JP5177730B2 - Hydroxyl group-containing cyclic phosphazene compound and process for producing the same - Google Patents

Description

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

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

  Among these, metal hydrate flame retardants exhibit a flame retardant effect because the endothermic reaction of dehydration pyrolysis and the accompanying water release occur in a temperature range that overlaps the thermal decomposition and combustion start temperature of the synthetic resin. However, in order to enhance the effect, it is necessary to add a large amount to the resin composition. For this reason, the molded article of the resin composition containing this type of flame retardant has a drawback that the mechanical strength is impaired. On the other hand, among phosphoric flame retardants, phosphoric acid ester and condensed phosphoric acid ester types have a plastic effect, so if they are added in a large amount to the resin composition in order to increase flame retardancy, resin molded products There are disadvantages such as a decrease in mechanical strength. In addition, phosphate ester-based, phosphate amide-based, and ammonium polyphosphate-based materials are easily hydrolyzed. Therefore, in materials for manufacturing resin molded products that require mechanical and electrical long-term reliability. It is practically difficult to use. In contrast, phosphazene-based flame retardants have a smaller plastic effect and hydrolyzability than other phosphorus-based flame retardants, and can increase the amount added to the resin composition. Thus, although it is being frequently used as an effective flame retardant for synthetic resins, if the amount added to the resin composition is increased, the reliability of the resin molded product at high temperatures may be impaired. Specifically, in the case of a thermoplastic resin-based resin composition, the phosphazene-based flame retardant is likely to bleed out (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 2005-8835 A JP 2005-248134 A

  Then, the improvement for improving the reliability (high temperature reliability) of the resin molded product under high temperature is examined for the phosphazene flame retardant, and as an example, Patent Documents 6 to 10 have a hydroxyl group. A phosphazene flame retardant and an epoxy resin composition using the same are disclosed. This type of phosphazene-based flame retardant is unlikely to impair the high temperature reliability of the resin molded product even when added in a large amount to the resin composition. It is insufficient in terms of the essential effect that it is difficult to effectively increase, and it also impairs the mechanical properties (particularly high glass transition temperature) of the resin molded product.

Japanese Patent Laid-Open No. 6-247989 JP-A-10-259292 JP 2003-342339 A JP 2004-143465 A JP 2004-143466 A

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

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

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

In formula (1), n shows the integer of 3-15. A represents a group selected from the group consisting of the following A1, A2 and A3 groups, and at least one is an A3 group.
A1 group: alkyl group having 1 to 6 carbon atoms, optionally substituted with at least one group selected from an alkenyl group and an aryl group, an alkoxy group having 1 to 8 carbon atoms.
A2 group: alkyl group having 1 to 6 carbon atoms, optionally substituted with at least one group selected from an alkenyl group and an aryl group, an aryloxy group having 6 to 20 carbon atoms.
A3 group: a hydroxyphenyl-substituted phenyloxy group represented by the following formula (3), a hydroxyphenyl-substituted indanoxy group represented by the following formula (4), and a hydroxyindan-substituted phenyloxy group represented by the following formula (5) A group selected from the group consisting of

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

In Formula (4) and Formula (5), R ¹ and R ² represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, or a phenyl group.

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

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

式（６）中、ｎは３〜１５の整数を示し、Ｘはハロゲン原子を示す。

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

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

Z in formula (8), formula (9) and formula (10) represents a protecting group capable of forming an OH group when eliminated. Y in Formula (8) represents O, S, SO ₂ , CH ₂ , CHCH ₃ , C (CH ₃ ) CH ₂ CH ₃ or CO. R ¹ and R ^{2 in} Formula (9) and Formula (10) represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, or a phenyl group.

[Step B]
A step of removing the protecting group (Z) from the E3 group of the substituted cyclic phosphonitrile obtained in step A.

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

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

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

  Since the method for producing a hydroxyl group-containing cyclic phosphazene compound according to the present invention includes the step A and the step B as described above, the hydroxyl group-containing cyclic phosphazene compound having the specific structure as described above according to the present invention is produced. can do.

  Since the resin composition of the present invention contains the hydroxyl group-containing cyclic phosphazene compound of the present invention as a flame retardant, it is possible to obtain a resin molded product exhibiting practical mechanical properties and flame retardancy and having high temperature reliability. it can.

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

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

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

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

[A1 group]
An alkoxy group having 1 to 8 carbon atoms; The alkoxy group, an alkyl group having 1 to 6 carbon atoms, optionally substituted with at least one group selected from an alkenyl group and an aryl group.
Examples of such alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy, and n-hexyloxy. Group, n-heptyloxy group, n-octyloxy group, ethenyloxy group, 1-propenyloxy group, 2-propenyloxy group, isopropenyloxy group, 3-butenyloxy group, 2-methyl-2-propenyloxy group, 4 -Pentenyloxy group, 2-hexenyloxy group, 1-propyl-2-butenyloxy group, 5-octenyloxy group, benzyloxy group, 2-phenylethoxy group and the like can be mentioned. Among these, a methoxy group, an ethoxy group, an n-propoxy group, a 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; The aryloxy group, an alkyl group having 1 to 6 carbon atoms, optionally substituted with at least one group selected from an alkenyl group and an aryl group.
Examples of such aryloxy groups include phenoxy group, methylphenoxy group, dimethylphenoxy group, ethylphenoxy group, ethylmethylphenoxy group, diethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, isopropylmethylphenoxy group, Isopropylethylphenoxy group, diisopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-pentylphenoxy group, n-hexylphenoxy group, ethenylphenoxy group, 1-propenylphenoxy group, 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 hydroxyphenyl-substituted phenyloxy group represented by the following formula (2) (that is, a 4′-hydroxyphenyl-4-phenyloxy group), a hydroxyphenyl-substituted phenyloxy group represented by the following formula (3), and the following formula A group selected from the group consisting of a hydroxyphenyl-substituted indanoxy group represented by (4) and a hydroxyindan-substituted phenyloxy group represented by the following formula (5).

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

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

  Examples of the hydroxyphenyl-substituted indanoxy group represented by the formula (4) and the hydroxyindan-substituted phenyloxy group represented by the formula (5) include 1,3,3-trimethyl-1- (4-hydroxyphenyl) indan- 6-ol, 1,3,3-trimethyl-1- (4-hydroxy-3-methylphenyl) indan-6-ol, 1,3,3-trimethyl-1- (4-hydroxy-3,5-di -Tert-butylphenyl) indan-6-ol, 1,3,3-trimethyl-5-tert-butyl-1- (4-hydroxy-3-tert-butylphenyl) indan-6-ol, 1,3, 3-trimethyl-5-tert-butyl-1- (4-hydroxy-3,5-di-tert-butylphenyl) indan-6-ol, 1,3,3- Limethyl-5-iso-propyl-1- (4-hydroxy-3-iso-propylphenyl) indan-6-ol and 1,3,3-trimethyl-5-phenyl-1- (4-hydroxy-3-phenyl) And a residue obtained by removing hydrogen from one hydroxyl group of two hydroxyl groups of an indane compound such as phenyl) indan-6-ol. That is, examples of the hydroxyphenyl-substituted indanoxy group represented by the formula (4) include a residue obtained by removing hydrogen from the hydroxyl group bonded to the 6-position of indan in the above-described various indan compounds. . Examples of the hydroxyindane-substituted phenyloxy group represented by the formula (5) include a residue obtained by removing hydrogen from the hydroxyl group of a phenol group bonded to the 1-position of indane in the various indane compounds described above. it can.

