎ Residual chlorine analysis:
<0.01%
◎ Hydroxyl equivalent:
371 g / eq. (Theoretical value 377 g / eq.)

From the above analysis results, the products obtained in this step are [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OH) (OC ₆ H ₅ ) ₅ ], [N ₃ P ₃ (OC ₆ H). ₃ (CH ₃ ) OH) ₂ (OC ₆ H ₅ ) ₄ ] and [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OH) ₃ (OC ₆ H ₅ ) ₃ ], and its average composition Was confirmed to be [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OH) _2.0 (OC ₆ H ₅ ) _4.0 ].

Synthesis Example 7 (Production of hydroxy group-containing cyclic phosphazene compound according to Form 2)
[Step 1: Production of acetyl group-containing cyclic phosphazene compound by method Bd above]
Under a nitrogen stream, sodium hydride (76.0 g, 3.20 mol) was charged into a 3 liter four-necked flask equipped with a thermometer, stirrer, condenser and dropping funnel, and hexachlorocyclotriphosphazene (173.8 g). , 1.50 unit mol) in THF (700 mL) was added. While maintaining this at 0 ° C., a solution of phenol (188.2 g, 2.00 mol) in THF (250 mL) was added dropwise over 1 hour. After stirring the reaction mixture for 1 hour, a solution of 2,6-dimethyl-4-acetylphenol (180.6 g, 1.10 mol) in THF (250 mL) was added dropwise over 1 hour and refluxed at 70 ° C. for 6 hours. did. The reaction mixture was cooled to room temperature, toluene (1,150 mL) and 5% aqueous sodium hydroxide solution (500 mL) were added, and the mixture was transferred to a separatory funnel. After separating the aqueous layer, the toluene layer was washed with a 5% aqueous sodium hydroxide solution (500 mL). The toluene layer was neutralized with dilute nitric acid and washed with water. The toluene layer was concentrated under reduced pressure to obtain 388.6 g (yield: 94.0%) of the product. The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.04 (12H), 2.49 (6H), 6.9 to 7.8 (24H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.3-9.7
◎ Residual chlorine analysis:
<0.01%

From the above analysis results, this product is obtained from [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ COCH ₃ ) (OC ₆ H ₅ ) ₅ ], [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ COCH ₃ ) ₂ (OC ₆ H ₅ ) ₄ ] and [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ COCH ₃ ) ₃ (OC ₆ H ₅ ) ₃ ] The composition was confirmed to be a cyclic phosphazene compound having a composition of [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ COCH ₃ ) _1.9 (OC ₆ H ₅ ) _4.1 ].

[Step 2: Buyer-Billiger oxidation step]
A 1 liter four-necked flask equipped with a thermometer, stirrer, reflux condenser and dropping funnel was charged with the compound obtained in Step 1 (192.9 g, 0.70 unit mol) and chloroform (300 mL), M-Chloroperbenzoic acid (207.1 g, 1.20 mol) was added in portions at an internal temperature of 0 ° C. or lower. The reaction solution was stirred under reflux for 2 hours, then transferred to a separatory funnel and washed with a 20% aqueous sodium hydrogen sulfite solution, a saturated aqueous sodium bicarbonate solution, and saturated brine. The chloroform layer was dried and concentrated under reduced pressure to obtain 185.0 g (yield 92.5%) of a brown oily product. The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.2 (6H), 2.3 (12H) 6.8 to 7.3 (24H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.4 to 10.6
From the above analysis results, this product is obtained from [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ OCOCH ₃ ) (OC ₆ H ₅ ) ₅ ], [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ OCOCH ₃ ) ₂ (OC ₆ H ₅ ) ₄ ] and [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ OCOCH ₃ ) ₃ (OC ₆ H ₅ ) ₃ ], the average It was confirmed that the composition was a cyclic phosphazene compound having a composition of [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ OCOCH ₃ ) _1.9 (OC ₆ H ₅ ) _4.1 ].

[Step 3: Deacetylation step]
In a 3 liter four-necked flask equipped with a thermometer, a stirrer and a reflux condenser, the compound obtained in Step 2 (171.4 g, 0.60 unit mol), acetone (200 mL) and 3M hydrochloric acid (20 mL) were added. The mixture was stirred at reflux for 3 hours. Acetone was distilled off under reduced pressure, saturated aqueous sodium bicarbonate (300 mL) was added to the concentrated residue, and the mixture was transferred to a separatory funnel. After extracting the product from the aqueous layer with MIBK, the MIBK layer was washed twice with deionized water. The MIBK layer was dried and concentrated to obtain 151.9 g (yield 96.6%) of the product. The analysis result of this product was as follows.

