JP5376388B2 - Reactive group-containing cyclic phosphazene compound and process for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To achieve a phosphazene compound that effectively enhances flame retardancy of a resin molded item without detriment to mechanical properties thereof and yet hardly injures high-temperature reliability and dielectric properties of the resin molded item. <P>SOLUTION: The reactive group-bearing cyclic phosphazene compound is represented by formula (1) [in formula (1), n is an integer of 3-15; one example of A is a group selected from the group consisting of an acryloyloxy group-substituted phenyl group and a methacryloyloxy group-substituted phenyl group represented by formula (2); in formula (2), E<SP>1</SP>-E<SP>5</SP>are each independent; at least one of them is an acryloyloxy group or a methacryloyloxy group; at least one of them is at least one group selected from among 1-6C alkyl and alkenyl groups and an aryl group; and the rest are each a hydrogen atom]. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a cyclic phosphazene compound and a method for producing the same, and particularly to a reactive 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, it is used extensively and the amount of its use 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 phosphorus-based flame retardants, phosphate ester-based and condensed phosphate ester-based flame retardants have a plastic effect. Therefore, when a large amount is added to the resin composition in order to increase flame retardancy, resin molding There are disadvantages such as a decrease in the mechanical strength of the product. In addition, phosphate ester, phosphate amide, ammonium polyphosphate, and aluminum phosphinate flame retardants are easily hydrolyzed, so resin molded products that require mechanical and electrical long-term reliability. It is substantially difficult to use in the manufacturing material. 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 (elution) from the resin molded body at a high temperature, and the thermosetting resin-based resin composition. In this case, deformation such as blistering occurs in the resin molded product at a high temperature, and when the resin molded product is used in the electric / electronic field such as a laminated substrate, a short circuit due to deformation may occur.

JP 2000-103939 A JP 2004-83671 A JP 2004-210849 A JP 2005-248134 A JP 2007-45916 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 include acryloyloxy group or A phosphazene compound having a methacryloyloxy group and a polymer using the same are disclosed. Since this type of phosphazene-based flame retardant has a polymerized acryloyloxy group or methacryloyloxy group, it can be used alone as a thermosetting resin. It can also be used as a part. The polymer of the phosphazene compound and the polymer obtained by using the phosphazene compound as a part of the monomer have good high temperature reliability of the molded product, and also exhibit flame retardancy due to the phosphazene compound. Therefore, it is expected to be used as a resin material for products for electric and electronic parts. However, a resin molded body made of this type of polymer is insufficient in terms of flame retardancy required as an essential effect, and is also insufficient in mechanical properties (particularly high glass transition temperature). .

JP-A 64-14239 JP-A 64-14240 JP 2001-335678 A Japanese Patent Laid-Open No. 6-247989 JP-A-8-193091

  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 high temperature reliability in the resin molded body. . In addition, the flame-retardant resin molded article obtained by the present invention does not deteriorate the original characteristics of the resin, does not generate toxic substances during combustion, and has very little environmental load. It is useful for parts, adhesives, paints, various films, OA equipment, food containers, household kitchen utensils, electronic parts and sealing materials.

  As a result of repeated studies to solve the above-mentioned problems, the present inventors have found that a molded article comprising a resin composition containing a novel phosphazene compound having a reactive group exhibits excellent mechanical properties and flame retardancy. At the same time, the inventors have found that the reliability at high temperatures is high and the dielectric properties are excellent.

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

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

In formula (2), E ^{1 to} E ⁵ are each independently at least one of an acryloyloxy group or a methacryloyloxy group, and at least one of them is an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and It is at least one group selected from aryl groups, and the remainder represents a hydrogen atom. )

  In the reactive group-containing cyclic phosphazene compound, for example, in formula (1), 1 to (2n-2) of 2n A are A3 groups. In the reactive group-containing cyclic phosphazene compound, for example, n in the formula (1) is 3 or 4. Furthermore, the reactive group-containing cyclic phosphazene compound includes, for example, two or more reactive group-containing cyclic phosphazene compounds in which n in formula (1) is different.

  The method for producing a reactive group-containing cyclic phosphazene compound according to the present invention includes the following step 1, step 2, step 3, and step 4.

[Step 1]
Selected from the group consisting of the following G1, G2, and G3 groups such that at least one of the halogen atoms of the cyclic phosphonitrile dihalide represented by the following formula (3) is substituted by the following G3 group: A step of producing an acyl group-containing cyclic phosphonitrile substitution product by substitution with a group.

In formula (3), n represents an integer of 3 to 8, and X represents a halogen atom.
G1 group: an alkoxy group having 1 to 8 carbon atoms in which at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group may be substituted.
G2 group: an aryloxy group having 6 to 20 carbon atoms in which at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group may be substituted.
G3 group: a group selected from the group consisting of an acyl-substituted phenyloxy group represented by the following formula (4).

In formula (4), at least one of L ^{1 to} L ⁵ is an acyl group, and at least one is at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group. And the remainder represents a hydrogen atom.

[Step 2]
A step of producing an acyloxy group-containing cyclic phosphonitrile substitution product by oxidizing the acyl group-containing cyclic phosphonitrile substitution product obtained in step 1 (typified by the Bayer-Billiger method).

[Step 3]
A step of producing a hydroxy group-containing cyclic phosphonitrile substitution product by deacylating (hydrolyzing) the acyloxy group-containing cyclic phosphonitrile substitution product obtained in Step 2.

[Step 4]
A step of reacting the hydroxy group-containing cyclic phosphonitrile substitution product obtained in step 3 with acrylic acid, methacrylic acid or a derivative thereof.

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

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

  Since the reactive 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 body, In addition, the high temperature reliability and dielectric properties of the resin molding are unlikely to be impaired.

  Since the method for producing a reactive group-containing cyclic phosphazene compound according to the present invention includes Step 1, Step 2, Step 3, and Step 4 as described above, the reaction having the specific structure as described above according to the present invention. A functional group-containing cyclic phosphazene compound can be produced.

  Since the resin composition of the present invention contains the reactive group-containing cyclic phosphazene compound of the present invention as a flame retardant, the resin composition exhibits practical mechanical properties and flame retardancy, and has high temperature reliability and excellent dielectric properties. A molded body can be obtained.

  Since the resin molded body 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 temperature reliability and excellent dielectric properties.

Reactive group-containing cyclic phosphazene compound The reactive 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 8, preferably an integer of 3 to 6, and particularly preferably 3 or 4. That is, particularly preferable as the reactive group-containing cyclic phosphazene compound are a reactive group-containing cyclotriphosphazene (trimer) in which n is 3 and a reactive group-containing cyclotetraphosphazene (tetramer) in which n is 4. is there. The reactive 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; In the alkoxy group, at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group may be substituted.
Examples of such 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 2-propenyloxy group and a benzyloxy group are preferable, and an ethoxy group and an n-propoxy group are particularly preferable.

[Group A2]
An aryloxy group having 6 to 20 carbon atoms; In the aryloxy group, at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group may be substituted.
Examples of such aryloxy groups include phenoxy group, methylphenoxy group, dimethylphenoxy group, ethylphenoxy group, ethylmethylphenoxy group, diethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, isopropylmethylphenoxy group, Isopropylethylphenoxy group, diisopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-pentylphenoxy group, n-hexylphenoxy group, ethenylphenoxy group, 1-propenylphenoxy group, 2-propenylphenoxy group, isopropenylphenoxy group, 1-butenylphenoxy group, sec-butenylphenoxy group, 1-pentenylphenoxy group, 1-hexenylphenoxy group, Nirufenokishi group, naphthyloxy group, and an anthryl group and phenanthryloxy groups and the like. Of these, phenoxy group, methylphenoxy group, dimethylphenoxy group, diethylphenoxy group, 2-propenylphenoxy group, phenylphenoxy group and naphthyloxy group are preferable, and phenoxy group, methylphenoxy group, dimethylphenoxy group and naphthyloxy group are particularly preferable. preferable.

[Group A3]
A group selected from the group consisting of reactive groups represented by the following formula (2).

In formula (2), E ^{1 to} E ⁵ are each independently at least one of an acryloyloxy group or a methacryloyloxy group, and at least one of them is an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and It is at least one group selected from aryl groups, and the remainder represents a hydrogen atom.

Specific examples of the reactive group-substituted phenyloxy group represented by the formula (2) include 2-acryloyloxy-3-methyl-phenyloxy group, 2-acryloyloxy-4-methyl-phenyloxy group, and 2-acryloyl. Oxy-5-methyl-phenyloxy group, 2-acryloyloxy-6-methyl-phenyloxy group, 2-methyl-3-acryloyloxy-phenyloxy group, 3-acryloyloxy-4-methyl-phenyloxy group, 3 -Acryloyloxy-5-methyl-phenyloxy group, 3-acryloyloxy-6-methyl-phenyloxy group, 2-methyl-4-acryloyloxy-phenyloxy group, 3-methyl-4-acryloyloxy-phenyloxy group 2-acryloyloxy-3,4-dimethyl-phenyloxy group, 2- Acryloyloxy-3,5-dimethyl-phenyloxy group, 2-acryloyloxy-3,6-dimethyl-phenyloxy group, 2-acryloyloxy-4,5-dimethyl-phenyloxy group, 2-acryloyloxy-4 , 6-dimethyl-phenyloxy group, 2-acryloyloxy-5,6-dimethyl-phenyloxy group, 2,4-dimethyl-3-acryloyloxy-phenyloxy group, 2,5-dimethyl-3-acryloyloxy- Phenyloxy group, 2,6-dimethyl-3-acryloyloxy-phenyloxy group, 3-acryloyloxy-4,5-dimethyl-phenyloxy group, 3-acryloyloxy-4,6-dimethyl-phenyloxy group, 3 -Acryloyloxy-5,6-dimethyl-phenyloxy group, 2,3-di Tyl-4-acryloyloxy-phenyloxy group, 2,5-dimethyl-4-acryloyloxy-phenyloxy group, 2,6-dimethyl-4-acryloyloxy-phenyloxy group, 3,5-dimethyl-4-acryloyl Oxy-phenyloxy group, 2-acryloyloxy-3,4,5-trimethyl-phenyloxy group, 2-acryloyloxy-3,4,6-trimethyl-phenyloxy group, 2-acryloyloxy-3,5,6 -Trimethyl-phenyloxy group, 2-acryloyloxy-4,5,6-trimethyl-phenyloxy group, 2,4,5-trimethyl-3-acryloyloxy-phenyloxy group, 2,5,6-trimethyl-3 -Acryloyloxy-phenyloxy group, 3-acryloyloxy-4,5,6-trime Tyl-phenyloxy group, 2,3,5-trimethyl-4-acryloyloxy-phenyloxy group, 2,3,6-trimethyl-4-acryloyloxy-phenyloxy group, 2-acryloyloxy-3,4,5 , 6-tetramethyl-phenyloxy group, 2,4,5,6-tetramethyl-3-acryloyloxy-phenyloxy group, 2,3,5,6-tetramethyl-4-acryloyloxy-phenyloxy group, 2,3-di (acryloyloxy) -4-methyl-phenyloxy group, 2,3-di (acryloyloxy) -5-methyl-phenyloxy group, 2,3-di (acryloyloxy) -6-methyl- Phenyloxy group, 2,4-di (acryloyloxy) -3-methyl-phenyloxy group, 2,4-di (acryloyloxy) -5 Til-phenyloxy group, 2,4-di (acryloyloxy) -6-methyl-phenyloxy group, 2,5-di (acryloyloxy) -3-methyl-phenyloxy group, 2,5-di (acryloyloxy) ) -4-methyl-phenyloxy group, 2,5-di (acryloyloxy) -6-methyl-phenyloxy group, 2,6-di (acryloyloxy) -3-methyl-phenyloxy group, 2,6- Di (acryloyloxy) -4-methyl-phenyloxy group, 2-acryloyloxy-3-ethyl-phenyloxy group, 2-acryloyloxy-4-ethyl-phenyloxy group, 2-acryloyloxy-5-ethyl-phenyl Oxy group, 2-acryloyloxy-6-ethyl-phenyloxy group, 2-ethyl-3-acryloyloxy-phenol Ruoxy group, 3-acryloyloxy-4-ethyl-phenyloxy group, 3-acryloyloxy-5-ethyl-phenyloxy group, 3-acryloyloxy-6-ethyl-phenyloxy group, 2-ethyl-4-acryloyloxy -Phenyloxy group, 3-ethyl-4-acryloyloxy-phenyloxy group, 2-acryloyloxy-3-allyl-phenyloxy group, 2-acryloyloxy-4-allyl-phenyloxy group, 2-acryloyloxy-5 -Allyl-phenyloxy group, 2-acryloyloxy-6-allyl-phenyloxy group, 2-allyl-3-acryloyloxy-phenyloxy group, 3-acryloyloxy-4-allyl-phenyloxy group, 3-acryloyloxy -5-allyl-phenyloxy group, 3-a Acryloyloxy-6-allyl-phenyloxy group, 2-allyl-4-acryloyloxy-phenyloxy group, 3-allyl-4-acryloyloxy-phenyloxy group, 2-acryloyloxy-3-phenyl-phenyloxy group 2-acryloyloxy-4-phenyl-phenyloxy group, 2-acryloyloxy-5-phenyl-phenyloxy group, 2-acryloyloxy-6-phenyl-phenyloxy group, 2-phenyl-3-acryloyloxy-phenyl Oxy group, 3-acryloyloxy-4-phenyl-phenyloxy group, 3-acryloyloxy-5-phenyl-phenyloxy group, 3-acryloyloxy-6-phenyl-phenyloxy group, 2-phenyl-4-acryloyloxy -Phenyloxy group, 3-phenyl Nyl-4-acryloyloxy-phenyloxy group, 2-methyl-3-ethyl-4-acryloyloxy-phenyloxy group, 2-methyl-4-acryloyloxy-5-ethyl-phenyloxy group, 2-methyl-4 -Acryloyloxy-6-ethyl-phenyloxy group, 2-ethyl-3-methyl-4-acryloyloxy-phenyloxy group, 2-ethyl-4-acryloyloxy-5-methyl-phenyloxy group, 2-ethyl- 4-acryloyloxy-6-methyl-phenyloxy group, 2-methacryloyloxy-3-methyl-phenyloxy group, 2-methacryloyloxy-4-methyl-phenyloxy group, 2-methacryloyloxy-5-methyl-phenyloxy Group, 2-methacryloyloxy-6-methyl-phenyloxy 2-methyl-3-methacryloyloxy-phenyloxy group, 3-methacryloyloxy-4-methyl-phenyloxy group, 3-methacryloyloxy-5-methyl-phenyloxy group, 3-methacryloyloxy-6-methyl-phenyl Oxy group, 2-methyl-4-methacryloyloxy-phenyloxy group, 3-methyl-4-methacryloyloxy-phenyloxy group, 2-methacryloyloxy-3,4-dimethyl-phenyloxy group, 2-methacryloyloxy-3 , 5-dimethyl-phenyloxy group, 2-methacryloyloxy-3,6-dimethyl-phenyloxy group, 2-methacryloyloxy-4,5-dimethyl-phenyloxy group, 2-methacryloyloxy-4,6-dimethyl- Phenyloxy group, 2-methacryloyl Oxy-5,6-dimethyl-phenyloxy group, 2,4-dimethyl-3-methacryloyloxy-phenyloxy group, 2,5-dimethyl-3-methacryloyloxy-phenyloxy group, 2,6-dimethyl-3- Methacryloyloxy-phenyloxy group, 3-methacryloyloxy-4,5-dimethyl-phenyloxy group, 3-methacryloyloxy-4,6-dimethyl-phenyloxy group, 3-methacryloyloxy-5,6-dimethyl-phenyloxy Group, 2,3-dimethyl-4-methacryloyloxy-phenyloxy group, 2,5-dimethyl-4-methacryloyloxy-phenyloxy group, 2,6-dimethyl-4-methacryloyloxy-phenyloxy group, 3,5 -Dimethyl-4-methacryloyloxy-phenyloxy group, 2 Methacryloyloxy-3,4,5-trimethyl-phenyloxy group, 2-methacryloyloxy-3,4,6-trimethyl-phenyloxy group, 2-methacryloyloxy-3,5,6-trimethyl-phenyloxy group, 2 -Methacryloyloxy-4,5,6-trimethyl-phenyloxy group, 2,4,5-trimethyl-3-methacryloyloxy-phenyloxy group, 2,5,6-trimethyl-3-methacryloyloxy-phenyloxy group, 3-methacryloyloxy-4,5,6-trimethyl-phenyloxy group, 2,3,5-trimethyl-4-methacryloyloxy-phenyloxy group, 2,3,6-trimethyl-4-methacryloyloxy-phenyloxy group 2-methacryloyloxy-3,4,5,6-tetramethyl- Enyloxy group, 3-methacryloyloxy-2,4,5,6-tetramethyl-phenyloxy group, 4-methacryloyloxy-2,3,5,6-tetramethyl-phenyloxy group, 2,3-di (methacryloyl) Oxy) -4-methyl-phenyloxy group, 2,3-di (methacryloyloxy) -5-methyl-phenyloxy group, 2,3-di (methacryloyloxy) -6-methyl-phenyloxy group, 2,4 -Di (methacryloyloxy) -3-methyl-phenyloxy group, 2,4-di (methacryloyloxy) -5-methyl-phenyloxy group, 2,4-di (methacryloyloxy) -6-methyl-phenyloxy group 2,5-di (methacryloyloxy) -3-methyl-phenyloxy group, 2,5-di (methacryloyloxy) -4- Methyl-phenyloxy group, 2,5-di (methacryloyloxy) -6-methyl-phenyloxy group, 2,6-di (methacryloyloxy) -3-methyl-phenyloxy group, 2,6-di (methacryloyloxy) ) -4-methyl-phenyloxy group, 2-methacryloyloxy-3-ethyl-phenyloxy group, 2-methacryloyloxy-4-ethyl-phenyloxy group, 2-methacryloyloxy-5-ethyl-phenyloxy group, 2 -Methacryloyloxy-6-ethyl-phenyloxy group, 2-ethyl-3-methacryloyloxy-phenyloxy group, 3-methacryloyloxy-4-ethyl-phenyloxy group, 3-methacryloyloxy-5-ethyl-phenyloxy group 3-methacryloyloxy-6-ethyl-phenyloxy Group, 2-ethyl-4-methacryloyloxy-phenyloxy group, 3-ethyl-4-methacryloyloxy-phenyloxy group, 2-methacryloyloxy-3-allyl-phenyloxy group, 2-methacryloyloxy-4-allyl- Phenyloxy group, 2-methacryloyloxy-5-allyl-phenyloxy group, 2-methacryloyloxy-6-allyl-phenyloxy group, 2-allyl-3-methacryloyloxy-phenyloxy group, 3-methacryloyloxy-4- Allyl-phenyloxy group, 3-methacryloyloxy-5-allyl-phenyloxy group, 3-methacryloyloxy-6-allyl-phenyloxy group, 2-allyl-4-methacryloyloxy-phenyloxy group, 3-allyl-4 -Methacryloyloxy-pheny Oxy group, 2-methacryloyloxy-3-phenyl-phenyloxy group, 2-methacryloyloxy-4-phenyl-phenyloxy group, 2-methacryloyloxy-5-phenyl-phenyloxy group, 2-methacryloyloxy-6-phenyl -Phenyloxy group, 2-phenyl-3-methacryloyloxy-phenyloxy group, 3-methacryloyloxy-4-phenyl-phenyloxy group, 3-methacryloyloxy-5-phenyl-phenyloxy group, 3-methacryloyloxy-6 -Phenyl-phenyloxy group, 2-phenyl-4-methacryloyloxy-phenyloxy group, 3-phenyl-4-methacryloyloxy-phenyloxy group, 2-methyl-3-ethyl-4-methacryloyloxy-phenyloxy group, 2-methyl Ru-4-methacryloyloxy-5-ethyl-phenyloxy group, 2-methyl-4-methacryloyloxy-6-ethyl-phenyloxy group, 2-ethyl-3-methyl-4-methacryloyloxy-phenyloxy group, 2 -Ethyl-4-methacryloyloxy-5-methyl-phenyloxy group and 2-ethyl-4-methacryloyloxy-6-methyl-phenyloxy group.

  Preferred as the above-mentioned A3 group are 2-acryloyloxy-3-methyl-phenyloxy group, 2-acryloyloxy-4-methyl-phenyloxy group, 2-acryloyloxy-5-methyl-phenyloxy group, 2- Acryloyloxy-6-methyl-phenyloxy group, 2-methyl-3-acryloyloxy-phenyloxy group, 3-acryloyloxy-4-methyl-phenyloxy group, 3-acryloyloxy-5-methyl-phenyloxy group, 3-acryloyloxy-6-methyl-phenyloxy group, 2-methyl-4-acryloyloxy-phenyloxy group, 3-methyl-4-acryloyloxy-phenyloxy group, 2,4-dimethyl-3-acryloyloxy- Phenyloxy group, 2,5-dimethyl-3-acryloyl Oxy-phenyloxy group, 3-acryloyloxy-4,5-dimethyl-phenyloxy group, 3-acryloyloxy-4,6-dimethyl-phenyloxy group, 3-acryloyloxy-5,6-dimethyl-phenyloxy group 4-acryloyloxy-2,3-dimethyl-phenyloxy group, 4-acryloyloxy-2,5-dimethyl-phenyloxy group, 4-acryloyloxy-3,5-dimethyl-phenyloxy group, 3-acryloyloxy -4-ethyl-phenyloxy group, 3-acryloyloxy-5-ethyl-phenyloxy group, 3-ethyl-4-acryloyloxy-phenyloxy group, 2-allyl-3-acryloyloxy-phenyloxy group, 3- Acryloyloxy-4-allyl-phenyloxy group, 3-acyl Royloxy-5-allyl-phenyloxy group, 3-acryloyloxy-6-allyl-phenyloxy group, 2-allyl-4-acryloyloxy-phenyloxy group, 3-allyl-4-acryloyloxy-phenyloxy group, 2 -Phenyl-3-acryloyloxy-phenyloxy group, 3-acryloyloxy-4-phenyl-phenyloxy group, 3-acryloyloxy-5-phenyl-phenyloxy group, 3-acryloyloxy-6-phenyl-phenyloxy group 2-phenyl-4-acryloyloxy-phenyloxy group, 3-phenyl-4-acryloyloxy-phenyloxy group, 2-methacryloyloxy-3-methyl-phenyloxy group, 2-methacryloyloxy-4-methyl-phenyl Oxy group, 2-methacryl Royloxy-5-methyl-phenyloxy group, 2-methacryloyloxy-6-methyl-phenyloxy group, 2-methyl-3-methacryloyloxy-phenyloxy group, 3-methacryloyloxy-4-methyl-phenyloxy group, 3 -Methacryloyloxy-5-methyl-phenyloxy group, 3-methacryloyloxy-6-methyl-phenyloxy group, 2-methyl-4-methacryloyloxy-phenyloxy group, 3-methyl-4-methacryloyloxy-phenyloxy group 3-methacryloyloxy-2,4-dimethyl-phenyloxy group, 3-methacryloyloxy-2,5-dimethyl-phenyloxy group, 3-methacryloyloxy-4,5-dimethyl-phenyloxy group, 3-methacryloyloxy -4,6-dimethyl- Enyloxy group, 3-methacryloyloxy-5,6-dimethyl-phenyloxy group, 4-methacryloyloxy-2,3-dimethyl-phenyloxy group, 4-methacryloyloxy-2,5-dimethyl-phenyloxy group, 4- Methacryloyloxy-3,5-dimethyl-phenyloxy group, 3-methacryloyloxy-4-ethyl-phenyloxy group, 3-methacryloyloxy-5-ethyl-phenyloxy group, 3-ethyl-4-methacryloyloxy-phenyloxy Group, 2-allyl-3-methacryloyloxy-phenyloxy group, 3-methacryloyloxy-4-allyl-phenyloxy group, 3-methacryloyloxy-5-allyl-phenyloxy group, 3-methacryloyloxy-6-allyl- Phenyloxy group, 2-ali -4-methacryloyloxy-phenyloxy group, 3-allyl-4-methacryloyloxy-phenyloxy group, 2-phenyl-3-methacryloyloxy-phenyloxy group, 3-methacryloyloxy-4-phenyl-phenyloxy group, 3 -Methacryloyloxy-5-phenyl-phenyloxy group, 3-methacryloyloxy-6-phenyl-phenyloxy group, 2-phenyl-4-methacryloyloxy-phenyloxy group or 3-phenyl-4-methacryloyloxy-phenyloxy group It is.

this house,
2-methyl-3-acryloyloxy-phenyloxy group,
3-acryloyloxy-4-methyl-phenyloxy group,
3-acryloyloxy-5-methyl-phenyloxy group,
3-acryloyloxy-6-methyl-phenyloxy group,
2-methyl-4-acryloyloxy-phenyloxy group,
3-methyl-4-acryloyloxy-phenyloxy group,
4-acryloyloxy-3,5-dimethyl-phenyloxy group,
3-acryloyloxy-4-ethyl-phenyloxy group,
3-acryloyloxy-5-ethyl-phenyloxy group,
3-ethyl-4-acryloyloxy-phenyloxy group,
2-methyl-3-methacryloyloxy-phenyloxy group,
3-methacryloyloxy-4-methyl-phenyloxy group,
3-methacryloyloxy-5-methyl-phenyloxy group,
3-methacryloyloxy-6-methyl-phenyloxy group,
2-methyl-4-methacryloyloxy-phenyloxy group,
3-methyl-4-methacryloyloxy-phenyloxy group,
4-Amethacryloyloxy-3,5-dimethyl-phenyloxy group,
3-methacryloyloxy-4-ethyl-phenyloxy group,
A 3-methacryloyloxy-5-ethyl-phenyloxy group or a 3-ethyl-4-methacryloyloxy-phenyloxy group is particularly preferred.

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

[Form A]
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 such a reactive group-containing cyclic phosphazene compound include a reactive group-containing cyclotriphosphazene compound in which n in formula (1) is 3, and a reactive group in which n in formula (1) is 4. Containing cyclotetraphosphazene compound, reactive group-containing cyclopentaphosphazene compound in which n in formula (1) is 5, and reactive group-containing cyclohexaphosphazene compound in which n in formula (1) is 6, But,
2-methyl-3-acryloyloxy-phenyloxy group,
3-acryloyloxy-4-methyl-phenyloxy group,
3-acryloyloxy-5-methyl-phenyloxy group,
3-acryloyloxy-6-methyl-phenyloxy group,
2-methyl-4-acryloyloxy-phenyloxy group,
3-methyl-4-acryloyloxy-phenyloxy group,
4-acryloyloxy-3,5-dimethyl-phenyloxy group,
3-acryloyloxy-4-ethyl-phenyloxy group,
3-acryloyloxy-5-ethyl-phenyloxy group,
3-ethyl-4-acryloyloxy-phenyloxy group,
2-methyl-3-methacryloyloxy-phenyloxy group,
3-methacryloyloxy-4-methyl-phenyloxy group,
3-methacryloyloxy-5-methyl-phenyloxy group,
3-methacryloyloxy-6-methyl-phenyloxy group,
2-methyl-4-methacryloyloxy-phenyloxy group,
3-methyl-4-methacryloyloxy-phenyloxy group,
4-methacryloyloxy-3,5-dimethyl-phenyloxy group,
3-methacryloyloxy-4-ethyl-phenyloxy group,
What is a kind of A3 group selected from A3 group consisting of 3-methacryloyloxy-5-ethyl-phenyloxy group or 3-ethyl-4-methacryloyloxy-phenyloxy group and all of A are said A3 group The thing which is 2 or more types of A3 group chosen from these, and these arbitrary mixtures can be mentioned.

[Form B]
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.

  Preferred as the reactive group-containing cyclic phosphazene compound of this form is one in which 2 to 2 of A to (2n-2) A3 groups. In particular, a reactive group-containing cyclotriphosphazene compound in which n in formula (1) is 3, a reactive group-containing cyclotetraphosphazene compound in which n in formula (1) is 4, and n in formula (1) is 5. A reactive group-containing cyclopentaphosphazene compound and a reactive group-containing cyclohexaphosphazene compound in which n in formula (1) is 6, wherein 1 to 2n-2 of 2n A are A3 groups As well as any mixtures thereof. This type of reactive group-containing cyclic phosphazene compound realizes a resin molded article with higher high-temperature reliability and mechanical strength (especially glass transition temperature) than other reactive group-containing cyclic phosphazene compounds of the present invention. It is advantageous where possible.

  In addition, it is confirmed by TOF-MS analysis of the reactive group-containing cyclic phosphazene compound or an intermediate in the production process thereof, whether 1 to (2n-2) of 2n A are A3 groups or not. be able to.

Specific examples of such a reactive group-containing cyclic phosphazene compound include a reactive group-containing cyclotriphosphazene compound in which n in formula (1) is 3, and a reactive group in which n in formula (1) is 4. Containing cyclotetraphosphazene compound, reactive group-containing cyclopentaphosphazene compound in which n in formula (1) is 5, or reactive containing cyclohexaphosphazene compound in which n in formula (1) is 6.
A is
A combination of a 2-methyl-3-acryloyloxy-phenyloxy group that is an A3 group and an n-propoxy group that is an A1 group;
A combination of a 2-methyl-3-acryloyloxy-phenyloxy group that is an A3 group and a phenoxy group that is an A2 group;
A combination of 2-methyl-3-acryloyloxy-phenyloxy group which is A3 group and methylphenoxy group which is A2 group,
A combination of 3-acryloyloxy-4-methyl-phenyloxy group which is A3 group and n-propoxy group which is A1 group,
A combination of 3-acryloyloxy-4-methyl-phenyloxy group which is A3 group and phenoxy group which is A2 group,
A combination of 3-acryloyloxy-4-methyl-phenyloxy group which is A3 group and methylphenoxy group which is A2 group,
A combination of 3-acryloyloxy-5-methyl-phenyloxy group which is A3 group and n-propoxy group which is A1 group,
A combination of 3-acryloyloxy-5-methyl-phenyloxy group which is A3 group and phenoxy group which is A2 group,
A combination of a 3-acryloyloxy-5-methyl-phenyloxy group that is an A3 group and a methylphenoxy group that is an A2 group;
A combination of a 3-acryloyloxy-6-methyl-phenyloxy group that is an A3 group and an n-propoxy group that is an A1 group;
A combination of 3-acryloyloxy-6-methyl-phenyloxy group which is A3 group and phenoxy group which is A2 group,
A combination of a 3-acryloyloxy-6-methyl-phenyloxy group that is an A3 group and a methylphenoxy group that is an A2 group;
A combination of 2-methyl-4-acryloyloxy-phenyloxy group which is A3 group and n-propoxy group which is A1 group,
A combination of 2-methyl-4-acryloyloxy-phenyloxy group which is A3 group and phenoxy group which is A2 group,
A combination of 2-methyl-4-acryloyloxy-phenyloxy group that is A3 group and methylphenoxy group that is A2 group,
A combination of 3-methyl-4-acryloyloxy-phenyloxy group which is A3 group and n-propoxy group which is A1 group,
A combination of a 3-methyl-4-acryloyloxy-phenyloxy group that is an A3 group and a phenoxy group that is an A2 group;
A combination of a 3-methyl-4-acryloyloxy-phenyloxy group that is an A3 group and a methylphenoxy group that is an A2 group,
A combination of 4-acryloyloxy-3,5-dimethyl-phenyloxy group which is A3 group and n-propoxy group which is A1 group,
A combination of a 4-acryloyloxy-3,5-dimethyl-phenyloxy group that is an A3 group and a phenoxy group that is an A2 group;
A combination of a 4-acryloyloxy-3,5-dimethyl-phenyloxy group that is an A3 group and a methylphenoxy group that is an A2 group;
A combination of 3-acryloyloxy-4-ethyl-phenyloxy group which is A3 group and n-propoxy group which is A1 group,
A combination of 3-acryloyloxy-4-ethyl-phenyloxy group which is A3 group and phenoxy group which is A2 group,
A combination of a 3-acryloyloxy-4-ethyl-phenyloxy group that is an A3 group and a methylphenoxy group that is an A2 group;
A combination of 3-acryloyloxy-5-ethyl-phenyloxy group which is A3 group and n-propoxy group which is A1 group,
A combination of 3-acryloyloxy-5-ethyl-phenyloxy group which is A3 group and phenoxy group which is A2 group,
A combination of 3-acryloyloxy-5-ethyl-phenyloxy group which is A3 group and methylphenoxy group which is A2 group,
A combination of 3-ethyl-4-acryloyloxy-phenyloxy group which is A3 group and n-propoxy group which is A1 group,
A combination of 3-ethyl-4-acryloyloxy-phenyloxy group which is A3 group and phenoxy group which is A2 group,
A combination of 3-ethyl-4-acryloyloxy-phenyloxy group which is A3 group and methylphenoxy group which is A2 group,
A combination of 2-methyl-3-methacryloyloxy-phenyloxy group which is A3 group and n-propoxy group which is A1 group,
A combination of 2-methyl-3-methacryloyloxy-phenyloxy group which is A3 group and phenoxy group which is A2 group,
A combination of a 2-methyl-3-methacryloyloxy-phenyloxy group that is an A3 group and a methylphenoxy group that is an A2 group;
A combination of a 3-methacryloyloxy-4-methyl-phenyloxy group that is an A3 group and an n-propoxy group that is an A1 group;
A combination of a 3-methacryloyloxy-4-methyl-phenyloxy group that is an A3 group and a phenoxy group that is an A2 group,
A combination of a 3-methacryloyloxy-4-methyl-phenyloxy group that is an A3 group and a methylphenoxy group that is an A2 group;
A combination of a 3-methacryloyloxy-5-methyl-phenyloxy group which is an A3 group and an n-propoxy group which is an A1 group;
A combination of a 3-methacryloyloxy-5-methyl-phenyloxy group that is an A3 group and a phenoxy group that is an A2 group;
A combination of a 3-methacryloyloxy-5-methyl-phenyloxy group that is an A3 group and a methylphenoxy group that is an A2 group;
A combination of a 3-methacryloyloxy-6-methyl-phenyloxy group which is an A3 group and an n-propoxy group which is an A1 group;
A combination of 3-methacryloyloxy-6-methyl-phenyloxy group which is A3 group and phenoxy group which is A2 group,
A combination of a 3-methacryloyloxy-6-methyl-phenyloxy group that is an A3 group and a methylphenoxy group that is an A2 group;
A combination of 2-methyl-4-methacryloyloxy-phenyloxy group which is A3 group and n-propoxy group which is A1 group,
A combination of 2-methyl-4-methacryloyloxy-phenyloxy group which is A3 group and phenoxy group which is A2 group,
A combination of 2-methyl-4-methacryloyloxy-phenyloxy group which is A3 group and methylphenoxy group which is A2 group,
A combination of 3-methyl-4-methacryloyloxy-phenyloxy group which is A3 group and n-propoxy group which is A1 group,
A combination of a 3-methyl-4-methacryloyloxy-phenyloxy group that is an A3 group and a phenoxy group that is an A2 group,
A combination of a 3-methyl-4-methacryloyloxy-phenyloxy group that is an A3 group and a methylphenoxy group that is an A2 group;
A combination of 4-methacryloyloxy-3,5-dimethyl-phenyloxy group which is A3 group and n-propoxy group which is A1 group,
A combination of 4-methacryloyloxy-3,5-dimethyl-phenyloxy group which is A3 group and phenoxy group which is A2 group,
A combination of a 4-methacryloyloxy-3,5-dimethyl-phenyloxy group that is an A3 group and a methylphenoxy group that is an A2 group;
A combination of 3-methacryloyloxy-4-ethyl-phenyloxy group which is A3 group and n-propoxy group which is A1 group,
A combination of a 3-methacryloyloxy-4-ethyl-phenyloxy group that is an A3 group and a phenoxy group that is an A2 group;
A combination of a 3-methacryloyloxy-4-ethyl-phenyloxy group that is an A3 group and a methylphenoxy group that is an A2 group;
A combination of 3-methacryloyloxy-5-ethyl-phenyloxy group which is A3 group and n-propoxy group which is A1 group,
A combination of 3-methacryloyloxy-5-ethyl-phenyloxy group which is A3 group and phenoxy group which is A2 group,
A combination of a 3-methacryloyloxy-5-ethyl-phenyloxy group as an A3 group and a methylphenoxy group as an A2 group;
A combination of 3-ethyl-4-methacryloyloxy-phenyloxy group which is A3 group and n-propoxy group which is A1 group,
A combination of 3-ethyl-4-methacryloyloxy-phenyloxy group which is A3 group and phenoxy group which is A2 group or 3-ethyl-4-methacryloyloxy-phenyloxy group which is A3 group and A2 group Mention may be made of combinations with combinations with methylphenoxy groups and any mixtures thereof.

Among these, the reactive group-containing cyclotriphosphazene compound in which n in the formula (1) is 3, a reactive group-containing cyclotetraphosphazene compound in which n in the formula (1) is 4, and n in the formula (1) is 5. A reactive group-containing cyclopentaphosphazene compound, a reactive group-containing cyclohexaphosphazene compound in which n in formula (1) is 6, wherein A is
A combination of a 3-methyl-4-acryloyloxy-phenyloxy group that is an A3 group and a phenoxy group that is an A2 group;
A combination of a 3-methyl-4-acryloyloxy-phenyloxy group that is an A3 group and a methylphenoxy group that is an A2 group,
A combination of 2-methyl-4-acryloyloxy-phenyloxy group which is A3 group and phenoxy group which is A2 group,
A combination of 2-methyl-4-acryloyloxy-phenyloxy group that is A3 group and methylphenoxy group that is A2 group,
A combination of 4-acryloyloxy-2,6-dimethyl-phenyloxy group which is A3 group and phenoxy group which is A2 group,
A combination of a 4-acryloyloxy-2,6-dimethyl-phenyloxy group that is an A3 group and a methylphenoxy group that is an A2 group;
A combination of a 3-methyl-4-methacryloyloxy-phenyloxy group that is an A3 group and a phenoxy group that is an A2 group,
A combination of a 3-methyl-4-methacryloyloxy-phenyloxy group that is an A3 group and a methylphenoxy group that is an A2 group;
A combination of 2-methyl-4-methacryloyloxy-phenyloxy group which is A3 group and phenoxy group which is A2 group,
A combination of 2-methyl-4-methacryloyloxy-phenyloxy group which is A3 group and methylphenoxy group which is A2 group,
Combination of 4-methacryloyloxy-2,6-dimethyl-phenyloxy group which is A3 group and phenoxy group which is A2 group or 4-methacryloyloxy-2,6-dimethyl-phenyloxy group which is A3 group , And a combination of the A2 group methylphenoxy group and any mixtures thereof.

In particular, a reactive group-containing cyclotriphosphazene compound in which n in formula (1) is 3 or a reactive group-containing cyclotetraphosphazene compound in which n in formula (1) is 4, wherein A is
A combination of a 3-methyl-4-acryloyloxy-phenyloxy group that is an A3 group and a phenoxy group that is an A2 group;
A combination of a 3-methyl-4-acryloyloxy-phenyloxy group that is an A3 group and a methylphenoxy group that is an A2 group,
A combination of 2-methyl-4-acryloyloxy-phenyloxy group which is A3 group and phenoxy group which is A2 group,
A combination of 2-methyl-4-acryloyloxy-phenyloxy group that is A3 group and methylphenoxy group that is A2 group,
A combination of 4-acryloyloxy-2,6-dimethyl-phenyloxy group which is A3 group and phenoxy group which is A2 group,
A combination of a 4-acryloyloxy-2,6-dimethyl-phenyloxy group that is an A3 group and a methylphenoxy group that is an A2 group;
A combination of a 3-methyl-4-methacryloyloxy-phenyloxy group that is an A3 group and a phenoxy group that is an A2 group,
A combination of a 3-methyl-4-methacryloyloxy-phenyloxy group that is an A3 group and a methylphenoxy group that is an A2 group;
A combination of 2-methyl-4-methacryloyloxy-phenyloxy group which is A3 group and phenoxy group which is A2 group,
A combination of 2-methyl-4-methacryloyloxy-phenyloxy group which is A3 group and methylphenoxy group which is A2 group,
Combination of 4-methacryloyloxy-2,6-dimethyl-phenyloxy group which is A3 group and phenoxy group which is A2 group or 4-methacryloyloxy-2,6-dimethyl-phenyloxy group which is A3 group , And a combination of the A2 group methylphenoxy group and any mixtures thereof.

Method for Producing Reactive Group-Containing Cyclic Phosphazene Compound The reactive group-containing cyclic phosphazene compound of the present invention can be produced by the following method.

First, a cyclic phosphonitrile dihalide represented by the following formula (3) is prepared.

  In the formula (3), n represents an integer of 3 to 8. X represents a halogen atom, preferably a fluorine atom or a chlorine atom. Incidentally, the cyclic phosphonitrile dihalide prepared here may be a mixture of several kinds having different n.

  The production method of such a cyclic phosphonitrile dihalide and 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 (3) is usually composed of a cyclic phosphonitrile dihalide having a degree of polymerization of about 3 to 8 and a chain phosphonitrile dihalide. Obtained as a mixture. For this reason, the cyclic phosphonitrile dihalide represented by the formula (3) removes the chain phosphonitrile dihalide using the difference in solubility in the solvent from the mixture, as described in the above 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 5), dodecafluorocyclohexaphosphazene (where n is 6), a mixture of hexafluorocyclotriphosphazene and octafluorocyclotetraphosphazene, a mixture of cyclic phosphonitrile difluorides where n is 3 to 8, hexachlorocyclo Triphosphazene (n is 3), octachlorocyclotetraphosphazene (n is 4), decachlorocyclopentaphosphazene (n is 5), dodecachlorocyclohexaphosphazene (n is 6), hexac B is a cyclotriphosphazene and mixtures cyclic phosphonate nitrile dichloride mixtures and n is 3 to 8 of the octa-chloro cyclotetrasiloxane phosphazene like. Of these, hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, a mixture of hexachlorocyclotriphosphazene and octachlorocyclotetraphosphazene, and a mixture of cyclic phosphonitrile dichloride having n of 3 to 8, more preferably hexachlorocyclotriphosphazene, hexachloro Particular preference is given to mixtures of cyclotriphosphazene and octachlorocyclotetraphosphazene and mixtures of cyclic phosphonitrile dichlorides with n of 3 to 8.

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

[Compound B1]
Alcohols having 1 to 8 carbon atoms.
In these alcohols, at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group may be substituted.

  Examples of such 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.
In this phenol, at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group may be substituted.

  Examples of such phenols include phenol, cresol, dimethylphenol, ethylphenol, ethylmethylphenol, diethylphenol, n-propylphenol, isopropylphenol, isopropylmethylphenol, isopropylethylphenol, diisopropylphenol, n-butylphenol, sec-butylphenol, tert-butylphenol, n-pentylphenol, n-hexylphenol, vinylphenol, 1-propenylphenol, 2-propenylphenol, isopropenylphenol, 1-butenylphenol, sec-butenylphenol, 1-pentenyl Phenol, 1-hexenylphenol, phenylphenol, naphthol, anthranol and phenanthate Mention may be made of the Nord and the like. Among these, phenol, cresol, dimethylphenol, diethylphenol, 2-propenylphenol, phenylphenol and naphthol are preferable, and phenol, cresol, dimethylphenol and naphthol are particularly preferable.

[Compound B3]
Acyl group-substituted phenols represented by the following formula (4).

In formula (4), at least one of L ^{1 to} L ⁵ is an acyl group, and at least one is at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group. And the rest are hydrogen atoms.

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

  Examples of such acyl group-substituted phenols include 2-methyl-3-acetylphenol, 3-acetyl-4-methylphenol, 3-acetyl-5-methylphenol, 3-acetyl-6-methylphenol, and 2 -Methyl-4-acetylphenol, 3-methyl-4-acetylphenol, 4-acetyl-3,5-dimethylphenol, 3-acetyl-4-ethylphenol, 3-acetyl-5-ethylphenol and 3-ethyl- 4-acetylphenol etc. can be mentioned. Of these, 3-acetyl-4-methylphenol, 3-acetyl-5-methylphenol, 2-methyl-4-acetylphenol, 3-methyl-4-acetylphenol, 4-acetyl-3,5-dimethylphenol and 3-ethyl-4-acetylphenol is preferred, especially 3-acetyl-4-methylphenol, 2-methyl-4-acetylphenol, 3-methyl-4-acetylphenol and 4-acetyl-3,5-dimethylphenol. preferable.

  In the method for producing a reactive group-containing cyclic phosphazene compound of the present invention, first, the cyclic phosphonitrile dihalide is reacted with the cyclic phosphonitrile dihalide represented by the above formula (3) and the above-mentioned compounds B1 to B3. All halogen atoms of the halide are substituted with a group selected from the group consisting of the following G1, G2, and G3 groups so that at least one is substituted with the following G3 group, and an acyl group-containing cyclic phosphonitrile substituted product is obtained. Manufacture (step 1).

[G1 group]
The C1-C8 alkoxy group in which the at least 1 sort (s) chosen from a C1-C6 alkyl group, an alkenyl group, and an aryl group may be substituted.
This group is substituted with a halogen atom by the compound B1, and corresponds to the A1 group described above.

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

[G3 group]
A group selected from the group consisting of an acyl group-substituted phenyloxy group represented by the following formula (4).

This group is substituted with a halogen atom by the compound B3. In formula (4), at least one of L ^{1 to} L ⁵ is an acyl group, and at least one is at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group. And the rest are hydrogen atoms.

  In this production process, the kind of the acyl group-containing cyclic phosphazene compound to be produced, that is, the case of producing the acyl group-containing cyclic phosphazene compound according to the above-described form A, and the production of the acyl group-containing cyclic phosphazene compound according to the above-described form B are produced. When selected, compounds B1 to B3 are appropriately selected and used. Specifically, it is as follows.

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

<Method Aa>
A cyclic phosphonitrile dihalide is reacted with an alkali metal salt of compound B3.
In the case of this method, the amount of the alkali metal salt of compound B3 is usually preferably set to 1.0 to 2.0 equivalents of the amount of active halogen atom of cyclic phosphonitrile dihalide, and 1.05 to 1 More preferably, it is set to 3 equivalents. When the amount used is less than 1.0 equivalent, some of the active halogen atoms remain, and the target reactive 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 Ab>
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, some of the active halogen atoms remain, and the target reactive 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 atom remains, and the target reactive 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 an acyl group-containing cyclic phosphazene compound of Form B]
In this case, at least one of compound B3 and at least one compound of compound B1 and compound B2 are reacted with cyclic phosphonitrile dihalide, and a part of the active halogen atoms of cyclic phosphonitrile dihalide is reacted. Is substituted with the G3 group derived from the compound B3, and all of the remaining other active halogen atoms are replaced with at least one group of the G1 group derived from the compound B1 and the G2 group derived from the compound B2. As a method for this, any of the following methods can be adopted.

<Method Ba>
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 acyl 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, some of the active halogen atoms remain, and the target reactive 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 B-b>
A cyclic phosphonitrile dihalide is reacted with a mixture of compound B3 and at least one of compound B1 and compound B2 in the presence of a base 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 acyl 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, some of the active halogen atoms remain, and the target reactive 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 atom remains, and the target reactive 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 Bc>
First, compound B3 is reacted with cyclic phosphonitrile dihalide to obtain a partially substituted product in which a part of the active halogen atom of cyclic phosphonitrile dihalide is substituted with G3 group derived from compound B3 (first step). Next, at least one of compound B1 and compound B2 is reacted with the obtained partially substituted product, and all of the remaining active halogen atoms are converted to G1 group derived from compound B1 and G2 derived from compound B2. Substitution with at least one of the groups (second step).

  The first step of this method may be carried out by reacting an alkali metal salt of compound B3 with a cyclic phosphonitrile dihalide, or captures a hydrogen halide of compound B3 with respect to the cyclic phosphonitrile dihalide. The reaction may be performed in the presence of a base. In addition, the second step may be carried out by reacting the partially substituted product obtained in the first step with an alkali metal salt of at least one of the compounds B1 and B2, or the first step. The partially substituted product obtained in (1) may be reacted with at least one of compound B1 and compound B2 in the presence of a base that captures hydrogen halide.

<Method Bd>
First, at least one of compound B1 and compound B2 is reacted with cyclic phosphonitrile dihalide, and a part of the active halogen atom of cyclic phosphonitrile dihalide is converted to G1 group derived from compound B1 and compound B2. A partially substituted product substituted with at least one of the derived G2 groups is obtained (first step). Next, compound B3 is reacted with the obtained partially substituted product, and all remaining active halogen atoms are substituted with G3 groups derived from compound B3 (second step).

  The first step of this method may be carried out by reacting cyclic phosphonitrile dihalide with an alkali metal salt of at least one of compound B1 and compound B2, or for cyclic phosphonitrile dihalide. Alternatively, at least one of compound B1 and compound B2 may be reacted in the presence of a base that captures hydrogen halide. In addition, the second step may be carried out by reacting the alkali metal salt of compound B3 with the partial substituent obtained in the first step, or with respect to the partial substituent obtained in the first step. Compound B3 may be reacted in the presence of a base that captures hydrogen halide.

  In general, the alkali metal salt used in each of the above methods is preferably a lithium salt, a sodium salt, a potassium salt, or a cesium salt. In particular, sodium salt and potassium salt are preferable. Such an alkali metal salt is a dehydrogenation reaction between the compounds B1 to B3 and metal lithium, metal sodium or metal potassium, or the compounds B1 to B3 and lithium hydroxide, sodium hydroxide or potassium hydroxide. 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-dimethylaminopyridine, 4-diethylamino Aliphatic or aromatic amines such as pyridine and 4-diisopropylaminopyridine, alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate, sodium hydroxide, potassium hydroxide and lithium hydroxide Alkali metal hydroxides are preferred. In particular, alkali metal hydroxides such as triethylamine, pyridine and sodium 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 −20 ° C. to the boiling point of the solvent. On the other hand, when carrying out the reaction without solvent, the reaction temperature is usually preferably set in the range of 40 to 200 ° C.

  As the reactive group-containing cyclic phosphazene compound of the present invention, a compound according to the above-mentioned Form B, in particular, one having 2 to 3 (2n-2) of 2n A in formula (1) is an A3 group. When manufacturing, it is preferable to employ the above-mentioned method Bc or Method Bd.

  Here, when adopting Method Bc, first, 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 G3 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. All of the remaining active halogen atoms are removed from the G1 group derived from the compound B1 and the G2 group derived from the compound B2. Replace with at least one of them.

  On the other hand, when adopting Method Bd, first, an ether solvent solution or an aromatic hydrocarbon solvent solution of cyclic phosphonitrile dihalide is prepared. Then, with respect to this solvent solution, at least one selected from an ether solvent solution or an aromatic hydrocarbon solvent solution of an alkali metal salt of at least one compound selected from Compound B1 and Compound B2 or from Compound B1 and Compound B2 An ether solvent solution or an aromatic hydrocarbon solvent solution of one compound and a base 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 G1 group derived from compound B1 and G2 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 with G3 groups derived from compound B3.

  In the production method of the present invention, the acyl group-containing cyclic phosphonitrile substitution product obtained in the above-mentioned step 1 is then subjected to Bayer-Villiger oxidation (step 2), and then it is deacylated (hydrolyzed). Decomposition) (step 3) to produce a hydroxy group-containing cyclic phosphonitrile substitution product. Thereby, the hydroxy group containing cyclic phosphazene compound which is a precursor of the target reactive group containing cyclic phosphazene compound is obtained.

  A method for producing a hydroxy group-containing cyclic phosphazene compound by subjecting the acyl group of the G3 group to Bayer-Billiger oxidation and then deacylating (hydrolyzing) it is described in various literatures, for example, Patent Documents 3 to 5 describe this.

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

  The oxidizing agents that can be used in the process of the present invention are all oxidizing agents known for buyer-bilger oxidation as described in the above non-patent literature. The oxidizing agent can be used either in pure form or in the form of a mixture thereof, but is preferably used in pure form. The oxidizing agents used are, for example, inorganic or organic peroxides, hydrogen peroxide, urea peroxide, peroxo complexes of transition metals, peroxo compounds and organic acids and / or inorganic acids and / or Lewis acids, organic peracids, inorganic A mixture with peracid, dioxirane or a mixture of these oxidizing agents. A buyer-biller monooxygenase (oxygenase) can also be used.

  The inorganic peroxide used is preferably ammonium peroxide, alkali metal peroxide, ammonium persulfate, alkali metal persulfate, ammonium perborate, alkali metal perborate, ammonium percarbonate, alkali metal peroxide. Carbonates, alkaline earth metal peroxides, zinc peroxides or mixtures of these oxidants. The alkali metal peroxide used is preferably sodium peroxide.

  The organic peroxide used is preferably tert-butyl hydroperoxide, cumene hydroperoxide, menthyl hydroperoxide, 1-methylcyclohexane hydroperoxide or a mixture of these compounds.

  The transition metal peroxo complex used is preferably a peroxo complex of a transition metal such as iron, manganese, vanadium or molybdenum, or a mixture of these peroxo complexes. It is also possible here that the peroxo complex comprises two or more of the same or different transition metals.

  The peroxo compound having an inorganic acid is preferably potassium peroxodisulfate having sulfuric acid, and the peroxo compound having a Lewis acid is particularly preferably hydrogen peroxide having boron trifluoride.

  The organic peracid used is preferably formic acid, peracetic acid, trifluoroperacetic acid, perbenzoic acid, m-chloroperbenzoic acid, magnesium monoperphthalate or a mixture of these peracids.

  The inorganic peracid used is preferably persulfuric acid, percarbonate, permonophosphoric acid or a mixture of these peracids.

  The production method of the present invention comprises the acyl group-substituted phenyloxy group-containing cyclic phosphonitrile-substituted product, the type and amount of the oxidant, the presence or absence of a reaction solvent, and the hydroxy group-containing cyclic phosphonitrile substitution to be obtained. It can be appropriately selected from a wide range according to various conditions such as physical properties and uses of the body. The equivalent of the cyclic phosphonitrile substituent having an acyl group-substituted phenyloxy group to the oxidant relative to the acyl group depends in particular on the reactivity of the cyclic phosphonitrile substituent having an acyl group-substituted phenyloxy group and the oxidizing agent used. . The equivalent of the oxidizing agent with respect to the acyl group of the cyclic phosphonitrile substituted product having an acyl group-substituted phenyloxy group can usually be selected from the range of 1-10. Preferably it is 1.05-1.5, More preferably, it is 1.1-1.3.

  The production method of the present invention comprises isolating a compound having an acyloxy group obtained by oxidizing a cyclic phosphonitrile substituted product having an acyl group-substituted phenyloxy group (step 2), and then hydrolyzing the compound (step 3). The hydroxy group-containing cyclic phosphazene compound can be produced. Moreover, the target hydroxy group-containing cyclic phosphazene compound can be produced by directly deacylating (hydrolyzing) a compound having an acyloxy group generated by oxidation in one pot (step 2 → 3). It can be appropriately selected from a wide range according to various conditions such as physical properties and applications of the hydroxy group-containing cyclic phosphonitrile substitution product to be obtained.

  The reactive group-containing cyclic phosphazene compound of the present invention can be produced by deacylating (hydrolyzing) a precursor compound having an acyloxy group under acidic or alkaline conditions. It can also be produced by a deacylation (hydrolysis) reaction using an enzyme. These production conditions can be appropriately selected from conventionally known methods. Hydrolysis reactions under acidic or alkaline conditions are known, for example, in an organic solvent miscible with water (ethanol, tetrahydrofuran, dioxane, etc.), acid (mineral acid, organic acid, etc.) or alkali (sodium hydroxide, The reaction can be performed at −10 to 90 ° C. using an aqueous solution of potassium hydroxide, potassium carbonate, or the like. In addition, hydrolysis using an enzyme is known. For example, in a mixed solution of an organic solvent (ethanol, dimethyl sulfoxide, etc.) miscible with water and water, in the presence or absence of a buffer, an esterolytic enzyme ( Esterase, lipase, etc.) can be performed at 0 to 50 ° C.

  In the production method of the present invention, a cyclic phosphonitrile substituted product having an acyl group-substituted phenyloxy group is converted to an acyloxy group by oxidation and then deacylated (hydrolyzed) to produce a hydroxy group-containing cyclic phosphazene compound. In this method, any of the above-described oxidation reactions and subsequent hydrolysis methods can be carried out without a solvent, or can be carried out using a solvent. When a solvent is used, the type of the solvent is not particularly limited as long as it does not adversely affect the reaction. Usually, a halogenated hydrocarbon compound (dichloromethane, chloroform, 1,2-dichloroethane or 1 , 1,2,2-tetrachloroethane), paraffinic compounds (hexane, pentane or ligroin), ether compounds (diethyl ether), acid amide compounds (N, N-dimethylformamide), nitrile compounds (acetonitrile), Carbon disulfide and nitro compounds (nitromethane or nitrobenzene) or mixtures of the aforementioned solvents can be used. Of these, it is particularly preferable to use a halogenated hydrocarbon compound.

  In the production of the reactive group-containing cyclic phosphazene compound of the present invention, if it is necessary to take out the target hydroxy group-containing cyclic phosphazene compound or the intermediate acyloxy group-containing cyclic phosphazene compound depending on the production conditions, filtration, solvent extraction, It can be isolated and purified from the reaction system by ordinary methods such as column chromatography and recrystallization.

  The hydroxy group-containing cyclic phosphazene compound which is a precursor of the reactive group-containing cyclic phosphazene compound of the present invention, in addition to the production method described above, from a cyclic phosphazene compound having a structure that becomes a hydroxy group by removing the protective group, It can also be produced by deprotecting the protecting group. Examples of the protective group for the hydroxy group include a methyl group, a methoxymethyl group, a methylthiomethyl group, a 2-methoxyethoxymethyl group, a tetrahydropyranyl group, a tetrahydrothiopyranyl group, a 4-methoxytetrahydropyranyl group, and a 4-methoxy group. Tetrahydrothiopyranyl group, tetrahydrofuranyl group, tetrahydrofuranyl group, 1-ethoxyethyl group, tert-butyl group, allyl group, benzyl group, o-nitrobenzyl group, triphenylmethyl group, trimethylsilyl group, tert-butyl Examples thereof include a dimethylsilyl group, a tert-butyldiphenylsilyl group, a tribenzylsilyl group, and a triisopropylsilyl group. Of these protecting groups, methyl group, methoxymethyl group, tetrahydropyranyl group, 4-methoxytetrahydropyranyl group, tert-butyl group, allyl group, benzyl group and tert-butyldimethylsilyl group are preferred, methyl group, A methoxymethyl group, a tert-butyl group, an allyl group and a benzyl group are particularly preferred.

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

  The hydroxy group-containing phosphazene compound, which is a precursor of the target reactive group-containing cyclic phosphazene compound obtained by elimination of such a protective group, is subjected to usual methods such as filtration, solvent extraction, column chromatography and recrystallization. Can be isolated and purified from the reaction system.

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

  In the production method of the present invention, the hydroxy group-containing cyclic phosphazene compound obtained in the above-mentioned step 3 is then reacted with acrylic acid, methacrylic acid, an acrylic acid halide or a methacrylic acid halide to form the hydroxy group-containing cyclic phosphazene compound in step 3. The hydroxy group is converted into an acryloyloxy group or methacryloyloxy (step 4). Thereby, the target reactive group containing cyclic phosphazene compound is obtained.

  A method for converting a hydroxy group into an acryloyloxy group or a methacryloyloxy group, that is, a method for producing a carboxylic acid ester, comprises a hydroxy group-containing cyclic phosphazene compound, acrylic acid and methacrylic acid, a mineral acid such as hydrochloric acid and sulfuric acid, Reaction in the presence of an organic acid such as benzenesulfonic acid and p-toluenesulfonic acid, a metal halide such as tin chloride, zinc chloride, ferric chloride and aluminum chloride, or in the presence of a dehydrating condensing agent such as dicyclohexylcarbodiimide. Can be obtained. The catalyst and dehydrating condensing agent used here may be used alone or in combination. Hydroxyl group-containing cyclic phosphazene compounds and acrylic acid halides and methacrylic acid halides in the presence of adsorbents such as tertiary amines such as triethylamine and pyridine, alkali metal salts such as potassium carbonate and sodium carbonate, or synthetic zeolites It can also be obtained by reacting with At that time, a reaction accelerator such as 4-dimethylaminopyridine and a polymerization inhibitor such as methoquinone may be used.

  The target reactive group-containing cyclic phosphazene compound obtained by reacting such a substituted cyclic phosphonitrile having a hydroxy group with acrylic acid, methacrylic acid and derivatives thereof is filtered, solvent extracted, column chromatographed and re-reacted. It can be isolated and purified from the reaction system by ordinary methods such as crystallization.

Resin Composition The resin composition of the present invention comprises a flame retardant comprising the reactive group-containing cyclic phosphazene compound of the present invention and a resin component. One type of flame retardant composed of the reactive 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 polyphenylene ether, those obtained by introducing a reactive functional group such as a carboxyl group, an epoxy group, an amino group, a hydroxyl group, and an anhydrous dicarboxyl group into some or all of the polyphenylene ether by some method such as graft reaction or copolymerization. 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 polyimide 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 flame retardant comprising the reactive group-containing cyclic phosphazene compound 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, more preferably set to 0.5 to 40 parts by weight, and set to 1 to 30 parts by weight with respect to 100 parts by weight of the resin component in terms of solid content. More preferably. When the usage-amount of the flame retardant which consists of a reactive 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.

  Furthermore, the resin composition of the present invention is at least selected from a polymerizable material group consisting of a thermopolymerizable monomer, a thermopolymerizable oligomer, a photopolymerizable monomer, a photopolymerizable oligomer, a radiation polymerizable monomer, and a radiation polymerizable oligomer. One polymerizable material may be further included. In this case, the resin composition of the present invention has a polymerization effect of these polymerizable materials and a flame retardant comprising the reactive group-containing cyclic phosphazene compound of the present invention, so that electromagnetic waves such as heat, ultraviolet rays and visible rays, electron beams, etc. It can be cured by irradiation with an energy beam such as an electron beam.

  Examples of the polymerizable material used here include vinyl compounds, vinylidene compounds, diene compounds, cyclic compounds such as lactones, lactams and cyclic ethers, acrylic compounds, and epoxy compounds. More specifically, vinyl chloride, butadiene, styrene, impact polystyrene precursor, acrylonitrile-styrene resin (AS resin) precursor, acrylonitrile-butadiene-styrene resin (ABS resin) precursor, methyl methacrylate-butadiene-styrene. Resin (MBS resin) precursor, methyl methacrylate-acrylonitrile-butadiene-styrene resin (MABS resin) precursor, acrylonitrile-acrylic rubber-styrene resin (AAS resin) precursor, methyl (meth) acrylate, epoxy acrylate resin precursor, Epoxidized oil acrylate resin precursor, urethane acrylate resin precursor, polyester acrylate resin precursor, polyether acrylate resin precursor, acrylic acrylate resin precursor, unsaturated polyester resin Precursor, vinyl / acrylate resin precursor, vinyl ether resin precursor, polyene / thiol resin precursor, silicon acrylate resin precursor, polybutadiene acrylate resin precursor, polystyryl (ethyl) methacrylate resin precursor, polycarbonate acrylate resin precursor, Light or thermosetting polyimide resin precursor, light or thermosetting polyphenylene ether resin precursor, light or thermosetting silicon-containing resin precursor, light or thermosetting epoxy resin precursor, alicyclic epoxy resin precursor, A glycidyl ether epoxy resin precursor etc. can be mentioned. Among these, styrene, butadiene, an epoxy acrylate resin precursor, a urethane acrylate resin precursor, a polyester acrylate resin precursor, and the like are preferable. These polymerizable materials may be used alone or in combination of two or more.

  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 of 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 flame retardant comprising the reactive group-containing cyclic phosphazene compound of the present invention in the epoxy resin composition is: 0.1 to 80% by weight is preferable, and 0.5 to 70% by weight is more preferable. When the ratio of the flame retardant composed of the reactive group-containing cyclic phosphazene compound is less than 0.1% by weight, the resin molded body composed of the epoxy resin composition may not exhibit sufficient flame retardancy. On the other hand, if it exceeds 80% by weight, the original properties of the epoxy 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 flame retardant comprising the reactive group-containing cyclic phosphazene compound of the present invention reacts with the resin component, crosslinks, and is stably held in the cured product. It is hard to lose reliability. Moreover, the flame retardant comprising the reactive 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, In addition, low smoke generation can be imparted to the cured product. 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.

Polymerizable composition The polymerizable composition of the present invention contains a flame retardant comprising the reactive group-containing cyclic phosphazene compound of the present invention. Two or more flame retardants composed of a reactive group-containing cyclic phosphazene compound used here may be used.

  This polymerizable composition usually undergoes polymerization between flame retardants composed of a reactive group-containing cyclic phosphazene compound by heating or irradiation with energy rays such as ultraviolet rays or electron beams, and a polymer is obtained. When this polymerizable composition is polymerized by heating, it is preferable to use a polymerization initiator. Examples of the polymerization initiator used here include peroxides such as benzoyl peroxide, dicumyl peroxide and diisopropyl peroxydicarbonate, 2,2-azobisisobutyronitrile, azobis-2,4-dimethyl. Examples thereof include azo compounds such as valeronitrile, azobiscyclohexylnitrile, azobiscyanovaleric acid, and 2,2-azobis (2-methylbutyronitrile). When polymerizing a polymerizable composition by heating, a flame retardant composed of a reactive group-containing cyclic phosphazene compound is usually added to an organic solvent, and a polymerization initiator is added to this and heated to advance the polymerization reaction. Let And after completion | finish of reaction, a target polymer can be obtained by removing a solvent and a polymerization initiator by operation, such as concentration and washing | cleaning. For example, when obtaining a polymer of a flame retardant comprising a reactive group-containing cyclic phosphazene compound having an acryloyloxy group or a methacryloyloxy group, benzoyl peroxide is added in an organic solvent such as benzene, toluene, xylene, ether, tetrahydrofuran, etc. Used as a polymerization initiator, the reaction is carried out at a temperature from 50 ° C. to reflux of the solvent for 1 to 20 hours. And after completion | finish of reaction, a target polymer can be obtained by removing a solvent and a polymerization initiator by operation, such as concentration and washing | cleaning.

  On the other hand, when this polymerizable composition is polymerized by irradiation with energy rays, it is preferable to use a photopolymerization initiator and, if necessary, a sensitizer. Examples of the photopolymerization initiator used here include an acetophenone photopolymerization initiator, a benzophenone photopolymerization initiator, a benzoin photopolymerization initiator, a thioxanthone photopolymerization initiator, a sulfonium photopolymerization initiator, and an iodonium system. A photoinitiator etc. can be mentioned. Moreover, as a sensitizer, a tertiary amine etc. are used, for example. When the polymerizable composition is polymerized by irradiation with energy rays, usually a photopolymerization initiator and a sensitizer are added to the polymerizable composition as necessary, and various energy rays are irradiated to this. Then, the target polymer can be obtained. For example, when obtaining a polymer of a flame retardant comprising a reactive group-containing cyclic phosphazene compound having an acryloyloxy group or a methacryloyloxy group, benzophenone is added to the polymerizable composition as a photopolymerizable initiator, and 400 watts is added. When a high pressure mercury lamp is irradiated with ultraviolet rays for 30 seconds, the desired polymer can be obtained.

  The polymerizable composition of the present invention may contain other polymerizable material copolymerizable with a flame retardant comprising the reactive group-containing cyclic phosphazene compound of the present invention, if necessary. The polymerizable material used here is not particularly limited, but usually a compound having a vinyl group such as an aromatic vinyl monomer, a polar functional group-containing vinyl monomer and a vinyl ether monomer is preferably used. Two or more of these polymerizable materials may be used in combination. Examples of the aromatic vinyl monomer include styrene, methyl styrene, dimethyl styrene, ethyl styrene, isopropyl styrene, chlorostyrene, dichlorostyrene, and bromostyrene. Of these, styrene is particularly preferred. Examples of the polar functional group-containing vinyl monomer include vinyl chloride, vinylidene chloride, acrylonitrile, acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, and methacrylic. Propyl butyl, butyl acrylate, butyl methacrylate, octyl acrylate, octyl methacrylate, nonyl acrylate, nonyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, vinyl acrylate, vinyl methacrylate, etc. And vinyl esters such as vinyl acetate, vinyl butyrate, vinyl caproate and vinyl stearate. Of these, acrylonitrile, methyl acrylate and methyl methacrylate are particularly preferred. As the vinyl ether monomer, it is usually preferable to use divinyl ethers.

  Furthermore, the polymerizable composition of the present invention may contain a known reactive diluent or additive as necessary. 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, 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, the thing similar to what is used in the resin composition of this invention can be used.

  In addition, the polymeric composition of this invention is obtained by mixing each component uniformly.

  When the polymerizable composition of the present invention is heated at a temperature of 150 to 250 ° C. for 2 to 15 hours, a sufficient curing reaction proceeds and becomes a cured product (polymer). Can be a material. The cured product thus obtained is excellent in heat resistance properties, electrical properties, mechanical properties (particularly high glass transition temperature and adhesion) and high temperature reliability, and comprises a reactive group-containing cyclic phosphazene compound. Excellent flame retardancy and low smoke generation based on flame retardant. For this reason, this polymerizable composition can be widely used as a material for production of various resin molded products, a coating material, an adhesive, and other uses. In particular, this polymerizable composition is suitable for semiconductor encapsulation and circuit boards (particularly metal-clad laminates, printed wiring board substrates, printed wiring board adhesives, printed wiring board adhesive sheets, printed wiring board insulation). Suitable for use in the production of electrical / electronic parts such as conductive circuit protective films, conductive pastes for printed wiring boards, sealing agents for multilayer printed wiring boards, circuit protective agents, coverlay films, cover inks).

EXAMPLES The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited by these.
In the following, “unit” in “unit mol” means the smallest structural unit of the cyclic phosphazene compound, for example, (PNA ₂ ) for general formula (1) and (PNX ₂ ) for general formula (3). ). In the general formula (3), when X is chlorine, its 1 unit mol is 115.87 g.
In the following, unless otherwise specified, “%” and “parts” mean “% by weight” and “parts by weight”, respectively.

The phosphazene compounds obtained in the examples and synthesis examples were measured by ¹ H-NMR spectrum and ³¹ P-NMR spectrum, CHN elemental analysis, IR spectrum measurement, and chlorine by potentiometric titration using silver nitrate after alkali melting. It was identified based on the results of elemental (residual chlorine) analysis, phosphorus elemental analysis by ICP-AES after microwave wet decomposition, and 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 methods for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponified product of chemical products”. The hydroxyl value mgKOH / g was measured according to the method, and the hydroxyl equivalent weight g / eq. Converted to.

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

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

From the above analysis results, the products obtained in this step are [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) COCH ₃ ) (OC ₆ H ₅ ) ₅ ], [N ₃ P ₃ (OC ₆ H _3). (CH ₃ ) COCH ₃ ) ₂ (OC ₆ H ₅ ) ₄ ], [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) COCH ₃ ) ₃ (OC ₆ H ₅ ) ₃ ], and its average It was confirmed that the composition was an acyl group-containing cyclic phosphazene compound having a composition of [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) COCH ₃ ) _2.0 (OC ₆ H ₅ ) _4.0 ].

[Step 2: Buyer-Billiger oxidation step]
Into a 1 liter four-necked flask equipped with a thermometer, a stirrer and a dropping funnel, the compound obtained in Step 1 (187.8 g, 0.70 unit mol), trifluoroacetic anhydride (100 mL) and dichloromethane ( 200 mL) was added, and 60% hydrogen peroxide (48.7 g, 0.86 mol) was added dropwise at an internal temperature of 0 ° C. or lower. Thereafter, the mixture was stirred for 3 hours at an internal temperature of 25 ° C. After confirming the completion of the reaction, the reaction mixture was transferred to a separatory funnel, washed in order with 20% aqueous sodium hydrogen sulfite solution, saturated aqueous sodium bicarbonate solution and saturated brine, dried and concentrated to 193.3 g (yield 98.9). %) As a brown oily product. The analysis result of this product was as follows.

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

From the above analysis results, this product is [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OCOCH ₃ ) (OC ₆ H ₅ ) ₅ ], [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ )). OCOCH ₃ ) ₂ (OC ₆ H ₅ ) ₄ ], [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OCOCH ₃ ) ₃ (OC ₆ H ₅ ) ₃ ], with an average composition of [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OCOCH ₃ ) _2.0 (OC ₆ H ₅ ) _4.0 ] was confirmed to be an acyloxy group-containing cyclic phosphazene compound.

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

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

From the above analysis results, this product is [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OH) (OC ₆ H ₅ ) ₅ ], [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OH]. ) ₂ (OC ₆ H ₅ ) ₄ ], [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OH) ₃ (OC ₆ H ₅ ) ₃ ], the average composition of which is [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OH) _2.0 (OC ₆ H ₅ ) _4.0 ] was confirmed to be a hydroxy group-containing cyclic phosphazene compound.

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

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

From the above analysis results, this product is [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) COCH ₃ ) (OC ₆ H ₅ ) ₅ ], [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ )). COCH ₃ ) ₂ (OC ₆ H ₅ ) ₄ ], [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) COCH ₃ ) ₃ (OC ₆ H ₅ ) ₃ ], the average composition of which is [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) COCH ₃ ) _2.0 (OC ₆ H ₅ ) _4.0 ] was confirmed to be an acyl group-containing cyclic phosphazene compound.

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

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

From the above analysis results, this product is [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OCOCH ₃ ) (OC ₆ H ₅ ) ₅ ], [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ )). OCOCH ₃ ) ₂ (OC ₆ H ₅ ) ₄ ], [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OCOCH ₃ ) ₃ (OC ₆ H ₅ ) ₃ ], with an average composition of [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OCOCH ₃ ) _2.0 (OC ₆ H ₅ ) _4.0 ] was confirmed to be an acyloxy group-containing cyclic phosphazene compound.

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

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

From the above analysis results, this product is [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OH) (OC ₆ H ₅ ) ₅ ], [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OH]. ) ₂ (OC ₆ H ₅ ) ₄ ], [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OH) ₃ (OC ₆ H ₅ ) ₃ ], the average composition of which is [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OH) _2.0 (OC ₆ H ₅ ) _4.0 ] was confirmed to be a hydroxy group-containing cyclic phosphazene compound.

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

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

From the above analysis results, this product is [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ COCH ₃ ) (OC ₆ H ₅ ) ₅ ], [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ COCH ₃ ) ₂ (OC ₆ H ₅ ) ₄ ], [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ COCH ₃ ) ₃ (OC ₆ H ₅ ) ₃ ], average composition Was an acyl group-containing cyclic phosphazene compound of [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ COCH ₃ ) _1.9 (OC ₆ H ₅ ) _4.1 ].

[Step 2: Buyer-Billiger oxidation step]
A 1 liter four-necked flask equipped with a thermometer, stirrer, reflux condenser and dropping funnel was charged with the compound obtained in Step 1 (192.9 g, 0.70 unit mol) and chloroform (300 mL), 3-Chloroperbenzoic acid (207.1 g, 1.20 mol) was added in portions at an internal temperature of 0 ° C. or lower. The reaction mixture was stirred at reflux for 2 hours, then transferred to a separatory funnel and washed with a 20% aqueous sodium hydrogensulfite solution, a saturated aqueous sodium bicarbonate solution, and saturated brine. The chloroform layer was dried and concentrated under reduced pressure to obtain 185.0 g (yield 92.5%) of a brown oily product. The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.2 (6H), 2.3 (12H) 6.8 to 7.3 (24H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.4 to 10.6

From the above analysis results, this product is [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ OCOCH ₃ ) (OC ₆ H ₅ ) ₅ ], [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ OCOCH ₃ ) ₂ (OC ₆ H ₅ ) ₄ ], [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ OCOCH ₃ ) ₃ (OC ₆ H ₅ ) ₃ ] and its average composition Was an acyloxy group-containing cyclic phosphazene compound of [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ OCOCH ₃ ) _1.9 (OC ₆ H ₅ ) _4.1 ].

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

¹ H-NMR spectrum (in heavy acetone, δ, ppm):
2.0 (12H), 6.4 to 7.3 (26H)
◎ ³¹ P-NMR spectrum (in heavy acetone, δ, ppm):
Trimer (P = N) ₃ 9.2 to 10.2.
◎ CHNP elemental analysis:
Theoretical value C: 61.4%, H: 4.9%, N: 5.4%, P: 11.9%
Measured value C: 61.2%, H: 4.8%, N: 5.5%, P: 11.7%
◎ TOF-MS (m / z):
738, 782, 826
◎ Hydroxyl equivalent:
373 g / eq. (Theoretical value 374 g / eq.)

From the above analysis results, the product _{[N 3 P 3 (OC 6} H 2 (CH 3) 2 OH) (OC 6 H 5) 5], [N 3 P 3 (OC 6 H 2 (CH 3) ₂ OH) ₂ (OC ₆ H ₅ ) ₄ ], [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ OH) ₃ (OC ₆ H ₅ ) ₃ ], and the average composition thereof is [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ OH) _2.1 (OC ₆ H ₅ ) _3.9 ] was confirmed to be a hydroxy group-containing cyclic phosphazene compound.

Synthesis Example 4 (Production of cyclic phosphazene compound)
PHOSPHORUS-NITROGEN COMPOUNDS, H.P. R. According to the method described in ALLCOCK, 1972, page 151, ACADEMIC PRESS, 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.).

Example 1 (Production of acryloyloxy-containing cyclic phosphazene compound)
100.0 g of a hydroxy group-containing cyclic phosphazene compound (hydroxyl equivalent: 375 g / eq.) Synthesized in Synthesis Example 1 in a 1 liter flask equipped with a stirrer, a thermometer and a nitrogen introduction tube, acrylic acid chloride (50. 8 g, 0.561 mol), 250.0 g of synthetic zeolite (3A) and 700 mL of acetonitrile were charged and stirred under reflux for 24 hours. After completion of the reaction, the synthetic zeolite was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain 111.0 g (yield 97%) of a brown solid.

IR spectrum (KBr Pellet, cm ⁻¹ ):
1732, 1634, 1,171
◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.1, 5.8, 6.1, 6.4, 6.8 to 7.3
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 10.5
◎ TOF-MS (m / z):
862, 946, 1030

From the above analysis results, this product is [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OCOCH═CH ₂ ) (OC ₆ H ₅ ) ₅ ], [N ₃ P ₃ (OC ₆ H ₃ (CH _{3) OCOCH = CH 2) 2} (OC 6 H 5) 4], a mixture of _{[N 3 P 3 (OC 6} H 3 (CH 3) OCOCH = CH 2) 3 (OC 6 H 5) 3], It was confirmed that the average composition was an acryloyloxy-containing cyclic phosphazene compound having [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OCOCH═CH ₂ ) _2.01 (OC ₆ H ₅ ) _3.99 ].

Example 2 (Production of acryloyloxy-containing cyclic phosphazene compound)
100.0 g of a hydroxy group-containing cyclic phosphazene compound (hydroxyl equivalent: 371 g / eq.) Synthesized in Synthesis Example 2 in a 1 liter flask equipped with a stirrer, a thermometer and a nitrogen introduction tube, acrylic acid chloride (51. 2 g, 0.566 mol), 250.0 g of synthetic zeolite (3A) and 700 mL of acetonitrile were charged and stirred under reflux for 24 hours. After completion of the reaction, the synthetic zeolite was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain 109.9 g (yield 96%) of a brown solid.

IR spectrum (KBr Pellet, cm ⁻¹ ):
1732, 1634, 1,171
◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.0, 5.8, 6.1, 6.4, 6.9 to 7.4
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 10.5
◎ TOF-MS (m / z):
862, 946, 1030

From the above analysis results, this product is [N ₃ P ₃ (OC ₆ H ₃ (CH ₃ ) OCOCH═CH ₂ ) (OC ₆ H ₅ ) ₅ ], [N ₃ P ₃ (OC ₆ H ₃ (CH _{3) OCOCH = CH 2) 2} (OC 6 H 5) 4], a mixture of _{[N 3 P 3 (OC 6} H 3 (CH 3) OCOCH = CH 2) 3 (OC 6 H 5) 3], its average composition was calculated as follows acryloyloxy-containing cyclic phosphazene of _{[N 3 P 3 (OC 6} H 3 (CH 3) OCOCH = CH 2) 2.04 (OC 6 H 5) 3.96].

Example 3 (Production of a reactive group (acryloyloxy group) -containing cyclic phosphazene compound)
A hydroxy group-containing cyclic phosphazene compound (hydroxyl group equivalent: 373 g / eq.) 100.0 synthesized in Synthesis Example 3 in a 1 liter flask equipped with a stirrer, a thermometer and a nitrogen introduction tube, acrylic acid chloride (51. 0 g, 0.563 mol), 250.0 g of synthetic zeolite (3A) and 700 mL of acetonitrile were charged and stirred under reflux for 24 hours. After completion of the reaction, the synthetic zeolite was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain 109.9 g (yield 96%) of acryloyloxy-containing cyclic phosphazene as a brown solid.

IR spectrum (KBr Pellet, cm ⁻¹ ):
1732, 1634, 1,171
◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.0, 5.8, 6.1, 6.4 to 7.3
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 10.5
TOF-MS (m / z):
890, 988, 1086

From the above analysis results, this product is [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ OCOCH═CH ₂ ) (OC ₆ H ₅ ) ₅ ], [N ₃ P ₃ (OC ₆ H ₂ ( CH ₃ ) ₂ OCOCH═CH ₂ ) ₂ (OC ₆ H ₅ ) ₄ ], [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ OCOCH═CH ₂ ) ₃ (OC ₆ H ₅ ) ₃ ] And an average composition of [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ OCOCH═CH ₂ ) _2.1 (OC ₆ H ₅ ) _3.9 ] is an acryloyloxy group-containing cyclic phosphazene compound. It was confirmed.

Example 4 (Production of methacryloyloxy-containing cyclic phosphazene compound)
100.0 g of a hydroxy group-containing cyclic phosphazene compound (hydroxyl equivalent: 375 g / eq.) Synthesized in Synthesis Example 1 in a 1 liter flask equipped with a stirrer, a thermometer and a nitrogen introduction tube, methacrylic acid chloride (58. 6 g, 0.561 mol), 250.0 g of synthetic zeolite (3A) and 700 mL of acetonitrile were charged and stirred under reflux for 24 hours. After completion of the reaction, the synthetic zeolite was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain 113.4 g (yield 96%) of a brown solid.

IR spectrum (KBr Pellet, cm ⁻¹ ):
1728, 1634, 1,171
◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.1, 5.5, 6.1, 6.8 to 7.3
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 10.5
◎ TOF-MS (m / z):
890, 988, 1086

From the above analysis results, the product _{[N 3 P 3 (OC 6} H 3 (CH 3) OCOC (CH 3) = CH 2) (OC 6 H 5) 5], [N 3 P 3 (OC 6 _{H 3 (CH 3) OCOC (} CH 3) = CH 2) 2 (OC 6 H 5) 4], [N 3 P 3 (OC 6 H 3 (CH 3) OCOC (CH 3) = CH 2) 3 ( OC ₆ H _{5) 3]} is a mixture of the average composition _{[N 3 P 3 (OC 6} H 3 (CH 3) OCOC (CH 3) = CH 2) 2.01 (OC 6 H 5) 3. ₉₉ ] methacryloyloxy-containing cyclic phosphazene compound.

Example 5 (Production of methacryloyloxy-containing cyclic phosphazene compound)
100.0 g of a hydroxy group-containing cyclic phosphazene compound (hydroxyl equivalent: 371 g / eq.) Synthesized in Synthesis Example 2 in a 1 liter flask equipped with a stirrer, a thermometer and a nitrogen introduction tube, methacrylic acid chloride (51. 2 g, 0.566 mol), 250.0 g of synthetic zeolite (3A) and 700 mL of acetonitrile were charged and stirred under reflux for 24 hours. After completion of the reaction, the synthetic zeolite was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain 112.4 g (yield 95%) of a brown solid.

IR spectrum (KBr Pellet, cm ⁻¹ ):
1728, 1634, 1,171
◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.0, 5.5, 6.1, 6.9-7.4
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 10.5
◎ TOF-MS (m / z):
890, 988, 1086

From the above analysis results, the product _{[N 3 P 3 (OC 6} H 3 (CH 3) OCOC (CH 3) = CH 2) (OC 6 H 5) 5], [N 3 P 3 (OC 6 _{H 3 (CH 3) OCOC (} CH 3) = CH 2) 2 (OC 6 H 5) 4], [N 3 P 3 (OC 6 H 3 (CH 3) OCOC (CH 3) = CH 2) 3 ( OC ₆ H _{5) 3]} is a mixture of the average composition _{[N 3 P 3 (OC 6} H 3 (CH 3) OCOC (CH 3) = CH 2) 2.04 (OC 6 H 5) 3. ₉₆ ] methacryloyloxy-containing cyclic phosphazene.

Example 6 (Production of methacryloyloxy group-containing cyclic phosphazene compound)
Hydroxy group-containing cyclic phosphazene compound synthesized in Synthesis Example 3 (hydroxyl equivalent: 373 g / eq.), Methacrylic acid chloride (51.0 g, 0) in a 1 liter flask equipped with a stirrer, thermometer and nitrogen introduction tube .563 mol), 250.0 g of synthetic zeolite (3A) and 700 mL of acetonitrile were charged and stirred under reflux for 24 hours. After completion of the reaction, the synthetic zeolite was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain 113.6 g of a brown solid (yield 96%).

IR spectrum (KBr Pellet, cm ⁻¹ ):
1728, 1634, 1,171
◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.0, 5.5, 6.1, 6.4 to 7.3
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 10.5
◎ TOF-MS (m / z):
918, 1029, 1142

From the above analysis results, this product is obtained from [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ OCOC (CH ₃ ) ═CH ₂ ) (OC ₆ H ₅ ) ₅ ], [N ₃ P ₃ (OC _{6 H 2 (CH 3) 2} OCOC (CH 3) = CH 2) 2 (OC 6 H 5) 4], [N 3 P 3 (OC 6 H 2 (CH 3) 2 OCOC (CH 3) = CH 2 ) ₃ (OC ₆ H ₅ ) ₃ ], the average composition of which is [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ OCOC (CH ₃ ) ═CH ₂ ) _2.1 (OC ₆ H ₅ ) It was confirmed that it was a methacryloyloxy group-containing cyclic phosphazene compound of _3.9 ].

Examples 7 to 12 and Comparative Example 1 (Preparation of resin composition)
Table 1 shows the reactive group-containing cyclic phosphazene compound produced in Examples 1 to 6 or the cyclic phosphazene compound produced in Synthesis Example 4 with respect to 100 parts of PC resin (polycarbonate resin: “Iupilon S3000” manufactured by Mitsubishi Gas Chemical Co., Ltd.). And melt kneaded at 220 ° C. for 7 minutes.

  The resin composition thus obtained was heated and pressed at 200 ° C. for 10 minutes using a press molding machine to obtain a sheet having a thickness of 1/24 inch. At this stage, the reactive group of the reactive group-containing cyclic phosphazene compound contained in the resin composition was not reacted. Both surfaces of this sheet were irradiated with an electron beam at room temperature under the conditions of an acceleration voltage of 200 KV, an irradiation dose of 2 MRad, and an absorbed dose of 10 KGy. A specimen having a length of 5 inches, a width of 0.5 inches, and a thickness of 1/24 inches was cut out from the cured sheet thus obtained, and a flammability test (UL-94 flame retardant test) was performed on the specimen. In addition, the heat distortion temperature and blooming property were examined. The evaluation method for each item is as follows. The results are shown in Table 1.

(Flammability test)
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.

(Heat deformation temperature)
According to ASTM D-648, the load was tested at 1.82 MPa.

(High temperature reliability: blooming)
The test piece was heated at 150 ° C. for 4 hours, and the state of seepage on the surface of the test piece (leaching state from inside of the test piece: blooming property) was visually observed. The criteria for evaluation are as follows.
A: No oozing is observed.
◯: Almost no seepage is seen.
Δ: Some exudation is observed.
X: Significant exudation is observed.

  As is apparent from Table 1, the sheets (resin molded bodies) made of the resin compositions of Examples 7 to 12 are superior in flame retardancy and have a high heat distortion temperature compared to those of Comparative Example 1. Excellent mechanical properties. Moreover, the bleedout of the flame retardant composed of the phosphazene compound evaluated by blooming property is not substantially observed, and the adhesiveness is excellent.

Example 13 (Production of a flame retardant comprising an oligomer of a reactive group-containing cyclic phosphazene compound)
The reactive group (acryloyloxy group) -containing cyclic phosphazene compound produced in Example 1 and 400 ml of toluene were charged into a 1 liter flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube. To this solution, 1.0 g of benzoyl peroxide was added under a nitrogen atmosphere, and then reacted at 90 ° C. for 10 hours. After the reaction, toluene was concentrated and poured into a large excess amount of methanol, and the precipitated solid was separated by filtration and dried at 60 ° C. under reduced pressure for 12 hours. As a result, 97.9 g of a pale yellow powdered solid product, which is a flame retardant comprising an oligomer of a methacryloyloxy group-containing cyclic phosphazene compound, was obtained. An IR spectrum of this product showed that the double bond of the methacryloyloxy group disappeared.

Example 14 (Production of a flame retardant comprising an oligomer of a reactive group-containing cyclic phosphazene compound)
Example 13 and Example 13 except that the reactive group (acryloyloxy group) -containing cyclic phosphazene compound produced in Example 2 was used instead of the reactive group (acryloyloxy group) -containing cyclic phosphazene compound produced in Example 1 By operating in the same manner, 96.9 g of a pale yellow powdery solid product which is an oligomer of an acryloyloxy group-containing cyclic phosphazene compound and styrene was obtained. The IR spectrum of this product showed the disappearance of the double bond, and the production of a flame retardant comprising the above oligomer obtained by reacting styrene with a reactive group (acryloyloxy group) -containing cyclic phosphazene compound as a copolymerization component. showed that.

Example 15 (Production of flame retardant comprising oligomer of reactive group-containing cyclic phosphazene compound)
Example 13 and Example 13 except that the reactive group (acryloyloxy group) -containing cyclic phosphazene compound produced in Example 2 was used instead of the reactive group (acryloyloxy group) -containing cyclic phosphazene compound produced in Example 1 The same operation was performed to obtain 97.5 g of a pale yellow powdered solid product which is an oligomer of an acryloyloxy group-containing cyclic phosphazene compound and styrene. The IR spectrum of this product showed the disappearance of the double bond, and the production of a flame retardant comprising the above oligomer obtained by reacting styrene with a reactive group (acryloyloxy group) -containing cyclic phosphazene compound as a copolymerization component. showed that.

Example 16 (Production of a flame retardant comprising an oligomer of a reactive group-containing cyclic phosphazene compound)
Example 13 and Example 13 except that the reactive group (acryloyloxy group) -containing cyclic phosphazene compound produced in Example 1 was replaced by the reactive group (methacryloyloxy group) -containing cyclic phosphazene compound produced in Example 4 By operating in the same manner, 98.0 g of a pale yellow powdered solid product which is an oligomer of an acryloyloxy group-containing cyclic phosphazene compound and styrene was obtained. The IR spectrum of this product showed the disappearance of the double bond, and the production of a flame retardant comprising the above oligomer obtained by reacting styrene with a reactive group (acryloyloxy group) -containing cyclic phosphazene compound as a copolymerization component. showed that.

Example 17 (Production of a flame retardant comprising an oligomer of a reactive group-containing cyclic phosphazene compound)
Example 13 and Example 13 except that the reactive group (methacryloyloxy group) -containing cyclic phosphazene compound produced in Example 5 was used instead of the reactive group (acryloyloxy group) -containing cyclic phosphazene compound produced in Example 1. By operating in the same manner, 97.4 g of a pale yellow powdered solid product which is an oligomer of an acryloyloxy group-containing cyclic phosphazene compound and styrene was obtained. The IR spectrum of this product showed the disappearance of the double bond, and the production of a flame retardant comprising the above oligomer obtained by reacting styrene with a reactive group (acryloyloxy group) -containing cyclic phosphazene compound as a copolymerization component. showed that.

Example 18 (Production of a flame retardant comprising an oligomer of a reactive group-containing cyclic phosphazene compound)
Example 13 and Example 13 except that the reactive group (methacryloyloxy group) -containing cyclic phosphazene compound produced in Example 6 was used instead of the reactive group (acryloyloxy group) -containing cyclic phosphazene compound produced in Example 1. The same operation was performed to obtain 98.2 g of a pale yellow powdery solid product which is an oligomer of an acryloyloxy group-containing cyclic phosphazene compound and styrene. The IR spectrum of this product showed the disappearance of the double bond, and the production of a flame retardant comprising the above oligomer obtained by reacting styrene with a reactive group (acryloyloxy group) -containing cyclic phosphazene compound as a copolymerization component. Was showing.

Examples 19 to 24 and Comparative Examples 3 and 4 (Preparation of resin composition)
Obtained by oligomers produced in Examples 13 to 18 or Synthesis Example 4 with respect to 100 parts of ABS resin (“Santac” manufactured by Mitsui Chemicals, Inc.) or PC resin (polycarbonate resin: “Iupilon S3000” manufactured by Mitsubishi Gas Chemical Co., Ltd.) The obtained cyclic phosphazene compound was added at a ratio shown in Table 2, and melt kneaded at 180 to 220 ° C. for 5 minutes. The resin composition thus obtained was heated and pressed at 150 to 200 ° C. for 10 minutes using a press molding machine to obtain a sheet having a thickness of 1.2 mm. The sheet was subjected to UL-94 flame retardancy test, and the heat distortion temperature and blooming property were examined. The test method for each item is the same as in Examples 7 to 12 and Comparative Example 1. The results are shown in Table 2.

  As is clear from Table 2, the sheets (resin molded bodies) made of the resin compositions of Examples 19 to 30 are superior in flame retardancy and have a high heat distortion temperature compared to those of Comparative Examples 2 and 3. Therefore, the mechanical properties are excellent, and further, bleedout of the phosphazene compound evaluated by blooming property is not substantially observed, and the adhesiveness is excellent.

Examples 31 to 24 and Comparative Example 4 (Preparation of resin composition)
Epicote 1001 which is a bisphenol A type epoxy resin (trade name of Japan Epoxy Resin Co., Ltd .: epoxy equivalent 456 g / eq., Resin solid content 70%) 651 parts, YDCN-704P which is a cresol novolac epoxy resin (Toto Kasei Co., Ltd.) Product name: Epoxy equivalent 210 g / eq., Resin solid content 70% 300 parts, novolac type phenolic resin BRG-558 (Showa Polymer Co., Ltd. product name: hydroxyl value 106 g / eq., Resin solid content 70 %) Reactive group-containing cyclic phosphazene compounds or oligomers obtained in Examples 1 to 6 and 13 to 18 with respect to a mixture of 303 parts, 361 parts of aluminum hydroxide and 0.9 parts of 2-ethyl-4-methylimidazole Alternatively, the cyclic phosphazene compound obtained in Synthesis Example 4 was added at the ratio shown in Table 3. And, g of propylene glycol monomethyl ether (PGM) to prepare a resin solid content of 65% epoxy resin varnish as a solvent.

  Next, the prepared epoxy resin varnish was applied and impregnated on a 180 μm glass woven fabric, and dried at a temperature of 160 ° C. 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 4.2 MPa for 90 minutes to obtain a glass epoxy laminated plate having a thickness of 1.2 mm.

  A test piece having a length of 5 inches, a width of 0.5 inches and a thickness of 1.2 mm was cut out from the glass epoxy laminate, and its combustibility, glass transition temperature (Tg) and heat resistance were examined. Here, the flammability was evaluated by a method based on the UL-94 standard vertical combustion test, as in Examples 6 to 9 and Comparative Example 2. The glass transition temperature was measured by DSC according to JIS K 7121-1987 “Method for measuring plastic transition temperature”. Furthermore, for heat resistance as an evaluation of high temperature reliability, the test piece was treated at 290 ° C. for 20 minutes, and changes in appearance were observed. The results are shown in Table 3. In the results of heat resistance in Table 3, “Yes” means that there is no bleed out of the reactive group-containing cyclic phosphazene compound and the like added to the above-mentioned mixture, and “No” indicates that bleed out. It means that.

  As is clear from Table 3, the glass epoxy laminate (resin molded body) made of the resin compositions of Examples 31 to 42 is superior in flame retardancy to that of Comparative Example 5, and has a glass transition temperature. Since it is high, the mechanical properties are excellent, and furthermore, the bleedout of the phosphazene compound evaluated by heat resistance is substantially not seen, and the adhesion is excellent.

Synthesis Example 5 (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, 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. 2,500 g of the resulting 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 748 g of a soluble polyimide resin. Obtained.

Synthesis Example 6 (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 further washing with ion-exchanged water. The obtained solution was concentrated and further dried under reduced pressure to obtain 100.9 g of a PPE oligomer having hydroxyl groups at both ends. This oligomer has a number average molecular weight of 860, a weight average molecular weight of 1150, and a hydroxyl group equivalent of 454 g / eq. Met.

  Next, in a 1 liter glass flask equipped with a stirrer, a thermometer and a reflux condenser, 50 g of PPE oligomer (hydroxyl group 0.11 mol) having hydroxyl groups at both ends obtained in the above step, potassium carbonate 15 .3 g and 400 ml of acetone were charged and refluxed for 3 hours under nitrogen. Thereafter, 22.1 g of 6-bromo-1-hexanol was added dropwise over 1 hour, and the mixture was refluxed for 24 hours after completion of the addition. After the reaction, the reaction solution was neutralized with hydrochloric acid, a large amount of deionized water was added to precipitate the product, and toluene was added for extraction. The obtained solution was concentrated and dropped into methanol for reprecipitation, and the solid was recovered by filtration, followed by drying under reduced pressure. As a result, 55.5 g of a PPE oligomer having hydroxyl hexyl groups at both ends was obtained. This oligomer has a number average molecular weight of 1,045, a weight average molecular weight of 1,390, and a hydroxyl group equivalent of 551 g / eq. Met.

  Next, in a 0.3 liter glass flask equipped with a stirrer, a thermometer and a reflux condenser, 30 g of PPE oligomer having hydroxyl hexyl groups at both ends obtained in the above step, 6.0 g of acrylic acid chloride 7.0 g of triethylamine toluene, 0.03 g of hydroquinone and 100 ml of toluene were charged. This was heated to reflux and reacted for 2 hours. After the reaction, the reaction mixture was concentrated and 60 ml of toluene was added. This was washed twice with 2% hydrochloric acid and then three times with deionized water. Thereby, toluene was distilled off under reduced pressure to obtain 30.3 g of a PPE oligomer having acrylate groups at both ends. The PPE oligomer having acrylate groups at both ends had a number average molecular weight of 1,190 and a weight average molecular weight of 1,590.

Examples 43 to 48 (Preparation of resin composition)
50.0 g of the soluble polyimide resin obtained in Synthesis Example 5, 20.0 g of the reactive group-containing cyclic phosphazene compound synthesized in Examples 1 to 6, EO-modified bisphenol A diacrylate (trade name “Shin-Nakamura Chemical Co., Ltd.” 15.0 g of NK ester A-BPE-30 ") and 1.0 g of 1-hydroxycyclohexyl phenyl ketone (trade name" IRGACURE 184 "from Ciba Specialty Chemicals) as a photoinitiator and bis (2,4,6- A varnish of a photosensitive resin composition was prepared by mixing 1.0 g of trimethylbenzoyl) phenylphosphine oxide (trade name “IRGACURE 819” from Ciba Specialty Chemicals).

  By applying this varnish on a PET film (thickness 25 μm) so that the thickness after drying is 25 μm, the organic solvent is removed by drying at 45 ° C. for 5 minutes and then at 65 ° C. for 5 minutes. A photosensitive film layer having a B-stage formed thereon was formed, and a photosensitive dry film resist in which a B-staged photosensitive film was laminated on a PET film was produced. A protective film made of a copolymer of polyethylene resin and ethylene vinyl alcohol resin (trade name “Protect (# 6221F) film” from Sekisui Chemical Co., Ltd.)) is laminated on the photosensitive film layer of this photosensitive dry film resist ( Conditions: roll temperature 40 ° C., nip pressure 1500 Pa · m) to prepare a sheet-like photosensitive dry film resist having a three-layer structure. When a developability test was performed on this, fine holes of 100 μmφ and lines of 100 μm / 100 μm could be developed. Moreover, the blooming property as an evaluation of the flammability (flame retardancy), the glass transition temperature and the high temperature reliability of the sheet obtained by curing the photosensitive dry film resist was measured. The results are shown in Table 5. Here, the flammability was evaluated in the same manner as in Examples 7 to 12 and Comparative Example 1. Moreover, the glass transition temperature was measured by the same method as Examples 31-42 and Comparative Example 4. Furthermore, blooming property was evaluated as follows. The results are shown in Table 4.

The cured sheet was heated at 170 ° C. for 6 hours, and the oozing state (leaching state from the inside of the sheet) on the sheet surface was visually observed. The criteria for evaluation are as follows.
A: No oozing is observed.
○: Almost no seepage is seen.
Δ: Some exudation is observed.
X: Significant exudation is observed.

Comparative Example 5 (Preparation of resin composition)
A resin composition was obtained in the same manner as in Examples 43 to 48 except that 20.0 g of the cyclic phosphazene compound produced in Synthesis Example 4 was used instead of the cyclic phosphazene compound produced in Example 1. A cured sheet was prepared using this resin composition, and the flammability (flame retardancy), glass transition temperature, and blooming property of this sheet were measured under the same methods and conditions as in Examples 43 to 48. The results are shown in Table 4.

  As is clear from Table 4, the cured sheets of Examples 43 to 48 are superior in flame retardancy and have a high glass transition temperature as compared with those in Comparative Example 5, and are excellent in mechanical properties and blooming properties. No bleed-out of the cyclic phosphazene compound evaluated in (1) was observed, and the adhesion was excellent.

Examples 49 to 54 (Preparation of resin composition)
45.0 g of a PPE oligomer having an acrylate group at both ends obtained in Synthesis Example 6, 15.0 g of the cyclic phosphazene compound obtained in Examples 1 to 6, EO-modified bisphenol A diacrylate (of Shin-Nakamura Chemical Co., Ltd.) Product name “NK Ester A-BPE-10”) 5.0 g, 2,2′-azobisisobutyronitrile (AIBN) 0.5 g and toluene 60 ml were mixed and dissolved, then melted and degassed at 150 ° C. Thus, a resin composition was obtained. This resin composition was molded into a sheet and heated at 200 ° C. for 6 hours. Thereby, a cured resin sheet was obtained. About this resin sheet, it carried out similarly to Examples 43-48, and measured blooming property, glass transition temperature, and combustibility (flame retardance). The results are shown in Table 5.

Comparative Example 6 (Preparation of resin composition)
A resin composition was obtained in the same manner as in Example 29 except that 15.0 g of the cyclic phosphazene compound produced in Synthesis Example 4 was used instead of the cyclic phosphazene compound produced in Examples 1-6. And this resin composition was shape | molded and hardened by the method and conditions similar to Example 29, and the cured resin sheet was obtained. About this resin sheet, it carried out similarly to Examples 49-54, and measured blooming property, glass transition temperature, and combustibility (flame retardance). The results are shown in Table 5.

As is clear from Table 5, the cured sheets of Examples 49 to 54 are superior in flame retardancy and have a high glass transition temperature as compared with those in Comparative Example 6, and are excellent in mechanical properties and blooming properties. No bleed-out of the cyclic phosphazene compound evaluated in (1) was observed, and the adhesion was excellent.

Claims (9)

A reactive group-containing cyclic phosphazene compound represented by the following formula (1).
(In the formula (1), n represents an integer of 3 to 8, A represents a group selected from the group consisting of the following A1, A2, and A3 groups, and at least one is an A3 group.
A1 group: an alkoxy group having 1 to 8 carbon atoms, which may be substituted with at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group.
A2 group: an aryloxy group having 6 to 20 carbon atoms in which at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group may be substituted.
A3 group: acryloyloxy group-substituted phenyl group and methacrylonitrile group selected from the group consisting of acryloyloxy group-substituted phenyl group represented by the following formula (2).
In formula (2), E ^{1 to} E ⁵ are each independently at least one of an acryloyloxy group or a methacryloyloxy group, and at least one of them is an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and It is at least one group selected from aryl groups, and the remainder represents a hydrogen atom. )   In the formula (1), the A3 group is a 2-methyl-4-acryloyloxy-phenyloxy group, a 3-methyl-4-acryloyloxy-phenyloxy group, a 3,5-dimethyl-4-acryloyloxy-phenyloxy group, At least one selected from the group consisting of 2-methyl-4-methacryloyloxy-phenyloxy group, 3-methyl-4-methacryloyloxy-phenyloxy group and 3,5-dimethyl-4-methacryloyloxy-phenyloxy group The reactive group-containing cyclic phosphazene compound according to claim 1.   The reactive group-containing cyclic phosphazene compound according to claim 1 or 2, wherein 1 to (2n-2) of 2n A's are A3 groups in formula (1).   The reactive group containing cyclic phosphazene compound in any one of Claim 1 to 3 whose n of Formula (1) is 3 or 4. N comprises different two or more kinds of the reactive group-containing cyclic phosphazene compound, a reactive group-containing cyclic phosphazene compound according to any one of claims 1 to 4 of formula (1). Selected from the group consisting of the following G1, G2, and G3 groups such that at least one of the halogen atoms of the cyclic phosphonitrile dihalide represented by the following formula (3) is substituted by the following G3 group: Step 1 for producing an acyl group-containing cyclic phosphonitrile substitution product by substitution with a group,
(In formula (3), n represents an integer of 3 to 8, and X represents a halogen atom.
G1 group: an alkoxy group having 1 to 8 carbon atoms in which at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group may be substituted.
G2 group: an aryloxy group having 6 to 20 carbon atoms in which at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group may be substituted.
G3 group: a group selected from the group consisting of an acyl-substituted phenyloxy group represented by the following formula (4).
In formula (4), at least one of L ^{1 to} L ⁵ is an acyl group, and at least one is at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group. And the remainder represents a hydrogen atom. )
Step 2 for producing the acyloxy group-containing cyclic phosphonitrile substitute by oxidizing the acyl group-containing cyclic phosphonitrile substitute;
Step 3 for producing a hydroxy group-containing cyclic phosphonitrile substitute by deacylating the acyloxy group-containing cyclic phosphonitrile substitute;
The hydroxy group-containing cyclic phosphonitrile substituents and acrylic acid, a step 4 of reacting the methacrylic acid or a derivative thereof,
The manufacturing method of the reactive group containing cyclic phosphazene compound of Claim 1 containing this.   A resin composition comprising a resin component and the reactive group-containing cyclic phosphazene compound according to any one of claims 1 to 5.   The resin according to claim 7, wherein the resin component is selected from the group consisting of an epoxy resin, a polyimide resin, a bismaleimide resin, a cyanate ester resin, a bismaleimide-cyanate ester resin, and a modified polyphenylene ether resin. Composition.   The resin molding which consists of a resin composition of Claim 7 or 8.