  Preferred as the above-mentioned A3 group are 4′-hydroxyphenyl-4-phenyloxy group, 4′-hydroxyphenyloxy-4-phenyloxy group, 4′-hydroxyphenylthio-4-phenyloxy group, 4′- Hydroxyphenylsulfonyl-4-phenyloxy group, 4′-hydroxyphenylisopropylidene-4-phenyloxy group, 4′-hydroxybenzoyl-4-phenyloxy group and 1,3,3-trimethyl-1- (4-hydroxy) Hydrogen is removed from one of the two hydroxyl groups of phenyl) indan-6-ol and 1,3,3-trimethyl-1- (4-hydroxy-3-methylphenyl) indan-6-ol. Residue. Among these, 4'-hydroxyphenyl-4-phenyloxy group, 4'-hydroxyphenyloxy-4-phenyloxy group, 4'-hydroxyphenylsulfonyl-4-phenyloxy group, 4'-hydroxyphenylisopropylidene-4 A residue obtained by removing hydrogen from one of the two hydroxyl groups of the phenyloxy group and 1,3,3-trimethyl-1- (4-hydroxyphenyl) indan-6-ol is particularly preferable.

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

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

  Specific examples of the hydroxyl group-containing cyclic phosphazene compound having such a form include a hydroxyl group-containing cyclotriphosphazene compound in which n is 3 in the formula (1), and a hydroxyl group-containing cyclotetrazine in which n is 4 in the formula (1). A phosphazene compound, a hydroxyl group-containing cyclopentaphosphazene compound in which n in formula (1) is 5 and a hydroxyl group-containing cyclohexaphosphazene compound in which n is 6 in formula (1), wherein all of A is 4′-hydroxy Phenyl-4-phenyloxy group, 4′-hydroxyphenyloxy-4-phenyloxy group, 4′-hydroxyphenylthio-4-phenyloxy group, 4′-hydroxyphenylsulfonyl-4-phenyloxy group, 4′- Hydroxyphenyl isopropylidene-4-phenyloxy group, 4'- Roxybenzoyl-4-phenyloxy group and 1,3,3-trimethyl-1- (4-hydroxyphenyl) indan-6-ol and 1,3,3-trimethyl-1- (4-hydroxy-3-methylphenyl) ) What is an A3 group selected from the A3 group consisting of residues obtained by removing hydrogen from one of the two hydroxyl groups of indan-6-ol, and all of A are said A3 groups The thing which is 2 or more types of A3 group chosen from the group, and these arbitrary mixtures can be mentioned.

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

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

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

  Specific examples of the hydroxyl group-containing cyclic phosphazene compound having such a form include a hydroxyl group-containing cyclotriphosphazene compound in which n is 3 in the formula (1), and a hydroxyl group-containing cyclotetrazine in which n is 4 in the formula (1). A phosphazene compound, a hydroxyl group-containing cyclopentaphosphazene compound in which n in formula (1) is 5 or a hydroxyl group-containing cyclohexaphosphazene compound in which n is 6 in formula (1), wherein A is an A3 group 4 Combination of '-hydroxyphenyl-4-phenyloxy group and n-propoxy group which is A1 group, combination of 4'-hydroxyphenyl-4-phenyloxy group which is A3 group and phenoxy group which is A2 group 4'-hydroxyphenyl-4-phenyloxy group which is A3 group and methyl which is A2 group In combination with an enoxy group, in combination with 4'-hydroxyphenylsulfonyl-4-phenyloxy group as an A3 group and n-propoxy group as an A1 group, 4'-hydroxyphenylsulfonyl- as an A3 group Combination of 4-phenyloxy group and phenoxy group which is A2 group, combination of 4'-hydroxyphenylsulfonyl-4-phenyloxy group which is A3 group and methylphenoxy group which is A2 group, A3 group 4'-hydroxyphenylisopropylidene-4-phenyloxy group and A1-group n-propoxy group, A3 group 4'-hydroxyphenylisopropylidene-4-phenyloxy group and A2 group In combination with a phenoxy group, 4′-hydroxyphenylisopropylide, which is an A3 group A combination of a 4-phenyloxy group and a methylphenoxy group which is an A2 group, and two hydroxyl groups of the 1,3,3-trimethyl-1- (4-hydroxyphenyl) indan-6-ol which is an A3 group A combination of a residue obtained by removing hydrogen from one hydroxyl group and an n-propoxy group which is an A1 group, 1,3,3-trimethyl-1- (4-hydroxyphenyl) which is an A3 group A combination of a residue obtained by removing hydrogen from one of two hydroxyl groups of indan-6-ol and a phenoxy group which is an A2 group, 1,3,3-trimethyl which is an A3 group A residue obtained by removing hydrogen from one hydroxyl group of two hydroxyl groups of 1- (4-hydroxyphenyl) indan-6-ol and a group that is an A2 group. Mention may be made of combinations with tilphenoxy groups and any mixtures thereof.

  Of these, a hydroxyl group-containing cyclotriphosphazene compound in which n in formula (1) is 3, a hydroxyl group-containing cyclotetraphosphazene compound in which n in formula (1) is 4, and a hydroxyl in which n in formula (1) is 5 A group-containing cyclopentaphosphazene compound, a hydroxyl group-containing cyclohexaphosphazene compound in which n in formula (1) is 6, wherein A is a group of 4′-hydroxyphenyl-4-phenyloxy and A2 group A combination with a certain phenoxy group, a combination of 4'-hydroxyphenylsulfonyl-4-phenyloxy group which is an A3 group and a phenoxy group which is an A2 group, 4'-hydroxyphenylsulfonyl-4 which is an A3 group -A combination of a phenyloxy group and a methylphenoxy group which is an A2 group, 4'-hydro which is an A3 group A combination of a cyclophenylisopropylidene-4-phenyloxy group and a phenoxy group that is an A2 group, a 4'-hydroxyphenylisopropylidene-4-phenyloxy group that is an A3 group, and a methylphenoxy group that is an A2 group In combination, a residue obtained by removing hydrogen from one hydroxyl group of two hydroxyl groups of 1,3,3-trimethyl-1- (4-hydroxyphenyl) indan-6-ol, which is an A3 group, One of the two hydroxyl groups of the 1,3,3-trimethyl-1- (4-hydroxyphenyl) indan-6-ol which is a combination with the phenoxy group which is the A2 group and the A3 group Preferred are combinations of residues from which hydrogen has been removed and methylphenoxy groups which are A2 groups, and any mixtures thereof. There. In particular, a hydroxyl group-containing cyclotriphosphazene compound in which n in formula (1) is 3 or a hydroxyl group-containing cyclotetraphosphazene compound in which n is 4 in formula (1), wherein A is an A3 group A combination of a 4′-hydroxyphenylsulfonyl-4-phenyloxy group and a phenoxy group that is an A2 group, a 4′-hydroxyphenylsulfonyl-4-phenyloxy group that is an A3 group, and a methylphenoxy group that is an A2 group; A combination of 4'-hydroxyphenylisopropylidene-4-phenyloxy group as the A3 group and a phenoxy group as the A2 group, 1,3,3-trimethyl-1- ( 4-hydroxyphenyl) indan-6-ol is one of the two hydroxyl groups Those and any mixture thereof in combination with a phenoxy group which is a residue and A2 groups than hydrogen are preferred.

  The hydroxyl group-containing cyclic phosphazene compound of the present invention as described above is not crosslinked with the hydroxyl group of the A3 group. That is, the hydroxyl group-containing cyclic phosphazene compound of the present invention does not have any cross-linking structure between hydroxyl group-containing cyclic phosphazene compounds. The hydroxyl group-containing cyclic phosphazene compound of the present invention is novel in terms of such characteristics, and is different from conventional hydroxyl group-containing cyclic phosphazene compounds.

Method for producing hydroxyl group-containing cyclic phosphazene compound The hydroxyl 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 (6) is prepared.

  In the formula (6), n represents an integer of 3 to 15. X represents a halogen atom, preferably a fluorine atom or a chlorine atom. Incidentally, the cyclic phosphonitrile dihalide prepared here may be a mixture of several kinds having different n.

  The production method of such a cyclic phosphonitrile dihalide and the like are described in various documents, for example, Non-Patent Documents 1 and 2 as described below.

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

  As described in these documents, the cyclic phosphonitrile dihalide represented by the formula (6) is usually composed of a cyclic phosphonitrile dihalide having a degree of polymerization of about 3 to 15 and a chain phosphonitrile dihalide. Obtained as a mixture. For this reason, the cyclic phosphonitrile dihalide represented by the formula (6) removes the chain phosphonitrile dihalide using the difference in solubility in the solvent from the mixture, as described in the above-mentioned documents. Or the cyclic phosphonitrile dihalide must be separated from the mixture by distillation or recrystallization.

  Preferred examples of the cyclic phosphonitrile dihalide used in this production method include hexafluorocyclotriphosphazene (where n is 3), octafluorocyclotetraphosphazene (where n is 4), decafluorocyclopentaphosphazene (n ), Dodecafluorocyclohexaphosphazene (n = 6), a mixture of hexafluorocyclotriphosphazene and octafluorocyclotetraphosphazene, a mixture of cyclic phosphonitrile difluorides where n is from 3 to 15, hexachlorocyclo Triphosphazene (n is 3), octachlorocyclotetraphosphazene (n is 4), decachlorocyclopentaphosphazene (n is 5), dodecachlorocyclohexaphosphazene (n is 6), hexac A mixture of olocyclotriphosphazene and octachlorocyclotetraphosphazene, a mixture of cyclic phosphonitrile dichlorides having n of 3 to 15, and the like. Of these, hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, a mixture of hexachlorocyclotriphosphazene and octachlorocyclotetraphosphazene, and a mixture of cyclic phosphonitrile dichloride having n of 3 to 15 are more preferable, hexachlorocyclotriphosphazene, hexachloro Particular preference is given to mixtures of cyclotriphosphazene and octachlorocyclotetraphosphazene and mixtures of cyclic phosphonitrile dichlorides with n of 3 to 15.

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

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

[Compound B3]
The following four types of protected diphenols of Compound B3-1, Compound B3-2, Compound B3-3, and Compound B3-4.

式（１１）中、Ｚは、脱離したときにＯＨ基を形成可能な保護基を示している。 Compound B3-1
Protected diphenols represented by the following formula (11), wherein one hydroxyl group is protected by a protecting group.

In formula (11), Z represents a protecting group capable of forming an OH group when eliminated.

These diphenols can be obtained by protecting one hydroxyl group of a diphenol compound represented by the following formula (12), that is, 4,4′-diphenol, with the above protecting group.

式（１３）中、Ｚは、脱離したときにＯＨ基を形成可能な保護基を示している。また、Ｙは、次に説明する式（１４）中のＹと同じである。 Compound B3-2
Protected diphenols represented by the following formula (13), wherein one hydroxyl group is protected by a protecting group.

In formula (13), Z represents a protecting group capable of forming an OH group when eliminated. Y is the same as Y in formula (14) described below.

式（１４）中、Ｙは、Ｏ、Ｓ、ＳＯ_２、ＣＨ_２、ＣＨＣＨ_３、Ｃ（ＣＨ_３）_２、Ｃ（ＣＨ_３）ＣＨ_２ＣＨ_３若しくはＣＯを示す。式（１４）で表されるジフェノール類は、具体的には、４，４’−オキシジフェノール、４，４’−チオジフェノール、４，４’−スルホニルジフェノール（ビスフェノール−Ｓ）、４，４’−メチレンジフェノール（ビスフェノール−Ｆ）、４，４’−エチリデンジフェノール、４，４’−イソプロピリデンジフェノール（ビスフェノール−Ａ）、４，４’−（１−メチルプロピリデン）ジフェノール（ビスフェノール−Ｂ）および４，４−ジヒドロキシベンゾフェノンである。 This protected diphenol can be obtained by protecting one hydroxyl group of a diphenol compound represented by the following formula (14) with the above-mentioned protecting group.

In the formula (14), Y represents O, S, SO ₂ , CH ₂ , CHCH ₃ , C (CH ₃ ) ₂ , C (CH ₃ ) CH ₂ CH ₃ or CO. Specific examples of the diphenols represented by the formula (14) include 4,4′-oxydiphenol, 4,4′-thiodiphenol, 4,4′-sulfonyldiphenol (bisphenol-S), 4,4′-methylenediphenol (bisphenol-F), 4,4′-ethylidene diphenol, 4,4′-isopropylidenediphenol (bisphenol-A), 4,4 ′-(1-methylpropylidene) Diphenol (bisphenol-B) and 4,4-dihydroxybenzophenone.

式（１５）中、Ｚは、脱離したときにＯＨ基を形成可能な保護基を示している。また、Ｒ^１およびＲ^２は、それぞれ、次に説明する式（１６）中のＲ^１およびＲ^２と同じである。 Compound B3-3
Protected diphenols represented by the following formula (15), wherein one hydroxyl group, that is, the hydroxyl group of 4-hydroxyphenyl group located at the 1-position of indane is protected by a protecting group.

In formula (15), Z represents a protecting group capable of forming an OH group when eliminated. R ¹ and R ² are the same as R ¹ and R ² in formula (16) described below.

式（１６）中、Ｒ^１およびＲ^２は、水素原子、炭素数１〜４のアルキル基、シクロアルキル基若しくはフェニル基を示し、当該アルキル基、シクロアルキル基若しくはフェニル基の場合は、結合している環構造に対して同種若しくは異種のものが複数個結合していてもよい。式（１６）で表されるジフェノール類は、ｐ−イソプロペニルフェノールの線状二量体、すなわち、２，４−ジ（４−ヒドロキシフェニル）−４−メチル−ペンテン−１および２，４−ジ（４−ヒドロキシフェニル）−４−メチル−ペンテン−２の混合物を酸触媒の存在下に環化反応させて得た、１，３，３−トリメチル−１−（４−ヒドロキシフェニル）インダン−６−オールまたはそのアルキル、シクロアルキル若しくはフェニル誘導体である。具体的には、１，３，３−トリメチル−１−（４−ヒドロキシフェニル）インダン−６−オール、１，３，３−トリメチル−１−（４−ヒドロキシ−３−メチルフェニル）インダン−６−オール、１，３，３―トリメチル―１−（４−ヒドロキシ−３，５−ジ−ｔｅｒｔ−ブチルフェニル）インダン−６−オール、１，３，３―トリメチル―５−ｔｅｒｔ−ブチル−１−（４−ヒドロキシ−３−ｔｅｒｔ−ブチルフェニル）インダン−６−オール、１，３，３―トリメチル―５−ｔｅｒｔ−ブチル−１−（４−ヒドロキシ−３，５−ジ−ｔｅｒｔ−ブチルフェニル）インダン−６−オール、１，３，３―トリメチル―５−ｉｓｏ−プロピル−１−（４−ヒドロキシ−３−ｉｓｏ−プロピルフェニル）インダン−６−オール、１，３，３―トリメチル―５−フェニル−１−（４−ヒドロキシ−３−フェニルフェニル）インダン−６−オール等を挙げることができる。 This protected diphenol can be obtained by protecting the hydroxyl group of the 4-hydroxyphenyl group located at the 1-position of indane with the above protecting group in the diphenol compound represented by the following formula (16). .

In Formula (16), R ¹ and R ² represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, or a phenyl group, and in the case of the alkyl group, cycloalkyl group, or phenyl group, they are bonded. A plurality of the same or different species may be bonded to the ring structure. The diphenols represented by the formula (16) are linear dimers of p-isopropenylphenol, that is, 2,4-di (4-hydroxyphenyl) -4-methyl-pentene-1 and 2,4. 1,3,3-trimethyl-1- (4-hydroxyphenyl) indane obtained by cyclizing a mixture of di- (4-hydroxyphenyl) -4-methyl-pentene-2 in the presence of an acid catalyst 6-ol or its alkyl, cycloalkyl or phenyl derivatives. Specifically, 1,3,3-trimethyl-1- (4-hydroxyphenyl) indan-6-ol, 1,3,3-trimethyl-1- (4-hydroxy-3-methylphenyl) indan-6 -Ol, 1,3,3-trimethyl-1- (4-hydroxy-3,5-di-tert-butylphenyl) indan-6-ol, 1,3,3-trimethyl-5-tert-butyl-1 -(4-Hydroxy-3-tert-butylphenyl) indan-6-ol, 1,3,3-trimethyl-5-tert-butyl-1- (4-hydroxy-3,5-di-tert-butylphenyl) ) Indan-6-ol, 1,3,3-trimethyl-5-iso-propyl-1- (4-hydroxy-3-iso-propylphenyl) indan-6-ol, 1,3,3-tri Chill-5-phenyl-1- (4-hydroxy-3-phenyl-phenyl) indan-6-ol, and the like.

式（１７）中、Ｚは、脱離したときにＯＨ基を形成可能な保護基を示している。また、Ｒ^１およびＲ^２は、それぞれ、上記式（１６）中のＲ^１およびＲ^２と同じである。 Compound B3-4
Protected diphenols represented by the following formula (17), wherein one hydroxyl group, that is, the hydroxyl group located at the 6-position of indane is protected by a protecting group.

In formula (17), Z represents a protecting group capable of forming an OH group when eliminated. Further, ^{R 1} and ^{R 2} are respectively the same as ^{R 1} and ^{R 2} in the formula (16).

  This protected diphenol can be obtained by protecting the hydroxyl group located at the 6-position of indane with the protecting group in the diphenol compound represented by the above formula (16).

  Four types of protected diphenols of the above-mentioned compound B3-1, compound B3-2, compound B3-3 and compound B3-4, that is, formula (11), formula (13), formula (15) and formula (17) In the protected diphenols represented by (II), the type of protecting group represented by Z is described in many known documents such as Non-Patent Document 3 and Non-Patent Document 4 below. In addition, protected diphenols represented by formula (11), formula (13) and formula (15) or formula (17) are converted from diphenols represented by formula (12), formula (14) and formula (16). Methods for selective preparation are also described in these non-patent documents.

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

  Specific examples of the protecting group represented by Z include methyl group, methoxymethyl group, methylthiomethyl group, 2-methoxyethoxymethyl group, tetrahydropyranyl group, tetrahydrothiopyranyl group, 4-methoxytetrahydropyranyl group, 4 -Methoxytetrahydrothiopyranyl group, tetrahydrofuranyl group, tetrahydrofuranyl group, 1-ethoxyethyl group, tert-butyl group, allyl group, benzyl group, o-nitrobenzyl group, triphenylmethyl group, trimethylsilyl group, tert -Butyldimethylsilyl group, tert-butyldiphenylsilyl group, tribenzylsilyl group, triisopropylsilyl group and the like can be mentioned. Of these protecting groups, methyl group, methoxymethyl group, tetrahydropyranyl group, 4-methoxytetrahydropyranyl group, tert-butyl group, allyl group, benzyl group and tert-butyldimethylsilyl group are preferred, methyl group, A methoxymethyl group, a tert-butyl group, an allyl group and a benzyl group are particularly preferred.

Specific examples of preferable compounds as the compound B3-1, compound B3-2, compound B3-3, and compound B3-4 are as follows.
[Compound B3-1]
4'-methoxyphenyl-4-phenol, 4'-methoxymethoxyphenyl-4-phenol, 4'-tert-butyloxyphenyl-4-phenol, 4'-allyloxyphenyl-4-phenol, 4'-benzyloxy Phenyl-4-phenol and the like.

[Compound B3-2]
4′-methoxyphenyloxy-4-phenol, 4′-methoxymethoxyphenyloxy-4-phenol, 4′-tert-butyloxyphenyloxy-4-phenol, 4′-allyloxyphenyloxy-4-phenol, 4 '-Benzyloxyphenyloxy-4-phenol, 4'-methoxyphenylthio-4-phenol, 4'-methoxymethoxyphenylthio-4-phenol, 4'-tert-butyloxyphenylthio-4-phenol, 4' -Allyloxyphenylthio-4-phenol, 4'-benzyloxyphenylthio-4-phenol, 4'-methoxyphenylsulfonyl-4-phenol, 4'-methoxymethoxyphenylsulfonyl-4-phenol, 4'-tert- Butyloxyphenylsulfonyl-4-phenol 4'-allyloxyphenylsulfonyl-4-phenol, 4'-benzyloxyphenylsulfonyl-4-phenol, 4'-methoxybenzyl-4-phenol, 4'-methoxymethoxybenzyl-4-phenol, 4'-tert -Butyloxybenzyl-4-phenol, 4'-allyloxybenzyl-4-phenol, 4'-benzyloxybenzyl-4-phenol, 4'-methoxyphenylethyl-4-phenol, 4'-methoxymethoxyphenylethyl- 4-phenol, 4′-tert-butyloxyphenylethyl-4-phenol, 4′-allyloxyphenylethyl-4-phenol, 4′-benzyloxyphenylethyl-4-phenol, 4′-methoxyphenylisopropylidene- 4-phenol, 4'-methoxymethoxy Enylisopropylidene-4-phenol, 4′-tert-butyloxyphenylisopropylidene-4-phenol, 4′-allyloxyphenylisopropylidene-4-phenol, 4′-benzyloxyphenylisopropylidene-4-phenol, 4 '-Methoxyphenyl (1-methylpropylidene) -4-phenol, 4'-methoxymethoxyphenyl (1-methylpropylidene) -4-phenol, 4'-tert-butyloxyphenyl (1-methylpropylidene)- 4-phenol, 4′-allyloxyphenyl (1-methylpropylidene) -4-phenol, 4′-benzyloxyphenyl (1-methylpropylidene) -4-phenol, 4′-methoxybenzoyl-4-phenol, 4'-methoxymethoxybenzoyl-4-fe Lumpur, 4'-tert-butyloxy benzoyl-4-phenol, 4'-allyloxy-benzoyl-4-phenol, 4'-benzyloxy-benzoyl-4-phenol.

[Compound B3-3]
1,3,3-trimethyl-1- (4-methoxyphenyl) indan-6-ol, 1,3,3-trimethyl-1- (4-methoxymethoxyphenyl) indan-6-ol, 1,3,3 -Trimethyl-1- (4-tert-butyloxyphenyl) indan-6-ol, 1,3,3-trimethyl-1- (4-allyloxyphenyl) indan-6-ol, 1,3,3-trimethyl -1- (4-benzyloxyphenyl) indan-6-ol and the like.

[Compound B3-4]
1,3,3-trimethyl-1- (4-hydroxyphenyl) -6-methoxyindane, 1,3,3-trimethyl-1- (4-hydroxyphenyl) -6-methoxymethoxyindane, 1,3,3 -Trimethyl-1- (4-hydroxyphenyl) -6-tert-butyloxyindane, 1,3,3-trimethyl-1- (4-hydroxyphenyl) -6-allyloxyindane, 1,3,3-trimethyl -1- (4-hydroxyphenyl) -6-benzyloxyindane and the like.

  Compound B3-1, Compound B3-2, Compound B3-3, and Compound B3-4 are all commercially available or manufactured according to known methods such as the methods described in Non-Patent Documents 3 and 4 above. Can be used.

  In the method for producing a hydroxyl 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 (6) and the above-mentioned compounds B1 to B3. Are substituted with a group selected from the group consisting of the following E1, E2 and E3 groups so that at least one of them is substituted with the following E3 group to produce a cyclic phosphonitrile substituted product (step) A).

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

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

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

In the formulas (7) to (10), Z represents a protecting group capable of forming an OH group when eliminated, specifically, the above-mentioned compound B3-1, compound B3-2, compound B3-3 and This is the same as that described for the four types of protected diphenols of compound B3-4. In Formula (8), Y represents O, S, SO ₂ , CH ₂ , CHCH ₃ , C (CH ₃ ) ₂ , C (CH ₃ ) CH ₂ CH ₃ or CO. Furthermore, in Formula (9) and Formula (10), R ¹ and R ² represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, or a phenyl group.

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

[When producing hydroxyl group-containing cyclic phosphazene compound of Form 1]
In this case, the cyclic phosphonitrile dihalide is reacted with the compound B3, and all of the halogen atoms (hereinafter sometimes referred to as active halogen atoms) of the cyclic phosphonitrile dihalide are replaced with the E3 group derived from the compound B3. The compound B3 used here is one kind or two or more kinds of the above-mentioned four kinds of protected diphenols of the compound B3-1, the compound B3-2, the compound B3-3, and the compound B3-4. As a method of reacting the cyclic phosphonitrile dihalide with the compound B3 and substituting all the active halogen atoms of the cyclic phosphonitrile dihalide with the E3 group, any of the following methods can be employed.

<Method 1-A>
A cyclic phosphonitrile dihalide is reacted with an alkali metal salt of compound B3.
In the case of this method, the amount of the alkali metal salt of compound B3 is usually preferably set to 1.0 to 2.0 equivalents of the amount of active halogen atom of cyclic phosphonitrile dihalide, and 1.05 to 1 More preferably, it is set to 3 equivalents. When the amount used is less than 1.0 equivalent, some of the active halogen atoms remain, and the target hydroxyl group-containing cyclic phosphazene compound may not exhibit the required effect. On the other hand, if the amount used exceeds 2.0 equivalents, it may be difficult to separate and purify the reaction product, which is uneconomical.

<Method 1-B>
Cyclic phosphonitrile dihalide and compound B3 are reacted in the presence of a base that captures hydrogen halide.
In the case of this method, the amount of compound B3 used is preferably set to 1.0 to 2.0 equivalents, preferably 1.05 to 1.3 equivalents, of the amount of the active halogen atom of the cyclic phosphonitrile dihalide. Is more preferable. When the amount used is less than 1.0 equivalent, some of the active halogen atoms remain, and the target hydroxyl 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, some of the active halogen atoms remain, and the target hydroxyl 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 a hydroxyl group-containing cyclic phosphazene compound of Form 2]
In this case, at least one of compound B3 and at least one compound of compound B1 and compound B2 are reacted with cyclic phosphonitrile dihalide, and a part of the active halogen atoms of cyclic phosphonitrile dihalide is reacted. Is substituted with E3 group derived from compound B3, and all of the remaining other active halogen atoms are replaced with at least one group of E1 group derived from compound B1 and E2 group derived from compound B2. As a method for this, any of the following methods can be adopted.

<Method 2-A>
A cyclic phosphonitrile dihalide is reacted with a mixture of an alkali metal salt of compound B3 and an alkali metal salt of at least one of compound B1 and compound B2 to replace all active halogen atoms. In the said mixture, the ratio of the alkali metal salt of compound B3 can be suitably set according to the kind of hydroxyl 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 hydroxyl group-containing cyclic phosphazene compound may not exhibit the required effect. On the other hand, if the amount used exceeds 2.0 equivalents, it may be difficult to separate and purify the reaction product, which is uneconomical.

<Method 2-B>
A cyclic phosphonitrile dihalide is reacted with a mixture of compound B3 and at least one of compound B1 and compound B2 in the presence of a base that captures hydrogen halide to replace all active halogen atoms. To do. In the said mixture, the ratio of compound B3 can be suitably set according to the kind of hydroxyl 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 hydroxyl 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, some of the active halogen atoms remain, and the target hydroxyl group-containing cyclic phosphazene compound may not exhibit the required effect. On the other hand, if the amount used exceeds 2.1 equivalents, it may be difficult to separate and purify the reaction product, which is uneconomical.

<Method 2-C>
First, compound B3 is reacted with cyclic phosphonitrile dihalide to obtain a partially substituted product in which a part of the active halogen atom of cyclic phosphonitrile dihalide is substituted with E3 group derived from compound B3 (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 into E1 group derived from compound B1 and E2 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 2-D>
First, at least one of compound B1 and compound B2 is reacted with cyclic phosphonitrile dihalide, and a part of the active halogen atom of cyclic phosphonitrile dihalide is converted into E1 group derived from compound B1 and compound B2. A partially substituted product substituted with at least one of the derived E2 groups is obtained (first step). Next, compound B3 is reacted with the partially substituted product thus obtained, and all of the remaining active halogen atoms are substituted with E3 group 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, lithium salt and sodium salt are preferable. Such an alkali metal salt is a dehydrogenation reaction between the compounds B1 to B3 and metal lithium, metal sodium or metal potassium, or the compounds B1 to B3 and sodium hydroxide, potassium hydroxide, lithium hydroxide or the like. It can be obtained by a dehydration reaction from a mixture with an alkali metal hydroxide.

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

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

  The reaction temperature at the time of reacting the above-mentioned cyclic phosphonitrile dihalide and the compounds B1 to B3 can be set as appropriate depending on any of the above-mentioned methods or considering the thermal stability of the reaction product. . However, when the reaction is carried out using a solvent, it is usually preferable to set the reaction temperature in a temperature range from 0 ° C. to the boiling point of the solvent. On the other hand, when carrying out the reaction without solvent, the reaction temperature is usually preferably set in the range of 40 to 200 ° C.

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

  Here, when the method 2-C is employed, first, an ether solvent solution or an aromatic hydrocarbon solvent solution of a cyclic phosphonitrile dihalide is prepared. Then, with respect to this solvent solution, an ether solvent solution or an aromatic hydrocarbon solvent solution of an alkali metal salt of compound B3 or an ether solvent solution or an aromatic hydrocarbon system of compound B3 and a base for capturing hydrogen halide. The solvent solution is usually added at a temperature of −20 to 50 ° C. over 3 to 24 hours, and is allowed to react for 1 to 24 hours in the same temperature range, and a part of the active halogen atom of the cyclic phosphonitrile dihalide is compounded. A partially substituted product substituted with the E3 group derived from B3 is produced. Next, an ether solvent solution or an aromatic solvent of an alkali metal salt of at least one compound selected from the compound B1 and the compound B2 is added to the ether solvent solution or aromatic hydrocarbon solvent solution of the partially substituted product obtained. A hydrocarbon solvent solution or an ether solvent solution or an aromatic hydrocarbon solvent solution of at least one compound selected from Compound B1 and Compound B2 and a base that captures hydrogen halide is usually at 0 to 50 ° C. The reaction is carried out at a temperature from 3 to 24 hours, and the reaction is carried out at a temperature from 0 ° C. to the boiling point of the solvent. Replace with at least one of them.

  On the other hand, when Method 2-D is employed, first, an ether solvent solution or an aromatic hydrocarbon solvent solution of cyclic phosphonitrile dihalide is prepared. Then, with respect to this solvent solution, at least one selected from an ether solvent solution or an aromatic hydrocarbon solvent solution of an alkali metal salt of at least one compound selected from Compound B1 and Compound B2 or from Compound B1 and Compound B2 An ether solvent solution or an aromatic hydrocarbon solvent solution of one compound and a base for capturing a hydrogen halide is usually added over a period of 3 to 24 hours at a temperature of -20 to 50 ° C. To produce a partially substituted product in which a part of the active halogen atom of cyclic phosphonitrile dihalide is substituted with at least one of E1 group derived from compound B1 and E2 group derived from compound B2 To do. Next, the ether solvent solution or aromatic hydrocarbon solvent solution of the partially substituted product thus obtained is subjected to halogenation with an ether solvent solution or aromatic hydrocarbon solvent solution of compound B3 or compound B3. An ether solvent solution or an aromatic hydrocarbon solvent solution with a base that captures hydrogen is usually added at a temperature of 0 to 50 ° C. over 3 to 24 hours, and a temperature from 0 ° C. to the boiling point of the solvent. And all of the remaining active halogen atoms are replaced by the E3 group from compound B3.

  In the production method of the present invention, next, the protecting group (Z) is eliminated from the E3 group of the cyclic phosphonitrile-substituted product obtained in the above-mentioned step A, and the —OZ group portion of the E3 group is converted to an —OH group. (Step B). Methods for removing protecting groups are described in many known documents such as Non-Patent Documents 3 and 4 described above, and various deprotection reactions can be performed depending on the type of protecting group and the stability of the protecting group. You can choose from. For example, when the protecting group is a methyl group, the cyclic phosphonitrile substituent is preferably reacted with boron trifluoride, trimethylsilane iodide or pyridine hydrochloride. When the protecting group is a tert-butyl group, the cyclic phosphonitrile substituent is preferably reacted with trifluoroacetic acid, hydrogen bromide or trimethylsilane iodide. Furthermore, when the protecting group is a benzyl group, the cyclic phosphonitrile substituent is reacted with hydrogen / Pd-C, metallic sodium / ammonia, trimethylsilane iodide, lithium aluminum hydride, boron tribromide or boron trifluoride. Is preferred.

  The target hydroxyl group-containing cyclic phosphazene compound obtained by such elimination of the protecting group can be isolated and purified from the reaction system by ordinary methods such as filtration, solvent extraction, column chromatography and recrystallization. it can.

  In the production method of the present invention, all or part of the active halogen atom of the cyclic phosphonitrile dihalide is substituted with the E3 group in Step A, and the protecting group of the E3 group is eliminated in the next Step B. As described above, the resulting hydroxyl group-containing cyclic phosphazene compound is a novel compound having no cross-linking structure between hydroxyl group-containing cyclic phosphazene compounds due to hydroxyl groups.

Resin Composition The resin composition of the present invention comprises the hydroxyl group-containing cyclic phosphazene compound of the present invention and a resin component. As the hydroxyl group-containing cyclic phosphazene compound of the present invention, one type 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, a reactive functional group such as a carboxyl group, an epoxy group, an amino group, a hydroxyl group, and an anhydrous dicarboxyl group is introduced into a part or all of the polyphenylene ether by some method such as graft reaction or copolymerization. Things are used. When the resin composition of the present invention is used as a material for casings or parts for electronic equipment, particularly OA equipment, AV equipment, communication equipment, and home appliances, polyester resin, ABS resin, It is preferable to use polycarbonate, modified polyphenylene ether, polyamide or the like.

  On the other hand, specific examples of thermosetting resins that can be used here include polyurethane, phenol resin, melamine resin, urea resin, unsaturated polyester resin, diallyl phthalate resin, silicon resin, bismaleimide resin, cyanate ester resin, polybenz Examples thereof include 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, 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 hydroxyl group-containing cyclic phosphazene compound used can be appropriately set according to various conditions such as the type of the resin component and the use of the resin composition. It is preferably set to 0.1 to 50 parts by weight with respect to 100 parts by weight of the resin component, more preferably set to 0.5 to 40 parts by weight, and further preferably set to 1 to 30 parts by weight. . When the usage-amount of a hydroxyl group containing cyclic phosphazene compound is less than 0.1 weight part, there exists a possibility that the resin molding which consists of the said resin composition may not show sufficient flame retardance. On the other hand, if it exceeds 50 parts by weight, the original properties of the resin component may be impaired, and a resin molded product having such properties may not be obtained.

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

  When the resin composition of the present invention is used for a material for the electric / electronic field, specifically, a sealant or a substrate for an electronic component such as LSI, the resin component is preferably an epoxy resin. Specific examples of usable epoxy resins include phenol novolac type epoxy resins, brominated phenol novolac type epoxy resins, orthocresol novolak type epoxy resins and naphthol novolak type epoxy resins, which are obtained by reaction of phenols with aldehydes. Novolak type epoxy resin, bisphenol-A type epoxy resin, brominated bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, bisphenol-AD type epoxy resin, bisphenol-S type epoxy resin, biphenol type epoxy resin, alkyl-substituted Biphenol type epoxy resin, phenol type epoxy resin obtained by reaction of phenols such as tris (hydroxyphenyl) methane and epichlorohydrin, trimethylolpropane, Obtained by reaction of aliphatic epoxy resin, hexahydrophthalic acid, tetrahydrophthalic acid or phthalic acid with epichlorohydrin or 2-methylepichlorohydrin obtained by reaction of alcohols such as ligopropylene glycol and hydrogenated bisphenol-A with epichlorohydrin Glycidyl ester epoxy resin, glycidylamine epoxy resin obtained by reaction of amine such as diaminodiphenylmethane and aminophenol and epichlorohydrin, heterocyclic epoxy resin obtained by reaction of polyamine such as isocyanuric acid and epichlorohydrin, glycidyl group Examples thereof include phosphazene compounds, epoxy-modified phosphazene resins, cycloaliphatic epoxy resins, and urethane-modified epoxy resins. 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 hydroxyl group-containing cyclic phosphazene compound of the present invention can function as a curing agent for the epoxy resin. Moreover, the epoxy resin composition may contain the other hardening | curing agent together with the hydroxyl group containing cyclic phosphazene compound of this invention. When the epoxy resin composition uses the hydroxyl group-containing cyclic phosphazene compound of the present invention in combination with another curing agent as a curing agent, the total amount of the curing agent (that is, the hydroxyl group-containing cyclic phosphazene compound of the present invention and other The proportion of the hydroxyl group-containing cyclic phosphazene compound of the present invention in the total amount) of the present invention is preferably from 0.1 to 80% by weight, more preferably from 0.5 to 70% by weight. When the proportion of the hydroxyl group-containing cyclic phosphazene compound is less than 0.1% by weight, the resin molded body made of the resin composition may not exhibit sufficient flame retardancy. On the other hand, if it exceeds 80% by weight, the original properties of the resin component may be impaired, and a resin molded product having such properties may not be obtained.

  Other curing agents that can be used in combination with the hydroxyl group-containing cyclic phosphazene compound of the present invention are not particularly limited. For example, polyamine-based 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 other hydroxyl groups (hydroxyl group-containing phosphazene compounds other than the present invention), three Examples include Lewis acids such as boron fluoride and salts thereof, dicyandiamides, and the like. 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 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 hydroxyl group-containing cyclic phosphazene compound of the present invention reacts with the resin component and is stably held in the cured product. Therefore, the high temperature reliability of the cured product is improved. Hard to lose. Further, the hydroxyl group-containing cyclic phosphazene compound of the present invention can increase the flame retardancy without impairing the mechanical properties (particularly the glass transition temperature) of such a cured product, Low smoke generation. For this reason, the resin composition of this invention can be widely used as a material for manufacture of various resin moldings, for coating materials, for adhesives, and for other uses. In particular, the resin composition of the present invention is used for semiconductor encapsulation and circuit boards (in particular, metal-clad laminates, printed wiring board substrates, printed wiring board adhesives, printed wiring board adhesive sheets, and printed wiring board use. Insulating circuit protective films, conductive pastes for printed wiring boards, sealing agents for multilayer printed wiring boards, circuit protective agents, coverlay films, cover inks) and the like are suitable as materials for manufacturing electrical and electronic parts.

EXAMPLES The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited by these. Of the following examples, Examples 1, 7, 9, 15, 16, 18, 23, 28, 32, and 33 are reference examples.
In the following, “unit” in “unit mol” means the smallest structural unit of the cyclic phosphazene compound, for example, (PNA ₂ ) for general formula (1) and (PNX ₂ ) for general formula (6). ). In General formula (6), when X is chlorine, the 1 unit mol is 115.87g.
In the following, unless otherwise specified, “%” and “parts” mean “% by weight” and “parts by weight”, respectively.

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

Example 1 (Production of hydroxyl group-containing cyclic phosphazene compound according to Form 2)
[Step 1: Production of substituted cyclic phosphonitrile by method 2-C above]
In a 2 liter flask equipped with a stirrer, thermometer, reflux condenser, water separator and nitrogen inlet, 41.7 g (0.50 mol) of 48% aqueous NaOH, 1,000 ml of toluene and 4′-methoxy 100.1 g (0.50 mol) of phenyl-4-phenol was charged. This was stirred and heated in a nitrogen atmosphere, and the water in the flask was removed by azeotropic dehydration (recovered water: about 30 ml) to prepare a sodium salt of 4′-methoxyphenyl-4-phenol. The slurry solution was cooled to 20 ° C., and 500 ml of tetrahydrofuran (THF) was charged to obtain a uniform solution.

  Next, a THF solution of hexachlorocyclotriphosphazene [58.0 g of hexachlorocyclotriphosphazene (0.50 unit mol), 500 ml of THF] was placed in a 3 liter flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube. The sodium salt solution of 4′-methoxyphenyl-4-phenol was added dropwise at 5 ° C. over 6 hours with stirring, and the stirring reaction was carried out under reflux (85 ° C.) for 12 hours. After completion of the reaction, the reaction solution was concentrated to about 700 ml, 300 ml of toluene and 500 ml of water were added to dissolve the reaction product, and the organic layer was separated using a separatory funnel. This organic layer was washed with water three times, and then water-toluene was azeotropically dehydrated to obtain an anhydrous toluene solution of 4'-methoxyphenyl-4-phenoxy partially substituted product.

  Next, in a 3 liter flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube, a toluene solution of the above-mentioned anhydrous 4′-methoxyphenyl-4-phenoxy partially substituted product, n-propanol 39. 1 g (0.65 mol), 111.3 ml (0.80 mol) of triethylamine and 0.6 g (5 mmol) of dimethylaminopyridine were charged, and the reaction was stirred at the reflux temperature (103 ° C.) for 10 hours. After completion of the reaction, the reaction solution was concentrated to about 700 ml, and after adding 300 ml of toluene and 500 ml of water to dissolve the contents, the organic layer was separated using a separatory funnel. This organic layer was washed twice with 2% hydrochloric acid and then washed with water three times, and then toluene was distilled off. As a result, 122.7 g (yield: 84%) of a pale brown viscous liquid product was obtained. )was gotten. The analysis result of this product was as follows.

¹ H-NMR spectrum (in heavy acetone, δ, ppm):
_{-CH 3 0.9 (3H), -} CH 2 - 1.6 (2H), - CH 2 - 3.6 (2H), - CH 3 3.7 (3H), phenyl CH 6.5 to 7.8 (8H)
◎ ³¹ P-NMR spectrum (in heavy acetone, δ, ppm):
Trimer (P = N) ₃ 12.3
◎ CHNP elemental analysis:
Theoretical value C: 62.5%, H: 6.1%, N: 4.8%, P: 10.6%
Actual measurement C: 62.3%, H: 6.2%, N: 4.9%, P: 10.4%
◎ Residual chlorine analysis:
<0.01%
◎ TOF-MS (m / z):
771,911,1051

From the above analysis results, the products obtained in this step are [N ₃ = P ₃ (OC ₆ H ₄ -C ₆ H ₄ OCH ₃ ) ₂ (OCH ₂ CH ₂ CH ₃ ) ₄ ], [N ₃ = _{P 3 (OC 6 H 4 -C} 6 H 4 OCH 3) 3 (OCH 2 CH 2 CH 3) 3], [N 3 = P 3 (OC 6 H 4 -C 6 H 4 OCH 3) 4 (OCH 2 a mixture of CH ₂ CH _{3) 2],} the average composition in the _{[N = P (OC 6 H} 4 -C 6 H 4 OCH 3) 0.92 (OCH 2 CH 2 CH 3) 1.08] 3 I confirmed that there was.

[Step 2: Deprotecting group step]
87.6 g (0.30 unit mol) of the product obtained in Step 1 and 650 ml of toluene were charged in a 1-liter flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube. Under a nitrogen atmosphere, 75.5 ml (0.28 mol) of 47% boron trifluoride ethyl ether was added dropwise at 5 to 10 ° C. over 1 hour, followed by stirring and aging at the same temperature for 2 hours. After the reaction, the reaction solution was added to 400 ml of water, and the organic layer was separated using a separatory funnel. When this organic layer was washed with water three times and then toluene was distilled off, 76.2 g (yield: 91%) of a pale brown viscous liquid product was obtained. The analysis result of this product was as follows.

¹ H-NMR spectrum (in heavy acetone, δ, ppm):
_{-CH 3 0.9 (3H), -} CH 2 - 1.6 (2H), - CH 2 - 3.3 (2H), phenyl CH 6.5~7.9 (8H)
◎ ³¹ P-NMR spectrum (in heavy acetone, δ, ppm):
Trimer (P = N) ₃ 9.8
◎ CHNP elemental analysis:
Theoretical value C: 61.6%, H: 5.4%, N: 5.0%, P: 11.1%
Measured value C: 61.4%, H: 5.7%, N: 4.9%, P: 10.9%
◎ Hydroxyl equivalent:
276 g / eq. (Theoretical value 279 g / eq.)

It From the above analysis results, the product obtained in this step is _{[N = P (OC 6 H} 4 -C 6 H 4 OH) 0.92 (OCH 2 CH 2 CH 3) 1.08] which is ₃ It was confirmed.

Example 2 (Production of hydroxyl group-containing cyclic phosphazene compound according to Form 2)
[Step 1: Production of substituted cyclic phosphonitrile by method 2-C above]
In a 500 ml flask equipped with a stirrer, thermometer, reflux condenser, water separator and nitrogen inlet tube, 58.4 g (0.50 mol) of 48% KOH aqueous solution, 200 ml of chlorobenzene and 4′-isopropyloxy 146.2 g (0.50 mol) of phenylsulfonyl-4-phenol was charged. This was stirred and heated in a nitrogen atmosphere, and the water in the flask was removed by azeotropic dehydration (recovered water: about 39 ml) to prepare a potassium salt of 4′-isopropyloxyphenylsulfonyl-4-phenol. The slurry solution was cooled to 20 ° C., and 200 ml of THF was charged to make a uniform solution.

  On the other hand, in a 1 liter flask equipped with a stirrer, a thermometer, a reflux condenser, a water separator and a nitrogen inlet tube, 87.7 g (0.75 mol) of a 48% KOH aqueous solution, 500 ml of chlorobenzene and 70. 6 g (0.75 mol) was charged. This was stirred and heated in a nitrogen atmosphere, and water in the flask was removed by azeotropic dehydration (recovered water: about 59 ml) to prepare a potassium potassium salt. The slurry solution was cooled to 20 ° C. and charged with 300 ml of THF to obtain a uniform solution.

  Next, a THF solution of hexachlorocyclotriphosphazene [58.0 g (0.50 unit mol), THF 250 ml] of hexachlorocyclotriphosphazene was placed in a 2 liter flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube. The potassium salt solution of 4′-isopropyloxyphenylsulfonyl-4-phenol was added dropwise at 5 ° C. over 6 hours with stirring, and the stirring reaction was performed at the same temperature for 4 hours. Subsequently, the potassium salt solution of the phenol was added dropwise to the reaction solution at 45 ° C. or lower over 0.5 hours with stirring, and the stirring reaction was performed under reflux (85 ° C.) for 5 hours. After completion of the reaction, the reaction solution was concentrated to about 700 ml, 300 ml of chlorobenzene and 500 ml of water were added to dissolve the contents, and the organic layer was separated using a separatory funnel. This organic layer was washed twice with 5% NaOH aqueous solution, then neutralized with 2% sulfuric acid, further washed with water three times, and chlorobenzene was distilled off to obtain a pale yellow solid product. 184.3 g (yield: 90%) was obtained. The melting point (melting peak temperature) of this product was 68 ° C. The analysis result of this product was as follows.

¹ H-NMR spectrum (in heavy acetone, δ, ppm):
—CH ₃ 1.4 (6H), —CH <4.8 (1H), phenyl C—H 6.7 to 7.3 (9H), 7.8 to 8.0 (4H)
◎ ³¹ P-NMR spectrum (in heavy acetone, δ, ppm):
Trimer (P = N) ₃ 9.6
◎ CHNP elemental analysis:
Theoretical value C: 58.9%, H: 4.7%, N: 3.4%, P: 7.6%
Measured value C: 58.8%, H: 4.9%, N: 3.4%, P: 7.3%
◎ Residual chlorine analysis:
<0.01%
◎ TOF-MS (m / z):
1091,1289,1488

From the above analysis results, the product obtained in this step is [N ₃ = P ₃ (OC ₆ H ₄ —SO ₂ —C ₆ H ₄ OCH (CH ