JP5177731B2 - Epoxy group-containing cyclic phosphazene compound and method for producing the same - Google Patents

Description

  The present invention relates to a cyclic phosphazene compound and a method for producing the same, and more particularly to an epoxy group-containing cyclic phosphazene compound and a method for producing the same.

  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. Since it has many, it is used frequently, and the 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 sealants and substrates of electronic components such as LSIs, such as epoxy resin compositions, are made of 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. In contrast, phosphazene-based flame retardants have a smaller plastic effect and hydrolyzability than other phosphorus-based flame retardants, and can increase the amount added to the resin composition. Thus, although it is being frequently used as an effective flame retardant for synthetic resins, if the amount 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 (elute) from the resin molded product at a high temperature, and the thermosetting resin-based resin composition In such a 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.

JP 2000-103939 A JP 2004-83671 A JP 2004-210849 A JP 2005-8835 A JP 2005-248134 A

  Then, the improvement for improving the reliability (high temperature reliability) of the resin molded product under high temperature is examined for the phosphazene flame retardant, and as an example, Patent Documents 6 to 10 have an epoxy group. A phosphazene flame retardant and an epoxy 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 insufficient in terms of the essential effect that it is difficult to effectively increase, and it also impairs the mechanical properties (particularly high glass transition temperature) of the resin molded product.

JP-A-3-163090 Japanese Patent Laid-Open No. 6-247989 JP-A-8-193091 JP 2001-335676 A JP 2004-83823 A

  An object of the present invention is to realize a phosphazene compound that can effectively enhance the flame retardancy without impairing the mechanical properties of the resin molded body and that does not easily impair the high temperature reliability of the resin molded body.

  As a result of repeated studies to solve the above-mentioned problems, the present inventors have exhibited excellent mechanical properties and flame retardancy of a molded product comprising a resin composition containing a novel phosphazene compound having an epoxy group, and at the same time It has been found that the reliability at high temperatures is high.

  The phosphazene compound of the present invention is an epoxy group-containing cyclic phosphazene compound represented by the following formula (1).

式（１）中、ｎは３〜１５の整数を示す。また、Ａは、下記のＡ１基、Ａ２基およびＡ３基からなる群から選ばれた基を示しかつ少なくとも一つがＡ３基である。
Ａ１基：炭素数１〜６のアルキル基、アルケニル基およびアリール基から選ばれる少なくとも一種の基で置換されていてもよい、炭素数が１〜８のアルコキシ基。
Ａ２基：炭素数１〜６のアルキル基、アルケニル基およびアリール基から選ばれる少なくとも一種の基で置換されていてもよい、炭素数６〜２０のアリールオキシ基。
Ａ３基：下記の式（３）で示されるエポキシオキシフェニル置換フェニルオキシ基、下記の式（４）で示されるエポキシオキシフェニル置換インダンオキシ基および下記の式（５）で示されるエポキシオキシインダン置換フェニルオキシ基からなる群から選ばれる基。

In formula (1), n shows the integer of 3-15. 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: alkyl group having 1 to 6 carbon atoms, optionally substituted with at least one group selected from an alkenyl group and an aryl group, an alkoxy group having 1 to 8 carbon atoms.
A2 group: alkyl group having 1 to 6 carbon atoms, optionally substituted with at least one group selected from an alkenyl group and an aryl group, an aryloxy group having 6 to 20 carbon atoms.
A3 group: epoxyoxyphenyl substituted phenyloxy group represented by the following formula (3), epoxyoxyphenyl substituted indanoxy group represented by the following formula (4), and epoxyoxyindane substitution represented by the following formula (5) A group selected from the group consisting of phenyloxy groups.

E in the formulas (3), (4) and (5) represents an epoxyoxy group having 2 to 6 carbon atoms. Y in Formula (3) represents O, S, SO ₂ , CH ₂ , CHCH ₃ , C (CH ₃ ) CH ₂ CH ₃ or CO. Furthermore, R ¹ and R ² in Formula (4) and Formula (5) represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, or a phenyl group.

In the epoxy group-containing cyclic phosphazene compound, for example, in formula (1), 2- (2n-2) of 2n A are A3 groups. In the epoxy group-containing cyclic phosphazene compound, for example, the epoxyoxy group represented by E in the formulas (3), (4) and (5) is a glycidyloxy group.

  In the epoxy group-containing cyclic phosphazene compound, for example, n in the formula (1) is 3 or 4. Further, the epoxy group-containing cyclic phosphazene compound includes, for example, two or more epoxy group-containing cyclic phosphazene compounds in which n in formula (1) is different.

The method for producing an epoxy group-containing cyclic phosphazene compound according to the present invention includes the following step 1 and step 2.
[Step 1]
Selected from the group consisting of the following E1, E2, and E3 groups such that at least one of the halogen atoms of the cyclic phosphonitrile dihalide represented by the following formula (6) is substituted by the following E3 group: A step of producing a cyclic phosphonitrile substitution product by substitution with a group.

式（６）中、ｎは３〜１５の整数を示し、Ｘはハロゲン原子を示す。

In formula (6), n represents an integer of 3 to 15, and X represents a halogen atom.

E1 group: alkyl group having 1 to 6 carbon atoms, optionally substituted with at least one group selected from an alkenyl group and an aryl group, an alkoxy group having 1 to 8 carbon atoms.
E2 group: alkyl group having 1 to 6 carbon atoms, optionally substituted with at least one group selected from an alkenyl group and an aryl group, an aryloxy group having 6 to 20 carbon atoms.
E3 group: selected from the group consisting of a substituted phenyloxy group represented by the following formula (8), a substituted indanoxy group represented by the following formula (9), and a substituted phenyloxy group represented by the following formula (10) Group.

G in Formula (8), Formula (9), and Formula (10) represents an alkenyl group having 2 to 6 carbon atoms. Y in Formula (8) represents O, S, SO ₂ , CH ₂ , CHCH ₃ , C (CH ₃ ) CH ₂ CH ₃ or CO. R ¹ and R ^{2 in} Formula (9) and Formula (10) represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, or a phenyl group.

[Step 2]
A step of oxidizing the alkenyl group represented by G at the E3 group of the cyclic phosphonitrile substituted product obtained in step 1 to convert it to an epoxy group.

Moreover, the other manufacturing method of the epoxy-group containing cyclic phosphazene compound which concerns on this invention includes the following process 1-process 3.
[Step 1]
Selected from the group consisting of the following Q1, Q2, and Q3 groups such that at least one of the all halogen atoms of the cyclic phosphonitrile dihalide represented by the above formula (6) is substituted by the following Q3 group: A step of producing a cyclic phosphonitrile substitution product by substitution with a group.

Q1 group: alkyl group having 1 to 6 carbon atoms, optionally substituted with at least one group selected from an alkenyl group and an aryl group, an alkoxy group having 1 to 8 carbon atoms.
Q2 group: alkyl group having 1 to 6 carbon atoms, optionally substituted with at least one group selected from an alkenyl group and an aryl group, an aryloxy group having 6 to 20 carbon atoms.
Q3 group: selected from the group consisting of a substituted phenyloxy group represented by the following formula (12), a substituted indanoxy group represented by the following formula (13), and a substituted phenyloxy group represented by the following formula (14) Group.

式（１２）、式（１３）および式（１４）中のＺは、脱離したときにＯＨ基を形成可能な保護基を示す。式（１２）中のＹは、Ｏ、Ｓ、ＳＯ_２、ＣＨ_２、ＣＨＣＨ _３ 、Ｃ（ＣＨ _３ ）ＣＨ _２ ＣＨ _３ 若しくはＣＯを示す。式（１３）および式（１４）中のＲ^１およびＲ^２は、水素原子、炭素数１〜４のアルキル基、シクロアルキル基若しくはフェニル基を示す。

Z in formula (12), formula (13) and formula (14) represents a protecting group capable of forming an OH group when eliminated. Y in Formula (12) represents O, S, SO ₂ , CH ₂ , CHCH ₃ , C (CH ₃ ) CH ₂ CH ₃ or CO. R ¹ and R ^{2 in} Formula (13) and Formula (14) represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, or a phenyl group.

[Step 2]
A step of removing the protecting group (Z) from the Q3 group of the substituted cyclic phosphonitrile obtained in step 1 to obtain a hydroxyl group-containing cyclic phosphazene compound.

[Step 3]
A step of reacting the hydroxyl group-containing cyclic phosphazene compound obtained in Step 2 with an epihalohydrin in the presence of a base.

  The resin composition of the present invention contains a resin component and the epoxy group-containing cyclic phosphazene compound of the present invention. The resin component used here is, for example, selected from the group consisting of an epoxy resin, a polyimide resin, and a modified polyphenylene ether resin.

  The resin molded body of the present invention is composed of the resin composition of the present invention.

  Since the epoxy group-containing cyclic phosphazene compound of the present invention has a specific structure as described above, its flame retardancy can be effectively enhanced without impairing the mechanical properties of the resin molded article, It is difficult to impair the high temperature reliability of the resin molding.

  Since each manufacturing method of the epoxy group-containing cyclic phosphazene compound according to the present invention includes the steps as described above, the epoxy group-containing cyclic phosphazene compound having the specific structure as described above according to the present invention can be manufactured. it can.

  Since the resin composition of the present invention contains the epoxy group-containing cyclic phosphazene compound of the present invention as a flame retardant, it is possible to obtain a resin molded product that exhibits practical mechanical properties and flame retardancy and has high reliability at high temperatures. it can.

  Since the resin molded product of the present invention is composed of the resin composition of the present invention, it exhibits practical mechanical properties and flame retardancy, and has high reliability at high temperatures.

Epoxy group-containing cyclic phosphazene compound The epoxy group-containing cyclic phosphazene compound of the present invention is represented by the following formula (1).

  In the formula (1), n represents an integer of 3 to 15, preferably an integer of 3 to 8, and particularly preferably 3 or 4. That is, particularly preferable as the epoxy group-containing cyclic phosphazene compound are epoxy group-containing cyclotriphosphazene (trimer) in which n is 3 and epoxy group-containing cyclotetraphosphazene (tetramer) in which n is 4. The epoxy group-containing cyclic phosphazene compound of the present invention may be a mixture of two or more different n.

  In the 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; The alkoxy group, an alkyl group having 1 to 6 carbon atoms, optionally substituted with at least one group selected from 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. Among these, a methoxy group, an ethoxy group, an n-propoxy group, a 1-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; The aryloxy group, an alkyl group having 1 to 6 carbon atoms, optionally substituted with at least one group selected from 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, Isopropenylphenoxy group, 1-butenylphenoxy group, sec-butenylphenoxy group, 1-pentenylphenoxy group, 1-hexenylphenoxy group, phenylphenoxy group, naphthyl Alkoxy group, anthryl group and phenanthryloxy groups and the like. Of these, a phenoxy group, a methylphenoxy group, a dimethylphenoxy group, a diethylphenoxy group, a 1-propenylphenoxy group, a phenylphenoxy group, and a naphthyloxy group are preferable, and a phenoxy group, a methylphenoxy group, a dimethylphenoxy group, and a naphthyloxy group are particularly preferable. preferable.

[Group A3]
An epoxyoxyphenyl-substituted phenyloxy group represented by the following formula (2), an epoxyoxyphenyl-substituted phenyloxy group represented by the following formula (3), and an epoxyoxyphenyl-substituted indanoxy group represented by the following formula (4) And a group selected from the group consisting of epoxyoxyindane-substituted phenyloxy groups represented by the following formula (5).

  In the formulas (2), (3), (4) and (5), E represents an epoxyoxy group having 2 to 6 carbon atoms. Examples of the epoxyoxy group having 2 to 6 carbon atoms include 1,2-epoxyethoxy group, 1,2-epoxypropyloxy group, 2,3-epoxypropyloxy group (that is, glycidyloxy group), 1, 2-epoxy-1-methylethoxy group, 1,2-epoxybutoxy group, 2,3-epoxybutoxy group, 3,4-epoxybutoxy group, 1-methyl-1,2-epoxypropyloxy group, 4,5 -An epoxypentyloxy group, a 5,6-epoxyhexyloxy group, etc. can be mentioned. Among these epoxyoxy groups, epoxyethoxy group, 1,2-epoxypropyloxy group, 2,3-epoxypropyloxy group (glycidyloxy group), 1,2-epoxy-1-methylethoxy group, 1,2 -Epoxybutoxy group, 2,3-epoxybutoxy group and 3,4-epoxybutoxy group are preferred, 1,2-epoxypropyloxy group, 2,3-epoxypropyloxy group (glycidyloxy group) and 3,4- Epoxybutoxy groups are particularly preferred.

  In particular, when E is a glycidyloxy group, when the epoxy group-containing cyclic phosphazene compound of the present invention is used in a resin composition described later, the epoxy group (reactive group) is likely to be immobilized by reacting with the resin component. Thus, the glass transition temperature of the resin composition can be further increased, and the high temperature reliability of the resin molded body made of the resin composition can be more effectively increased.

In Formula (3), Y represents O, S, SO ₂ , CH ₂ , CHCH ₃ , C (CH ₃ ) ₂ , C (CH ₃ ) CH ₂ CH ₃ or CO.

Furthermore, in Formula (4) and Formula (5), R ¹ and R ² represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, or a phenyl group, and an alkyl group, a cycloalkyl group, or In the case of a phenyl group, a plurality of the same or different types may be bonded to the bonded ring structure.

Specific examples of the A3 group described above include the following.
<Epoxyoxyphenyl-substituted phenyloxy group represented by formula (2)>
4 ′-(1,2-epoxyethoxy) phenyl-4-phenyloxy group, 4 ′-(1,2-epoxypropyloxy) phenyl-4-phenyloxy group, 4′-glycidyloxyphenyl-4-phenyloxy group Group, 4 ′-(1,2-epoxy-1-methylethoxy) phenyl-4-phenyloxy group, 4 ′-(1,2-epoxybutoxy) phenyl-4-phenyloxy group, 4 ′-(2, 3-epoxybutoxy) phenyl-4-phenyloxy group, 4 ′-(3,4-epoxybutoxy) phenyl-4-phenyloxy group, 4 ′-(1-methyl-1,2-epoxypropyloxy) phenyl- 4-phenyloxy group, 4 ′-(4,5-epoxypentyloxy) phenyl-4-phenyloxy group and 4 ′-(5,6-epoxyhexyloxy) phenyl-4 -Phenyloxy group and the like. Among these, 4 ′-(1,2-epoxyethoxy) phenyl-4-phenyloxy group, 4 ′-(1,2-epoxypropyloxy) phenyl-4-phenyloxy group, 4′-glycidyloxyphenyl-4 -Phenyloxy group, 4 '-(1,2-epoxy-1-methylethoxy) phenyl-4-phenyloxy group, 4'-(1,2-epoxybutoxy) phenyl-4-phenyloxy group, 4'- (2,3-epoxybutoxy) phenyl-4-phenyloxy group, 4 ′-(3,4-epoxybutoxy) phenyl-4-phenyloxy group is preferred, 4 ′-(1,2-epoxypropyloxy) phenyl -4-phenyloxy group, 4′-glycidyloxyphenyl-4-phenyloxy group, 4 ′-(3,4-epoxybutoxy) phenyl-4-phenyloxy group Particularly preferred.

<Epoxyoxyphenyl-substituted phenyloxy group represented by formula (3)>
4'-epoxyoxyphenyloxy-4-phenyloxy group, 4'-epoxyoxyphenylthio-4-phenyloxy group, 4'-epoxyoxyphenylsulfonyl-4-phenyloxy group, 4'-epoxyoxybenzyl-4 -Phenyloxy group, 4'-epoxyoxyphenylethylidene-4-phenyloxy group, 4'-epoxyoxyphenylisopropylidene-4-phenyloxy group, 4'-epoxyoxyphenyl (1'-methylpropylidene) -4 -Phenyloxy group and 4'-epoxyoxybenzoyl-4-phenyloxy group and the like. Among these, 4'-epoxyoxyphenyloxy-4-phenyloxy group, 4'-epoxyoxyphenylthio-4-phenyloxy group, 4'-epoxyoxyphenylsulfonyl-4-phenyloxy group, 4'-epoxyoxy A phenylisopropylidene-4-phenyloxy group and a 4′-epoxyoxybenzoyl-4-phenyloxy group are preferred. In particular, 4′-epoxyoxyphenyloxy-4-phenyloxy group, 4′-epoxyoxyphenylsulfonyl-4-phenyloxy group and 4′-epoxyoxyphenylisopropylidene-4-phenyloxy group are preferable.

  Specific examples of the 4′-epoxyoxyphenyloxy-4-phenyloxy group include 4 ′-(1,2-epoxyethoxy) phenyloxy-4-phenyloxy group and 4 ′-(1,2-epoxypropyl group). Oxy) phenyloxy-4-phenyloxy group, 4′-glycidyloxyphenyloxy-4-phenyloxy group, 4 ′-(1,2-epoxy-1-methylethoxy) phenyloxy-4-phenyloxy group, 4 '-(1,2-epoxybutoxy) phenyloxy-4-phenyloxy group, 4'-(2,3-epoxybutoxy) phenyloxy-4-phenyloxy group, 4 '-(3,4-epoxybutoxy) Phenyloxy-4-phenyloxy group, 4 ′-(1-methyl-1,2-epoxypropyloxy) phenyloxy-4-pheny An oxy group, 4 '-(4,5-epoxypentyloxy) phenyloxy-4-phenyloxy group, 4'-(5,6-epoxyhexyloxy) phenyloxy-4-phenyloxy group and the like can be mentioned. . Of these, 4 ′-(1,2-epoxyethoxy) phenyloxy-4-phenyloxy group, 4 ′-(1,2-epoxypropyloxy) phenyloxy-4-phenyloxy group, 4′-glycidyloxyphenyl Oxy-4-phenyloxy group, 4 ′-(1,2-epoxy-1-methylethoxy) phenyloxy-4-phenyloxy group, 4 ′-(1,2-epoxybutoxy) phenyloxy-4-phenyloxy The groups 4 ′-(2,3-epoxybutoxy) phenyloxy-4-phenyloxy and 4 ′-(3,4-epoxybutoxy) phenyloxy-4-phenyloxy are preferred. In particular, 4 ′-(1,2-epoxypropyloxy) phenyloxy-4-phenyloxy group, 4′-glycidyloxyphenyloxy-4-phenyloxy group and 4 ′-(3,4-epoxybutoxy) phenyloxy A -4-phenyloxy group is preferred.

  Specific examples of the 4′-epoxyoxyphenylthio-4-phenyloxy group include 4 ′-(1,2-epoxyethoxy) phenylthio-4-phenyloxy group, 4 ′-(1,2-epoxypropyloxy). ) Phenylthio-4-phenyloxy group, 4'-glycidyloxyphenylthio-4-phenyloxy group, 4 '-(1,2-epoxy-1-methylethoxy) phenylthio-4-phenyloxy group, 4'-( 1,2-epoxybutoxy) phenylthio-4-phenyloxy group, 4 ′-(2,3-epoxybutoxy) phenylthio-4-phenyloxy group, 4 ′-(3,4-epoxybutoxy) phenylthio-4-phenyl Oxy group, 4 ′-(1-methyl-1,2-epoxypropyloxy) phenylthio-4-phenyloxy group, 4′- 4,5 epoxy pentyloxy) phenylthio-4-phenyl group and 4 '- (5,6-epoxy hexyloxy) may be mentioned phenylthio-4-phenyl group and the like. Among these, 4 '-(1,2-epoxyethoxy) phenylthio-4-phenyloxy group, 4'-(1,2-epoxypropyloxy) phenylthio-4-phenyloxy group, 4'-glycidyloxyphenylthio- 4-phenyloxy group, 4 ′-(1,2-epoxy-1-methylethoxy) phenylthio-4-phenyloxy group, 4 ′-(1,2-epoxybutoxy) phenylthio-4-phenyloxy group, 4 ′ -(2,3-epoxybutoxy) phenylthio-4-phenyloxy group, 4 '-(3,4-epoxybutoxy) phenylthio-4-phenyloxy group is preferred.

  Specific examples of the 4′-epoxyoxyphenylsulfonyl-4-phenyloxy group include 4 ′-(1,2-epoxyethoxy) phenylsulfonyl-4-phenyloxy group, 4 ′-(1,2-epoxypropyl group). Oxy) phenylsulfonyl-4-phenyloxy group, 4′-glycidyloxyphenylsulfonyl-4-phenyloxy group, 4 ′-(1,2-epoxy-1-methylethoxy) phenylsulfonyl-4-phenyloxy group, 4 '-(1,2-epoxybutoxy) phenylsulfonyl-4-phenyloxy group, 4'-(2,3-epoxybutoxy) phenylsulfonyl-4-phenyloxy group, 4 '-(3,4-epoxybutoxy) Phenylsulfonyl-4-phenyloxy group, 4 ′-(1-methyl-1,2-epoxypropylo Ii) phenylsulfonyl-4-phenyloxy group, 4 '-(4,5-epoxypentyloxy) phenylsulfonyl-4-phenyloxy group and 4'-(5,6-epoxyhexyloxy) phenylsulfonyl-4-phenyl An oxy group etc. can be mentioned. Among these, 4 ′-(1,2-epoxyethoxy) phenylsulfonyl-4-phenyloxy group, 4 ′-(1,2-epoxypropyloxy) phenylsulfonyl-4-phenyloxy group, 4′-glycidyloxyphenyl Sulfonyl-4-phenyloxy group, 4 ′-(1,2-epoxy-1-methylethoxy) phenylsulfonyl-4-phenyloxy group, 4 ′-(1,2-epoxybutoxy) phenylsulfonyl-4-phenyloxy The groups 4 ′-(2,3-epoxybutoxy) phenylsulfonyl-4-phenyloxy and 4 ′-(3,4-epoxybutoxy) phenylsulfonyl-4-phenyloxy are preferred. In particular, 4 ′-(1,2-epoxypropyloxy) phenylsulfonyl-4-phenyloxy group, 4′-glycidyloxyphenylsulfonyl-4-phenyloxy group, 4 ′-(3,4-epoxybutoxy) phenylsulfonyl A -4-phenyloxy group is preferred.

  Specific examples of the 4′-epoxyoxybenzyl-4-phenyloxy group include 4 ′-(1,2-epoxyethoxy) benzyl-4-phenyloxy group and 4 ′-(1,2-epoxypropyloxy). Benzyl-4-phenyloxy group, 4 ′-(glycidyloxy) benzyl-4-phenyloxy group, 4 ′-(1,2-epoxy-1-methylethoxy) benzyl-4-phenyloxy group, 4 ′-( 1,2-epoxybutoxy) benzyl-4-phenyloxy group, 4 ′-(2,3-epoxybutoxy) benzyl-4-phenyloxy group, 4 ′-(3,4-epoxybutoxy) benzyl-4-phenyl Oxy group, 4 ′-(1-methyl-1,2-epoxypropyloxy) benzyl-4-phenyloxy group, 4 ′-(4,5-epoxypentyloxy Benzyl-4-phenyl group and 4 '- (5,6-epoxy hexyloxy) and benzyl-4-phenyl group and the like.

  Specific examples of the 4′-epoxyoxyphenylethylidene-4-phenyloxy group include 4 ′-(1,2-epoxyethoxy) phenylethylidene-4-phenyloxy group and 4 ′-(1,2-epoxypropyl group). Oxy) phenylethylidene-4-phenyloxy group, 4′-glycidyloxyphenylethylidene-4-phenyloxy group, 4 ′-(1,2-epoxy-1-methylethoxy) phenylethylidene-4-phenyloxy group, 4 '-(1,2-epoxybutoxy) phenylethylidene-4-phenyloxy group, 4'-(2,3-epoxybutoxy) phenylethylidene-4-phenyloxy group, 4 '-(3,4-epoxybutoxy) Phenylethylidene-4-phenyloxy group, 4 ′-(1-methyl-1,2-epoxypropylio Ii) phenylethylidene-4-phenyloxy group, 4 '-(4,5-epoxypentyloxy) phenylethylidene-4-phenyloxy group and 4'-(5,6-epoxyhexyloxy) phenylethylidene-4-phenyl An oxy group etc. can be mentioned.

  Specific examples of the 4′-epoxyoxyphenylisopropylidene-4-phenyloxy group include 4 ′-(1,2-epoxyethoxy) phenylisopropylidene-4-phenyloxy group, 4 ′-(1,2- Epoxypropyloxy) phenylisopropylidene-4-phenyloxy group, 4′-glycidyloxyphenylisopropylidene-4-phenyloxy group, 4 ′-(1,2-epoxy-1-methylethoxy) phenylisopropylidene-4- Phenyloxy group, 4 ′-(1,2-epoxybutoxy) phenylisopropylidene-4-phenyloxy group, 4 ′-(2,3-epoxybutoxy) phenylisopropylidene-4-phenyloxy group, 4 ′-( 3,4-epoxybutoxy) phenylisopropylidene-4-phenyloxy group 4 ′-(1-methyl-1,2-epoxypropyloxy) phenylisopropylidene-4-phenyloxy group, 4 ′-(4,5-epoxypentyloxy) phenylisopropylidene-4-phenyloxy group and 4 ′ -(5,6-epoxyhexyloxy) phenylisopropylidene-4-phenyloxy group and the like can be mentioned. Of these, 4 ′-(1,2-epoxyethoxy) phenylisopropylidene-4-phenyloxy group, 4 ′-(1,2-epoxypropyloxy) phenylisopropylidene-4-phenyloxy group, 4′-glycidyl Oxyphenylisopropylidene-4-phenyloxy group, 4 ′-(1,2-epoxy-1-methylethoxy) phenylisopropylidene-4-phenyloxy group, 4 ′-(1,2-epoxybutoxy) phenylisopropylidene group A 4-phenyloxy group, 4 ′-(2,3-epoxybutoxy) phenylisopropylidene-4-phenyloxy group and 4 ′-(3,4-epoxybutoxy) phenylisopropylidene-4-phenyloxy group are preferred. . In particular, 4 ′-(1,2-epoxypropyloxy) phenylisopropylidene-4-phenyloxy group, 4′-glycidyloxyphenylisopropylidene-4-phenyloxy group, 4 ′-(3,4-epoxybutoxy) A phenylisopropylidene-4-phenyloxy group is preferred.

  Specific examples of 4′-epoxyoxyphenyl (1′-methylpropylidene) -4-phenyloxy include 4 ′-(1,2-epoxyethoxy) phenyl (1′-methylpropylidene) -4-phenyl. Oxy group, 4 ′-(1,2-epoxypropyloxy) phenyl (1′-methylpropylidene) -4-phenyloxy group, 4′-glycidyloxyphenyl (1′-methylpropylidene) -4-phenyloxy Group, 4 ′-(1,2-epoxy-1-methylethoxy) phenyl (1′-methylpropylidene) -4-phenyloxy group, 4 ′-(1,2-epoxybutoxy) phenyl (1′-methyl) Propylidene) -4-phenyloxy group, 4 ′-(2,3-epoxybutoxy) phenyl (1′-methylpropylidene) -4-phenyloxy group 4 '-(3,4-epoxybutoxy) phenyl (1'-methylpropylidene) -4-phenyloxy group, 4'-(1-methyl-1,2-epoxypropyloxy) phenyl (1'-methylpropioxy) Ridene) -4-phenyloxy group, 4 ′-(4,5-epoxypentyloxy) phenyl (1′-methylpropylidene) -4-phenyloxy group and 4 ′-(5,6-epoxyhexyloxy) phenyl (1'-methylpropylidene) -4-phenyloxy group and the like can be mentioned.

  Specific examples of the 4′-epoxyoxybenzoyl-4-phenyloxy group include 4 ′-(1,2-epoxyethoxy) benzoyl-4-phenyloxy group and 4 ′-(1,2-epoxypropyloxy). Benzoyl-4-phenyloxy group, 4′-glycidyloxybenzoyl-4-phenyloxy group, 4 ′-(1,2-epoxy-1-methylethoxy) benzoyl-4-phenyloxy group, 4 ′-(1, 2-epoxybutoxy) benzoyl-4-phenyloxy group, 4 ′-(2,3-epoxybutoxy) benzoyl-4-phenyloxy group, 4 ′-(3,4-epoxybutoxy) benzoyl-4-phenyloxy group 4 ′-(1-methyl-1,2-epoxypropyloxy) benzoyl-4-phenyloxy group, 4 ′-(4,5-epoxy Nchiruokishi) benzoyl-4-phenyl group and 4 '- (5,6-epoxy hexyloxy) a benzoyl-4-phenyl group and the like. Among these, 4 '-(1,2-epoxyethoxy) benzoyl-4-phenyloxy group, 4'-(1,2-epoxypropyloxy) benzoyl-4-phenyloxy group, 4'-glycidyloxybenzoyl-4 -Phenyloxy group, 4 '-(1,2-epoxy-1-methylethoxy) benzoyl-4-phenyloxy group, 4'-(1,2-epoxybutoxy) benzoyl-4-phenyloxy group, 4'- (2,3-epoxybutoxy) benzoyl-4-phenyloxy group and 4 ′-(3,4-epoxybutoxy) benzoyl-4-phenyloxy group are preferred.

<Epoxyoxyphenyl-substituted indanoxy group represented by formula (4)>
1,3,3-trimethyl-1- [4 ′-(1,2-epoxyethoxy) phenyl] indane-6-oxy group, 1,3,3-trimethyl-1- [4 ′-(1,2- Epoxypropyloxy) phenyl] indane-6-oxy group, 1,3,3-trimethyl-1- [4 ′-(glycidyloxy) phenyl] indane-6-oxy group 1,3,3-trimethyl-1- [ 4 ′-(1,2-epoxy-1-methylethoxy) phenyl] indane-6-oxy group, 1,3,3-trimethyl-1- [4 ′-(1,2-epoxybutoxy) phenyl] indane- 6-oxy group, 1,3,3-trimethyl-1- [4 ′-(2,3-epoxybutoxy) phenyl] indane-6-oxy group, 1,3,3-trimethyl-1- [4′- (3,4-Epoxybutoxy) phenyl] inda -6-oxy group, 1,3,3-trimethyl-1- [4 '-(1,2-epoxyethoxy) -3'-methylphenyl] indane-6-oxy group, 1,3,3-trimethyl -1- [4 ′-(1,2-epoxypropyloxy) -3′-methylphenyl] indane-6-oxy group, 1,3,3-trimethyl-1- [4 ′-(glycidyloxy) -3 -Methylphenyl] indan-6-oxy group, 1,3,3-trimethyl-1- [4 '-(1,2-epoxy-1-methylethoxy) -3'-methylphenyl] indan-6-oxy group 1,3,3-trimethyl-1- [4 ′-(1,2-epoxybutoxy) -3′-methylphenyl] indan-6-oxy group, 1,3,3-trimethyl-1- [4 ′ -(2,3-epoxybutoxy) -3'-methylphenyl] inda -6-oxy group, 1,3,3-trimethyl-1- [4 '-(3,4-epoxybutoxy) -3'-methylphenyl] indane-6-oxy group, 1,3,3-trimethyl- 5-tert-butyl-1- (4 ′-(1,2-epoxyethoxy) -3′-tert-butylphenyl) indan-6-oxy group, 1,3,3-trimethyl-5-tert-butyl- 1- (4 ′-(1,2-epoxypropyloxy) -3′-tert-butylphenyl) indane-6-oxy group, 1,3,3-trimethyl-5-tert-butyl-1- (4 ′ -(Glycidyloxy) -3'-tert-butylphenyl) indan-6-oxy group, 1,3,3-trimethyl-5-tert-butyl-1- (4 '-(1,2-epoxy-1-) Methylethoxy) -3'-tert-buty Phenyl) indan-6-oxy group, 1,3,3-trimethyl-5-tert-butyl-1- (4 ′-(1,2-epoxybutoxy) -3-tert-butylphenyl) indan-6-oxy 1,3,3-trimethyl-5-tert-butyl-1- (4 ′-(2,3-epoxybutoxy) -3′-tert-butylphenyl) indan-6-oxy group, 1,3, 3-trimethyl-5-tert-butyl-1- (4 ′-(3,4-epoxybutoxy) -3′-tert-butylphenyl) indan-6-oxy group, 1,3,3-trimethyl-5- Phenyl-1- [4 ′-(1,2-epoxyethoxy) -3′-phenylphenyl] indane-6-oxy group, 1,3,3-trimethyl-5-phenyl-1- [4 ′-(1 , 2-epoxypropyloxy) 3′-phenylphenyl] indan-6-oxy group, 1,3,3-trimethyl-5-phenyl-1- [4 ′-(glycidyloxy) -3-phenylphenyl] indane-6-oxy group, 3,3-trimethyl-5-phenyl-1- [4 ′-(1,2-epoxy-1-methylethoxy) -3′-phenylphenyl] indan-6-oxy group, 1,3,3-trimethyl- 5-phenyl-1- [4 ′-(1,2-epoxybutoxy) -3′-phenylphenyl] indan-6-oxy group, 1,3,3-trimethyl-5-phenyl-1- [4′- (2,3-epoxybutoxy) -3′-phenylphenyl] indan-6-oxy group, 1,3,3-trimethyl-5-phenyl-1- [4 ′-(3,4-epoxybutoxy) -3 '-Phenylphenyl] indane-6 Such as oxy group. Among these, 1,3,3-trimethyl-1- [4 ′-(1,2-epoxypropyloxy) phenyl] indan-6-oxy group, 1,3,3-trimethyl-1- [4 ′-( Glycidyloxy) phenyl] indan-6-oxy group, 1,3,3-trimethyl-1- [4 ′-(3,4-epoxybutoxy) phenyl] indane-6-oxy group, 1,3,3-trimethyl -1- [4 ′-(1,2-epoxypropyloxy) -3′-methylphenyl] indane-6-oxy group, 1,3,3-trimethyl-1- [4 ′-(glycidyloxy) -3 -Methylphenyl] indan-6-oxy group, 1,3,3-trimethyl-1- [4 '-(3,4-epoxybutoxy) -3'-methylphenyl] indan-6-oxy group, 1,3 , 3-Trimethyl-5-tert-buty -1- (4 ′-(1,2-epoxypropyloxy) -3′-tert-butylphenyl) indan-6-oxy group, 1,3,3-trimethyl-5-tert-butyl-1- (4 '-(Glycidyloxy) -3'-tert-butylphenyl) indan-6-oxy group, 1,3,3-trimethyl-5-tert-butyl-1- (4'-(3,4-epoxybutoxy) -3′-tert-butylphenyl) indan-6-oxy group, 1,3,3-trimethyl-5-phenyl-1- [4 ′-(1,2-epoxypropyloxy) -3′-phenylphenyl] Indan-6-oxy group, 1,3,3-trimethyl-5-phenyl-1- [4 '-(glycidyloxy) -3'-phenylphenyl] indan-6-oxy group, 1,3,3-trimethyl -5-phenyl- -[4 '-(3,4-epoxybutoxy) -3'-phenylphenyl] indane-6-oxy group is preferred, 1,3,3-trimethyl-1- [4'-(1,2-epoxypropyl) Oxy) phenyl] indan-6-oxy group, 1,3,3-trimethyl-1- [4 ′-(glycidyloxy) phenyl] indan-6-oxy group, 1,3,3-trimethyl-1- [4 The '-(3,4-epoxybutoxy) phenyl] indane-6-oxy group is particularly preferred.

<Epoxyoxyindane-substituted phenyloxy group represented by formula (5)>
4- [1 ′, 3 ′, 3′-trimethyl-6 ′-(1 ″, 2 ″ -epoxyethoxy) indan-1′-yl] phenoxy group, 4- [1 ′, 3 ′, 3 ′ -Trimethyl-6 '-(1 ", 2" -epoxypropyloxy) indan-1'-yl] phenoxy group, 4- [1', 3 ', 3'-trimethyl-6'-glycidyloxyindan- 1′-yl] phenoxy group, 4- [1 ′, 3 ′, 3′-trimethyl-6 ′-(1 ″, 2 ″ -epoxy-1-methylethoxy) indan-1′-yl] phenoxy group 4- [1 ′, 3 ′, 3′-trimethyl-6 ′-(1 ″, 2 ″ -epoxybutoxy) indan-1′-yl] phenoxy group, 4- [1 ′, 3 ′, 3 '-Trimethyl-6'-(2 '', 3 ''-epoxybutoxy) indan-1'-yl] phenoxy group, 4- [1 ', 3', 3'-trimethyl-6 '-(3'' , 4 ''-D Poxybutoxy) indan-1′-yl] phenoxy group, 3-methyl-4- [1 ′, 3 ′, 3′-trimethyl-6 ′-(1 ″, 2 ″ -epoxyethoxy) indan-1′- Yl] phenoxy group, 3-methyl-4- [1 ′, 3 ′, 3′-trimethyl-6 ′-(1 ″, 2 ″ -epoxypropyloxy) indan-1′-yl] phenoxy group, 3 -Methyl-4- [1 ', 3', 3'-trimethyl-6'-glycidyloxyindan-1'-yl] phenoxy group, 3-methyl-4- [1 ', 3', 3'-trimethyl- 6 ′-(1 ″, 2 ″ -epoxy-1-methylethoxy) indan-1′-yl] phenoxy group, 3-methyl-4- [1 ′, 3 ′, 3′-trimethyl-6′- (1 ″, 2 ″ -epoxybutoxy) indan-1′-yl] phenoxy group, 3-methyl-4- [1 ′, 3 ′, 3′-trimethyl 6 ′-(2 ″, 3 ″ -epoxybutoxy) indan-1′-yl] phenoxy group, 3-methyl-4- [1 ′, 3 ′, 3′-trimethyl-6 ′-(3 ″) , 4 ″ -epoxybutoxy) indan-1′-yl] phenoxy group, 3-tert-butyl-4- [1 ′, 3 ′, 3′-trimethyl-5′-tert-butyl-6 ′-(1 '', 2 ''-epoxyethoxy) indan-1′-yl] phenoxy group, 3-tert-butyl-4- [1 ′, 3 ′, 3′-trimethyl-5′-tert-butyl-6′- (1 ″, 2 ″ -epoxypropyloxy) indan-1′-yl] phenoxy group, 3-tert-butyl-4- [1 ′, 3 ′, 3′-trimethyl-5′-tert-butyl- 6′-glycidyloxyindan-1′-yl] phenoxy group, 3-tert-butyl-4- [1 ′, 3 ′, 3′-trimethyl Ru-5′-tert-butyl-6 ′-(1 ″, 2 ″ -epoxy-1-methylethoxy) indan-1′-yl] phenoxy group, 3-tert-butyl-4- [1 ′, 3 ′, 3′-trimethyl-5′-tert-butyl-6 ′-(1 ″, 2 ″ -epoxybutoxy) indan-1′-yl] phenoxy group, 3-tert-butyl-4- [1 ', 3', 3'-trimethyl-5'-tert-butyl-6 '-(2 ", 3" -epoxybutoxy) indan-1'-yl] phenoxy group, 3-tert-butyl-4- [1 ′, 3 ′, 3′-Trimethyl-5′-tert-butyl-6 ′-(3 ″, 4 ″ -epoxybutoxy) indan-1′-yl] phenoxy group, 3-phenyl-4- [1 ′, 3 ′, 3′-Trimethyl-5′-phenyl-6 ′-(1 ″, 2 ″ -epoxyethoxy) indan-1′-yl] Enoxy group, 3-phenyl-4- [1 ′, 3 ′, 3′-trimethyl-5′-phenyl-6 ′-(1 ″, 2 ″ -epoxypropyloxy) indan-1′-yl] phenoxy Group, 3-phenyl-4- [1 ′, 3 ′, 3′-trimethyl-5′-phenyl-6 ′-(glycidyloxy) indan-1′-yl] phenoxy group, 3-phenyl-4- [1 ', 3', 3'-trimethyl-5'-phenyl-6 '-(1'',2''-epoxy-1-methylethoxy)indan-1'-yl] phenoxy group, 3-phenyl-4- [1 ′, 3 ′, 3′-Trimethyl-5′-phenyl-6 ′-(1 ″, 2 ″ -epoxybutoxy) indan-1′-yl] phenoxy group, 3-phenyl-4- [1 ', 3', 3'-Trimethyl-5'-phenyl-6 '-(2 ", 3" -epoxybutoxy) indan-1'-yl] pheno Si group, 3-phenyl-4- [1 ′, 3 ′, 3′-trimethyl-5′-phenyl-6 ′-(3 ″, 4 ″ -epoxybutoxy) indan-1′-yl] phenoxy group etc. Of these, 4- [1 ′, 3 ′, 3′-trimethyl-6 ′-(1 ″, 2 ″ -epoxypropyloxy) indan-1′-yl] phenoxy group, 4- [1 ′, 3 ', 3'-trimethyl-6'-glycidyloxyindan-1'-yl] phenoxy group, 4- [1', 3 ', 3'-trimethyl-6'-(3 ", 4" -epoxybutoxy ) Indan-1′-yl] phenoxy group, 3-methyl-4- [1 ′, 3 ′, 3′-trimethyl-6 ′-(1 ″, 2 ″ -epoxypropyloxy) indan-1′- Yl] phenoxy group, 3-methyl-4- [1 ′, 3 ′, 3′-trimethyl-6′-glycidyloxyindan-1′-yl] phenoxy group, 3-methyl-4- [1 ′, 3 ′ , 3′-trimethyl-6 ′-(3 ″, 4 ″ -epoxybutoxy) indan-1′-yl] phenoxy group, 3-tert-butyl-4- [1 ′, 3 ′, 3′-Trimethyl-5′-tert-butyl-6 ′-(1 ″, 2 ″ -epoxypropyloxy) indan-1′-yl] phenoxy group, 3-tert-butyl -4- [1 ', 3', 3'-trimethyl-5'-tert-butyl-6'-glycidyloxyindan-1'-yl] phenoxy group, 3-tert-butyl-4- [1 ', 3 ', 3'-trimethyl-5'-tert-butyl-6'-(3 '', 4 ''-epoxybutoxy) indan-1'-yl] phenoxy group, 3-phenyl-4- [1 ', 3 ', 3'-trimethyl-5'-phenyl-6'-(1 ″, 2 ″ -epoxypropyloxy) indan-1′-yl] phenoxy group, 3-phenyl-4- [1 ′, 3 ′ , 3′-Trimethyl-5′-phenyl-6 ′-(3 ″, 4 ″ -epoxybutoxy) indan-1′-yl] phenoxy And a 4- [1 ′, 3 ′, 3′-trimethyl-6 ′-(1 ″, 2 ″ -epoxypropyloxy) indan-1′-yl] phenoxy group, 4- [1 ′ , 3 ′, 3′-trimethyl-6′-glycidyloxyindan-1′-yl] phenoxy group, 4- [1 ′, 3 ′, 3′-trimethyl-6 ′-(3 ″, 4 ″- Epoxybutoxy) indan-1′-yl] phenoxy groups are particularly preferred.

  In the formula (1), 2n of A are included, and at least one of them is an A3 group. Therefore, the epoxy group-containing cyclic phosphazene compound of the present invention represented by the formula (1) can be roughly divided into the following forms.

[Form 1]
All 2n 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 preferable epoxy group-containing cyclic phosphazene compounds having such a form include an epoxy group-containing cyclotriphosphazene compound in which n in formula (1) is 3, and an epoxy group in which n in formula (1) is 4. A cyclotetraphosphazene compound, an epoxy group-containing cyclopentaphosphazene compound in which n in formula (1) is 5, and an epoxy group-containing cyclohexaphosphazene compound in which n in formula (1) is 6, wherein all of A are represented by the formula ( 2) an epoxyoxyphenyl substituted phenyloxy group represented by formula (3), an epoxyoxyphenyl substituted phenyloxy group represented by formula (3), an epoxyoxyphenyl substituted indanoxy group represented by formula (4), represented by formula (5) A type of A3 group selected from the group of A3 groups consisting of epoxyoxyindane-substituted phenyloxy groups Everything of Some 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 2n A's is an A3 group, and the other A is a group selected from an A1 group and an 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.

  A preferable example of the epoxy group-containing cyclic phosphazene compound of this form is one in which 2 to (2n-2) of 2n A are A3 groups. In particular, an epoxy group-containing cyclotriphosphazene compound in which n in formula (1) is 3, an epoxy group-containing cyclotetraphosphazene compound in which n in formula (1) is 4, and an epoxy group in which n in formula (1) is 5 -Containing cyclopentaphosphazene compound and epoxy group-containing cyclohexaphosphazene compound in which n in formula (1) is 6, wherein 2 to (2n-2) of 2n A are A3 groups, and these Any mixture of This type of epoxy group-containing cyclic phosphazene compound can realize a resin molded article having higher high temperature reliability and mechanical properties (particularly, glass transition temperature) than other epoxy group-containing cyclic phosphazene compounds of the present invention. This is advantageous.

  In addition, it is confirmed by TOF-MS analysis of an epoxy group-containing cyclic phosphazene compound or an intermediate in its production process whether 2 to (2n-2) of 2n A are A3 groups or not. Can do.

Specific examples of preferable epoxy group-containing cyclic phosphazene compounds having such a form include an epoxy group-containing cyclotriphosphazene compound in which n in formula (1) is 3, and an epoxy group in which n in formula (1) is 4. A cyclotetraphosphazene compound, an epoxy group-containing cyclopentaphosphazene compound in which n of formula (1) is 5, or an epoxy group-containing cyclohexaphosphazene compound in which n of formula (1) is 6, wherein A is an A3 group A combination of a 4 ′-(1,2-epoxypropyloxy) phenyl-4-phenyloxy group and an ethoxy group that is an A1 group, a 4′-glycidyloxyphenyl-4-phenyloxy group that is an A3 group, and Combination with ethoxy group which is A1 group, 4 ′-(3,4-epoxybutoxy) phenyl which is A3 group Combination of 4-phenyloxy group and ethoxy group which is A1 group, 4 ′-(1,2-epoxypropyloxy) phenyl-4-phenyloxy group which is A3 group and n-propoxy group which is A1 group A combination of 4'-glycidyloxyphenyl-4-phenyloxy group which is an A3 group and an n-propoxy group which is an A1 group, and a 4 '-(3,4-epoxy which is an A3 group Butoxy) a combination of phenyl-4-phenyloxy group and n-propoxy group which is A1 group, 4 ′-(1,2-epoxypropyloxy) phenyloxy-4-phenyloxy group which is A3 group and A1 In combination with an ethoxy group which is a group, 4'-glycidyloxyphenyloxy-4-phenyloxy group which is an A3 group and an ethoxy group which is an A1 group In combination with 4 '-(3,4-epoxybutoxy) phenyloxy-4-phenyloxy group which is A3 group and ethoxy group which is A1 group, 4'-(which is A3 group 1,2-epoxypropyloxy) phenyloxy-4-phenyloxy group in combination with n-propoxy group which is A1 group, 4'-glycidyloxyphenyloxy-4-phenyloxy group which is A3 group and A1 In combination with n-propoxy group which is a group, in combination with 4 '-(3,4-epoxybutoxy) phenyloxy-4-phenyloxy group which is A3 group and n-propoxy group which is A1 group , A3 group 4 ′-(1,2-epoxypropyloxy) phenylsulfonyl-4-phenyloxy group and A1 group ethoxy group , A combination of 4'-glycidyloxyphenylsulfonyl-4-phenyloxy group which is A3 group and ethoxy group which is A1 group, 4 '-(3,4-epoxybutoxy) phenyl which is A3 group Combination of sulfonyl-4-phenyloxy group and ethoxy group which is A1 group, 4 ′-(1,2-epoxypropyloxy) phenylsulfonyl-4-phenyloxy group which is A3 group and n which is A1 group -In combination with propoxy group, in combination with 4'-glycidyloxyphenylsulfonyl-4-phenyloxy group which is A3 group and n-propoxy group which is A1 group, 4 '-(3 , 4-epoxybutoxy) phenylsulfonyl-4-phenyloxy group in combination with n-propoxy group which is A1 group, A 4 ′-(1,2-epoxypropyloxy) phenylisopropylidene-4-phenyloxy group in combination with ethoxy group as A1 group, 4′-glycidyloxyphenylisopropylidene- as A3 group A combination of 4-phenyloxy group and A1 group ethoxy group, A3 group 4 ′-(3,4-epoxybutoxy) phenylisopropylidene-4-phenyloxy group and A1 group ethoxy group; A combination of 4 ′-(1,2-epoxypropyloxy) phenylisopropylidene-4-phenyloxy group which is an A3 group and an n-propoxy group which is an A1 group, 4 which is an A3 group Combination of '-glycidyloxyphenyl isopropylidene-4-phenyloxy group and n-propoxy group which is A1 group A combination of 4 '-(3,4-epoxybutoxy) phenylisopropylidene-4-phenyloxy group which is A3 group and n-propoxy group which is A1 group, 1,3 which is A3 group , 3-Trimethyl-1- [4 ′-(1,2-epoxypropyloxy) phenyl] indane-6-oxy group and an A1 group ethoxy group, A3 group 1,3,3 -Trimethyl-1- [4 '-(glycidyloxy) phenyl] indan-6-oxy group and A1 group ethoxy group, A3 group 1,3,3-trimethyl-1- [4 '-(3,4-epoxybutoxy) phenyl] indane-6-oxy group and A1 group ethoxy group, A3 group 1,3,3-trimethyl-1- [4'-( 1, -Epoxypropyloxy) phenyl] indan-6-oxy group in combination with the A1 group n-propoxy group, A3 group 1,3,3-trimethyl-1- [4 '-(glycidyloxy) [Phenyl] indane-6-oxy group and A1 group n-propoxy group, A3 group 1,3,3-trimethyl-1- [4 ′-(3,4-epoxybutoxy) phenyl A combination of indane-6-oxy group and n-propoxy group which is A1 group, 4- [1 ′, 3 ′, 3′-trimethyl-6 ′-(1 ″, 2 ′) which is A3 group '-Epoxypropyloxy) indan-1'-yl] phenoxy group in combination with A1 ethoxy group, A3 group 4- [1', 3 ', 3'-trimethyl-6'-glycidyl Oxyindan-1'-a ] Combination of phenoxy group and ethoxy group which is A1 group, 4- [1 ′, 3 ′, 3′-trimethyl-6 ′-(3 ″, 4 ″ -epoxybutoxy) indane which is A3 group -1'-yl] phenoxy group and A1 group ethoxy group, A3 group 4- [1 ', 3', 3'-trimethyl-6 '-(1 ", 2" -Epoxypropyloxy) indan-1'-yl] phenoxy group in combination with n-propoxy group which is A1 group, 4- [1 ', 3', 3'-trimethyl-6'- which is A3 group A combination of glycidyloxyindan-1′-yl] phenoxy group and n-propoxy group which is A1 group, 4- [1 ′, 3 ′, 3′-trimethyl-6 ′-(3 ′) which is A3 group ', 4 ″ -epoxybutoxy) indan-1′-yl] phenoxy group and A1 group n Combination with propoxy group, combination of 4 '-(1,2-epoxypropyloxy) phenyl-4-phenyloxy group which is A3 group and phenoxy group which is A2 group, 4' which is A3 group -A combination of glycidyloxyphenyl-4-phenyloxy group and phenoxy group which is A2 group, 4 '-(3,4-epoxybutoxy) phenyl-4-phenyloxy group which is A3 group and A2 group Combination with phenoxy group, combination of 4 ′-(1,2-epoxypropyloxy) phenyl-4-phenyloxy group which is A3 group and methylphenoxy group which is A2 group, 4 which is A3 group '-Glycidyloxyphenyl-4-phenyloxy group in combination with A2 group methylphenoxy group, A3 group 4'- 3,4-epoxybutoxy) phenyl-4-phenyloxy group and A2 group methylphenoxy group, A3 group 4 '-(1,2-epoxypropyloxy) phenyl-4-phenyloxy In combination with a dimethylphenoxy group which is an A2 group, in combination with a 4′-glycidyloxyphenyl-4-phenyloxy group which is an A3 group and a dimethylphenoxy group which is an A2 group, and an A3 group Combination of '-(3,4-epoxybutoxy) phenyl-4-phenyloxy group and dimethylphenoxy group which is A2 group, 4'-(1,2-epoxypropyloxy) phenyl-4 which is A3 group -A combination of a phenyloxy group and a naphthyloxy group that is an A2 group, 4'-glycidyloxyphene that is an A3 group Combination of ru-4-phenyloxy group and naphthyloxy group which is A2 group, 4 ′-(3,4-epoxybutoxy) phenyl-4-phenyloxy group which is A3 group and naphthyloxy which is A2 group In combination with a group, 4 ′-(1,2-epoxypropyloxy) phenyloxy-4-phenyloxy group as an A3 group and a phenoxy group as an A2 group, 4 ′ as an A3 group -Glycidyloxyphenyloxy-4-phenyloxy group in combination with A2 group phenoxy group, A3 group 4 '-(3,4-epoxybutoxy) phenyloxy-4-phenyloxy group and A2 group 4 '-(1,2-epoxypropyloxy) phenylsulfonyl-4-phenyl in combination with a phenoxy group Combination of oxy group and phenoxy group which is A1 group, combination of 4′-glycidyloxyphenylsulfonyl-4-phenyloxy group which is A3 group and phenoxy group which is A1 group, 4 which is A3 group Combination of '-(3,4-epoxybutoxy) phenylsulfonyl-4-phenyloxy group and phenoxy group which is A1 group, 4'-(1,2-epoxypropyloxy) phenylisopropylidene which is A3 group A combination of a -4-phenyloxy group and a phenoxy group which is an A1 group, a combination of a 4′-glycidyloxyphenylisopropylidene-4-phenyloxy group which is an A3 group and a phenoxy group which is an A1 group, 4 '-(3,4-epoxybutoxy) phenylisopropylidene-4-phenylo which is A3 group Combination of Si group and phenoxy group which is A1 group, combination of 4 ′-(1,2-epoxypropyloxy) phenyloxy-4-phenyloxy group which is A3 group and methylphenoxy group which is A2 group A combination of 4'-glycidyloxyphenyloxy-4-phenyloxy group as A3 group and methylphenoxy group as A2 group, 4 '-(3,4-epoxybutoxy) phenyl as A3 group Combination of oxy-4-phenyloxy group and methylphenoxy group which is A2 group, 4 ′-(1,2-epoxypropyloxy) phenylsulfonyl-4-phenyloxy group which is A3 group and A1 group 4'-glycidyloxyphenylsulfonyl-4-phenyloxy in combination with methylphenoxy group or A3 group And a combination of a methylphenoxy group which is an A1 group, a combination of a 4 ′-(3,4-epoxybutoxy) phenylsulfonyl-4-phenyloxy group which is an A3 group and a methylphenoxy group which is an A1 group , A combination of 4 '-(1,2-epoxypropyloxy) phenylisopropylidene-4-phenyloxy group which is A3 group and methylphenoxy group which is A1 group, 4'-glycidyloxyphenyl which is A3 group Combination of isopropylidene-4-phenyloxy group and methylphenoxy group which is A1 group, 4 ′-(3,4-epoxybutoxy) phenylisopropylidene-4-phenyloxy group which is A3 group and A1 group In combination with a certain methylphenoxy group, 4 ′-(1,2-epoxypropyloxy) which is an A3 group A combination of a phenyloxy-4-phenyloxy group and a dimethylphenoxy group that is an A2 group, a 4′-glycidyloxyphenyloxy-4-phenyloxy group that is an A3 group, and a dimethylphenoxy group that is an A2 group A combination of 4 ′-(3,4-epoxybutoxy) phenyloxy-4-phenyloxy group which is an A3 group and a dimethylphenoxy group which is an A2 group, 4 ′-(which is an A3 group 1,2-epoxypropyloxy) phenylsulfonyl-4-phenyloxy group in combination with A1 group dimethylphenoxy group, A3 group 4'-glycidyloxyphenylsulfonyl-4-phenyloxy group and A1 group In combination with a dimethylphenoxy group, 4 ′-(3,4-epoxy, which is an A3 group Sibutoxy) a combination of phenylsulfonyl-4-phenyloxy group and A1 group dimethylphenoxy group, A3 group 4 ′-(1,2-epoxypropyloxy) phenylisopropylidene-4-phenyloxy group and A combination with a dimethylphenoxy group which is an A1 group, a combination of 4′-glycidyloxyphenylisopropylidene-4-phenyloxy group which is an A3 group and a dimethylphenoxy group which is an A1 group, 4 which is an A3 group Combination of '-(3,4-epoxybutoxy) phenylisopropylidene-4-phenyloxy group and dimethylphenoxy group which is A1 group, 4'-(1,2-epoxypropyloxy) phenyl which is A3 group Combination of oxy-4-phenyloxy group and naphthyloxy group which is A2 group Combined, 4'-glycidyloxyphenyloxy-4-phenyloxy group as A3 group and naphthyloxy group as A2 group, 4 '-(3,4-epoxybutoxy) as A3 group Combination of phenyloxy-4-phenyloxy group and naphthyloxy group which is A2 group, 4 ′-(1,2-epoxypropyloxy) phenylsulfonyl-4-phenyloxy group which is A3 group and A1 group A combination with a certain naphthyloxy group, a combination of 4'-glycidyloxyphenylsulfonyl-4-phenyloxy group which is an A3 group and a dinaphthyloxy group which is an A1 group, 4 '-(which is an A3 group 3,4-Epoxybutoxy) phenylsulfonyl-4-phenyloxy group in combination with naphthyloxy group which is A1 group A combination of 4 '-(1,2-epoxypropyloxy) phenylisopropylidene-4-phenyloxy group as the A3 group and a naphthyloxy group as the A1 group, 4'-glycidyloxy as the A3 group Combination of phenylisopropylidene-4-phenyloxy group and naphthyloxy group which is A1 group, 4 ′-(3,4-epoxybutoxy) phenylisopropylidene-4-phenyloxy group and A1 group which is A3 group In combination with a naphthyloxy group which is A3 group, 1,3,3-trimethyl-1- [4 ′-(1,2-epoxypropyloxy) phenyl] indan-6-oxy group and A2 group In combination with a certain phenoxy group, 1,3,3-trimethyl-1- [4 ′-(glycidyloxy) phenyl] which is an A3 group Combination of indan-6-oxy group and phenoxy group which is A2 group, 1,3,3-trimethyl-1- [4 ′-(3,4-epoxybutoxy) phenyl] indane-6 which is A3 group A combination of an oxy group and a phenoxy group which is an A2 group, an 1,3,3-trimethyl-1- [4 ′-(1,2-epoxypropyloxy) phenyl] indane-6-oxy which is an A3 group A combination of a group and a methylphenoxy group that is an A2 group, an A3 group that is a 1,3,3-trimethyl-1- [4 ′-(glycidyloxy) phenyl] indane-6-oxy group and an A2 group In combination with a methylphenoxy group, the A3 group 1,3,3-trimethyl-1- [4 ′-(3,4-epoxybutoxy) phenyl] indane-6-oxy group and the A2 group In combination with a tilphenoxy group, A3 group 1,3,3-trimethyl-1- [4 ′-(1,2-epoxypropyloxy) phenyl] indane-6-oxy group and A2 group dimethyl Combination of phenoxy group, combination of A3 group 1,3,3-trimethyl-1- [4 ′-(glycidyloxy) phenyl] indan-6-oxy group and A2 group dimethylphenoxy group A combination of 1,3,3-trimethyl-1- [4 ′-(3,4-epoxybutoxy) phenyl] indan-6-oxy group which is an A3 group and a dimethylphenoxy group which is an A2 group, 1,3,3-trimethyl-1- [4 ′-(1,2-epoxypropyloxy) phenyl] indane-6-oxy group which is A3 group and naphthyloxy group which is A2 group In combination with 1,3,3-trimethyl-1- [4 ′-(glycidyloxy) phenyl] indan-6-oxy group which is A3 group and naphthyloxy group which is A2 group, 1,3,3-trimethyl-1- [4 ′-(3,4-epoxybutoxy) phenyl] indan-6-oxy group which is an A3 group and a naphthyloxy group which is an A2 group, an A3 group 4- [1 ′, 3 ′, 3′-trimethyl-6 ′-(1 ″, 2 ″ -epoxypropyloxy) indan-1′-yl] phenoxy group and A2 group phenoxy group A combination of 4- [1 ′, 3 ′, 3′-trimethyl-6′-glycidyloxyindan-1′-yl] phenoxy group which is an A3 group and a phenoxy group which is an A2 group, A3 4- [1 ′, which is a group ', 3'-trimethyl-6'-(3 ″, 4 ″ -epoxybutoxy) indan-1′-yl] phenoxy group in combination with A2 group phenoxy group, A3 group 4- Combination of [1 ′, 3 ′, 3′-trimethyl-6 ′-(1 ″, 2 ″ -epoxypropyloxy) indan-1′-yl] phenoxy group and methylphenoxy group which is A2 group A combination of 4- [1 ′, 3 ′, 3′-trimethyl-6′-glycidyloxyindan-1′-yl] phenoxy group which is an A3 group and a methylphenoxy group which is an A2 group, Combination of certain 4- [1 ′, 3 ′, 3′-trimethyl-6 ′-(3 ″, 4 ″ -epoxybutoxy) indan-1′-yl] phenoxy group and methylphenoxy group which is A2 group 4- [1 ′, 3 ′, 3′-trimethyl which is an A3 group -6 ′-(1 ″, 2 ″ -epoxypropyloxy) indan-1′-yl] phenoxy group in combination with A2 group dimethylphenoxy group, A3 group 4- [1 ′, Combination of 3 ′, 3′-trimethyl-6′-glycidyloxyindan-1′-yl] phenoxy group and dimethylphenoxy group which is A2 group, 4- [1 ′, 3 ′, 3 which is A3 group '-Trimethyl-6'-(3 ″, 4 ″ -epoxybutoxy) indan-1′-yl] phenoxy group in combination with dimethylphenoxy group which is A2 group, 4- [1 which is A3 group ', 3', 3'-trimethyl-6 '-(1 ″, 2 ″ -epoxypropyloxy) indan-1′-yl] phenoxy group in combination with naphthyloxy group which is A2 group, A3 4- [1 ′, 3 ′, 3′-trimethyl group 6'-glycidyloxyindan-1'-yl] phenoxy group and A2 group naphthyloxy group, A3 group 4- [1 ', 3', 3'-trimethyl-6 '-( 3 ", 4" -epoxybutoxy) indan-1'-yl] phenoxy groups and naphthyloxy groups which are A2 groups and any mixtures thereof.

  Among them, an epoxy group-containing cyclotriphosphazene compound in which n in formula (1) is 3, an epoxy group-containing cyclotetraphosphazene compound in which n in formula (1) is 4, and an epoxy in which n in formula (1) is 5 A group-containing cyclopentaphosphazene compound, an epoxy group-containing cyclohexaphosphazene compound in which n in formula (1) is 6, wherein A is an A3 group 4′-glycidyloxyphenyl-4-phenyloxy group and an A1 group A combination with an n-propoxy group that is A3, a combination of a 4 ′-(3,4-epoxybutoxy) phenyl-4-phenyloxy group that is an A3 group and an n-propoxy group that is an A1 group, A3 A combination of a 4′-glycidyloxyphenyloxy-4-phenyloxy group as a group and an n-propoxy group as an A1 group, an A3 group Combination of a certain 4 ′-(3,4-epoxybutoxy) phenyloxy-4-phenyloxy group and n-propoxy group which is A1 group, 4′-glycidyloxyphenylsulfonyl-4-phenyl which is A3 group A combination of an oxy group and an n-propoxy group that is an A1 group, an A3 group that is a 4 ′-(3,4-epoxybutoxy) phenylsulfonyl-4-phenyloxy group, and an n-propoxy group that is an A1 group; A combination of 4'-glycidyloxyphenylisopropylidene-4-phenyloxy group which is A3 group and n-propoxy group which is A1 group, 4 '-(3,4-) which is A3 group Epoxybutoxy) phenylisopropylidene-4-phenyloxy group in combination with n-propoxy group which is A1 group A combination of 1,3,3-trimethyl-1- [4 ′-(glycidyloxy) phenyl] indane-6-oxy group which is an A3 group and an n-propoxy group which is an A1 group, 1 which is an A3 group , 3,3-Trimethyl-1- [4 ′-(3,4-epoxybutoxy) phenyl] indane-6-oxy group and an A1 group n-propoxy group, A3 group 4- [1 ′, 3 ′, 3′-Trimethyl-6′-glycidyloxyindan-1′-yl] phenoxy group in combination with A1 group n-propoxy group, A3 group 4- [1 ′ , 3 ′, 3′-trimethyl-6 ′-(3 ″, 4 ″ -epoxybutoxy) indan-1′-yl] phenoxy group and A1 group n-propoxy group, A3 group 4'-gri Combination of sidyloxyphenyl-4-phenyloxy group and phenoxy group which is A2 group, 4 ′-(3,4-epoxybutoxy) phenyl-4-phenyloxy group which is A3 group and phenoxy which is A2 group In combination with a group, a combination of 4'-glycidyloxyphenyl-4-phenyloxy group as an A3 group and a methylphenoxy group as an A2 group, 4 '-(3,4-epoxy as an A3 group Butoxy) Combination of phenyl-4-phenyloxy group and methylphenoxy group which is A2 group, Combination of 4'-glycidyloxyphenyloxy-4-phenyloxy group which is A3 group and phenoxy group which is A2 group 4 '-(3,4-epoxybutoxy) phenyloxy-4-phenyloxy group and A3 group In combination with a phenoxy group as a group, in combination with a 4′-glycidyloxyphenylsulfonyl-4-phenyloxy group as an A3 group and a phenoxy group as an A1 group, 4 ′-(3 , 4-epoxybutoxy) phenylsulfonyl-4-phenyloxy group and a phenoxy group that is A1 group, 4′-glycidyloxyphenylisopropylidene-4-phenyloxy group that is A3 group and A1 group Combination with phenoxy group, combination of 4 '-(3,4-epoxybutoxy) phenylisopropylidene-4-phenyloxy group which is A3 group and phenoxy group which is A1 group, 4 which is A3 group '-Glycidyloxyphenyloxy-4-phenyloxy group and A2 group methylphenoxy In combination with a group, in combination with 4 ′-(3,4-epoxybutoxy) phenyloxy-4-phenyloxy group which is an A3 group and a methylphenoxy group which is an A2 group, 4 ′ which is an A3 group -Glycidyloxyphenylsulfonyl-4-phenyloxy group and A1 group methylphenoxy group, A3 group 4 '-(3,4-epoxybutoxy) phenylsulfonyl-4-phenyloxy group and A1 In combination with a methylphenoxy group which is a group, in combination with a 4′-glycidyloxyphenylisopropylidene-4-phenyloxy group which is an A3 group and a methylphenoxy group which is an A1 group, 4 ′ which is an A3 group -(3,4-epoxybutoxy) phenylisopropylidene-4-phenyloxy group and A1 group In combination with a methylphenoxy group, a combination of 1,3,3-trimethyl-1- [4 ′-(glycidyloxy) phenyl] indan-6-oxy group as an A3 group and a phenoxy group as an A2 group A combination of A3 group 1,3,3-trimethyl-1- [4 ′-(3,4-epoxybutoxy) phenyl] indane-6-oxy group and A2 group phenoxy group, A combination of 1,3,3-trimethyl-1- [4 ′-(glycidyloxy) phenyl] indane-6-oxy group which is an A3 group and a methylphenoxy group which is an A2 group, A combination of a 3,3-trimethyl-1- [4 ′-(3,4-epoxybutoxy) phenyl] indane-6-oxy group and a methylphenoxy group which is an A2 group, A3 4- [1 ′, 3 ′, 3′-trimethyl-6′-glycidyloxyindan-1′-yl] phenoxy group and A2 group phenoxy group, and A3 group 4- [ 1 ′, 3 ′, 3′-trimethyl-6 ′-(3 ″, 4 ″ -epoxybutoxy) indan-1′-yl] phenoxy group in combination with A2 group, phenoxy group, A3 group 4- [1 ′, 3 ′, 3′-trimethyl-6′-glycidyloxyindan-1′-yl] phenoxy group and A2 group methylphenoxy group, and A3 group 4- Combinations of [1 ′, 3 ′, 3′-trimethyl-6 ′-(3 ″, 4 ″ -epoxybutoxy) indan-1′-yl] phenoxy groups with methylphenoxy groups which are A2 groups and these Any mixtures are preferred.

  In particular, an epoxy group-containing cyclotriphosphazene compound in which n in formula (1) is 3 or an epoxy group-containing cyclotetraphosphazene compound in which n is 4 in formula (1), wherein A is an A3 group 4 ′ A combination of a glycidyloxyphenylsulfonyl-4-phenyloxy group and an n-propoxy group which is an A1 group, and a 4 ′-(3,4-epoxybutoxy) phenylsulfonyl-4-phenyloxy group which is an A3 group In combination with n-propoxy group which is A1 group, in combination of 4'-glycidyloxyphenylisopropylidene-4-phenyloxy group which is A3 group and n-propoxy group which is A1 group, in A3 group Certain 4 ′-(3,4-epoxybutoxy) phenylisopropylidene-4-phenyloxy group and n1 which is A1 group A combination with a loxy group, a combination of 1,3,3-trimethyl-1- [4 ′-(glycidyloxy) phenyl] indan-6-oxy group which is an A3 group and an n-propoxy group which is an A1 group A combination of the A3 group 1,3,3-trimethyl-1- [4 ′-(3,4-epoxybutoxy) phenyl] indan-6-oxy group and the A1 group n-propoxy group A combination of 4- [1 ′, 3 ′, 3′-trimethyl-6′-glycidyloxyindan-1′-yl] phenoxy group which is an A3 group and an n-propoxy group which is an A1 group, A3 4- [1 ′, 3 ′, 3′-trimethyl-6 ′-(3 ″, 4 ″ -epoxybutoxy) indan-1′-yl] phenoxy group which is a group and n-propoxy group which is an A1 group Combination with A combination of 4'-glycidyloxyphenyl-4-phenyloxy group as A3 group and phenoxy group as A2 group, 4 '-(3,4-epoxybutoxy) phenyl as A3 group Combination of 4-phenyloxy group and phenoxy group which is A2 group, combination of 4'-glycidyloxyphenyl-4-phenyloxy group which is A3 group and methylphenoxy group which is A2 group, A3 group 4 ′-(3,4-epoxybutoxy) phenyl-4-phenyloxy group and A2 group methylphenoxy group, A3 group 4′-glycidyloxyphenyloxy-4-phenyloxy In combination with a phenoxy group which is an A2 group and 4 ′-(3,4-epoxybutoxy) phenyl which is an A3 group A combination of an oxy-4-phenyloxy group and a phenoxy group which is an A2 group, a combination of a 4′-glycidyloxyphenylsulfonyl-4-phenyloxy group which is an A3 group and a phenoxy group which is an A1 group, Combination of 4 '-(3,4-epoxybutoxy) phenylsulfonyl-4-phenyloxy group which is A3 group and phenoxy group which is A1 group, 4'-glycidyloxyphenyl isopropylidene-4 which is A3 group A combination of a phenyloxy group and a phenoxy group which is an A1 group, a 4 ′-(3,4-epoxybutoxy) phenylisopropylidene-4-phenyloxy group which is an A3 group and a phenoxy group which is an A1 group Combination, 4'-glycidyloxyphenyloxy-4-phenyloxy which is A3 group A combination of a group and a methylphenoxy group which is an A2 group, a combination of a 4 ′-(3,4-epoxybutoxy) phenyloxy-4-phenyloxy group which is an A3 group and a methylphenoxy group which is an A2 group A combination of 4'-glycidyloxyphenylsulfonyl-4-phenyloxy group as A3 group and methylphenoxy group as A1 group, 4 '-(3,4-epoxybutoxy) phenylsulfonyl as A3 group A combination of a 4-phenyloxy group and a methylphenoxy group which is an A1 group, a combination of a 4′-glycidyloxyphenylisopropylidene-4-phenyloxy group which is an A3 group and a methylphenoxy group which is an A1 group 4 '-(3,4-epoxybutoxy) phenylisopropylidene which is A3 group A combination of a 4-phenyloxy group and a methylphenoxy group which is an A1 group, and a 1,3,3-trimethyl-1- [4 ′-(glycidyloxy) phenyl] indane-6-oxy group which is an A3 group; In combination with the phenoxy group which is the A2 group, the 1,3,3-trimethyl-1- [4 ′-(3,4-epoxybutoxy) phenyl] indane-6-oxy group which is the A3 group and the A2 group Combination with a certain phenoxy group, combination of A3 group 1,3,3-trimethyl-1- [4 ′-(glycidyloxy) phenyl] indane-6-oxy group and A2 group methylphenoxy group 1,3,3-trimethyl-1- [4 ′-(3,4-epoxybutoxy) phenyl] indane-6-oxy group which is an A3 group and methylphenol which is an A2 group In combination with a xy group, a combination of 4- [1 ′, 3 ′, 3′-trimethyl-6′-glycidyloxyindan-1′-yl] phenoxy group which is an A3 group and a phenoxy group which is an A2 group 4- [1 ′, 3 ′, 3′-trimethyl-6 ′-(3 ″, 4 ″ -epoxybutoxy) indan-1′-yl] phenoxy and A2 groups which are A3 groups In combination with a phenoxy group, the A3 group 4- [1 ′, 3 ′, 3′-trimethyl-6′-glycidyloxyindan-1′-yl] phenoxy group and the A2 group methylphenoxy group In combination, the A3 group 4- [1 ′, 3 ′, 3′-trimethyl-6 ′-(3 ″, 4 ″ -epoxybutoxy) indan-1′-yl] phenoxy group and the A2 group A methylphenoxy group Those and any mixtures of these combinations are preferred.

  The epoxy group-containing cyclic phosphazene compounds of the present invention as described above are not crosslinked with each other. That is, the epoxy group-containing cyclic phosphazene compound of the present invention does not have any cross-linking structure between the epoxy group-containing cyclic phosphazene compounds. The epoxy group-containing cyclic phosphazene compound of the present invention is novel in terms of such characteristics, and is different from conventional epoxy group-containing cyclic phosphazene compounds.

Production method of epoxy group-containing cyclic phosphazene compound When producing the epoxy group-containing cyclic phosphazene compound of the present invention, first, a cyclic phosphonitrile dihalide represented by the following formula (6) is prepared.

  In the formula (6), n represents an integer of 3 to 15. 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 the like are described in various documents, for example, Non-Patent Documents 1 and 2 as described below.

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

  As described in these documents, the cyclic phosphonitrile dihalide represented by the formula (6) is usually composed of a cyclic phosphonitrile dihalide having a degree of polymerization of about 3 to 15 and a chain phosphonitrile dihalide. Obtained as a mixture. For this reason, the cyclic phosphonitrile dihalide represented by the formula (6) removes the chain phosphonitrile dihalide using the difference in solubility in the solvent from the mixture, as described in the above-mentioned documents. Or the cyclic phosphonitrile dihalide must be separated 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 ), Dodecafluorocyclohexaphosphazene (n = 6), a mixture of hexafluorocyclotriphosphazene and octafluorocyclotetraphosphazene, a mixture of cyclic phosphonitrile difluorides where n is from 3 to 15, hexachlorocyclo Triphosphazene (n is 3), octachlorocyclotetraphosphazene (n is 4), decachlorocyclopentaphosphazene (n is 5), dodecachlorocyclohexaphosphazene (n is 6), hexac A mixture of olocyclotriphosphazene and octachlorocyclotetraphosphazene, a mixture of cyclic phosphonitrile dichlorides having n of 3 to 15, and the like. Of these, hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, a mixture of hexachlorocyclotriphosphazene and octachlorocyclotetraphosphazene, and a mixture of cyclic phosphonitrile dichloride having n of 3 to 15 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 15.

  The epoxy group-containing cyclic phosphazene compound of the present invention can be usually produced by the following two methods using the cyclic phosphonitrile dihalide represented by the above formula (6) as a starting material.

[Production Method 1]
In this production method, the following compound B1, compound B2, and compound B3 are prepared as compounds to be reacted with the above-described cyclic phosphonitrile dihalide.

<Compound B1>
Alcohols having 1 to 8 carbon atoms.
The alcohols, alkyl group having 1 to 6 carbon atoms, optionally substituted with at least one group selected from 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.
The phenols, alkyl group having 1 to 6 carbon atoms, optionally substituted with at least one group selected from 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>
The following four alkenyl group-substituted diphenols of Compound B3-1, Compound B3-2, Compound B3-3, and Compound B3-4.

式（１５）中、Ｇは、炭素数が２〜６のアルケニル基を示しており、脱離したときにＯＨ基を形成可能なものである。 Compound B3-1
An alkenyl group-substituted diphenol represented by the following formula (15), wherein a hydrogen atom of one hydroxyl group is substituted with an alkenyl group.

In formula (15), G represents an alkenyl group having 2 to 6 carbon atoms, and can form an OH group when eliminated.

These alkenyl group-substituted diphenols can be obtained by substituting the hydrogen atom of one hydroxyl group of the diphenol compound represented by the following formula (16), that is, 4,4′-diphenol with the alkenyl group. be able to.

式（１７）中、Ｇは、炭素数が２〜６のアルケニル基を示しており、脱離したときにＯＨ基を形成可能なものである。また、Ｙは、次に説明する式（１８）中のＹと同じである。 Compound B3-2
An alkenyl group-substituted diphenol represented by the following formula (17), wherein a hydrogen atom of one hydroxyl group is substituted with an alkenyl group.

In formula (17), G represents an alkenyl group having 2 to 6 carbon atoms, and can form an OH group when eliminated. Y is the same as Y in formula (18) described next.

式（１８）中、Ｙは、Ｏ、Ｓ、ＳＯ_２、ＣＨ_２、ＣＨＣＨ_３、Ｃ（ＣＨ_３）_２、Ｃ（ＣＨ_３）ＣＨ_２ＣＨ_３若しくはＣＯを示す。式（１８）で表されるジフェノール類は、具体的には、４，４’−オキシジフェノール、４，４’−チオジフェノール、４，４’−スルホニルジフェノール（ビスフェノール−Ｓ）、４，４’−メチレンジフェノール（ビスフェノール−Ｆ）、４，４’−エチリデンジフェノール、４，４’−イソプロピリデンジフェノール（ビスフェノール−Ａ）、４，４’−（１−メチルプロピリデン）ジフェノール（ビスフェノール−Ｂ）および４，４−ジヒドロキシベンゾフェノンである。 This alkenyl group-substituted diphenol can be obtained by substituting the hydrogen atom of one hydroxyl group of the diphenol compound represented by the following formula (18) with the alkenyl group.

In formula (18), Y represents O, S, SO ₂ , CH ₂ , CHCH ₃ , C (CH ₃ ) ₂ , C (CH ₃ ) CH ₂ CH ₃ or CO. Specific examples of the diphenols represented by the formula (18) include 4,4′-oxydiphenol, 4,4′-thiodiphenol, 4,4′-sulfonyldiphenol (bisphenol-S), 4,4′-methylenediphenol (bisphenol-F), 4,4′-ethylidene diphenol, 4,4′-isopropylidenediphenol (bisphenol-A), 4,4 ′-(1-methylpropylidene) Diphenol (bisphenol-B) and 4,4-dihydroxybenzophenone.

式（１９）中、Ｇは、炭素数が２〜６のアルケニル基を示しており、脱離したときにＯＨ基を形成可能なものである。また、Ｒ^１およびＲ^２は、それぞれ、次に説明する式（２０）中のＲ^１およびＲ^２と同じである。 Compound B3-3
An alkenyl group-substituted diphenol represented by the following formula (19), wherein one of the hydroxyl groups, that is, the hydrogen atom of the hydroxyl group of the 4-hydroxyphenyl group located at the 1-position of indane is substituted with an alkenyl group.

In the formula (19), G represents an alkenyl group having 2 to 6 carbon atoms and can form an OH group when eliminated. R ¹ and R ² are the same as R ¹ and R ² in formula (20) described below.

This alkenyl group-substituted diphenol is a diphenol compound represented by the following formula (20), wherein the hydrogen atom of the hydroxyl group of 4-hydroxyphenyl group located at the 1-position of indane is substituted with the alkenyl group. Can be obtained at

In Formula (20), R ¹ and R ² represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, or a phenyl group, and in the case of the alkyl group, cycloalkyl group, or phenyl group, they are bonded. A plurality of the same or different species may be bonded to the ring structure. The diphenols represented by the formula (20) are linear dimers of p-isopropenylphenol, that is, 2,4-di (4-hydroxyphenyl) -4-methyl-pentene-1 and 2,4. 1,3,3-trimethyl-1- (4-hydroxyphenyl) indane obtained by cyclizing a mixture of di- (4-hydroxyphenyl) -4-methyl-pentene-2 in the presence of an acid catalyst 6-ol or its alkyl, cycloalkyl or phenyl derivatives. Specifically, 1,3,3-trimethyl-1- (4-hydroxyphenyl) indan-6-ol, 1,3,3-trimethyl-1- (4-hydroxy-3-methylphenyl) indan-6 -Ol, 1,3,3-trimethyl-1- (4-hydroxy-3,5-di-tert-butylphenyl) indan-6-ol, 1,3,3-trimethyl-5-tert-butyl-1 -(4-Hydroxy-3-tert-butylphenyl) indan-6-ol, 1,3,3-trimethyl-5-tert-butyl-1- (4-hydroxy-3,5-di-tert-butylphenyl) ) Indan-6-ol, 1,3,3-trimethyl-5-iso-propyl-1- (4-hydroxy-3-iso-propylphenyl) indan-6-ol, 1,3,3-tri Chill-5-phenyl-1- (4-hydroxy-3-phenyl-phenyl) indan-6-ol, and the like.

式（２１）中、Ｇは、炭素数が２〜６のアルケニル基を示しており、脱離したときにＯＨ基を形成可能なものである。また、Ｒ^１およびＲ^２は、それぞれ、上記式（２０）中のＲ^１およびＲ^２と同じである。 Compound B3-4
An alkenyl group-substituted diphenol represented by the following formula (21), wherein one of the hydroxyl groups, that is, the hydrogen atom of the hydroxyl group located at the 6-position of indane is substituted with an alkenyl group.

In formula (21), G represents an alkenyl group having 2 to 6 carbon atoms, and can form an OH group when eliminated. Further, ^{R 1} and ^{R 2} are respectively the same as ^{R 1} and ^{R 2} in the formula (20).

  This alkenyl group-substituted diphenol can be obtained by substituting the hydrogen atom of the hydroxyl group located at the 6-position of indane with the alkenyl group in the diphenol compound represented by the above formula (20).

  Four types of alkenyl group-substituted diphenols of the above-mentioned compound B3-1, compound B3-2, compound B3-3 and compound B3-4, that is, formula (15), formula (17), formula (19) and formula In the alkenyl group-substituted diphenols represented by (21), examples of the alkenyl group having 2 to 6 carbon atoms represented by G include an ethenyloxy group, a 1-propenyloxy group, and a 2-propenyloxy group (allyloxy group). , Isopropenyloxy group, 1-butenyloxy group, 2-butenyloxy group, 3-butenyloxy group, sec-butenyloxy group, 4-pentenyloxy group, or 5-hexenyloxy group. Of these, ethenyloxy group, 1-propenyloxy group, 2-propenyloxy group (allyloxy group), isopropenyloxy group, 1-butenyloxy group, 2-butenyloxy group, and 3-butenyloxy group are preferable, and 1-propenyloxy group 2-propenyloxy group (allyloxy group) and 3-butenyloxy group are particularly preferable.

  As such various alkenyl group-substituted diphenols, commercially available products may be used, or those produced by known methods may be used. Incidentally, from the diphenols represented by formula (16), formula (18) and formula (20), the alkenyl group-substituted diphenol represented by formula (15), formula (17) and formula (19) or formula (21) A method for selectively preparing a class is described in many known documents such as Non-Patent Document 3 and Non-Patent Document 4 below.

PROTECTIVE GROUPS IN ORGANIC SYNTHESIS, T. W. GREENE, P.M. G. M.M. WUTS, 1999, WILEY-INTERSCIENCE PROTECTING GROUP CHEMISTRY (OXFORD CHEMISTRY PRIMERS), J.A. ROBERTSON, 2000, OXFORD UNIVERSITY PRESS

Specific examples of preferable compounds as the compound B3-1, compound B3-2, compound B3-3, and compound B3-4 are as follows.
<Compound B3-1>
4 ′-(1 ″ -propenyloxy) phenyl-4-phenol, 4′-allyloxyphenyl-4-phenol, 4 ′-(3 ″ -butenyloxy) phenyl-4-phenol, etc. .

<Compound B3-2>
4 ′-(1 ″ -propenyloxy) phenyloxy-4-phenol, 4′-allyloxyphenyloxy-4-phenol, 4 ′-(3 ″ -butenyloxy) phenyloxy-4-phenol 4 '-(1''-propenyloxy) phenylthio-4-phenol, 4'-allyloxyphenylthio-4-phenol, 4'-(3 ''-butenyloxy) phenylthio-4- Phenol, 4 ′-(1 ″ -propenyloxy) phenylsulfonyl-4-phenol, 4′-allyloxyphenylsulfonyl-4-phenol, 4 ′-(3 ″ -butenyloxy) phenylsulfonyl -4-phenol, 4 ′-(1 ″ -propenyloxy) benzyl-4-phenol, 4′-allyloxybenzyl-4-phenol, 4 ′-(3 ″ -butenyloxy) benzyl -4-pheno- 4 ′-(1 ″ -propenyloxy) phenylethylidene-4-phenol, 4′-allyloxyphenylethylidene-4-phenol, 4 ′-(3 ″ -butenyloxy) phenylethylidene-4 4-phenol, 4 ′-(1 ″ -propenyloxy) phenylisopropylidene-4-phenol, 4′-allyloxyphenylisopropylidene-4-phenol, 4 ′-(3 ″ -butenyloxy) ) Phenylisopropylidene-4-phenol, [4 ′-(1 ″ -propenyloxy) phenyl-1-methylpropylidene] -4-phenol, 4′-allyloxyphenyl-1-methylpropylidene -4-phenol, [4 ′-(3 ″ -butenyloxy) phenyl-1-methylpropylidene] -4-phenol, 4 ′-(1 ″ -propenyloxy) benzoyl-4- E Bruno - le, 4'allyloxy benzoyl-4-phenol - le, 4 '- (3''- butenyloxy) benzoyl-4-phenol - Le like.

<Compound B3-3>
1,3,3-trimethyl-1- [4 ′-(1 ″ -propenyloxy) phenyl] indan-6-ol, 1,3,3-trimethyl-1- (4′-allyloxyphenyl) Indan-6-ol, 1,3,3-trimethyl-1- [4 ′-(3 ″ -butenyloxy) phenyl] indan-6-ol, 1,3,3-trimethyl-1- [ 4 ′-(1 ″ -propenyloxy) -3′-methylphenyl] indane-6-ol, 1,3,3-trimethyl-1- [4′-allyloxy-3′-methylphenyl] indane- 6-ol, 1,3,3-trimethyl-1- [4 ′-(3 ″ -butenyloxy) -3′-methylphenyl] indan-6-ol, 1,3,3-trimethyl- 1- [4 ′-(1 ″ -propenyloxy) -3′-phenylphenyl] indan-6-ol, , 3,3-trimethyl-1- (4′-allyloxy-3′-phenylphenyl) indan-6-ol, 1,3,3-trimethyl-1- [4 ′-(3 ″ -butenyloxy) -3'-phenylphenyl] indan-6-ol and the like.

<Compound B3-4>
1,3,3-trimethyl-1- (4′-hydroxyphenyl) -6- (1 ″ -propenyloxy) indane, 1,3,3-trimethyl-1- (4′-hydroxyphenyl) -6- Allyloxyindane, 1,3,3-trimethyl-1- (4′-hydroxyphenyl) -6- (3 ″ -butenyloxy) indane, 1,3,3-trimethyl-1- (4′-hydroxy-3) '-Methylphenyl) -6- (1 ″ -propenyloxy) indane, 1,3,3-trimethyl-1- (4′-hydroxy-3′-methylphenyl) -6-allyloxyindane, 1,3 , 3-Trimethyl-1- (4′-hydroxy-3′-methylphenyl) -6- (3 ″ -butenyloxy) indane, 1,3,3-trimethyl-1- (4′-hydroxy-3′-) Phenylphenyl) -6- (1 ″- Lopenyloxy) indane, 1,3,3-trimethyl-1- (4′-hydroxy-3′-phenylphenyl) -6-allyloxyindane, 1,3,3-trimethyl-1- (4′-hydroxy-3) '-Phenylphenyl) -6- (3''-butenyloxy) indane and the like.

  In this production method 1, at least one of all halogen atoms of the cyclic phosphonitrile dihalide is obtained by reacting the cyclic phosphonitrile dihalide represented by the above formula (6) with the above-mentioned compounds B1 to B3. Substitution with a group selected from the group consisting of the following E1, E2, and E3 groups so as to be substituted with the following E3 group, to produce a cyclic phosphonitrile substitution product (step 1).

<E1 group>
Alkyl group having 1 to 6 carbon atoms, at least one group selected from an alkenyl group and an aryl group which may be substituted, an alkoxy group having a carbon number of 1-8.
This group is substituted with a halogen atom by the compound B1, and corresponds to the A1 group described above.

<E2 group>
Alkyl group having 1 to 6 carbon atoms, optionally substituted with at least one group selected from an alkenyl group and an aryl group, an aryloxy group having 6 to 20 carbon atoms.
This group is substituted with a halogen atom by the compound B2, and corresponds to the A2 group described above.

<E3 group>
The substituted phenyloxy group represented by the following formula (7), the substituted phenyloxy group represented by the following formula (8), the substituted indanoxy group represented by the following formula (9), and the following formula (10) A group selected from the group consisting of substituted phenyloxy groups.

In the formulas (7) to (10), G is an alkenyl group having 2 to 6 carbon atoms as described above. In Formula (8), Y represents O, S, SO ₂ , CH ₂ , CHCH ₃ , C (CH ₃ ) ₂ , C (CH ₃ ) CH ₂ CH ₃ or CO. Furthermore, in Formula (9) and Formula (10), R ¹ and R ² represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, or a phenyl group.

  In this production process, the type of the epoxy group-containing cyclic phosphazene compound to be produced, that is, the case where the epoxy group-containing cyclic phosphazene compound according to the above-described form 1 is produced and the case where the epoxy group-containing cyclic phosphazene compound according to the above-described form 2 is produced. When selected, compounds B1 to B3 are appropriately selected and used. Specifically, it is as follows.

<When producing the epoxy group-containing cyclic phosphazene compound of Form 1>
In this case, the cyclic phosphonitrile dihalide is reacted with the compound B3, and all of the halogen atoms (hereinafter sometimes referred to as active halogen atoms) of the cyclic phosphonitrile dihalide are replaced with the E3 group derived from the compound B3. The compound B3 used here is one or two or more of the four types of alkenyl group-substituted diphenols of the above-mentioned compound B3-1, compound B3-2, compound B3-3, and compound B3-4. 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 E3 group, any of the following methods can be employed.

<Method 1-A>
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, a part of the active halogen atom remains, and the target epoxy group-containing cyclic phosphazene compound may not exhibit the required effect. 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 1-B>
Cyclic phosphonitrile dihalide and compound B3 are reacted in the presence of a base that captures 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, a part of the active halogen atom remains, and the target epoxy group-containing cyclic phosphazene compound may not exhibit the required effect. 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, a part of the active halogen atoms may remain, and the target epoxy group-containing cyclic phosphazene compound may not exhibit the required effect. 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.

<When producing the epoxy group-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 E3 group derived from compound B3, and all of the remaining other active halogen atoms are replaced with at least one group of E1 group derived from compound B1 and E2 group derived from compound B2. As a method for this, any of the following methods can be adopted.

<Method 2-A>
A 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 epoxy group 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, a part of the active halogen atom remains, and the target epoxy group-containing cyclic phosphazene compound may not exhibit the required effect. 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 2-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 that captures hydrogen halide to replace all active halogen atoms. To do. In the said mixture, the ratio of compound B3 can be suitably set according to the kind of epoxy group 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, a part of the active halogen atom remains, and the target epoxy group-containing cyclic phosphazene compound may not exhibit the required effect. 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, a part of the active halogen atoms may remain, and the target epoxy group-containing cyclic phosphazene compound may not exhibit the required effect. 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 2-C>
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 E3 group derived from compound B3 (step A). 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 into E1 group derived from compound B1 and E2 derived from compound B2. Substitution with at least one of the groups (step B).

  Step A of this method may be carried out by reacting an alkali metal salt of compound B3 with cyclic phosphonitrile dihalide, or a base that captures hydrogen halide with compound B3 against cyclic phosphonitrile dihalide. You may make it react in presence of. Step B may be carried out by reacting the partially substituted product obtained in Step A with an alkali metal salt of at least one of Compound B1 and Compound B2, or obtained in Step A. The partially substituted product may be reacted with at least one of compound B1 and compound B2 in the presence of a base that captures hydrogen halide.

<Method 2-D>
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 into E1 group derived from compound B1 and compound B2. A partially substituted product substituted with at least one of the derived E2 groups is obtained (step A). Next, compound B3 is reacted with the partially substituted product thus obtained, and all of the remaining active halogen atoms are substituted with E3 groups derived from compound B3 (step B).

  Step A 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 with respect to cyclic phosphonitrile dihalide, At least one of compound B1 and compound B2 may be reacted in the presence of a base that captures hydrogen halide. Step B may be carried out by reacting the partially substituted product obtained in Step A with an alkali metal salt of Compound B3. Alternatively, Compound B3 may be used on the partially substituted product obtained in Step A. You may make it react in presence of the base which capture | acquires a 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, lithium salt and sodium 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 sodium hydroxide, potassium hydroxide, lithium hydroxide or the like. It can be obtained by a dehydration reaction from a mixture with an alkali metal hydroxide.

  The base used in each of the above methods is not particularly limited. For example, trimethylamine, triethylamine, diisopropylethylamine, dimethylaniline, diethylaniline, diisopropylaniline, pyridine, 4,4-dimethylaminopyridine, 4 Aliphatic or aromatic amines such as 1,4-diethylaminopyridine and 4-diisopropylaminopyridine, alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate, sodium hydroxide, potassium hydroxide and water Alkali metal hydroxides such as lithium oxide are preferred. In particular, alkali metal hydroxides such as triethylamine, pyridine and potassium hydroxide are preferred.

  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 using a solvent, the type of the solvent is not particularly limited as long as it does not adversely affect the reaction, but usually diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, Ethers such as butyl methyl ether, diisopropyl ether, 1,2-diethoxyethane and diphenyl ether, aromatic hydrocarbons such as benzene, toluene, chlorobenzene, nitrobenzene, xylene, ethylbenzene and isopropylbenzene, halogens such as chloroform and methylene chloride Hydrocarbons, pentane, hexane, cyclohexane, heptane, octane, nonane, undecane, dodecane and other aliphatic hydrocarbons, pyridine and other heterocyclic aromatic hydrocarbons, tertiary amines, cyanide compounds, etc. of Preferable to use a machine solvent. 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 0 ° 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, when manufacturing the epoxy group containing cyclic phosphazene compound which concerns on the above-mentioned form 2, especially 2-(2n-2) of 2n A in Formula (1) manufacture an A3 group, it is the above-mentioned. It is preferable to employ Method 2-C or Method 2-D.

  Here, when the method 2-C is employed, an ether solvent solution or an aromatic hydrocarbon solvent solution of cyclic phosphonitrile dihalide is prepared. Then, with respect to this solvent solution, 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 system of compound B3 and a base for capturing hydrogen halide. The solvent solution is usually added at a temperature of −20 to 50 ° C. over 3 to 24 hours, and is allowed to react for 1 to 24 hours in the same temperature range, and a part of the active halogen atom of the cyclic phosphonitrile dihalide is compounded. A partially substituted product substituted with the E3 group derived from 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 that captures hydrogen halide is usually at 0 to 50 ° C. The reaction is carried out at a temperature from 3 to 24 hours, and the reaction is carried out at a temperature from 0 ° C. to the boiling point of the solvent. Replace with at least one of them.

  On the other hand, when Method 2-D is employed, 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 for capturing a hydrogen halide is usually added over a period of 3 to 24 hours at a temperature of -20 to 50 ° C. To produce a partially substituted product in which a part of the active halogen atom of cyclic phosphonitrile dihalide is substituted with at least one of E1 group derived from compound B1 and E2 group derived from compound B2 To do. 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 that captures hydrogen is usually added at a temperature of 0 to 50 ° C. over 3 to 24 hours, and a temperature from 0 ° C. to the boiling point of the solvent. And all of the remaining active halogen atoms are replaced by the E3 group from compound B3.

  In this production method 1, next, the alkenyl group represented by G in the E3 group of the cyclic phosphonitrile-substituted product obtained in the above step 1 is oxidized to be converted into an epoxy group (step 2). Thereby, E3 group is converted into the above-mentioned A3 group, and the epoxy group-containing cyclic phosphazene compound of the present invention is obtained. The method for oxidizing the alkenyl group represented by G in the E3 group to convert it into an epoxy group can be carried out by methods described in many known documents such as Non-Patent Documents 5 and 6 below. Specifically, peracids such as performic acid, peracetic acid and m-chloroperbenzoic acid, t-butyl hydroperoxide, cumene hydroperoxide and 1,1,3,3-tetramethylbutyl hydroperoxide, etc. Using an oxidizing agent such as hydroperoxide, hydrogen peroxide, hydrogen peroxide-heteropolyacid (condensed oxygen acid of V, Nb, Ta, Mo, W), N-oxide, sodium hypochlorite and sodium peroxide, When the cyclic phosphonitrile substituent obtained in the above-mentioned step 1 is oxidized, the above-mentioned alkenyl group can be converted to an epoxy group.

M.M. B. SMITH, J. et al. MARCH, MARCH'S ADVANCED ORGANIC CHEMISTRY: REACTIONS, MECHANISM, AND STRUCTURE, 5TH ED. , 2001, A WELY-INTERSCIENCE PUBLICATION B. S. LANE, K.M. BURGESS, CHEMICAL REVIEWS, 103 (7), 2003, "METAL-CATARYZED EPOXIDATIONS OF ALKENS WITH HYDROGEN PEROXIDE"

  When oxidizing the cyclic phosphonitrile substitution product using the above-mentioned oxidizing agent, the cyclic phosphonitrile substitution product is dissolved in an organic solvent and cooled to around 0 ° C. And an oxidizing agent is added with respect to this solution, and reaction is performed at room temperature for 5 to 10 hours. After completion of the reaction, an alkaline aqueous solution is added to the reaction solution to neutralize the oxidizing agent, and then an organic solvent is added to carry out a liquid separation treatment. When the organic layer thus obtained is concentrated, the target epoxy group-containing cyclic phosphazene compound represented by the formula (1) can be obtained.

  The organic solvent used here is usually preferably a halogen compound such as methylene chloride or a hydrocarbon such as hexane or toluene, but toluene is particularly preferred. Moreover, it is preferable to set the addition amount of an oxidizing agent to 1.1-3 mol with respect to 1 mol of alkenyl groups of a cyclic phosphonitrile substitution product. When the addition amount of the oxidizing agent is less than 1.1 mol, the reaction may not be completed and an alkenyl group may remain. On the other hand, when the amount exceeds 3 moles, oxidation of sites other than the target site may occur, and it is uneconomical.

  The target epoxy group-containing cyclic phosphazene compound contained in the concentrated organic layer can be usually isolated and purified by methods such as filtration, solvent extraction, column chromatography and recrystallization.

  In this production method 1, all or part of the active halogen atom of the cyclic phosphonitrile dihalide is substituted with E3 group in Step 1, and the alkenyl group of the E3 group is oxidized and converted to an epoxy group in the next Step 2. Therefore, the epoxy group-containing cyclic phosphazene compound obtained is a novel one having no cross-linking structure between the epoxy group-containing cyclic phosphazene compounds due to the epoxy group as described above. Further, in this production method, since the E3 alkenyl group is oxidized and converted to an epoxy group, the halogen atom derived from epihalohydrin does not remain in the product as compared with the case of the next production method 2 using epihalohydrin. . For this reason, the epoxy group containing cyclic phosphazene compound obtained by this manufacturing method can exhibit a required effect more effectively.

[Production Method 2]
This production method is a specific one of the epoxy group-containing cyclic phosphazene compounds represented by the formula (1), that is, E in the formulas (2), (3), (4) and (5) representing the A3 group. Is a method for producing a glycidyloxy group. In this production method, a cyclic phosphonitrile dihalide represented by the above formula (6) is used as a starting material, and a compound similar to that used in Production Method 1 is used as a compound to be reacted with the cyclic phosphonitrile dihalide. B1 and compound B2 and the following compound B4 are prepared.

<Compound B4>
The following four types of protected diphenols of Compound B4-1, Compound B4-2, Compound B4-3 and Compound B4-4.

式（２２）中、Ｚは、脱離したときにＯＨ基を形成可能な保護基を示している。 Compound B4-1
Protected diphenols represented by the following formula (22), wherein one hydroxyl group is protected by a protecting group.

In formula (22), Z represents a protecting group capable of forming an OH group when eliminated.

  These diphenols can be obtained by protecting one of the hydroxyl groups of the diphenol compound represented by the formula (16) described in Production Method 1, that is, 4,4′-diphenol, with the above protecting group. it can.

式（２３）中、Ｚは、脱離したときにＯＨ基を形成可能な保護基を示している。また、Ｙは、製造方法１において説明した式（１８）中のＹと同じである。 Compound B4-2
Protected diphenols represented by the following formula (23), wherein one hydroxyl group is protected by a protecting group.

In formula (23), Z represents a protecting group capable of forming an OH group when eliminated. Y is the same as Y in Formula (18) described in Production Method 1.

  This protected diphenol can be obtained by protecting one hydroxyl group of the diphenol compound represented by the formula (18) with the above protecting group.

式（２４）中、Ｚは、脱離したときにＯＨ基を形成可能な保護基を示している。また、Ｒ^１およびＲ^２は、それぞれ、製造方法１において説明した式（２０）中のＲ^１およびＲ^２と同じである。 Compound B4-3
Protected diphenols represented by the following formula (24), wherein one hydroxyl group, that is, the hydroxyl group of 4-hydroxyphenyl group located at the 1-position of indane is protected by a protecting group.

In formula (24), Z represents a protecting group capable of forming an OH group when eliminated. R ¹ and R ² are the same as R ¹ and R ^{2 in} Formula (20) described in Production Method 1, respectively.

  This protected diphenol can be obtained by protecting the hydroxyl group of the 4-hydroxyphenyl group located at the 1-position of indane with the above-described protecting group in the diphenol compound represented by the formula (20).

式（２５）中、Ｚは、脱離したときにＯＨ基を形成可能な保護基を示している。また、Ｒ^１およびＲ^２は、それぞれ、式（２０）中のＲ^１およびＲ^２と同じである。 Compound B4-4
Protected diphenols represented by the following formula (25), wherein one hydroxyl group, that is, the hydroxyl group located at the 6-position of indane is protected by a protecting group.

In formula (25), Z represents a protecting group capable of forming an OH group when eliminated. R ¹ and R ² are the same as R ¹ and R ^{2 in} Formula (20), respectively.

  This protected diphenol can be obtained by protecting the hydroxyl group located at the 6-position of indane with the above protecting group in the diphenol compound represented by the formula (20).

  Four types of protected diphenols of the above-mentioned compound B4-1, compound B4-2, compound B4-3 and compound B4-4, that is, formula (22), formula (23), formula (24) and formula (25) In the protected diphenols represented by), the kind of the protecting group represented by Z is described in a number of known documents such as Non-Patent Document 3 and Non-Patent Document 4 cited in the description of Production Method 1. Further, protected diphenols represented by formula (22), formula (23) and formula (24) or formula (25) are converted from diphenols represented by formula (16), formula (18) and formula (20). Methods for selective preparation are also described in these non-patent documents.

  Specific examples of the protecting group represented by Z include methyl group, methoxymethyl group, methylthiomethyl group, 2-methoxyethoxymethyl group, tetrahydropyranyl group, tetrahydrothiopyranyl group, 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, tert -Butyldimethylsilyl group, tert-butyldiphenylsilyl group, tribenzylsilyl group, triisopropylsilyl group and the like can be mentioned. 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.

Specific examples of preferred compounds B4-1, B4-2, B4-3 and B4-4 are as follows.
<Compound B4-1>
4'-methoxyphenyl-4-phenol, 4'-methoxymethoxyphenyl-4-phenol, 4'-tert-butyloxyphenyl-4-phenol, 4'-allyloxyphenyl-4-phenol, 4'-benzyloxy Phenyl-4-phenol and the like.

<Compound B4-2>
4′-methoxyphenyloxy-4-phenol, 4′-methoxymethoxyphenyloxy-4-phenol, 4′-tert-butyloxyphenyloxy-4-phenol, 4′-allyloxyphenyloxy-4-phenol, 4 '-Benzyloxyphenyloxy-4-phenol, 4'-methoxyphenylthio-4-phenol, 4'-methoxymethoxyphenylthio-4-phenol, 4'-tert-butyloxyphenylthio-4-phenol, 4' -Allyloxyphenylthio-4-phenol, 4'-benzyloxyphenylthio-4-phenol, 4'-methoxyphenylsulfonyl-4-phenol, 4'-methoxymethoxyphenylsulfonyl-4-phenol, 4'-tert- Butyloxyphenylsulfonyl-4-phenol 4'-allyloxyphenylsulfonyl-4-phenol, 4'-benzyloxyphenylsulfonyl-4-phenol, 4'-methoxybenzyl-4-phenol, 4'-methoxymethoxybenzyl-4-phenol, 4'-tert -Butyloxybenzyl-4-phenol, 4'-allyloxybenzyl-4-phenol, 4'-benzyloxybenzyl-4-phenol, 4'-methoxyphenylethyl-4-phenol, 4'-methoxymethoxyphenylethyl- 4-phenol, 4′-tert-butyloxyphenylethyl-4-phenol, 4′-allyloxyphenylethyl-4-phenol, 4′-benzyloxyphenylethyl-4-phenol, 4′-methoxyphenylisopropylidene- 4-phenol, 4'-methoxymethoxy Enylisopropylidene-4-phenol, 4′-tert-butyloxyphenylisopropylidene-4-phenol, 4′-allyloxyphenylisopropylidene-4-phenol, 4′-benzyloxyphenylisopropylidene-4-phenol, 4 '-Methoxyphenyl (1-methylpropylidene) -4-phenol, 4'-methoxymethoxyphenyl (1-methylpropylidene) -4-phenol, 4'-tert-butyloxyphenyl (1-methylpropylidene)- 4-phenol, 4′-allyloxyphenyl (1-methylpropylidene) -4-phenol, 4′-benzyloxyphenyl (1-methylpropylidene) -4-phenol, 4′-methoxybenzoyl-4-phenol, 4'-methoxymethoxybenzoyl-4-fe Lumpur, 4'-tert-butyloxy benzoyl-4-phenol, 4'-allyloxy-benzoyl-4-phenol, 4'-benzyloxy-benzoyl-4-phenol.

<Compound B4-3>
1,3,3-trimethyl-1- (4-methoxyphenyl) indan-6-ol, 1,3,3-trimethyl-1- (4-methoxymethoxyphenyl) indan-6-ol, 1,3,3 -Trimethyl-1- (4-tert-butyloxyphenyl) indan-6-ol, 1,3,3-trimethyl-1- (4-allyloxyphenyl) indan-6-ol, 1,3,3-trimethyl -1- (4-benzyloxyphenyl) indan-6-ol and the like.

<Compound B4-4>
1,3,3-trimethyl-1- (4-hydroxyphenyl) -6-methoxyindane, 1,3,3-trimethyl-1- (4-hydroxyphenyl) -6-methoxymethoxyindane, 1,3,3 -Trimethyl-1- (4-hydroxyphenyl) -6-tert-butyloxyindane, 1,3,3-trimethyl-1- (4-hydroxyphenyl) -6-allyloxyindane, 1,3,3-trimethyl -1- (4-hydroxyphenyl) -6-benzyloxyindane and the like.

  Compound B4-1, Compound B4-2, Compound B4-3, and Compound B4-4 are all commercially available or manufactured according to known methods such as the methods described in Non-Patent Documents 3 and 4 above. Can be used.

  In this production method 2, first, a cyclic phosphonitrile dihalide represented by the above formula (6) is reacted with a compound selected from the above-mentioned compound B1, compound B2, and compound B4. All halogen atoms of the halide are substituted with a group selected from the group consisting of the following Q1, Q2, and Q3 groups so that at least one is substituted with the following Q3 group to produce a cyclic phosphonitrile substitution product ( Step 1).

[Q1 group]
This is the same as the E1 group described in the production method 1. This group is substituted with a halogen atom by the compound B1, and corresponds to the A1 group described above.

[Q2 group]
This is the same as the E2 group described in the production method 1. This group is substituted with a halogen atom by the compound B2, and corresponds to the A2 group described above.

[Q3 group]
The substituted phenyloxy group represented by the following formula (11), the substituted phenyloxy group represented by the following formula (12), the substituted indanoxy group represented by the following formula (13), and the following formula (14) A group selected from the group consisting of substituted phenyloxy groups.

In the formulas (11) to (14), Z represents a protecting group capable of forming an OH group when eliminated, specifically, the above-mentioned compound B4-1, compound B4-2, compound B4-3 and This is the same as that described for the four types of protected diphenols of Compound B4-4. In formula (12), Y represents O, S, SO ₂ , CH ₂ , CHCH ₃ , C (CH ₃ ) ₂ , C (CH ₃ ) CH ₂ CH ₃ or CO. Further, in Formula (13) and Formula (14), R ¹ and R ² represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, or a phenyl group.

  In this production process, the type of the epoxy group-containing cyclic phosphazene compound to be produced, that is, the case where the epoxy group-containing cyclic phosphazene compound according to the above-described form 1 is produced and the case where the epoxy group-containing cyclic phosphazene compound according to the above-described form 2 is produced. And a compound selected from the group consisting of Compound B1, Compound B2 and Compound B4 as appropriate. Specifically, it is as follows.

<When producing the epoxy group-containing cyclic phosphazene compound of Form 1>
In this case, the cyclic phosphonitrile dihalide is reacted with the compound B4, and all of the halogen atoms (hereinafter sometimes referred to as active halogen atoms) of the cyclic phosphonitrile dihalide are substituted with the Q3 group derived from the compound B4. The compound B4 used here is one kind or two or more kinds among the above-mentioned four kinds of protected diphenols of the compound B4-1, the compound B4-2, the compound B4-3 and the compound B4-4. As a method of reacting the cyclic phosphonitrile dihalide with the compound B4 and substituting all the active halogen atoms of the cyclic phosphonitrile dihalide with the Q3 group, any of the following methods can be employed.

<Method 1-A>
A cyclic phosphonitrile dihalide is reacted with an alkali metal salt of compound B4.
In the case of this method, the amount of the alkali metal salt of compound B4 is usually preferably set to 1.0 to 2.0 equivalents of the amount of the active halogen atom of the 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, a part of the active halogen atom remains, and the target epoxy group-containing cyclic phosphazene compound may not exhibit the required effect. 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 1-B>
Cyclic phosphonitrile dihalide and compound B4 are reacted in the presence of a base that captures hydrogen halide.
In the case of this method, the amount of compound B4 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, a part of the active halogen atom remains, and the target epoxy group-containing cyclic phosphazene compound may not exhibit the required effect. 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, a part of the active halogen atoms may remain, and the target epoxy group-containing cyclic phosphazene compound may not exhibit the required effect. 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.

<When producing the epoxy group-containing cyclic phosphazene compound of Form 2>
In this case, at least one of compound B4 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 Q3 group derived from the compound B4, and all of the remaining other active halogen atoms are replaced with at least one group of the Q1 group derived from the compound B1 and the Q2 group derived from the compound B2. As a method for this, any of the following methods can be adopted.

<Method 2-A>
A cyclic phosphonitrile dihalide is reacted with a mixture of an alkali metal salt of compound B4 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 B4 can be suitably set according to the kind of epoxy group 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. If the amount used is less than 1.0 equivalent, it may be difficult to separate and purify the reaction product, which is uneconomical. 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 2-B>
A cyclic phosphonitrile dihalide is reacted with a mixture of compound B4 and at least one of compound B1 and compound B2 in the presence of a base that captures hydrogen halide to replace all active halogen atoms. To do. In the said mixture, the ratio of the compound B can be suitably set according to the kind of epoxy group 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, a part of the active halogen atom remains, and the target epoxy group-containing cyclic phosphazene compound may not exhibit the required effect. 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, a part of the active halogen atoms may remain, and the target epoxy group-containing cyclic phosphazene compound may not exhibit the required effect. 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 2-C>
First, compound B4 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 Q3 group derived from compound B4 (step A). 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 Q1 group derived from compound B1 and Q2 derived from compound B2. Substitution with at least one of the groups (step B).

  Step A of this method may be carried out by reacting an alkali metal salt of compound B4 with a cyclic phosphonitrile dihalide, or a base that captures a hydrogen halide with compound B4 against the cyclic phosphonitrile dihalide. You may make it react in presence of. Step B may be carried out by reacting the partially substituted product obtained in Step A with an alkali metal salt of at least one of Compound B1 and Compound B2, or obtained in Step A. The partially substituted product may be reacted with at least one of compound B1 and compound B2 in the presence of a base that captures hydrogen halide.

<Method 2-D>
First, at least one of the compound B1 and the compound B2 is reacted with the cyclic phosphonitrile dihalide, and a part of the active halogen atom of the cyclic phosphonitrile dihalide is converted into the Q1 group derived from the compound B1 and the compound B2. A partially substituted product substituted with at least one of the derived Q2 groups is obtained (step A). Next, compound B4 is reacted with the obtained partially substituted product, and all remaining active halogen atoms are substituted with Q3 group derived from compound B4 (step B).

  Step A 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 with respect to cyclic phosphonitrile dihalide, At least one of compound B1 and compound B2 may be reacted in the presence of a base that captures hydrogen halide. Step B may be carried out by reacting the partially substituted product obtained in Step A with an alkali metal salt of Compound B4. Alternatively, Compound B4 may be added to the partially substituted product obtained in Step A. You may make it react in presence of the base which capture | acquires a 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, lithium salt and sodium salt are preferable. Such an alkali metal salt includes a dehydrogenation reaction of compound B1, compound B2 or compound B4 with metal lithium, metal sodium or metal potassium or the like, or compound B1, compound B2 or compound B4 and sodium hydroxide, water. It can be obtained by a dehydration reaction from a mixture with an alkali metal hydroxide such as potassium oxide or lithium hydroxide.

  In addition, the base used in each of the above-described methods is not particularly limited, and is the same as that described in Step 1 of Production Method 1.

  The reaction of the above-mentioned cyclic phosphonitrile dihalide with a compound selected from Compound B1, Compound B2 and Compound B4 can be carried out without solvent for any of the above-mentioned methods, and using a solvent. It can also be implemented. When a solvent is used, the type of the solvent is not particularly limited as long as it does not adversely affect the reaction, and the same solvent as described in Step 1 of Production Method 1 can be used.

  The reaction temperature at the time of reacting the above-mentioned cyclic phosphonitrile dihalide with the compound selected from the compound B1, the compound B2 and the compound B4 is determined by any of the methods described above, or the thermal stability of the reaction product, etc. It can be set as appropriate in consideration. However, when the reaction is carried out using a solvent, it is usually preferable to set the reaction temperature in a temperature range from 0 ° 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.

  As the epoxy group-containing cyclic phosphazene compound of the present invention, those according to the above-described form 2, particularly those in which 2 to (2n-2) of 2n A in formula (1) are A3 groups are produced. In this case, it is preferable to employ the above-described method 2-C or method 2-D.

  Here, when the method 2-C is employed, first, an ether solvent solution or an aromatic hydrocarbon solvent solution of a cyclic phosphonitrile dihalide is prepared. Then, with respect to this solvent solution, an ether solvent solution or an aromatic hydrocarbon solvent solution of an alkali metal salt of compound B4 or an ether solvent solution or an aromatic hydrocarbon system of compound B4 and a base for capturing hydrogen halide. The solvent solution is usually added at a temperature of −20 to 50 ° C. over 3 to 24 hours, and is allowed to react for 1 to 24 hours in the same temperature range, and a part of the active halogen atom of the cyclic phosphonitrile dihalide is compounded. A partially substituted product substituted with the Q3 group derived from B4 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 that captures hydrogen halide is usually at 0 to 50 ° C. The reaction is carried out at a temperature from 3 to 24 hours, and the reaction is carried out at a temperature from 0 ° C. to the boiling point of the solvent. All the remaining active halogen atoms are removed from the Q1 group derived from the compound B1 and the Q2 group derived from the compound B2. Replace with at least one of them.

  On the other hand, when Method 2-D is employed, 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 for capturing a hydrogen halide is usually added over a period of 3 to 24 hours at a temperature of -20 to 50 ° C. To produce a partially substituted product in which a part of the active halogen atom of the cyclic phosphonitrile dihalide is substituted with at least one of the Q1 group derived from the compound B1 and the Q2 group derived from the compound B2 To do. Next, the ether solvent solution or aromatic hydrocarbon solvent solution of the partially substituted product thus obtained is halogenated with an ether solvent solution or aromatic hydrocarbon solvent solution of compound B4 or compound B4. An ether solvent solution or an aromatic hydrocarbon solvent solution with a base that captures hydrogen is usually added at a temperature of 0 to 50 ° C. over 3 to 24 hours, and a temperature from 0 ° C. to the boiling point of the solvent. And all of the remaining active halogen atoms are replaced by the Q3 group from compound B4.

  In this production method 2, next, a hydroxyl group-containing cyclic phosphazene compound is prepared from the cyclic phosphonitrile substitution product obtained in the above-mentioned step 1. Specifically, the protecting group (Z) is removed from the Q3 group of the cyclic phosphonitrile substituent obtained in the above-mentioned step 1, and the —OZ group portion of the Q3 group is converted to an —OH group (step 2). .

  Methods for removing protecting groups are described in many known documents such as Non-Patent Documents 3 and 4 described above, and various deprotection reactions can be performed depending on the type of protecting group and the stability of the protecting group. You can choose from. 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.

  Next, in the presence of a base, the hydroxyl group-containing cyclic phosphazene compound obtained in Step 2 described above is reacted with epihalohydrin (Step 3). Here, the ring closure reaction by dehydrohalogenation proceeds between the hydroxyl group formed by removal of the protecting group in Step 2 and the epihalohydrin to form a glycidyloxy group, and the epoxy group-containing cyclic of the present invention A phosphazene compound is obtained. The epihalohydrin used here is various, for example, epichlorohydrin, epibromohydrin, epiiodohydrin. This step can be performed by the following two methods.

<Method 1>
This is a method in which a hydroxyl group-containing cyclic phosphazene compound and an epihalohydrin are reacted in the same manner as in a normal epoxidation reaction. In this case, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, which is a base, is added to the dissolved mixture of the hydroxyl group-containing cyclic phosphazene compound and epihalohydrin, or the reaction (dehydrohalogenation is performed). Ring-closing reaction). The reaction temperature is preferably set to 20 to 120 ° C. Moreover, although reaction time is based on the reaction scale, it is preferable to set to 1 to 10 hours normally.

  In the case of this method, the amount of epihalohydrin used is usually preferably set in the range of 1.1 to 20 equivalents relative to 1 equivalent of the hydroxyl group of the hydroxyl group-containing cyclic phosphazene compound. Incidentally, the more the amount of epihalohydrin used, the closer the resulting epoxy group-containing cyclic phosphazene compound is to the theoretical structure, so that the secondary produced by the reaction of the unreacted hydroxyl group of the hydroxyl group-containing cyclic phosphazene compound with the epoxy group. Generation of hydroxyl groups can be suppressed. From this, it is more preferable to set the addition amount of epihalohydrin in the range of 2.5 to 20 equivalents relative to 1 equivalent of hydroxyl group of the hydroxyl group-containing cyclic phosphazene compound.

  The alkali metal hydroxide used in the above reaction may be an aqueous solution. In this case, the above-described reaction can be allowed to proceed while continuously adding an aqueous solution of an alkali metal hydroxide to the reaction system and continuously distilling water and epihalohydrin under reduced pressure or normal pressure. it can. At this time, it is also possible to employ a method in which water and epihalohydrin, which are distillate components, are separated and only the epihalohydrin is continuously returned to the reaction system.

<Method 2>
In this method, first, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide and trimethylbenzylammonium chloride is added as a catalyst to a dissolved mixture of a hydroxyl group-containing cyclic phosphazene compound and epihalohydrin, and 50 to 150 The reaction is carried out under the condition of ° C. to once form a halohydrin etherified product (Step A). The reaction time in this step is not particularly limited, but usually it is preferably set to 1 to 5 hours.

  Next, a solid or aqueous solution of an alkali metal hydroxide (for example, potassium hydroxide or sodium hydroxide) as a base is added to the halohydrin etherified product produced in Step A, and the condition of 20 to 120 ° C. is again applied. The reaction is performed below (ring closure reaction by dehydrohalogenation) (step B). The reaction time in this step is not particularly limited, but usually it is preferably set to 1 to 10 hours.

  In Step B, alcohols such as methanol, ethanol, isopropyl alcohol and butanol, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane, dimethyl sulfone and dimethyl sulfoxide are used so that the ring closure reaction by dehydrohalogenation proceeds smoothly. It is preferable to add a solvent such as an aprotic polar solvent to the reaction system. When using a solvent other than an aprotic polar solvent, the amount used is usually preferably set to 5 to 50% by mass and more preferably set to 10 to 30% by mass relative to the amount of epihalohydrin used. . On the other hand, when an aprotic polar solvent is used, the amount used is usually preferably set to 5 to 100% by mass and more preferably set to 10 to 60% by mass with respect to the amount of epihalohydrin.

  The reaction solution in Step B is usually placed under heating and reduced pressure at 110 to 250 ° C. and a pressure of 10 hPa or less after water washing or without water washing to remove epihalohydrin and other added solvents. The crude epoxy group-containing cyclic phosphazene compound thus obtained is dissolved again in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to the solution. It is preferable to make the ring closure reaction more reliable. In this way, an epoxy group-containing cyclic phosphazene compound with a small residual amount of hydrolyzable halogen can be obtained.

  When performing such treatment, the amount of alkali metal hydroxide used is usually set to 0.5 to 10 moles per mole of hydrolyzable halogen atoms remaining in the crude epoxy group-containing cyclic phosphazene compound. Is preferable, and it is more preferable to set to 1.2-5.0 mol. The reaction temperature is preferably set to 50 to 120 ° C., and the reaction time is preferably set to 0.5 to 3 hours. In this treatment, a phase transfer catalyst such as a quaternary ammonium salt or crown ether can be added for the purpose of improving the reaction rate. In this case, the amount of the phase transfer catalyst used is preferably set to 0.1 to 3.0% by mass with respect to the crude epoxy group-containing cyclic phosphazene compound.

  The epoxy group-containing cyclic phosphazene compound can be obtained by removing the produced salt by a method such as filtration or washing with water after completion of the reaction, and distilling off a solvent such as toluene or methyl isobutyl ketone under heating and reduced pressure.

  The target epoxy group-containing cyclic phosphazene compound obtained by the above-mentioned method 1 and method 2 can be isolated and purified from the reaction system by ordinary methods such as filtration, solvent extraction, column chromatography and recrystallization. .

  In this production method 2, all or part of the active halogen atom of the cyclic phosphonitrile dihalide is substituted with a Q3 group in Step 1, and the protecting group is removed from the Q3 group in the next Step 2 to remove the hydroxyl group-containing cyclic phosphazene. Since the compound is obtained and this hydroxyl group-containing cyclic phosphazene compound is reacted with epihalohydrin in the next step 3, the resulting epoxy group-containing cyclic phosphazene compound is an epoxy group-containing cyclic phosphazene compound due to two hydroxyl groups of diphenols. It becomes a novel thing which does not have a crosslinking structure between them.

Resin Composition The resin composition of the present invention comprises the epoxy group-containing cyclic phosphazene compound of the present invention and a resin component. One type of epoxy group-containing cyclic phosphazene compound of the present invention may be used, or two or more types may be used in combination. As the resin component, various thermoplastic resins or thermosetting resins can be used. These resin components may be natural or synthetic.

  Specific examples of the thermoplastic resin that can be used here include polyethylene, polyisoprene, polybutadiene, chlorinated polyethylene, polyvinyl chloride, styrene resin, impact-resistant polystyrene, acrylonitrile-styrene resin (AS resin), and acrylonitrile-butadiene-. Styrene resin (ABS resin), methyl methacrylate-butadiene-styrene resin (MBS resin), methyl methacrylate-acrylonitrile-butadiene-styrene resin (MABS resin), acrylonitrile-acrylic rubber-styrene resin (AAS resin), polymethyl acrylate, poly Methyl methacrylate, polycarbonate, polyphenylene ether (PPE), modified polyphenylene ether, aliphatic polyamide, aromatic polyamide, polyethylene terephthalate Polyester resins such as polypropylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate and polyethylene naphthalate, polyphenylene sulfide, polyether ether ketone, polysulfone, polyarylate, polyether ketone, polyether nitrile, polythioether sulfone, polyether sulfone and liquid crystal A polymer etc. can be mentioned. As the modified phenylene ether, a reactive functional group such as a carboxyl group, an epoxy group, an amino group, a hydroxyl group, and an anhydrous dicarboxyl group is introduced into some or all of the polyphenylene ether by some method such as graft reaction or copolymerization. Things are used. When the resin composition of the present invention is used as a material for casings or parts for electronic equipment, particularly OA equipment, AV equipment, communication equipment, and home appliances, polyester resin, ABS resin, It is preferable to use polycarbonate, modified polyphenylene ether, polyamide or the like.

  On the other hand, specific examples of thermosetting resins that can be used here include polyurethane, phenol resin, melamine resin, urea resin, unsaturated polyester resin, diallyl phthalate resin, silicon resin, bismaleimide resin, cyanate ester resin, polybenz Examples thereof include imide resins such as imidazole, polycarbodiimide, polyimide, polyamideimide, polyetherimide, and polyesterimide, and epoxy resins. The resin composition of the present invention is used as an electronic component, particularly as a sealing material for various IC elements, a substrate material for a wiring board, an insulating material such as an interlayer insulating material or an insulating adhesive material, a conductive material, and a surface protective material. In this case, it is preferable to use polyurethane, phenol resin, melamine resin, bismaleimide resin, cyanate ester resin, polyimide resin or epoxy resin as the thermosetting resin.

  The various resin components described above may be used alone or in combination of two or more as necessary.

  In the resin composition of the present invention, the amount of the epoxy group-containing cyclic phosphazene compound used can be appropriately set according to various conditions such as the type of the resin component and the use of the resin composition. It is preferably set to 0.1 to 50 parts by weight with respect to 100 parts by weight of the resin component, more preferably set to 0.5 to 40 parts by weight, and further preferably set to 1 to 30 parts by weight. . When the usage-amount of an epoxy group containing cyclic phosphazene compound is less than 0.1 weight part, there exists a possibility that the resin molding which consists of the said resin composition may not show sufficient flame retardance. On the other hand, if it exceeds 50 parts by weight, the original properties of the resin component may be impaired, and a resin molded product having such properties may not be obtained.

  Moreover, the resin composition of this invention can mix | blend various additives in the range which does not impair the target physical property according to the kind of resin component, the use of a resin composition, etc. Examples of usable additives include silica, alumina, aluminum hydroxide, magnesium hydroxide, calcium silicate, calcium carbonate, titanium oxide, zinc oxide, zinc molybdate, mica, talc, glass fiber, and potassium titanate fiber. Inorganic fillers, surface treatment agents for fillers such as silane coupling agents, waxes, release agents such as fatty acids and their metal salts, acid amides and paraffins, phosphate esters, condensed phosphate esters, phosphate amides , Phosphoric acid amide ester, ammonium phosphate, red phosphorus, chlorinated paraffin, melamine, melamine cyanurate, melam, melem, melon and succinoguanamine, etc. nitrogen flame retardant, silicone flame retardant and bromine flame retardant etc. Flame retardants, flame retardant aids such as antimony trioxide, polytetrafluoroethylene Anti-dripping agents such as PTFE, epoxy resins, phenol resins, curing agents, pigments, colorants, antioxidants, ultraviolet absorbers, light stabilizers, lubricants, plasticizers and antistatic agents. it can.

  When the resin composition of the present invention is used for a material for the electric / electronic field, specifically, a sealant or a substrate for an electronic component such as LSI, the resin component is preferably an epoxy resin. The epoxy resins that can be used are various types that are usually used in the electric and electronic fields. For example, phenol novolac type epoxy resins, brominated phenol novolak type epoxy resins, orthocresol novolak type epoxy resins, and naphthol novolak type epoxy resins. Novolac type epoxy resins obtained by reaction of phenols and aldehydes such as resins, bisphenol-A type epoxy resins, brominated bisphenol-A type epoxy resins, bisphenol-F type epoxy resins, bisphenol-AD type epoxy resins, It is obtained by reaction of phenols such as bisphenol-S type epoxy resin, biphenol type epoxy resin, alkyl-substituted biphenol type epoxy resin, tris (hydroxyphenyl) methane and epichlorohydrin. Aliphatic epoxy resins obtained by reaction of alcohols such as phenolic epoxy resins, trimethylolpropane, oligopropylene glycol and hydrogenated bisphenol-A with epichlorohydrin, hexahydrophthalic acid, tetrahydrophthalic acid or phthalic acid and epichlorohydrin or 2 -Glycidyl ester epoxy resin obtained by reaction with methyl epichlorohydrin, glycidyl amine epoxy resin obtained by reaction of amine such as diaminodiphenylmethane and aminophenol with epichlorohydrin, reaction with polyamine such as isocyanuric acid and epichlorohydrin Heterocyclic epoxy resin, phosphazene compound having glycidyl group, epoxy-modified phosphazene resin, cycloaliphatic epoxy resin Urethane-modified epoxy resins to. Among these, a phenol novolak type epoxy resin, an orthocresol novolak type epoxy resin, a bisphenol-A type epoxy resin, a biphenol type epoxy resin, and a phenol type epoxy resin obtained by a reaction of tris (hydroxyphenyl) methane and epichlorohydrin are preferable. These epoxy resins may be used alone or in combination of two or more.