¹ H-NMR spectrum (in heavy acetone, δ, ppm):
2.0 (12H), 6.4 to 7.3 (24H), 8.2 (2H)
◎ ³¹ P-NMR spectrum (in heavy acetone, δ, ppm):
Trimer (P = N) ₃ 9.2 to 10.2.
◎ CHNP elemental analysis:
Theoretical value C: 61.4%, H: 4.9%, N: 5.4%, P: 11.9%
Measured value C: 61.2%, H: 4.8%, N: 5.5%, P: 11.7%
◎ TOF-MS (m / z):
738, 782, 826
◎ Residual chlorine analysis:
<0.01%
◎ Hydroxyl equivalent:
373 g / eq. (Theoretical value 374 g / eq.)

From the above analysis results, this product is obtained from [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ OH) (OC ₆ H ₅ ) ₅ ], [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ )]. ) ₂ OH) ₂ (OC ₆ H ₅ ) ₄ ] and [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ OH) ₃ (OC ₆ H ₅ ) ₃ ] with an average composition of [ N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ OH) _2.1 (OC ₆ H ₅ ) _3.9 ].

Synthesis Example 8 (Production of cyclic phosphazene compound)
PHOSPHORUS-NITROGEN COMPOUNDS, H.P. R. Using a chlorocyclophosphazene mixture of 81% hexachlorocyclotriphosphazene and 19% octachlorocyclotetraphosphazene according to the method described in ALLCOCK, 1972, 151, ACADEMIC PRESS (Reference 17 mentioned above). To obtain a mixture of [NP (OC ₆ H ₅ ) ₂ ] ₃ and [NP (OC ₆ H ₅ ) ₂ ] ₄ (white solid / melting point: 65 to 112 ° C.).

Example 1 (Production of epoxy compound composition)
Hydroxy group-containing cyclic phosphazene compound prepared in Synthesis Example 1 (average composition: [NP (OC ₆ H ₄ OH) _1.01 ) in a 300 ml flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube (OC ₆ H ₅ ) _0.99 ] ₃ ) 24.7 g (0.10 unit mol), 40.9 g (0.12 mol) of 2,2′-bis (4-glycidyloxyphenyl) propane, which is a glycidyl ether, and Triphenylphosphine 1.31 g (0.005 mol) was charged, and a stirring reaction was performed at 140 ° C. for 2 hours. After completion of the reaction, the reaction solution was cooled to 25 ° C., and 66.8 g of a slightly yellow viscous substance was obtained. The analysis result of this product was as follows.

IR spectrum (KBr Pellet, cm ⁻¹ ):
Phosphazene ring (P = N) 1171, glycidyl group (epoxy C—O) 1243
◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
—CH ₃ 1.6, glycidyl 2.7, 2.9, 3.3, 4.0, 4.2, epoxy ring-opening site 4.2, 4.4, phenyl C—H 6.6-7. 2
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 10.5
◎ Epoxy equivalent 479 g / eq. (Theoretical value 478 g / eq.)

From the above analysis results and GPC analysis, this product does not contain the raw material [NP (OC ₆ H ₄ OH) _1.01 (OC ₆ H ₅ ) _0.99 ] ₃ and has a polyfunctionality having a phosphazene ring. It was confirmed that the mixture was composed of an epoxy compound and 2,2′-bis (4-glycidyloxyphenyl) propane used in excess.

Example 2 (Production of epoxy compound composition)
Hydroxy group-containing cyclic phosphazene compound prepared in Synthesis Example 1 (average composition: [NP (OC ₆ H ₄ OH) _1.01 ) in a 300 ml flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube (OC ₆ H ₅ ) _0.99 ] ₃ ) 24.7 g (0.10 unit mol), 2,2′-bis (4-glycidyloxyphenyl) propane 68.1 g (0.20 mol) as glycidyl ethers and 2.6 g (0.01 mol) of triphenylphosphine was charged, and a stirring reaction was performed at 140 ° C. for 2 hours. When the reaction solution was cooled to 25 ° C. after the completion of the reaction, 95.1 g of a slightly yellow viscous substance was obtained. The analysis result of this product was as follows.

IR spectrum (KBr Pellet, cm ⁻¹ ):
Phosphazene ring (P = N) 1172, glycidyl group (epoxy C—O) 1243
◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
—CH ₃ 1.6, glycidyl 2.7, 2.9, 3.3, 4.0, 4.2, epoxy ring-opening site 4.2, 4.4, phenyl C—H 6.6-7. 2
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 10.5
◎ Epoxy equivalent 322 g / eq. (Theoretical value 318 g / eq.)

From the above analysis results and GPC analysis, this product does not contain the raw material [NP (OC ₆ H ₄ OH) _1.01 (OC ₆ H ₅ ) _0.99 ] ₃ and has a polyfunctionality having a phosphazene ring. It was confirmed that the mixture was composed of an epoxy compound and 2,2′-bis (4-glycidyloxyphenyl) propane used in excess.

Example 3 (Production of epoxy compound composition)
Hydroxy group-containing cyclic phosphazene compound prepared in Synthesis Example 1 (average composition: [NP (OC ₆ H ₄ OH) _1.01 ) in a 300 ml flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube (OC ₆ H ₅ ) _0.99 ] ₃ ) 24.7 g (0.10 unit mol), glycidyl ether of orthocresol novolak which is a glycidyl ether (trade name “EOCN-104S” of Nippon Kayaku Co., Ltd .: epoxy equivalent 218 g / eq.) 43.6 g (0.20 eq.) And triphenylphosphine 1.3 g (0.005 mol) were charged, and a stirring reaction was performed at 130 ° C. for 2 hours. When the reaction solution was cooled to 25 ° C. after completion of the reaction, 69.3 g of a slightly yellow viscous substance was obtained. The analysis result of this product was as follows.

IR spectrum (KBr Pellet, cm ⁻¹ ):
Phosphazene ring (P = N) 1173, glycidyl group (epoxy C—O) 1241
◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
—CH ₃ 1.6, glycidyl 2.7, 2.9, 3.3, 4.0, 4.2, epoxy ring-opening site 4.2, 4.4, phenyl C—H 6.6-7. 2
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 10.5
◎ Epoxy equivalent 703 g / eq. (Theoretical value 696 g / eq.)

From the above analysis results and GPC analysis, this product does not contain the raw material [NP (OC ₆ H ₄ OH) _1.01 (OC ₆ H ₅ ) _0.99 ] ₃ and has a polyfunctionality having a phosphazene ring. It was confirmed that the mixture was composed of an epoxy compound and glycidyl ether of orthocresol novolak used in excess.

Example 4 (Production of epoxy compound composition)
Hydroxy group-containing cyclic phosphazene compound prepared in Synthesis Example 2 (average composition: [NP (OC ₆ H ₄ —SO ₂ —C) in a 300 ml flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube ₆ H ₄ OH) _0.95 (OC ₆ H ₅ ) _1.05 ] ₃ ) 38.7 g (0.10 unit mol), 2,2′-bis (4-glycidyloxyphenyl) propane 68, which is a glycidyl ether. 0.1 g (0.20 mol) and 2.6 g (0.01 mol) of triphenylphosphine were charged, and a stirring reaction was performed at 140 ° C. for 6 hours. When the reaction solution was cooled to 25 ° C. after completion of the reaction, 109.3 g of a brown solid oily substance was obtained. The analysis result of this product was as follows.

IR spectrum (KBr Pellet, cm ⁻¹ ):
Phosphazene ring (P = N) 1174, glycidyl group (epoxy C—O) 1241, sulfone (S═O) 1160, 1312
◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
Glycidyl 2.7, 2.9, 3.3, 4.0, 4.2, epoxy ring-opening site 4.2, 4.4, phenyl C—H 7.2-7.9
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 10.9
◎ Epoxy equivalent 368 g / eq. (Theoretical value 365 g / eq.)

From the above analysis results and GPC analysis, the product is free of _{[NP (OC 6 H 4 -SO} 2 -C 6 H 4 OH) 0.95 (OC 6 H 5) 1.05] 3 of the raw material It was confirmed that the mixture was composed of a polyfunctional epoxy compound having a phosphazene ring and 2,2′-bis (4-glycidyloxyphenyl) propane used in excess.

Example 5 (Production of epoxy compound composition)
A hydroxy group-containing cyclic phosphazene compound produced in Synthesis Example 3 ([NP (OC ₆ H ₄ —SO ₂ —C ₆ H ₄₎ was prepared in a 300 ml flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube. OH) ₂ ] ₃ and a mixture of [NP (OC ₆ H ₄ —SO ₂ —C ₆ H ₄ OH) ₂ ] ₄ ), 54.4 g (0.10 unit mol), 2,2′- which is a glycidyl ether Bis (4-glycidyloxyphenyl) propane 68.1 g (0.20 mol) and triphenylphosphine 2.6 g (0.01 mol) were charged, and a stirring reaction was performed at 130 ° C. for 1 hour. After completion of the reaction, the reaction solution was cooled to 25 ° C. to obtain 124.8 g of a brown oily substance. The analysis result of this product was as follows.

IR spectrum (KBr Pellet, cm ⁻¹ ):
Phosphazene ring (P = N) 1174, glycidyl group (epoxy C—O) 1241, sulfone (S═O) 1160, 1312
◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
—CH ₃ 1.6, glycidyl 2.7, 2.9, 3.3, 4.0, 4.2, epoxy ring-opening site 4.2, 4.4, phenyl C—H 7.2-7. 9
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 10.3
◎ Epoxy equivalent 633 g / eq. (Theoretical value 626 g / eq.)

From this analysis result and GPC analysis, this product was obtained from the raw material hydroxy group-containing cyclic phosphazene compounds ([NP (OC ₆ H ₄ —SO ₂ —C ₆ H ₄ OH) ₂ ] ₃ and [NP (OC _6). H ₄ —SO ₂ —C ₆ H ₄ OH) ₂ ] ₄ ), a polyfunctional epoxy compound having a phosphazene ring, and 2,2′-bis (4-glycidyloxyphenyl) used in excess ) Confirmed to be a mixture of propane.

Example 6 (Production of epoxy compound composition)
Hydroxy group-containing cyclic phosphazene compound prepared in Synthesis Example 4 in a 300 ml flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube (presumed structure: [NP (OC ₆ H ₄ -C (CH ₃ ) ₂ -C ₆ H ₄ OH) _1.03 (OC ₆ H ₅ ) _0.97 ] ₃ ) 36.9 g (0.10 unit mol), 2,2′-bis (4-glycidyloxy) which is a glycidyl ether 68.1 g (0.20 mol) of phenyl) propane and 2.6 g (0.01 mol) of triphenylphosphine were charged, and a stirring reaction was performed at 130 ° C. for 1 hour. After completion of the reaction, the reaction solution was cooled to 25 ° C. to obtain 107.3 g of a brown oily substance. The analysis result of this product was as follows.

IR spectrum (KBr Pellet, cm ⁻¹ ):
Phosphazene ring (P = N) 1174, glycidyl group (epoxy C—O) 1241
◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
—CH ₃ 1.6, glycidyl 2.7, 2.9, 3.3, 4.0, 4.2, epoxy ring-opening site 4.2, 4.4, phenyl C—H 6.6-7. 2
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 10.3
◎ Epoxy equivalent 361 g / eq. (Theoretical value 359 g / eq.)

From this analysis result and GPC analysis, this product was obtained as a raw material hydroxy group-containing cyclic phosphazene compound [NP (OC ₆ H ₄ -C (CH ₃ ) ₂ -C ₆ H ₄ OH) _1.03 (OC ₆ H _{5) 0.97] 3} contains no, it was confirmed that a mixture consisting of a polyfunctional epoxy compound, and excess was used 2,2'-bis (4-glycidyloxy-phenyl) propane having a phosphazene ring .

Example 7 (Production of epoxy compound composition)
Hydroxy group-containing cyclic phosphazene compound prepared in Synthesis Example 5 (average composition: [N ₃ P ₃ (OC ₆ H ₃ (CH)] in a 1 liter flask equipped with a stirrer, thermometer, reflux condenser and nitrogen introduction tube ₃ ) OH) _2.0 (OC ₆ H ₅ ) _4.0 ] / hydroxyl equivalent: 375 g / eq.) 100 g, 2,2′-bis (4-glycidyloxyphenyl) methane (epoxy equivalent) which is a glycidyl ether : 160 g / eq.) 90 g, 1,8-diazabicyclo [5.4.0] undecene-7 (DBU) 2 g and THF 200 mL were charged, and the reaction was stirred at 60 ° C. for 20 hours. After confirming disappearance of the raw material by GPC analysis, THF was distilled off under reduced pressure. The residue was diluted with 400 mL of chloroform, transferred to a separatory funnel, and washed with 200 mL of 1% nitric acid. The chloroform layer was washed with deionized water until neutral, then dried and concentrated under reduced pressure to obtain 190 g of an epoxy compound composition. The analysis result of this product was as follows.

IR spectrum (KBr Pellet, cm ⁻¹ ):
Phosphazene ring (P = N) 1,171, glycidyl group (epoxy C—O) 1,243
◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.1, 2.6, 2.8, 3.2, 3.8-4.2, 6.6-7.2
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 10.5
◎ Epoxy equivalent:
706 g / eq. (Theoretical value 699 g / eq.)

From the above analysis results and GPC analysis, this product does not contain the raw material [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OH) _2.0 (OC ₆ H ₅ ) _4.0 ], and phosphazene. It was confirmed that the mixture was composed of a polyfunctional epoxy compound having a ring and 2,2′-bis (4-glycidyloxyphenyl) methane used in excess.

Example 8 (Production of epoxy compound composition)
Cyclic phosphazene compound having a hydroxy group synthesized in Synthesis Example 6 in a 1 liter flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen introduction tube (average composition: [N ₃ P ₃ (OC ₆ H ₃ ( CH ₃ ) OH) _2.0 (OC ₆ H ₅ ) _4.0 ] / hydroxyl equivalent: 371 g / eq.) 100 g, 91 g of 2,2′-bis (4-glycidyloxyphenyl) methane, which is a glycidyl ether, DBU2g and THF200mL were prepared, and it stirred at 60 degreeC for 24 hours. After confirming disappearance of the raw material by GPC analysis, THF was distilled off under reduced pressure. The residue was diluted with 400 mL of chloroform, transferred to a separatory funnel, and washed with 200 mL of 1% nitric acid. The chloroform layer was washed with deionized water until neutral, then dried and concentrated under reduced pressure to obtain 191 g of an epoxy compound composition. The analysis result of this product was as follows.

IR spectrum (KBr Pellet, cm ⁻¹ ):
Phosphazene ring (P = N) 1,171, glycidyl group (epoxy C—O) 1,243
◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.0, 2.6, 2.8, 3.2, 3.8-4.2, 6.4-7.2
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 10.5
◎ Epoxy equivalent 705 g / eq. (Theoretical value 699 g / eq.)

From the above analysis results and GPC analysis, this product does not contain the raw material [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OH) _2.0 (OC ₆ H ₅ ) _4.0 ], It was confirmed that the mixture was composed of a polyfunctional epoxy compound having a phosphazene ring and 2,2′-bis (4-glycidyloxyphenyl) methane used in excess.

Example 9 (Production of epoxy compound composition)
Hydroxy group-containing cyclic phosphazene compound synthesized in Synthesis Example 7 in a 1 liter flask equipped with a thermometer, a stirrer, a reflux condenser and a nitrogen introduction tube (average composition: [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ OH) _2.1 (OC ₆ H ₅ ) _3.9 ] / hydroxyl equivalent: 373 g / eq.) 100 g, glycidyl ethers 2,2′-bis (4-glycidyloxyphenyl) methane 90 g, DBU2g and THF200mL were prepared, and it stirred at 60 degreeC for 24 hours. After confirming disappearance of the raw material by GPC analysis, THF was distilled off under reduced pressure. The residue was diluted with 400 mL of chloroform, transferred to a separatory funnel, and washed with 200 mL of 1% nitric acid. The chloroform layer was washed with deionized water until neutral, then azeotropically dehydrated and concentrated under reduced pressure to obtain 190 g of an epoxy compound composition. The analysis result of this product was as follows.

IR spectrum (KBr Pellet, cm ⁻¹ ):
Phosphazene ring (P = N) 1,171, glycidyl group (epoxy C—O) 1,243
◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.0, 2.6, 2.8, 3.8-4.2, 6.6-7.2
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 10.5
◎ Epoxy equivalent:
720 g / eq. (Theoretical value 713 g / eq.)

From the above analysis results and GPC analysis, this product does not contain the raw material [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ OH) _2.1 (OC ₆ H ₅ ) _3.9 ]. It was confirmed that the mixture was composed of a polyfunctional epoxy compound having a phosphazene ring and 2,2′-bis (4-glycidyloxyphenyl) methane used in excess.

Example 10 (Production of epoxy compound composition)
Hydroxy group-containing cyclic phosphazene compound prepared in Synthesis Example 5 (average composition: [N ₃ P ₃ (OC ₆ H ₃ (CH)] in a 300 ml flask equipped with a stirrer, thermometer, reflux condenser and nitrogen introduction tube ₃ ) OH) _2.0 (OC ₆ H ₅ ) _4.0 ] / hydroxyl equivalent: 375 g / eq.) 100.0 g, glycidyl ether of orthocresol novolak which is glycidyl ethers (trade name of Nippon Kayaku Co., Ltd.) "EOCN-1020-65": Epoxy equivalent 197 g / eq.) 105.1 g and triphenylphosphine 2.0 g were charged, and the mixture was heated and stirred at 130 ° C for 2 hours. The reaction solution was cooled to 25 ° C. to obtain 210.1 g of a slightly yellow solid substance. The analysis result of this product was as follows.

IR spectrum (KBr Pellet, cm ⁻¹ ):
Phosphazene ring (P = N) 1173, glycidyl group (epoxy C—O) 1241
◎ ¹ H-NMR spectrum (in _{DMSO-d 6, δ, ppm} ):
1.6, 2.1, 2.7, 2.9, 3.3, 4.0, 4.2, 4.4, 6.6-7.2
◎ ³¹ P-NMR spectrum (in DMSO-d ₆ , δ, ppm):
Trimer (P = N) ₃ 10.5
◎ Epoxy equivalent 739 g / eq. (Theoretical value: 727 g / eq.)

From the above analysis results and GPC analysis, this product does not contain the raw material [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OH) _2.0 (OC ₆ H ₅ ) _4.0 ], It was confirmed that the mixture was composed of a polyfunctional epoxy compound having a phosphazene ring and glycidyl ether of orthocresol novolak used in excess.

Example 11 (Production of epoxy compound composition)
Hydroxy group-containing cyclic phosphazene compound prepared in Synthesis Example 6 in a 300 ml flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube (average composition: [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OH) _2.0 (OC ₆ H ₅ ) _4.0 ] / hydroxyl equivalent: 371 g / eq.) 100.0 g, glycidyl ether of ortho-cresol novolak which is a glycidyl ether (trade name of Nippon Kayaku Co., Ltd.) “EOCN-1020-65”: Epoxy equivalent 197 g / eq.) 106.2 g and triphenylphosphine 2.0 g were charged, and the mixture was heated and stirred at 130 ° C. for 2 hours. The reaction solution was cooled to 25 ° C. to obtain 211.2 g of a brown solid substance. The analysis result of this product was as follows.

IR spectrum (KBr Pellet, cm ⁻¹ ):
Phosphazene ring (P = N) 1173, glycidyl group (epoxy C—O) 1241
◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
—CH ₃ 1.6, glycidyl 2.7, 2.9, 3.3, 4.0, 4.2, epoxy ring-opening site 4.2, 4.4, phenyl C—H 6.6-7. 2
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 10.5
◎ Epoxy equivalent 745 g / eq. (Theoretical value: 727 g / eq.)

From the above analysis results and GPC analysis, this product does not contain the raw material [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OH) _2.0 (OC ₆ H ₅ ) _4.0 ], It was confirmed that the mixture was composed of a polyfunctional epoxy compound having a phosphazene ring and glycidyl ether of orthocresol novolak used in excess.

Example 12 (Production of epoxy compound composition)
Hydroxy group-containing cyclic phosphazene compound produced in Synthesis Example 7 in a 300 ml flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube (average composition: [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ OH) _2.1 (OC ₆ H ₅ ) _3.9 ] / hydroxyl equivalent: 373 g / eq.) 100.0 g, glycidyl ether of orthocresol novolak which is glycidyl ether (product of Nippon Kayaku Co., Ltd.) Name “EOCN-1020-65”: 106.2 g of epoxy equivalent 197 g / eq.) And 2.0 g of triphenylphosphine were added, and the mixture was heated and stirred at 130 ° C. for 2 hours. The reaction solution was cooled to 25 ° C. to obtain 211.2 g of a brown solid substance. The analysis result of this product was as follows.

IR spectrum (KBr Pellet, cm ⁻¹ ):
Phosphazene ring (P = N) 1173, glycidyl group (epoxy C—O) 1241
◎ ¹ H-NMR spectrum (in _{DMSO-d 6, δ, ppm} ):
—CH ₃ 1.6, glycidyl 2.7, 2.9, 3.3, 4.0, 4.2, epoxy ring-opening site 4.2, 4.4, phenyl C—H 6.6-7. 2
◎ ³¹ P-NMR spectrum (in DMSO-d ₆ , δ, ppm):
Trimer (P = N) ₃ 10.5
◎ Epoxy equivalent 782 g / eq. (Theoretical value 765 g / eq.)

From the above analysis results and GPC analysis, this product does not contain the raw material [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ OH) _2.1 (OC ₆ H ₅ ) _3.9 ]. It was confirmed that the mixture was composed of a polyfunctional epoxy compound having a phosphazene ring and an excessively used glycidyl ether of orthocresol novolak.

Examples 13 to 18 (Production of resin molded body)
50.0 parts of one of the epoxy compound compositions prepared in Examples 1 to 6 and 1.0 part of dicyandiamide were mixed and made uniform, and then poured into a PTFE mold for 2 hours at 160 ° C. Then, it was cured by heating at 190 ° C. for 3 hours to produce two types of sheet-like cured products (resin moldings) having a thickness of 1/16 inch and 5 mm. This sheet-like cured product was confirmed by the IR spectrum that the absorption of epoxy groups completely disappeared.

Comparative Example 1
40.0 parts of diglycidyl ether of bisphenol-A (trade name “jER828”: epoxy equivalent 189 g / eq. Of Japan Epoxy Resin Co., Ltd.), 7.0 parts of cyclic phosphazene compound synthesized in Synthesis Example 8 and 1.0 of dicyandiamide Parts were mixed and made uniform, and a sheet-like cured product was produced in the same manner as in Examples 13-18.

Comparative Example 2
40.0 parts of diglycidyl ether of bisphenol-A (trade name “jER828”: epoxy equivalent 189 g / eq. Of Japan Epoxy Resin Co., Ltd.), 15.0 parts of cyclic phosphazene compound synthesized in Synthesis Example 8 and 1.0 of dicyandiamide Parts were mixed and made uniform, and a sheet-like cured product was produced in the same manner as in Examples 13-18.

Examples 19 to 24 (Production of resin molded body)
50.0 parts of one of the epoxy compound compositions produced in Examples 7 to 12 and 1.0 part of dicyandiamide were mixed and made uniform, and then poured into a PTFE mold at 160 ° C. for 2 hours. It was cured by heating at 190 ° C. for 3 hours and two types of sheet-like cured products (resin molded bodies) having a thickness of 1/16 inch and 5 mm. This sheet-like cured product was confirmed by the IR spectrum that the absorption of epoxy groups completely disappeared.

Evaluation 1
The sheet-like cured products obtained in Examples 13 to 24 and Comparative Examples 1 and 2 were examined for combustibility, high temperature reliability, and heat resistance. Flammability and heat resistance were evaluated using a 1/16 inch thick sheet-like cured product. The heat resistance was evaluated using a sheet-like cured product having a thickness of 5 mm. The evaluation method for each item is as follows. The results are shown in Table 1.

(Combustion quality)
Based on Underwriters Laboratories Inc.'s UL-94 standard vertical combustion test, V-0, V depending on the total combustion time at the 10th flame contact and the presence or absence of cotton ignition by dripping at the time of combustion. -1, V-2 and non-standard four stages. Evaluation criteria are shown below. The flame retardancy level decreases in the order of V-0>V-1>V-2> non-standard.
V-0: All the following conditions are satisfied.
(A) The total extinguishing time after 10 times of flame contact is within 50 seconds, 5 test pieces twice each.
(B) The test piece was fired twice for each of the five test pieces, and the flame-out time after each contact was within 5 seconds.
(C) There is no ignition of the absorbent cotton under 300 mm due to the drop in all the test pieces.
(D) Growing after the second flame contact is within 30 seconds for all specimens.
(E) All specimens are not framing to the clamp.
V-1: All the following conditions are satisfied.
(A) The total extinguishing time after a total of 10 flame contact times is less than 250 seconds, 5 test pieces twice each.
(B) Flame test was performed twice for each of five test pieces, and the flame extinguishing time after each flame contact was within 30 seconds.
(C) There is no ignition of the absorbent cotton under 300 mm due to the drop in all the test pieces.
(D) For all specimens, the glowing after the second flame contact is within 60 seconds.
(E) All specimens are not framing to the clamp.
V-2: All the following conditions are satisfied.
(A) The total extinguishing time after a total of 10 flame contact times is less than 250 seconds, 5 test pieces twice each.
(B) Flame test was performed twice for each of five test pieces, and the flame extinguishing time after each flame contact was within 30 seconds.
(C) At least one of the five test pieces is ignited on the absorbent cotton under 300 mm by the drop.
(D) For all specimens, the glowing after the second flame contact is within 60 seconds.
(E) All specimens are not framing to the clamp.

(High temperature reliability)
The sheet-like cured product was stored in a constant temperature and humidity apparatus at 80 ° C. and 85% relative humidity for 48 hours, then treated at 288 ° C. for 20 minutes, and the change in appearance was observed. In Table 1, “Yes” indicates that the surface of the sheet-like compound does not change in appearance due to bleed-out (that is, has high temperature reliability). “None” indicates that the surface of the sheet-like compound has an appearance change due to bleed-out (that is, there is no high temperature reliability).

(Heat-resistant)
Using the trade name “DMS-200” of Seiko Denshi Kogyo Co., Ltd., the storage length (measurement jig interval) is 20 mm, and the storage elastic modulus (ε ′) of the sheet-like cured product is measured under the following conditions. The inflection point of the storage elastic modulus (ε ′) was defined as the glass transition temperature (° C.). It shows that it is excellent in heat resistance, so that this glass transition temperature is high.
Measurement atmosphere: dry air atmosphere Measurement temperature: within the range of 20 to 400 ° C. Measurement sample: sheet-like cured product slit to 9 mm width and 40 mm length

  As is clear from Table 1, the cured sheets of Examples 13 to 24 and Comparative Examples 1 and 2 are all excellent in flame retardancy, but Comparative Examples 1 and 2 have heat resistance and high temperature reliability. On the other hand, Examples 13-24 are excellent also in these items.

Examples 25-30 (Preparation of a resin molding)
Epoxy compound compositions produced in Examples 1, 2, and 4, glycidyl ether of orthocresol novolak (trade name “EOCN-104S” of Nippon Kayaku Co., Ltd .: epoxy equivalent 218 g / eq.), Dicyandiamide and 2-ethyl- 4-Methylimidazole was mixed in the ratio shown in Table 2 to prepare a resin varnish. This varnish was impregnated and applied to glass cloth (trade name “WEA7628” manufactured by Nitto Boseki Co., Ltd .: treated silane) and dried at 150 ° C. to obtain a prepreg having a resin content of 50%.

Comparative Examples 3 and 4
Cyclic phosphazene compound produced in Synthesis Example 8, diglycidyl ether of bisphenol-A (trade name “jER828” of Japan Epoxy Resin Co., Ltd .: epoxy equivalent 189 g / eq.), Glycidyl ether of orthocresol novolac (Nippon Kayaku Co., Ltd.) Product name “EOCN-104S”: epoxy equivalent 218 g / eq.), Dicyandiamide and 2-ethyl-4-methylimidazole were mixed in the proportions shown in Table 2 to prepare a resin varnish. And using this resin varnish, it carried out similarly to Examples 25-30, and obtained the prepreg.