  When the above-mentioned epoxy resin is used as the resin component (hereinafter sometimes referred to as “epoxy resin composition”), the proportion of the epoxy group-containing cyclic phosphazene compound of the present invention in the epoxy resin composition is 0.1-80. % By weight is preferable, and 0.5 to 70% by weight is more preferable. When the ratio of the epoxy group-containing cyclic phosphazene compound is less than 0.1% by weight, the resin molded body made of the resin composition may not exhibit sufficient flame retardancy. On the other hand, if it exceeds 80% by weight, the original properties of the resin component may be impaired, and a resin molded product having such properties may not be obtained.

  The epoxy resin composition usually contains a curing agent. The type of curing agent is not particularly limited as long as it is used as a curing agent for epoxy resins. For example, polyamine curing agents such as aliphatic polyamines, aromatic polyamines and polyamide polyamines, anhydrous hexahydro Acid anhydride curing agents such as phthalic acid and methyltetrahydrophthalic anhydride, phenolic curing agents such as phenol novolak and cresol novolak, phosphazene compounds having a hydroxyl group, Lewis acids such as boron trifluoride and their salts, and dicyandiamides Etc. These may be used alone or in combination of two or more.

  In the epoxy resin composition, the amount of the curing agent used is preferably set to be 0.5 to 1.5 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin, and is 0.6 to 1.2 equivalents. It is more preferable to set so.

  The epoxy resin composition containing a curing agent may contain a curing accelerator. The available curing accelerators are various known ones, and are not particularly limited. For example, imidazole compounds such as 2-methylimidazole and 2-ethylimidazole, 2- (dimethylaminomethyl) phenol And tertiary amine compounds such as triphenylphosphine compounds. When using a hardening accelerator, it is preferable to set the usage-amount to 0.01-15 weight part with respect to 100 weight part of epoxy resins, and it is more preferable to set to 0.1-10 weight part.

  The epoxy resin composition may be blended with known reactive diluents and additives as required. Although the reactive diluent which can be utilized is not specifically limited, For example, aliphatic alkyl glycidyl ethers, such as butyl glycidyl ether, 2-ethylhexyl glycidyl ether, and allyl glycidyl ether, glycidyl methacrylate, and tertiary carboxylic acid glycidyl ester And alkyl glycidyl esters such as styrene oxide and phenyl glycidyl ether, cresyl glycidyl ether, ps-butylphenyl glycidyl ether and nonylphenyl glycidyl ether. These reactive diluents may be used alone or in combination of two or more. On the other hand, as the additive, those described above can be used.

  The resin composition of the present invention such as the above-described epoxy resin composition can be obtained by uniformly mixing each component. When this resin composition is allowed to stand for 1 to 36 hours in a temperature range of about 100 to 250 ° C. depending on the resin component, a sufficient curing reaction proceeds to form a cured product. For example, when the epoxy resin composition is usually left at a temperature of 150 to 250 ° C. for 2 to 15 hours, a sufficient curing reaction proceeds to form a cured product. In such a curing process, the epoxy group-containing cyclic phosphazene compound of the present invention crosslinks together with the resin component and is stably held in the cured product, so that the high temperature reliability of the cured product is unlikely to be impaired. In addition, the epoxy group-containing cyclic phosphazene compound of the present invention can increase the flame retardancy without impairing the mechanical properties (particularly the glass transition temperature) of such a cured product, Low smoke generation. For this reason, the resin composition of this invention can be widely used as a material for manufacture of various resin moldings, for coating materials, for adhesives, and for other uses. In particular, the resin composition of the present invention is used for semiconductor encapsulation and circuit boards (in particular, metal-clad laminates, printed wiring board substrates, printed wiring board adhesives, printed wiring board adhesive sheets, and printed wiring board use. Insulating circuit protective films, conductive pastes for printed wiring boards, sealing agents for multilayer printed wiring boards, circuit protective agents, coverlay films, cover inks) and the like are suitable as materials for manufacturing electrical and electronic parts.

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. Of the following examples, Examples 3, 4, 6, 9, 14, 15, 17, 20, 25, 26, 29, 30, 34, 35, 36, 39, 41, 44 and 45 are reference examples. is there.
In the following, “unit” in “unit mol” means the smallest structural unit of the cyclic phosphazene compound, for example, (PNA ₂ ) for general formula (1) and (PNX ₂ ) for general formula (6). ). In General formula (6), when X is chlorine, the 1 unit mol is 115.87g.
In the following, unless otherwise specified, “%” and “parts” mean “% by weight” and “parts by weight”, respectively.

The phosphazene compounds obtained in the Examples and the like were measured for ¹ H-NMR spectrum and ³¹ P-NMR spectrum, CHN elemental analysis, analysis of elemental chlorine (residual chlorine) by potentiometric titration using silver nitrate after alkali melting, Identification was performed based on the analysis of phosphorus element by ICP-AES after microwave wet decomposition and the results of TOF-MS analysis. The hydroxyl equivalent is determined by neutralization titration according to the method for measuring hydroxyl value defined in JIS K 0070-1992 "Testing method 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 method, and the hydroxyl equivalent weight g / eq. Converted to. The epoxy equivalent was measured according to the potentiometric titration method of JIS K 7236-1995 “Testing method for epoxy equivalent of epoxy resin”.

Example 1 (Production of epoxy group-containing cyclic phosphazene compound according to Form 1 according to Production Method 1)
[Step 1: Production of substituted cyclic phosphonitriles by method 1-A above]
In a 5 liter flask equipped with a stirrer, thermometer, reflux condenser, water separator and nitrogen inlet tube, 50.0 g (0.60 mol) of 48% NaOH aqueous solution, 70.1 g (0 .60 mol), 3,000 ml of toluene, and 348.4 g (1.20 mol) of 4′-allyloxyphenylsulfonyl-4-phenol. This was stirred and heated in a nitrogen atmosphere, and water in the flask was removed by azeotropic dehydration (recovered water: about 84 ml) to prepare sodium and potassium salts of 4′-allyloxyphenylsulfonyl-4-phenol. To this was added dropwise a toluene solution of hexachlorocyclotriphosphazene [58.0 g (0.50 unit mol) of hexachlorocyclotriphosphazene, 300 ml of toluene] with stirring at 20 to 25 ° C. over 1 hour, and under reflux (108 ° C.). The reaction was carried out with stirring for 8 hours. After completion of the reaction, 1,000 ml of water was added to the reaction solution to dissolve the reaction product, and the organic layer was separated using a separatory funnel. This organic layer was washed twice with 5% NaOH aqueous solution, then neutralized with 2% nitric acid, and further washed three times with water. After toluene was distilled off, 286.9 g of a white solid product (yield) was obtained. Rate: 92%). The melting point (melting peak temperature) of this product was 164 ° C. The analysis result of this product was as follows.

¹ H-NMR spectrum (in heavy acetone, δ, ppm):
_{-CH 2 - 4.6 (4H),} = CH 2 5.3~5.4 (4H), - CH = 6.0 (2H), phenyl CH 6.8~7.1 (8H), 7.8-8.0 (8H)
◎ ³¹ P-NMR spectrum (in heavy acetone, δ, ppm):
Trimer (P = N) ₃ 8.5
◎ CHNP elemental analysis:
Theoretical value C: 57.8%, H: 4.2%, N: 2.2%, P: 5.0%
Measured value C: 57.9%, H: 4.4%, N: 2.1%, P: 4.9%
◎ Residual chlorine analysis:
<0.01%

From the above analysis results, it was confirmed that the product in this step was [N = P (OC ₆ H ₄ —SO ₂ —C ₆ H ₄ OCH ₂ CH═CH ₂ ) ₂ ] ₃ .

[Step 2: Epoxidation step]
A 3 liter flask equipped with a stirrer, a thermometer, and a reflux condenser was charged with 23.0 g (8 mmol) of phosphotungstic acid, 117.6 ml (0.48 mol) of a 40 w / v% aqueous phosphoric acid solution and 800 ml of water, and stirred. The pH was adjusted to 2.0 with 28% aqueous ammonia solution. A solution prepared by dissolving 249.5 g (0.40 unit mol) of the product obtained in Step 1 and 3.9 g of trioctylmethylammonium chloride in 1,000 ml of chloroform was added thereto and heated to 70 ° C. vigorously. While stirring, 233.2 g (2.40 mol) of 35% aqueous hydrogen peroxide was added dropwise over 3 hours, and the reaction was stirred at the same temperature for 15 hours. After completion of the reaction, the organic layer was separated with a separatory funnel, and this organic layer was washed with 20% aqueous sodium sulfite solution and 5% aqueous sodium hydrogen carbonate solution, and further washed three times with water. The mixture was further stirred for 30 minutes. Thereafter, this solution was filtered, and chloroform was further distilled off. As a result, 238.7 g (yield: 91%) of a white powder product was obtained. This product did not show a clear melting point due to the glassy solid. The analysis result of this product is as follows.

◎ Epoxy equivalent:
324 g / eq. (Theoretical value 328 g / eq.)
◎ Residual chlorine analysis:
<0.01%

From the above analysis results, it was confirmed that the product in this step was [N = P (OC ₆ H ₄ —SO ₂ —C ₆ H ₄ OCH ₂ CH (O) CH ₂ ) ₂ ] ₃ .

Example 2 (Production of epoxy group-containing cyclic phosphazene compound according to Form 2 according to Production Method 1)
[Step 1: Production of substituted cyclic phosphonitriles by method 2-D above]
In a 1 liter flask equipped with a stirrer, thermometer, reflux condenser, water separation receiver and nitrogen inlet tube, 58.4 g (0.50 mol) of 48% KOH aqueous solution, 450 ml of chlorobenzene 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 39 ml) to prepare a potassium potassium salt. The slurry solution was cooled to 20 ° C., and 200 ml of tetrahydrofuran (THF) was charged to obtain a uniform solution.

  On the other hand, in a 2 liter flask equipped with a stirrer, a thermometer, a reflux condenser, a water separation receiver and a nitrogen introduction tube, 76.0 g (0.65 mol) of a 48% KOH aqueous solution, 800 ml of chlorobenzene and 4′- 188.8 g (0.65 mol) of allyloxyphenylsulfonyl-4-phenol was charged. This was stirred and heated in a nitrogen atmosphere, and the water in the flask was removed by azeotropic dehydration (recovered water: about 51 ml) to prepare a potassium salt of 4'-allyloxyphenylsulfonyl-4-phenol. The slurry solution was cooled to 20 ° C. and charged with 300 ml of THF to obtain a uniform solution.

  Next, a THF solution of hexachlorocyclotriphosphazene [58.0 g (0.50 unit mol), THF 200 ml] of hexachlorocyclotriphosphazene was placed in a 3 liter flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube. The phenol potassium salt solution was added dropwise with stirring at 5 ° C. over 10 hours, and the stirring reaction was carried out at 25 ° C. for 5 hours. Subsequently, the potassium salt solution of 4′-allyloxyphenylsulfonyl-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 (86 ° C.) for 10 hours. . After completion of the reaction, the reaction solution was concentrated to about 1,000 ml, and then 600 ml of chlorobenzene and 600 ml of water were added to dissolve the reaction product, and the organic layer was separated using a separatory funnel. This organic layer was washed twice with 5% NaOH aqueous solution, then neutralized with 2% sulfuric acid, further washed with water three times, and chlorobenzene was distilled off to obtain a pale yellow solid product. 207.1 g (yield: 96%) 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 - 4.6 (2H),} = CH 2 5.3~5.4 (2H), - CH = 6.0 (1H), phenyl CH 6.8~7.2 (9H), 7.8-8.0 (4H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 8.5
◎ CHNP elemental analysis:
Theoretical value C: 58.9%, H: 4.2%, N: 3.2%, P: 7.2%
Measured value C: 58.7%, H: 4.4%, N: 3.1%, P: 7.0%
◎ Residual chlorine analysis:
<0.01%
◎ TOF-MS (m / z):
1087, 1283, 1480

From the above analysis results, the product in this step is [N ₃ = P ₃ (OC ₆ H ₄ —SO ₂ —C ₆ H ₄ OCH ₂ CH═CH ₂ ) ₂ (OC ₆ H ₅ ) ₄ ], [ _{N 3 = P 3 (OC 6} H 4 -SO 2 -C 6 H 4 OCH 2 CH = CH 2) 3 (OC 6 H 5) 3], [N 3 = P 3 (OC 6 H 4 -SO 2 - C ₆ H ₄ OCH ₂ CH═CH ₂ ) ₄ (OC ₆ H ₅ ) ₂ ], the average composition of which is [N═P (OC ₆ H ₄ —SO ₂ —C ₆ H ₄ OCH ₂ CH═ it was confirmed that _{CH 2) 1.02 (OC 6 H} 5) 0.98] _3.

[Step 2: Epoxidation step]
A 2 liter flask equipped with a stirrer, thermometer and reflux condenser was charged with 172.5 g (0.40 unit mol) of the product obtained in Step 1, 700 ml of toluene and 2.0 g of trioctylmethylammonium chloride. . On the other hand, a solution prepared by adding 11.8 g (4 mmol) of phosphotungstic acid and 60.2 ml (0.24 mol) of a 40 w / v% phosphoric acid aqueous solution to 270 ml of water and adjusting the pH to 1.6 with 28% ammonia aqueous solution. In addition, while heating to 70 ° C. and vigorously stirring, 79.3 g (0.82 mol) of 35% aqueous hydrogen peroxide was added dropwise over 3 hours, and the reaction was stirred at the same temperature for 12 hours. After completion of the reaction, the organic layer was separated with a separatory funnel, and this organic layer was washed with a 20% aqueous sodium sulfite solution and a 5% aqueous sodium hydrogen carbonate solution, and further washed three times with water. The mixture was further stirred for 30 minutes. Thereafter, this solution was filtered, and toluene was further distilled off. As a result, 170.1 g (yield: 95%) of a white powder product was obtained. This product did not show a clear melting point due to the glassy solid. The analysis result of this product is as follows.

◎ Epoxy equivalent:
436 g / eq. (Theoretical value 439 g / eq.)
◎ Residual chlorine analysis:
<0.01%

From the above analysis results, the product in this step is [N = P (OC ₆ H ₄ —SO ₂ —C ₆ H ₄ OCH ₂ CH (O) CH ₂ ) _1.02 (OC ₆ H ₅ ) _{0. 98} ] ₃ .

Example 3 (Production of epoxy group-containing cyclic phosphazene compound according to Form 2 by Production Method 1)
[Step 1: Production of substituted cyclic phosphonitriles by method 2-D above]
Into a 2 liter flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube were charged 11.5 g (0.50 mol) of metal sodium and 800 ml of 1,2-dimethoxyethane (DME). . In contrast, a phenol DME solution [phenol 47.1 g (0.50 mol), DME 200 ml] was added dropwise at 15 to 20 ° C. over 2 hours with stirring in a nitrogen atmosphere, and then heated to 75 to 80 ° C., Further, the reaction solution was concentrated to 500 ml to prepare a sodium salt of phenol.

  On the other hand, 14.9 g (0.65 mol) of metal sodium fragmented and 800 ml of THF were charged into a 2 liter flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube. In contrast, 156.2 g (0.65 mol) of 4 ′-(3-butenyloxy) phenyl-4-phenol in THF [4 ′-(3-butenyloxy) phenyl-4-phenol] with stirring under a nitrogen atmosphere, THF 500 ml] was added dropwise at 15 to 20 ° C. over 2 hours, and then heated to 60 to 65 ° C., and the reaction solution was further concentrated to 500 ml, and 4 ′-(3-butenyloxy) phenyl-4-phenol sodium salt was added. Prepared.

  Next, in a 2 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 500 ml] was added, and the above sodium salt solution of phenol was added dropwise with stirring at 5 ° C. over 6 hours, followed by stirring at 25 ° C. for 2 hours. Subsequently, the sodium salt solution of 4 ′-(3-butenyloxy) phenyl-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 (70 ° C.) for 13 hours. went. After completion of the reaction, the reaction solution was concentrated to about 500 ml, 1000 ml of toluene and 500 ml of water were added to dissolve the reaction product, and then the organic layer was separated using a separatory funnel. This organic layer was washed twice with 5% aqueous NaOH solution, then neutralized with 2% sulfuric acid, and further washed twice with water, and then toluene was distilled off to obtain a white solid product 177. 5 g (yield: 93%) 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):
_{-CH 2 - 2.3 (2H),} - CH 2 - 3.6 (2H), = CH 2 5.1 (2H), - CH = 5.8 (1H), phenyl CH 6.8 to 7.8 (13H)
◎ ³¹ P-NMR spectrum (in heavy acetone, δ, ppm):
Trimer (P = N) ₃ 9.3, Tetramer (P = N) ₄ -12.
◎ CHNP elemental analysis:
Theoretical value C: 70.2%, H: 5.4%, N: 3.7%, P: 8.1%
Measured value C: 69.9%, H: 5.5%, N: 3.5%, P: 8.1%
◎ Residual chlorine analysis:
<0.01%

From the above analysis results, the product in this step is [N = P (OC ₆ H ₄ -C ₆ H ₄ OCH ₂ CH ₂ CH═CH ₂ ) _0.97 (OC ₆ H ₅ ) _1.03 ] ₃ and it confirmed the _{[N = P (OC 6 H} 4 -C 6 H 4 OCH 2 CH 2 CH = CH 2) 0.97 (OC 6 H 5) 1.03] from _4.

[Step 2: Epoxidation step]
A 2 liter flask equipped with a stirrer, thermometer and reflux condenser was charged with 152.7 g (0.40 unit mol) of the product obtained in step 1, 600 ml of toluene and 2.0 g of trioctylmethylammonium chloride. . Thereto, 12.4 g (49 mmol) of tungstic acid and 60.6 ml (0.25 mol) of a 40 w / v% phosphoric acid aqueous solution were added to 270 ml of water, and a solution adjusted to pH 1.6 with 28% aqueous ammonia solution was added. While heating to 70 ° C. and vigorously stirring, 80.8 g (0.82 mol) of 35% aqueous hydrogen peroxide was added dropwise over 3 hours, and a stirring reaction was performed at the same temperature for 12 hours. After completion of the reaction, the organic layer was separated with a separatory funnel, and this organic layer was washed with a 20% aqueous sodium sulfite solution, then with a 5% aqueous sodium bicarbonate solution, and further washed with water three times. The activated carbon 7.5g was added and it stirred for 30 minutes. Thereafter, this solution was filtered, and toluene was further distilled off. As a result, 146.6 g (yield: 95%) 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 is as follows.

◎ Epoxy equivalent:
389 g / eq. (Theoretical value 387 g / eq.)
◎ Residual chlorine analysis:
<0.01%

From the above analysis results, the product in this step is [N = P (OC ₆ H ₄ -C ₆ H ₄ OCH ₂ CH ₂ CH (O) CH ₂ ) _0.97 (OC ₆ H ₅ ) _1.03 ] was confirmed to be ₃ and _{[N = P (OC 6 H} 4 -C 6 H 4 OCH 2 CH 2 CH (O) CH 2) 0.97 (OC 6 H 5) 1.03] 4.

Example 4 (Production of epoxy group-containing cyclic phosphazene compound according to Form 2 by Production Method 1)
[Step 1: Production of substituted cyclic phosphonitrile by method 2-C above]
In a 2 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, 1,100 ml of toluene and 4 ′-( 1-Propenyloxy) phenylisopropylidene-4-phenol 134.2 g (0.50 mol) was charged. This was stirred and heated in a nitrogen atmosphere, and the water in the flask was removed by azeotropic dehydration (recovered water: about 29 ml) to prepare a sodium salt of 4 ′-(1-propenyloxy) phenylisopropylidene-4-phenol. did. The slurry solution was cooled to 20 ° C., and 500 ml of THF was charged to make a uniform solution.

  Next, a toluene solution of cyclophosphazene [46.4 g (0.40 unit mol) of hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene in a 3 liter flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen inlet tube. 5.8 g (0.05 unit mol), decachlorocyclopentaphosphazene 2.9 g (0.025 unit mol), dodecachlorocyclohexaphosphazene 1.7 g (0.015 unit mol), macrocycle greater than tetradecachlorocycloheptaphosphazene Product 1.2 g (0.01 unit mol), toluene 500 ml]. On the other hand, the sodium salt solution of 4 ′-(1-propenyloxy) phenylisopropylidene-4-phenol was added dropwise at 5 ° C. over 6 hours with stirring, and then the stirring reaction was carried out at reflux (85 ° C.) for 7 hours. Went for hours. After completion of the reaction, the reaction solution was concentrated to about 700 ml, 300 ml of toluene and 500 ml of water were added to dissolve the reaction product, and the organic layer was separated using a separatory funnel. This organic layer was washed three times with water, and then water-toluene was azeotropically dehydrated to obtain a toluene solution of a partially substituted 4 '-(1-propenyloxy) phenylisopropylidene-4-phenoxy partial product in an anhydrous state.

  Next, a toluene solution of the above 4 ′-(1-propenyloxy) phenylisopropylidene-4-phenoxy partially substituted in a 2-liter flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, n -39.1 g (0.65 mol) of propanol, 144.7 g (1.43 mol) of triethylamine and 0.6 g (5 mmol) of dimethylaminopyridine were charged, and a stirring reaction was performed at reflux (103 ° C.) for 10 hours. After completion of the reaction, the reaction solution was concentrated to about 700 ml, 300 ml of toluene and 1,000 ml of water were added to dissolve the reaction product, and then the organic layer was separated using a separatory funnel. This organic layer was washed twice with 5% NaOH aqueous solution, then neutralized with 2% hydrochloric acid and further washed twice with water, and then toluene was distilled off to produce a pale yellow viscous liquid. 164.7 g (yield: 90%) of the product was obtained. The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
_{-CH 3 0.9 (3H), -} CH 2 - 1.6 (2H), - CH 3 1.6~1.8 (9H), - CH 2 - 3.6 (2H), - CH = 4 .9 (1H), ═CH—5.7 (1H), phenyl C—H 6.7 to 7.2 (8H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 12.3, tetramer (P = N) ₄ -7.3, pentamer (P = N) _5,6 -11.1, more than heptamer ( P = N) _{≧ 7} −14.5 to −17.8
◎ CHNP elemental analysis:
Theoretical value C: 67.6%, H: 7.1%, N: 3.8%, P: 8.5%
Measured value C: 67.4%, H: 7.2%, N: 3.7%, P: 8.4%
◎ Residual chlorine analysis:
<0.01%

From the above analysis results, the product in this step is [N = P (OC ₆ H ₄ —C (CH ₃ ) ₂ —C ₆ H ₄ OCH═CHCH ₃ ) _0.97 (OCH ₂ CH ₂ CH ₃ ) _1.03 ] n.

[Step 2: Epoxidation step]
A 2 liter flask equipped with a stirrer, a thermometer and a reflux condenser was charged with 146.1 g (0.40 unit mol) of the product obtained in Step 1, 600 ml of toluene and 1.9 g of trioctylmethylammonium chloride. . Thereto, 11.4 g (70 mmol) of molybdic acid and 85.6 ml (0.35 mol) of 40 w / v phosphoric acid aqueous solution were added to 280 ml of water, and a solution adjusted to pH 2.5 with 28% aqueous ammonia solution was added. While being heated to ° C. and vigorously stirring, 75.4 g (0.78 mol) of 35% hydrogen peroxide solution was added dropwise over 3 hours, and stirring reaction was performed at the same temperature for 18 hours. After completion of the reaction, the organic layer was separated with a separatory funnel, and this organic layer was washed with a 20% aqueous sodium sulfite solution, then with a 5% aqueous sodium bicarbonate solution, and further washed with water three times. The activated carbon 7.2g was added and it stirred for 30 minutes. Thereafter, this solution was filtered and toluene was distilled off to obtain 135.5 g (yield: 89%) of a pale yellow solid product. This product did not show a clear melting point due to the glassy solid.

◎ Epoxy equivalent:
396 g / eq. (Theoretical value 392 g / eq.)
◎ Residual chlorine analysis:
<0.01%

From the above analysis results, the product in this step is [N = P (OC ₆ H ₄ —C (CH ₃ ) ₂ —C ₆ H ₄ OCH (O) CHCH ₃ ) _0.97 (OCH ₂ CH ₂ CH ₃ ) _1.03 ] n was confirmed.

Example 5 (Production of epoxy group-containing cyclic phosphazene compound according to Form 2 according to Production Method 1)
[Step 1: Production of substituted cyclic phosphonitriles by method 2-D above]
In a 1 liter flask equipped with a stirrer, thermometer, reflux condenser, water separator and nitrogen inlet, 41.7 g (0.50 mol) of 48% NaOH, 500 ml of toluene and 54.1 g of p-cresol (0 .65 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 30 ml) to prepare a sodium salt of p-cresol. The slurry solution was cooled to 20 ° C., and 200 ml of THF was charged to make a uniform solution.