Examples 31-36 (Preparation of resin molding)
The epoxy compound compositions produced in Examples 7 to 12, glycidyl ether of orthocresol novolak (trade name “EOCN-104S” of Nippon Kayaku Co., Ltd .: epoxy equivalent 218 g / eq.), Dicyandiamide and 2-methylimidazole The resin varnish was prepared by mixing at a ratio shown in 3. This varnish was impregnated and applied to a glass cloth (trade name “WEA 7628”: treated silane system of Nitto Boseki Co., Ltd.) and dried at 150 ° C. to obtain a prepreg having a resin content of 50%.

Comparative Examples 5 and 6
Cyclic phosphazene compound produced in Synthesis Example 8, diglycidyl ether of bisphenol-A (trade name “jER828” of Japan Epoxy Resin Co., Ltd .: epoxy equivalent 189 g / eq.), Glycidyl ether of orthocresol novolac (Nippon Kayaku Co., Ltd.) Trade name “EOCN-104S”: epoxy equivalent 218 g / eq.), Dicyandiamide and 2-methylimidazole were mixed in the proportions shown in Table 3 to prepare a resin varnish. And using this resin varnish, it carried out similarly to Examples 31-36, and obtained the prepreg.

Evaluation 2
Eight prepregs obtained in Examples 25 to 36 and Comparative Examples 3 to 6 were stacked one by one, and a copper foil having a thickness of 18 μm was stacked on both sides thereof at a temperature of 170 ° C. and a pressure of 32 kg / cm ² (3.1 MPa). It was heated and pressed under conditions for 1 hour. Both surfaces of the double-sided copper-clad laminate thus obtained were etched to obtain a sample (1.6 mm thickness). About the obtained sample, combustibility and high temperature reliability were evaluated by the same method as in Evaluation 1. Moreover, the heat resistance of the sample was evaluated by the glass transition temperature of the resin varnish obtained in Examples 25 to 36 and Comparative Examples 3 to 6. The glass transition temperature was measured by curing the resin varnish in an oven at 170 ° C. for 1 hour and using TMA (“TMA / SS220” manufactured by SEIKO) at a temperature rising rate of 10 ° C./min. The results are shown in Tables 2 and 3.

  As is clear from Tables 2 and 3, the samples prepared using the prepregs of Examples 25 to 36 and Comparative Examples 3 to 6 are all excellent in flame retardancy, but Comparative Examples 3 to 6 are heat resistant. In addition, while the high temperature reliability is lacking, Examples 25 to 36 are excellent also in these items.

Claims (11)

  An epoxy compound composition comprising at least two epoxy compounds having a phosphazene ring and an epoxy group, which are obtained by a reaction between a polyfunctional glycidyl compound and a hydroxy group-containing cyclic phosphazene compound.   The epoxy compound according to claim 1, wherein the polyfunctional glycidyl compound is at least one selected from the group consisting of glycidyl ethers, glycidyl esters, glycidyl amines, aliphatic epoxides and alicyclic epoxides. Composition. The epoxy compound composition according to claim 1 or 2, wherein the hydroxy group-containing cyclic phosphazene compound is represented by the following formula (1).

(In Formula (1), n shows the integer of 1-6, A shows the group chosen from the group which consists of following A1 group, A2 group, and A3 group, and at least one is A3 group.
A1 group: an alkoxy group having 1 to 8 carbon atoms which may be substituted with at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group and an aryl group.
A2 group: an aryloxy group having 6 to 20 carbon atoms which may be substituted with at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group and an aryl group.
A3 group: a group selected from the group consisting of a hydroxyaryloxy group represented by the following formula (2) and a hydroxyphenyl-substituted phenyloxy group represented by the following formula (3).

In formula (2), Y represents biphenylene.

In the formula (3), Z represents O, S, SO ₂ , CH ₂ , CHCH ₃ , C (CH ₃ ) ₂ , C (CF ₃ ) ₂ , C (CH ₃ ) CH ₂ CH ₃ or CO. )   The epoxy compound composition according to claim 3, wherein 1 to (2n + 2) of (2n + 4) A in formula (1) is an A3 group.   The epoxy compound composition according to claim 3 or 4, wherein n in formula (1) is 1 or 2.   The epoxy compound composition according to claim 3 or 4, wherein the hydroxy group-containing cyclic phosphazene compound includes two or more compounds having different n in the formula (1). The epoxy compound composition according to any one of claims 1 to 6,
At least one resin component selected from the group consisting of thermoplastic resins and thermosetting resins;
A resin molded body composition comprising:   The resin molding obtained by hardening the composition for resin moldings of Claim 7.   The resin molding obtained by hardening the epoxy compound composition in any one of Claim 1 to 6.   The electronic component using the resin molding of Claim 8.   The electronic component using the resin molding of Claim 9.