  Meanwhile, 76.0 g (0.65 mol) of 48% KOH, 1,000 ml of toluene and 1,3,3 in a 2 liter flask equipped with a stirrer, thermometer, reflux condenser, water separator and nitrogen inlet tube. 3-trimethyl-1- (4-allyloxyphenyl) indan-6-ol (44%) and 1,3,3-trimethyl-1- (4-bidoxyphenyl) -6-allyloxyindane (56%) And 190.7 g (0.65 mol) of the mixture. This was stirred and heated in a nitrogen atmosphere, and the water in the flask was removed by azeotropic dehydration (recovered water: about 51 ml). 1,3,3-trimethyl-1- (4-allyloxyphenyl) indan-6 A potassium salt of a mixture of ol and 1,3,3-trimethyl-1- (4-bidoxyphenyl) -6-allyloxyindane was prepared. 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 300 ml] of hexachlorocyclotriphosphazene was placed in a 3 liter flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube. Prepared. The sodium salt solution of p-cresol was added dropwise thereto at 5 ° C. over 10 hours with stirring, and the stirring reaction was carried out at 25 ° C. for 2 hours. Subsequently, the 1,3,3-trimethyl-1- (4-allyloxyphenyl) indan-6-ol (44%) and 1,3,3-trimethyl-1- (4-bidoxy) were added to the reaction solution. A potassium salt solution of a mixture of phenyl) -6-allyloxyindane (56%) was added dropwise at 20 ° C. over 1 hour with stirring, and the stirring reaction was carried out under reflux (85 ° C.) for 12 hours. 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 reaction product, and then the organic layer was separated using a separatory funnel. This organic layer was washed twice with 5% aqueous NaOH solution, then neutralized with 2% hydrochloric acid, and further washed twice with water, and then toluene was distilled off to obtain product 222 as a pale yellow solid. 0.1 g (yield: 94%) 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 3 1.0~1.6 (9H), -} CH 2 - 2.1~2.4 (2H), - CH 3 2.3 (3H), - CH 2 - 4.6 (2H), _{= CH 2 5.3~5.4 (2H),} - CH = 6.0 (1H), phenyl CH 6.8~7.9 (11H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.5
◎ CHNP elemental analysis:
Theoretical value C: 73.5%, H: 6.6%, N: 3.0%, P: 6.6%
Measured value C: 73.2%, H: 6.7%, N: 2.9%, P: 6.6%
◎ Residual chlorine analysis:
<0.01%
◎ TOF-MS (m / z):
1,179, 1,379, 1,580

From the above analysis results, the products obtained in this step are [N ₃ = P ₃ (OC ₆ H ₄ -Indane-OCH ₂ CH═CH ₂ ) ₂ (OC ₆ H ₄ CH ₃ ) ₄ ], [N _{3 = P 3 (O-Indane} -C 6 H 4 OCH 2 CH = CH 2) 2 (OC 6 H 4 CH 3) 4], [N 3 = P 3 (OC 6 H 4 -Indane-OCH 2 CH = _{CH 2) 3 (OC 6 H} 4 CH 3) 3], [N 3 = P 3 (O-Indane-C 6 H 4 OCH 2 CH = CH 2) 3 (OC 6 H 4 CH 3) 3], [ _{N 3 = P 3 (OC 6} H 4 -Indane-OCH 2 CH = CH 2) 4 (OC 6 H 4 CH 3) 2] and _{[N 3 = P 3 (O} -Indane-C 6 H 4 OCH 2 CH _{= CH 2) 4 (OC 6} H 4 CH ) _2] is a mixture of the average composition _{[N = P (OC 6 H} 4 -Indane-OCH 2 CH = CH 2) 1.04 (OC 6 H 4 CH 3) 0.96] 3 and [N = was confirmed to be _{P (O-Indane-C 6} H 4 OCH 2 CH = CH 2) 1.08 (OC 6 H 4 CH 3) 0.92] ₃ mixture.

[Step 2: Epoxidation step]
In a 3 liter flask equipped with a stirrer, thermometer and reflux condenser, 188.6 g (0.40 unit mol) of the product obtained in step 1, 1500 ml of toluene and 2.1 g of trioctylmethylammonium chloride were added. Prepared. Thereto, 12.8 g (51 mmol) of tungstic acid and 62.3 ml (0.25 mol) of a 40 w / v% aqueous phosphoric acid solution were added to 280 ml of water, and a solution adjusted to pH 1.6 with 28% aqueous ammonia solution was added. While heating at 70 ° C. and vigorously stirring, 82.4 g (0.85 mol) of 35% aqueous hydrogen peroxide was added dropwise over 3 hours, and the reaction was carried out by stirring for 15 hours while maintaining the temperature as it was. After completion of the reaction, the organic layer was separated with a separatory funnel, and this organic layer was washed with a 20% aqueous sodium sulfite solution, then with a 5% aqueous sodium bicarbonate solution, and further washed with water three times. 9.5 g of activated carbon was added and stirred for 30 minutes. Thereafter, this solution was filtered, and toluene was further distilled off. As a result, 153.9 g (yield: 90%) 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 is as follows.

◎ Epoxy equivalent:
421 g / eq. (Theoretical value 418 g / eq.)
◎ Residual chlorine analysis:
<0.01%

From the above analysis results, the product in this step is [N = P (OC ₆ H ₄ -Indane-OCH ₂ CH (O) CH ₂ ) _1.04 (OC ₆ H ₄ CH ₃ ) _0.96 ] ₃ and it was confirmed that _{[N = P (O-Indane} -C 6 H 4 OCH 2 CH (O) CH 2) 1.08 (OC 6 H 4 CH 3) 0.92] which is a mixture of _3.

Example 6 (Production of epoxy group-containing cyclic phosphazene compound according to Form 1 according to Production Method 2)
[Step 1: Production of substituted cyclic phosphonitriles by method 1-A above]
Under a nitrogen atmosphere, 500 ml of DME and 52.0 g (1.30 mol) of 60% NaH / oil were charged in a 3 liter flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube. On the other hand, under stirring, 4 '-(1-propenyloxy) phenyl-4-phenol in DME solution [4'-(1-propenyloxy) phenyl-4-phenol 294.2 g (1.30 mol), DME1, 000 ml] was added dropwise at 5 ° C. or lower over 2 hours and then stirred at 50 ° C. for 2 hours to prepare the sodium salt of 4 ′-(1-propenyloxy) phenyl-4-phenol.

  Next, a DME solution of chlorophosphazene [hexachlorocyclotriphosphazene 52.2 g (0.45 unit mol), octachlorocyclotetraphosphazene] was placed in a 3 liter flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube. 5.8 g (0.05 unit mol), DME 300 ml]. The above 4 ′-(1-propenyloxy) phenyl-4-phenol sodium salt solution was added dropwise thereto at 25 ° C. over 1 hour with stirring, and the mixture was stirred for 12 hours under reflux (68 ° C.) to carry out the reaction. . After completion of the reaction, the reaction solution was concentrated to about 500 ml, 1,000 ml of toluene and 1,500 ml of water were added to dissolve the reaction product, and then the organic layer was separated using a separatory funnel. This organic layer was washed twice with 5% NaOH aqueous solution, then neutralized with 2% sulfuric acid, further washed with water, and then toluene was distilled off. As a result, 225.5 g (yield: 91%) was obtained. This product did not show an accurate 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 1.7 (6H), -} CH = 4.9 (2H), = CH- 5.7 (2H), phenyl CH 6.5 to 7.8 (16H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 8.5, Tetramer (P = N) ₄ -13.2
◎ CHNP elemental analysis:
Theoretical value C: 72.7%, H: 5.3%, N: 2.8%, P: 6.3%
Measured value C: 72.5%, H: 5.4%, N: 2.8%, P: 6.3%
◎ Residual chlorine analysis:
<0.01%

From the above analysis results, the product of this step is _{[N = P (OC 6 H} 4 -C 6 H 4 OCH = CHCH 3) 2] 3 and _{[N = P (OC 6 H} 4 -C 6 H 4 OCH = it was confirmed that CHCH _{3) 2] 4.}

[Process: Deprotection group process]
In a 2 liter flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, 198.2 g (0.40 unit mol) of the product obtained in Step 1 and 1,000 ml of toluene were charged. Then, 200.4 g (0.80 mol) of boron tribromide was added dropwise at 5 to 10 ° C. over 4 hours under a nitrogen atmosphere, and then the mixture was aged and stirred at 25 to 30 ° C. for 12 hours. After the reaction, the reaction solution was added to 1,000 ml of water, and the organic layer was separated using a separatory funnel. The organic layer was washed 3 times with water and then toluene was distilled off to obtain 154.5 g (yield: 93%) of a pale yellow solid product. This product did not show an accurate 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):
Phenyl C—H 6.2-7.5 (16H), —OH 9.5 (2H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 8.3, Tetramer (P = N) ₄ -13.4
◎ CHNP elemental analysis:
Theoretical value C: 69.4%, H: 4.4%, N: 3.4%, P: 7.5%
Measured value C: 69.2%, H: 4.5%, N: 3.5%, P: 7.3%
◎ Hydroxyl equivalent:
209 g / eq. (Theoretical value 208 g / eq.)

From the above analysis results, the product of this step is _{[N = P (OC 6 H} 4 -C 6 H 4 OH) 2] 3 and _{[N = P (OC 6 H} 4 -C 6 H 4 OH) 2] ₄ was confirmed.

[Step 3: Epoxidation step]
124.6 g (0.30 unit mol) of the product obtained in step 2 and 333.1 g (3.60 mol) of epichlorohydrin in a 2 liter flask equipped with stirrer, thermometer, water separator and reflux condenser. ) Was dissolved by heating, followed by dropwise addition of 48% aqueous NaOH (NaOH: 24.0 g, 0.60 mol) at 95 to 118 ° C. over 2 hours. At this time, the distilled epichlorohydrin and water were separated in a water separation receiver, the epichlorohydrin was returned to the flask, and the water was discharged out of the system. In order to complete the reaction, an aging reaction was further performed at the same temperature for 1 hour. After completion of the reaction, epichlorohydrin was distilled off, 1,000 ml of chloroform and 1,000 ml of water were added to dissolve the reaction product, and the organic layer was separated using a separatory funnel. This organic layer was washed twice with water. After dehydrating the organic layer with anhydrous magnesium sulfate, chloroform was distilled off to obtain 148.8 g (yield: 94%) of a pale yellow solid product. This product did not show an accurate melting point due to the glassy solid.

◎ Epoxy equivalent:
265 g / eq. (Theoretical value 264 g / eq.)
◎ Residual chlorine analysis:
<0.03%

From the above analysis results, the products obtained in this step are [N═P (OC ₆ H ₄ —C ₆ H ₄ OCH ₂ CH (O) CH ₂ ) ₂ ] ₃ and [N═P (OC ₆ H). it was confirmed that _{4 -C 6 H 4 OCH 2 CH} (O) CH 2) 2] _4.

Example 7 (Production of epoxy group-containing cyclic phosphazene compound according to Form 2 by Production Method 2)
[Step 1: Production of substituted cyclic phosphonitriles by method 2-D above]
The product was operated under the same conditions as in Step 1 of Example 2 to obtain 207.9 g (yield: 96%) of a pale yellow solid product. This product is the same as that obtained in Step 1 of Example 2, [N ₃ = P ₃ (OC ₆ H ₄ —SO ₂ —C ₆ H ₄ OCH ₂ CH═CH ₂ ) ₂ (OC ₆ H _{5) 4], [N 3} = P 3 (OC 6 H 4 -SO 2 -C 6 H 4 OCH 2 CH = CH 2) 3 (OC 6 H 5) 3], [N 3 = P 3 (OC 6 H ₄ —SO ₂ —C ₆ H ₄ OCH ₂ CH═CH ₂ ) ₄ (OC ₆ H ₅ ) ₂ ], the average composition of which is [N═P (OC ₆ H ₄ —SO ₂ —C _6). it was confirmed that _{H 4 OCH 2 CH = CH 2} ) 1.02 (OC 6 H 5) 0.98] _3.

[Step 2: Deprotecting group step]
129.4 g (0.30 unit mol) of the product obtained in Step 1 and 500 ml of acetic acid were charged in a 1 liter flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube. Then, 161.8 ml (0.60 mol) of a 30% hydrobromic acid / acetic acid solution was added dropwise at 5 to 10 ° C. over 2 hours in a nitrogen atmosphere, followed by stirring and aging at 50 ° C. for 8 hours. After completion of the reaction, the reaction solution was concentrated to remove excess hydrobromic acid and acetic acid. Next, 400 ml of methyl isobutyl ketone (MIBK) and 400 ml of water were added to the residue and dissolved, and the organic layer was separated using a separatory funnel. The organic layer was washed three times with water and then MIBK was distilled off to obtain 99.6 g (yield: 85%) of a tan 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):
Phenyl C—H 6.8 to 7.2 (9H), 7.8 to 7.2 (4H), —OH 9.5 (1H)
◎ ³¹ P-NMR spectrum (in heavy acetone, δ, ppm):
Trimer (P = N) ₃ 9.5
◎ CHNP elemental analysis:
Theoretical value C: 55.7%, H: 3.6%, N: 3.6%, P: 7.9%
Measured value C: 55.5%, H: 3.7%, N: 3.5%, P: 7.7%
◎ Hydroxyl equivalent:
394 g / eq. (Theoretical value 391 g / eq.)

From the above analysis results, the product obtained in this process is the _{[N = P (OC 6 H} 4 -SO 2 -C 6 H 4 OH) 1.02 (OC 6 H 5) 0.98] 3 It was confirmed.

[Step 3: Epoxidation step]
78.1 g (0.20 unit mol) of the product obtained in step 2 and 113.2 g (1.22 mol) epichlorohydrin in a 1 liter flask equipped with stirrer, thermometer, water separator and reflux condenser. ) Was dissolved by heating, and a 48% NaOH aqueous solution (NaOH: 8.2 g, 0.20 mol) was added dropwise at 95 to 118 ° C. over 2 hours. At this time, the distilled epichlorohydrin and water were separated in a water separation receiver, the epichlorohydrin was returned to the flask, and the water was discharged out of the system. In order to complete the reaction, an aging reaction was further performed at the same temperature for 1 hour. After completion of the reaction, epichlorohydrin and water were distilled off, and 600 ml of chloroform was added, transferred to a separatory funnel, and washed with water three times. The separated organic layer was dehydrated with anhydrous magnesium sulfate, and chloroform was distilled off. As a result, 81.5 g (yield: 91%) of a pale yellow solid product was obtained. This product did not show an accurate melting point due to the glassy solid. The analysis result of this product was as follows.

◎ Epoxy equivalent:
442 g / eq. (Theoretical value 439 g / eq.)
◎ Residual chlorine analysis:
<0.03%

From the results of this analysis, ¹ H-NMR analysis and ³¹ P-NMR analysis, the product obtained in this step was [N = P (OC ₆ H ₄ —SO ₂ —C ₆ H ₄ OCH ₂ CH (O ) it was confirmed that _{CH 2)} a _{1.02 (OC 6 H 5) 0.98} ] 3.

Example 8 (Production of epoxy group-containing cyclic phosphazene compound according to Form 2 by Production Method 2)
[Step 1: Production of substituted cyclic phosphonitrile by method 2-C above]
In a 3 liter flask equipped with a stirrer, thermometer, reflux condenser, water separator and nitrogen inlet, 41.7 g (0.50 mol) of 48% aqueous NaOH, 1,200 ml of toluene and 4′-benzyl 170.2 g (0.50 mol) of oxyphenylsulfonyl-4-phenol was charged. This was stirred and heated under a nitrogen atmosphere, and the water in the flask was removed by azeotropic dehydration (recovered water: about 30 ml) to prepare a 4′-benzyloxyphenylsulfonyl-4-phenol sodium salt. 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% KOH aqueous 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 of hexachlorocyclotriphosphazene (0.50 unit mol), 300 ml of THF] 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 4′-benzyloxyphenylsulfonyl-4-phenol was added dropwise 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 over 1 hour at 25 ° C. 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, 200 ml of toluene and 400 ml of water were added to dissolve the reaction product, and the organic layer was separated using a separatory funnel. This organic layer was washed twice with 5% NaOH aqueous solution, then neutralized with 2% sulfuric acid, and further washed with water three times, and then toluene was distilled off to obtain a light yellow solid product 201. 0.1 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 products in this step are [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], [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 [N = P (OC ₆ H ₄ —SO ₂ —C ₆ H ₄ OCH ₂ C _6]. it was confirmed that _{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 inlet tube, 139.5 g (0.30 unit mol) of the product obtained in Step 1 and 800 ml of toluene were charged. Under a nitrogen atmosphere, 26.9 ml (0.29 mol) of boron tribromide 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. This organic layer was washed three times with water, and toluene was distilled off. As a result, 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 product obtained in this step is N = P (OC ₆ H ₄ —SO ₂ —C ₆ H ₄ OH) _0.95 (OC ₆ H ₅ ) _1.05 ] ₃ It was confirmed.

[Step 3: Epoxidation step]
A 1 liter flask equipped with a stirrer, a thermometer and a reflux condenser was charged with 75.9 g (0.20 unit mol) of the product obtained in Step 2 and 105.5 g (1.14 mol) of epichlorohydrin in a pellet form. 7.6 g (0.19 mol) of NaOH was gradually added in a 30 ° C. water bath, taking care of the exotherm. After completion of the addition, the reaction was carried out at 40 ° C. for 1 hour, 50 ° C. for 2 hours, and further at 70 ° C. for 1 hour. After completion of the reaction, 500 ml of MIBK was added, transferred to a separatory funnel and washed with water until the aqueous layer became neutral. Thereafter, when the solvent and unreacted epichlorohydrin were distilled off from the organic layer under reduced pressure, 75.3 g (yield: 87%) of a pale yellow glassy solid product was obtained. This product did not show an accurate melting point due to the glassy solid. The analysis result of this product was as follows.

◎ Epoxy equivalent:
458 g / eq. (Theoretical value 456 g / eq.)
◎ Residual chlorine analysis:
<0.03%

From the results of this analysis and the results of ¹ H-NMR analysis and ³¹ P-NMR analysis, the product obtained in this step was [N = P (OC ₆ H ₄ —SO ₂ —C ₆ H ₄ OCH ₂ CH (O ) it was confirmed that _{CH 2)} a _{0.95 (OC 6 H 5) 1.05} ] 3.

Example 9 (Production of epoxy group-containing cyclic phosphazene compound according to Form 2 by Production Method 2)
[Step 1: Production of substituted cyclic phosphonitriles by method 2-D above]
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, a thermometer, a reflux condenser, a water separator and a nitrogen inlet tube, 87.7 g (0.75 mol) of a 48% KOH aqueous solution, 1500 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) in a 5-liter flask equipped with a stirrer, a thermometer, a reflux condenser, a water separation receiver, and a nitrogen introduction tube. mol), 500 ml of THF] was added, and the sodium salt solution of the phenol was added dropwise with stirring at 5 ° C. over 6 hours, and the stirring reaction was carried out at 25 ° C. for 2 hours. Next, the potassium salt solution of 4′-benzyloxyphenylisopropylidene-4-phenol is added dropwise to the reaction solution over 1 hour at 25 ° C. with stirring, and the stirring reaction is 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 reaction product, and then the organic layer was separated using a separatory funnel. This organic layer was washed twice with 5% NaOH aqueous solution, then neutralized with 2% sulfuric acid, and further washed with water three times, and then toluene was distilled off to obtain a brown solid product 221. 9 g (yield: 96%) 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 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, the product of this step is _{[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], [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 [N = P (OC ₆ H ₄ -C and it was confirmed that _{(CH 3) 2 -C 6 H} 4 OCH 2 C 6 H 5) 1.03 (OC 6 H 5) 0.97] _3.

[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 tube, Pd / C (Degussa, “E 101 NE / W ″: 10% Pd) 3.8 g and 2,500 ml of methanol were charged, and the reaction was stirred 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 recover methanol. Next, 1,000 ml of MIBK 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 3 times with water, and MIBK 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 of this step is _{[N = P (OC 6 H} 4 -C (CH 3) 2 -C 6 H 4 OH) 1.03 (OC 6 H 5) 0.97] 3 I confirmed that there was.

[Step 3: Epoxidation step]
The same operation as in Step 3 of Example 7 was conducted except that 73.9 g (0.20 unit mol) of the product obtained in Step 2 was used, and 78.6 g (yield: 92) of a pale yellow solid product was obtained. %). This product did not show an accurate melting point due to the glassy solid. The analysis result of this product was as follows.

◎ Epoxy equivalent:
416 g / eq. (Theoretical value 415 g / eq.)
◎ Residual chlorine analysis:
<0.03%

From this analysis result and the results of ¹ H-NMR analysis and ³¹ P-NMR analysis, the product obtained in this step was [N = P (OC ₆ H ₄ -C (CH ₃ ) ₂ -C ₆ H ₄ OCH]. It was confirmed to be _{2 CH (O) CH 2)} 1.03 (OC 6 H 5) 0.97] 3.

Example 10 (Production of epoxy group-containing cyclic phosphazene compound according to Form 2 by Production Method 2)
[Step 1: Production of substituted cyclic phosphonitriles by method 2-D above]
In a 1 liter flask equipped with a stirrer, thermometer, reflux condenser, water separator and nitrogen inlet, 41.7 g (0.50 mol) of 48% NaOH, 300 ml of toluene and 54.1 g of p-cresol (0 .50 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 30 ml) to prepare a sodium salt of p-cresol. The slurry solution was cooled to 20 ° C., and 200 ml of THF was charged to make a uniform solution.

  Meanwhile, 76.0 g (0.65 mol) of 48% KOH, 1,000 ml of toluene and 1,3,3 in a 2 liter flask equipped with a stirrer, thermometer, reflux condenser, water separator and nitrogen inlet tube. 3-trimethyl-1- (4- (3-butenyloxy) phenyl) indan-6-ol (47%) and 1,3,3-trimethyl-1- (4-bidoxyphenyl) -6- (3-butenyloxy ) 209.6 g (0.65 mol) of a mixture with indane (53%) was charged. This was stirred and heated in a nitrogen atmosphere, and water in the flask was removed by azeotropic dehydration (recovered water: about 51 ml). 1,3,3-trimethyl-1- (4- (3-butenyloxy) phenyl) indane A potassium salt of a mixture of -6-ol and 1,3,3-trimethyl-1- (4-bidoxyphenyl) -6- (3-butenyloxy) indane was prepared. 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 cyclophosphazene [46.4 g (0.40 unit mol) of hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene] was placed in a 5-liter flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube. 5.8 g (0.05 unit mol), decachlorocyclopentaphosphazene 2.9 g (0.025 unit mol), dodecachlorocyclohexaphosphazene 1.7 g (0.015 unit mol), macrocycle greater than tetradecachlorocycloheptaphosphazene 1.2 g (0.01 unit mol) of product, 300 ml of THF] was added, and the sodium salt solution of cresol was added dropwise at 5 ° C. over 10 hours with stirring, and the stirring reaction was performed at 25 ° C. for 2 hours. Subsequently, 1,3,3-trimethyl-1- (4- (3-butenyloxy) phenyl) indan-6-ol (53%) and 1,3,3-trimethyl-1- (4 -Bidroxyphenyl) -6- (3-butenyloxy) indane (47%) in potassium salt solution was added dropwise with stirring at 20 ° C. over 1 hour, and the stirring reaction was carried out under reflux (85 ° C.) for 12 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 reaction product, and then the organic layer was separated using a separatory funnel. This organic layer was washed twice with 5% NaOH aqueous solution, then neutralized with 2% sulfuric acid, and further washed with water, and then toluene was distilled off to obtain a pale yellow viscous liquid product. 211.2 g (yield: 87%) was obtained. The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
_{-CH 3 1.0~1.6 (9H), -} CH 2 - 2.1~2.4 (4H), - CH 3 2.3 (3H), - CH 2 - 3.6 (2H), _{= CH 2 5.1 (2H),} - CH = 5.8 (1H), phenyl CH 6.8~7.9 (11H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer _{(P =} N) 3 9.5, tetramer _(P = N) 4 -12.4, V. hexamer _(P = N) 5,6 -17.0, heptamer or more ( P = N) _≧ 7−18.0 to −20.0
◎ CHNP elemental analysis:
Theoretical value C: 73.8%, H: 6.9%, N: 2.9%, P: 6.4%
Measured value C: 73.6%, H: 7.2%, N: 2.8%, P: 6.5%
◎ Residual chlorine analysis:
<0.01%

From the above analysis results, the product obtained in this step is _{[N = P (OC 6 H} 4 -Indane-OCH 2 CH 2 CH = CH 2) 1.04 (OC 6 H 4 CH 3) 0.96 ] was confirmed to be n and _{[n = P (O-Indane} -C 6 H 4 OCH 2 CH 2 CH = CH 2) 1.07 (OC 6 H 4 CH 3) 0.93] mixture of n.

[Step 2: Deprotecting group step]
Into a 2 liter flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube was charged 194.1 g (0.40 unit mol) of the product obtained in Step 1 and 700 ml of acetic acid. A 31% hydrobromic acid / acetic acid solution (310.4 g, 1.27 mol) was added dropwise at 5 to 10 ° C. over 1 hour, and the mixture was stirred at the same temperature for 16 hours. After completion of the reaction, the reaction solution was concentrated to remove excess hydrobromic acid and acetic acid. Then, 500 ml of MIBK and 500 ml of water were added and dissolved in the residue, and the organic layer was separated using a separatory funnel. When this organic layer was washed twice with water and MIBK was distilled off, 161.0 g (yield: 94%) of a pale yellow viscous liquid product was obtained. The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
—CH ₃ 1.0 to 1.6 (9H), —CH ₂ − 2.1 to 2.4 (2H), —CH ₃ 2.3 (3H), phenyl C—H 6.8 to 7.9 (11H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer _{(P =} N) 3 9.6, tetramer _(P = N) 4 -12.5, V. hexamer _(P = N) 5,6 -17.0, heptamer or more ( P = N) _≧ 7−18.0 to −23.0
◎ CHNP elemental analysis:
Theoretical value C: 71.8%, H: 6.3%, N: 3.3%, P: 7.2%
Measured value C: 71.9%, H: 6.3%, N: 3.2%, P: 7.1%
◎ Hydroxyl equivalent:
409 g / eq. (Theoretical value 406 g / eq.)

From the above analysis results, the products obtained in this step are [N = P (OC ₆ H ₄ -Indane-OH) _1.04 (OC ₆ H ₄ CH ₃ ) _0.96 ] n and [N = P _{(O-Indane-C 6 H} 4 OH) 1.07 (OC 6 H 4 CH 3) 0.93] was confirmed to be n.

[Step 3: Epoxidation step]
The same operation as in Step 3 of Example 8 except that 128.5 g (0.30 unit mol) of the product obtained in Step 2 was used, and 134.5 g of a pale yellow solid product (yield: 92) %). This product did not show an accurate melting point due to the glassy solid. The analysis result of this product is as follows.

◎ Epoxy equivalent:
465 g / eq. (Theoretical value 462 g / eq.)
◎ Residual chlorine analysis:
<0.03%

From the results of this analysis and the results of ¹ H-NMR analysis and ³¹ P-NMR analysis, the product obtained in this step was [N = P (OC ₆ H ₄ -Indane-OCH ₂ CH (O) CH ₂ ) _{1 .04} (OC ₆ H ₄ CH ₃ ) _0.96 ] n and [N═P (O-Indane-C ₆ H ₄ OCH ₂ CH (O) CH ₂ ) _1.07 (OC ₆ H ₄ CH ₃ ) _{0 .93} ] n .

Comparative Example 1 (Production of cyclic phosphazene compound)
PHOSPHORUS-NITROGEN COMPOUNDS, H.P. R. According to the method described in ALLCOCK, 1972, 151, ACADEMIC PRES, using a cyclophosphazene mixture of 81% hexachlorocyclotriphosphazene and 19% octachlorocyclotetraphosphazene [N = P (OC ₆ H ₅ ) ₂ ] ₃ and a mixture of [N = P (OC ₆ H ₅ ) ₂ ] ₄ (white solid / melting point: 65-112 ° C.).

Examples 11 to 21 and Comparative Examples 2 and 3 (Preparation of resin composition)
Epicoat 1001, a bisphenol A type epoxy resin (Japan Epoxy Resin Co., Ltd .: epoxy equivalent 456 g / eq., Resin solid content 70%) 651 parts, novolac type phenol resin BRG-558 (Showa Polymer Co., Ltd .: hydroxyl group) The epoxy group-containing cyclic phosphazene obtained in Examples 1 to 10 with respect to 302 parts, 361 parts of aluminum hydroxide and 0.9 parts of 2-ethyl-4-methylimidazole (equivalent 106 g / eq., Resin solid content 70%) Compound or cyclic phosphazene compound obtained in Comparative Example 1 and cresol novolac epoxy resin YDCN-704P (manufactured by Tohto Kasei Co., Ltd .: epoxy equivalent 210 g / eq., Resin solid content 70%) were added at the ratio shown in Table 1. And propylene glycol monomethyl ether as a solvent. (PGM) of the resin solid content of 65% epoxy resin varnish was prepared by adding.

  Next, the prepared epoxy resin varnish was applied and impregnated on a 180 μm glass woven fabric, and dried at a temperature of 160 to produce a prepreg. Eight 180 μm glass woven prepregs thus obtained were laminated and heated and pressurized at a temperature of 170 ° C. and a pressure of 4 MPa for 100 minutes to obtain a glass epoxy laminated plate having a thickness of 1/16 inch.

  A test piece having a length of 5 inches, a width of 0.5 inch, and a thickness of 1/16 inch was cut out from the glass epoxy laminate, and the test piece was examined for flammability, glass transition temperature, and heat resistance. The evaluation method for each item is as follows. The results are shown in Table 1.

(Combustion quality)
Based on Underwriter's Laboratories Inc.'s UL-94 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. It was classified into 1, V-2 and non-standard four stages. The 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.

(Glass-transition temperature)
It was measured by DSC according to JIS K 7121-1987 “Method for measuring transition temperature of plastic”.

(Heat-resistant)
The specimen was treated at 290 ° C. for 20 minutes and the change in appearance was observed. In Table 1, “Yes” indicates that there is no change in appearance due to bleeding out of the cyclic phosphazene compound. “None” indicates that there is a change in appearance due to bleeding out of the cyclic phosphazene compound.

  As is clear from Table 1, the glass epoxy laminates (resin molded bodies) made of the resin compositions of Examples 11 to 21 are superior in flame retardancy compared to those of Comparative Examples 2 and 3, and have a glass transition. Since the temperature is high, the mechanical properties are excellent, and the bleedout of the cyclic phosphazene compound evaluated by heat resistance is not substantially observed.

Examples 22 to 31 and Comparative Examples 4 and 5 (Preparation of resin composition)
DL-92 (manufactured by Meiwa Kasei Co., Ltd .: phenolic hydroxyl group equivalent 110 g / eq.) 5.5 parts, 100 parts of spherical fused silica (manufactured by Tatsumori Co., Ltd .: average particle size 20 μm), carnauba wax ( It is obtained in Examples 1 to 6, 9, and 10 with respect to a mixture of 0.5 part of Toa Kasei Co., Ltd.) and 0.5 part of DBU (1,8-diazabicyclo (5,4,0) undecene-7). The epoxy group-containing cyclic phosphazene compound or the cyclic phosphazene compound obtained in Comparative Example 1 and ESCN-195XL (manufactured by Sumitomo Chemical Co., Ltd .: epoxy equivalent 200 g / eq.), Which is a cresol novolac type epoxy resin, are blended in the proportions shown in Table 2. And mixed at room temperature. The mixture was kneaded at 90 to 95 ° C. and then cooled and pulverized to produce a molding material. The molded product made of this molding material was evaluated for flammability and high temperature storage reliability. The evaluation method is as follows. The results are shown in Table 2.

(Combustion quality)
The molding material is transferred into a mold heated to 175 ° C. and post-cured for 8 hours, and a molded product (sealed product) 5 inches long, 0.5 inches wide and 1/32 inches thick. Got. About this molded article, the combustibility was evaluated based on the UL-94 standard vertical combustion test as in Examples 11 to 21 and Comparative Example 2.

(High temperature storage reliability)
In order to evaluate the stability of the epoxy group-containing cyclic phosphazene compound and the like added to the above mixture, the following test was performed. Using a molding material, a silicon chip (test element) having two aluminum wirings was bonded to a normal 42 alloy frame, which was transfer molded at 170 ° C. for 4 minutes and then post-cured at 170 ° C. for 4 hours. . The 20 molded articles thus obtained were subjected to moisture absorption treatment at 30 ° C., 60%, 100 hours, and then immersed in a solder bath at 250 ° C. for 10 seconds. Thereafter, a high-temperature standing test at 200 ° C. was conducted for 2,000 hours, and an aluminum wiring that was open / short-circuited was evaluated as a defective molded product.

  As is apparent from Table 2, the molding materials of Examples 22 to 31 can form resin molded products having excellent flame retardancy and high temperature storage reliability as compared with those of Comparative Examples 4 and 5.

Synthesis Example 1 (Synthesis of soluble polyimide resin)
In a 3 liter glass flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube, 277.7 g (0.95 mol) of 1,3-bis (3-aminophenoxy) benzene and 3,3 ′ -Dihydroxy-4,4'-diaminobiphenyl (10.7 g, 0.05 mol) and N, N-dimethylformamide (DMF) (700 ml) were charged and dissolved under stirring in a nitrogen atmosphere. Next, the solution in the flask was stirred under a nitrogen atmosphere, and a DMF solution of 4,4 ′-(4,4′-isopropylidenediphenoxy) bisphthalic anhydride (IPBP) [IPBP 520.5 g (1.00 mol) ), DMF 1,100 ml] was added dropwise at 5 to 10 ° C. over 2 hours, and further stirred at room temperature for 3 hours to obtain a polyamic acid solution. The obtained polyamic acid solution was transferred to a tray coated with a fluororesin (PTFE) and heated under reduced pressure in a vacuum oven (conditions: 200 ° C., 5.7 hPa or less, 6 hours) to obtain 750 g of a soluble polyimide resin.

Synthesis Example 2 (Synthesis of soluble polyimide resin)
[2,2′-bis (4,4′-hydroxyphenyl) propanedibenzoate] -3,3 ′ in a 2 liter glass flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet. , 4,4′-tetracarboxylic anhydride 173.0 g (0.30 mol) and 350 ml of DMF were added and dissolved by stirring under a nitrogen atmosphere. Next, a DMF solution of bis [(4-amino-3-carboxy) phenyl] methane (ACPM) [ACPM 51.5 g (0.18 mol), DMF 150 ml] was added dropwise at 5 to 10 ° C. over 1 hour, and further to room temperature. For 1 hour. Next, 81.0 g (0.09 mol) of amino group-containing modified silicone (trade name “KF-8010” of Shin-Etsu Silicone Co., Ltd .: amino group equivalent: 450 g / eq.) Was added dropwise at 5 to 10 ° C. over 1 hour. The mixture was further stirred at room temperature for 1 hour. Further, a DMF solution of bis [4- (3-aminophenoxy) phenyl] sulfone (APPS) [APPS 13.0 g (0.09 mol), DMF 150 ml] was added dropwise at 10 to 15 ° C. over 1 hour, and further at room temperature 2 Stirring for a time gave a polyamic acid solution. This polyamic acid solution was transferred to a tray coated with fluororesin (PTFE) and heated under reduced pressure in a vacuum oven (conditions: 200 ° C., 5.7 hPa or less, 6 hours) to obtain 298 g of a soluble polyimide resin.

Synthesis Example 3 (Synthesis of bifunctional PPE oligomer)
In a 2 liter glass flask equipped with a stirrer, thermometer, reflux condenser and air inlet tube, 1.3 g (0.012 mol) of CuCl, 70.7 g (0.55 mol) of di-n-butylamine and 500 ml of methyl ethyl ketone Was stirred at a reaction temperature of 40 ° C., and 45.4 g (0.16 mol) of 4,4 ′-(1-methylethylidene) bis (2,6-dimethylphenol) previously dissolved in 1,000 ml of methyl ethyl ketone. And 58.6 g (0.48 mol) of 2,6-dimethylphenol were added dropwise over 2 hours while bubbling air at 2 liters / minute, and after 1 hour after completion of the dropwise addition, air was bubbled at 2 liters / minute. Stirring was performed while continuing. Ethylenediaminetetraacetic acid dihydrogen disodium aqueous solution was added thereto to stop the reaction. Thereafter, washing was performed 3 times with a 3% hydrochloric acid aqueous solution, followed by washing with ion-exchanged water. The resulting solution was concentrated and further dried under reduced pressure to obtain 101.3 g of a bifunctional PPE oligomer having hydroxyl groups at both ends. This oligomer has a number average molecular weight of 860, a weight average molecular weight of 1,150, and a hydroxyl group equivalent of 455 g / eq. Met.

Example 32 (Preparation of resin composition)
50.0 g of the soluble polyimide resin obtained in Synthesis Example 1 and 13.9 g of a dicyclopentadiene-based epoxy resin (trade name “HP7200” of Dainippon Ink & Chemicals, Inc .: epoxy equivalent of 277 g / eq.) The produced cyclic phosphazene compound (epoxy equivalent 324 g / eq.) 16.2 g, phenol novolac type phenol resin (trade name “PSM-4324” of Gunei Chemical Co., Ltd .: hydroxyl equivalent 104 g / eq.) 10.4 g, curing acceleration 0.3 g of 2-ethyl-4-methylimidazole (trade name “2E4MZ” from Shikoku Kasei Co., Ltd.) as an agent was dissolved in dioxolane to obtain a resin solution (resin composition).

  The obtained resin solution was cast on the surface of a 125 μm thick PET film (trade name “Therapy HP” from Toyo Metallizing Co., Ltd.). Then, it heat-dried at 60 degreeC, 80 degreeC, 100 degreeC, 120 degreeC, and 140 degreeC each temperature for 3 minutes, respectively in the hot air oven, and obtained the two-layer resin sheet which uses a PET film as a support body. From this two-layer resin sheet, the PET film was peeled and removed to obtain a single-layer resin sheet (thickness before heat curing 50 μm). The obtained resin sheet (resin molded body) is sandwiched between 18 μm rolled copper foil (trade name “BHY-22B-T” of Japan Energy Co., Ltd.) so that the resin surface and the roughened surface of the copper foil are in contact with each other, and the temperature is 180 ° C. Then, heating and pressing were performed for 1 hour under the condition of a pressure of 3 MPa to obtain a copper foil laminate (a monolayer resin sheet sandwiched between rolled copper foils). The thus obtained copper foil laminate having copper foil layers on both sides was evaluated for solder heat resistance. Moreover, the copper foil of the obtained copper foil laminated body was removed by etching, and the cured sheet was obtained. About the obtained hardening sheet, it carried out similarly to Examples 11-21 and Comparative Examples 2 and 3, and measured combustibility and glass transition temperature. The results are shown in Table 3. The solder heat resistance evaluation method is as follows.

  A test piece having a length of 30 mm and a width of 15 mm was cut out from the copper foil laminate, and the test piece was left in an environment of a temperature of 22.5 to 23.5 ° C. and a humidity of 39.5 to 40.5% for 24 hours. Then, the test piece was dipped in molten solder at 270 ° C. for 1 minute, and only the copper foil on one side was etched. Thereafter, the resin portion was visually observed, and if there was no abnormality such as foaming or swelling, it was determined to be acceptable, and the number of failures in 20 samples was examined.

Examples 33 to 36 (Preparation of resin composition)
Instead of the cyclic phosphazene compound produced in Example 1, the cyclic phosphazene compound shown in Table 3 was used in the same manner as in Example 32 except that the compounding amount indicated in the table was used to obtain a resin composition. It was. Using this resin composition, a copper foil laminate and a cured sheet were obtained by the same method and conditions as in Example 32, and the solder heat resistance, glass transition temperature and combustibility were evaluated. The results are shown in Table 3.

Comparative Example 6 (Preparation of resin composition)
Instead of the cyclic phosphazene compound produced in Example 1, 25.0 g of the cyclic phosphazene compound produced in Comparative Example 1 and a dicyclopentadiene epoxy resin (trade name “HP7200” from Dainippon Ink & Chemicals, Inc .: epoxy equivalent of 277 g / Eq.) 27.7 g and phenol novolac type phenolic resin (Gunei Chemical Co., Ltd., trade name “PSM-4324”: hydroxyl group equivalent 104 g / eq.) 9.4 g were used in the same manner as in Example 32. Thus, a resin composition was obtained. Using this resin composition, a copper foil laminate and a cured sheet were obtained by the same method and conditions as in Example 32, and the solder heat resistance, glass transition temperature and flame retardancy were evaluated. The results are shown in Table 3.

  As is clear from Table 3, the resin molded bodies of Examples 32-36 are superior in flame retardancy and have a high glass transition temperature as compared with that of Comparative Example 6, and also have excellent mechanical properties, and solder. The bleed-out of the cyclic phosphazene compound evaluated by heat resistance is not substantially seen.

Example 37 (Preparation of resin composition)
80.0 g of the soluble polyimide resin obtained in Synthesis Example 2, 32.4 g of the cyclic phosphazene compound obtained in Example 1 (epoxy equivalent 324 g / eq.), Bisphenol A type epoxy resin (of Japan Epoxy Resin Co., Ltd.) 9.4 g of the trade name “Epicote 828”: epoxy equivalent of 188 g / eq. It melt | dissolved and the resin solution (resin composition) was obtained.

  This resin solution was cast on the surface of a 125 μm-thick PET film (trade name “Therapy HP” from Toyo Metallizing Co., Ltd.). Thereafter, it was heated and dried for 3 minutes at 60 ° C., 80 ° C., 100 ° C., 120 ° C. and 140 ° C. in a hot air oven to obtain a two-layer resin sheet using a PET film as a support. From this two-layer resin sheet, the PET film was peeled and removed to obtain a single-layer resin sheet (thickness before heat curing 50 μm). The obtained resin sheet (resin molded body) is sandwiched with 18 μm rolled copper foil (trade name “BHY-22B-T” of Japan Energy Co., Ltd.) so that the resin surface and the copper foil roughened surface are in contact with each other. A copper foil laminate (a single layer resin sheet sandwiched between rolled copper foils) was obtained by heating and pressing for 1 hour under the conditions of 180 ° C. and a pressure of 3 MPa. And about this copper foil laminated body, the solder heat resistance was evaluated by the method similar to Example 32. FIG. In addition, the flammability and glass transition temperature of the cured sheet obtained by etching the copper foil of the copper foil laminate were measured in the same manner as in Example 32. The results are shown in Table 4.

Examples 38 to 41 (Preparation of resin composition)
Instead of the cyclic phosphazene compound produced in Example 1, the cyclic phosphazene compound shown in Table 4 was used in the same manner as in Example 37 except that the compounding amount indicated in the table was used to obtain a resin composition. It was. Using this resin composition, a copper foil laminate and a cured sheet were obtained by the same method and conditions as in Example 37, and the solder heat resistance, glass transition temperature and combustibility were evaluated. The results are shown in Table 4.

Comparative Example 7 (Preparation of resin composition)
Instead of the cyclic phosphazene compound produced in Example 1, 40.0 g of the cyclic phosphazene compound produced in Comparative Example 1 and a bisphenol A type epoxy resin (trade name “Epikote 828” of Japan Epoxy Resin Co., Ltd .: epoxy equivalent of 188 g / eq.) The same operation as in Example 37 except that 28.2 g was used, to obtain a resin composition. Using this resin composition, a copper foil laminate and a cured sheet were obtained by the same method and conditions as in Example 37, and the solder heat resistance, glass transition temperature and combustibility were evaluated. The results are shown in Table 4.

  As is clear from Table 4, the resin molded bodies of Examples 37 to 41 are superior to those of Comparative Example 7 in terms of flame retardancy and a high glass transition temperature, so that they have excellent mechanical properties and solder. The bleed-out of the cyclic phosphazene compound evaluated by heat resistance is not substantially seen.

Example 42 (Preparation of resin composition)
45.5 g of bifunctional PPE oligomer obtained in Synthesis Example 3 (hydroxyl equivalent: 455 g / eq), 16.2 g of cyclic phosphazene compound obtained in Example 1 (epoxy equivalent: 324 g / eq.) And bisphenol A type epoxy resin 9.4 g (trade name “Epikote 828”: Epoxy equivalent 188 g / eq.) Of Japan Epoxy Resin Co., Ltd.) was dissolved in dioxolane to obtain a resin solution (resin composition).

  This resin solution was cast on the surface of a 125 μm-thick PET film (trade name “Therapy HP” from Toyo Metallizing Co., Ltd.). Thereafter, it was heated and dried for 3 minutes at 60 ° C., 80 ° C., 100 ° C., 120 ° C. and 140 ° C. in a hot air oven to obtain a two-layer resin sheet using a PET film as a support. The PET film was peeled and removed from the two-layer resin sheet to obtain a single-layer resin sheet (thickness before heat curing was 50 μm). The obtained resin sheet is sandwiched between 18 μm rolled copper foil (trade name “BHY-22B-T” of Japan Energy Co., Ltd.) so that the resin surface is in contact with the roughened surface of the copper foil, and the temperature is 180 ° C. and the pressure is 3 MPa. A copper foil laminate (single layer resin sheet sandwiched between rolled copper foils) was obtained by heating and pressing for 1 hour under the above conditions. And about this copper foil laminated body, the solder heat resistance was evaluated by the method similar to Example 32. FIG. In addition, the flammability and glass transition temperature of the cured sheet obtained by etching the copper foil of the copper foil laminate were measured in the same manner as in Example 32. The results are shown in Table 5.

Examples 43 to 45 (Preparation of resin composition)
In place of the cyclic phosphazene compound produced in Example 1, the cyclic phosphazene compound shown in Table 5 was used in the same manner as in Example 42 except that the compounding amount indicated in the table was used to obtain a resin composition. It was. Using this resin composition, a copper foil laminate and a cured sheet were obtained by the same method and conditions as in Example 42, and the solder heat resistance, glass transition temperature and combustibility were evaluated. The results are shown in Table 5.

Comparative Example 8 (Preparation of resin composition)
Instead of the cyclic phosphazene compound produced in Example 1, 20.0 g of the cyclic phosphazene compound produced in Comparative Example 1 and a bisphenol A type epoxy resin (trade name “Epikote 828” of Japan Epoxy Resin Co., Ltd .: epoxy equivalent of 188 g / eq.) The same operation as in Example 42 was performed except that 28.2 g was used, and a resin composition was obtained. Using this resin composition, a copper foil laminate and a cured sheet were obtained by the same method and conditions as in Example 33, and the solder heat resistance, glass transition temperature and combustibility were evaluated. The results are shown in Table 5.

  As is apparent from Table 5, the molding materials of Examples 42 to 45 are superior in flame retardancy and have a high glass transition temperature as compared with that of Comparative Example 8, and thus have excellent mechanical properties and solder heat resistance. No bleed out of the cyclic phosphazene compound evaluated by the property was observed.

Claims (10)

An epoxy group-containing cyclic phosphazene compound represented by the following formula (1).

(In the formula (1), n represents an integer of 3 to 15, 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: alkyl group having 1 to 6 carbon atoms, optionally substituted with at least one group selected from an alkenyl group and an aryl group, an alkoxy group having 1 to 8 carbon atoms.
A2 group: alkyl group having 1 to 6 carbon atoms, optionally substituted with at least one group selected from an alkenyl group and an aryl group, an aryloxy group having 6 to 20 carbon atoms.
A3 group: epoxyoxyphenyl substituted phenyloxy group represented by the following formula (3), epoxyoxyphenyl substituted indanoxy group represented by the following formula (4), and epoxyoxyindane substitution represented by the following formula (5) A group selected from the group consisting of phenyloxy groups.

E in the formulas (3), (4), and (5) represents an epoxyoxy group having 2 to 6 carbon atoms, and Y in the formula (3) represents O, S, SO ₂ , CH ₂ , CHCH ₃ , C (CH ₃ ) CH ₂ CH ₃ or CO, wherein R ¹ and R ² in formula (4) and formula (5) are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group or Represents a phenyl group; )   The epoxy group-containing cyclic phosphazene compound according to claim 1, wherein 2 (2n-2) of 2n A's are A3 groups in the formula (1). The epoxy group-containing cyclic phosphazene compound according to claim 1 or 2, wherein the epoxyoxy group represented by E in the formulas (3), (4) and (5) is a glycidyloxy group.   The epoxy group-containing cyclic phosphazene compound according to any one of claims 1 to 3, wherein n in the formula (1) is 3 or 4.   The epoxy group-containing cyclic phosphazene compound according to any one of claims 1 to 4, comprising two or more epoxy group-containing cyclic phosphazene compounds having different n in the formula (1). Selected from the group consisting of the following E1, E2, and E3 groups such that at least one of the halogen atoms of the cyclic phosphonitrile dihalide represented by the following formula (6) is substituted by the following E3 group: Substituting with a group to produce a cyclic phosphonitrile substituent,

(In formula (6), n represents an integer of 3 to 15, and X represents a halogen atom.)
E1 group: alkyl group having 1 to 6 carbon atoms, optionally substituted with at least one group selected from an alkenyl group and an aryl group, an alkoxy group having 1 to 8 carbon atoms.
E2 group: alkyl group having 1 to 6 carbon atoms, optionally substituted with at least one group selected from an alkenyl group and an aryl group, an aryloxy group having 6 to 20 carbon atoms.
E3 group: selected from the group consisting of a substituted phenyloxy group represented by the following formula (8), a substituted indanoxy group represented by the following formula (9), and a substituted phenyloxy group represented by the following formula (10) Group.

(G in Formula (8), Formula (9), and Formula (10) represents an alkenyl group having 2 to 6 carbon atoms, and Y in Formula (8) represents O, S, SO ₂ , CH ₂ , CHCH ₃ , C (CH ₃ ) CH ₂ CH ₃ or CO, wherein R ¹ and R ² in formula (9) and formula (10) are a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group Or a phenyl group.)
Oxidizing the alkenyl group represented by G at the E3 group of the cyclic phosphonitrile substituent to convert it to an epoxy group;
The manufacturing method of the epoxy-group containing cyclic phosphazene compound containing this. Selected from the group consisting of the following Q1, Q2, and Q3 groups such that at least one of the halogen atoms of the cyclic phosphonitrile dihalide represented by the following formula (6) is substituted by the following Q3 group: Substituting with a group to produce a cyclic phosphonitrile substituent,

(In formula (6), n represents an integer of 3 to 15, and X represents a halogen atom.)
Q1 group: alkyl group having 1 to 6 carbon atoms, optionally substituted with at least one group selected from an alkenyl group and an aryl group, an alkoxy group having 1 to 8 carbon atoms.
Q2 group: alkyl group having 1 to 6 carbon atoms, optionally substituted with at least one group selected from an alkenyl group and an aryl group, an aryloxy group having 6 to 20 carbon atoms.
Q3 group: selected from the group consisting of a substituted phenyloxy group represented by the following formula (12), a substituted indanoxy group represented by the following formula (13), and a substituted phenyloxy group represented by the following formula (14) Group.

(Z in Formula (12), Formula (13) and Formula (14) represents a protecting group capable of forming an OH group when eliminated, and Y in Formula (12) represents O, S, SO) ₂ , CH ₂ , CHCH ₃ , C (CH ₃ ) CH ₂ CH ₃ or CO, wherein R ¹ and R ² in formula (13) and formula (14) are a hydrogen atom, an alkyl having 1 to 4 carbon atoms Group, cycloalkyl group or phenyl group.)
Removing the protecting group from the Q3 group of the cyclic phosphonitrile substituent to obtain a hydroxyl group-containing cyclic phosphazene compound;
Reacting the hydroxyl group-containing cyclic phosphazene compound with epihalohydrin in the presence of a base;
The manufacturing method of the epoxy-group containing cyclic phosphazene compound containing this. A resin component;
An epoxy group-containing cyclic phosphazene compound according to any one of claims 1 to 5;
A resin composition comprising:   The resin composition according to claim 8, wherein the resin component is selected from the group consisting of an epoxy resin, a polyimide resin, and a modified polyphenylene ether resin.   The resin molding which consists of a resin composition of Claim 8 or 9.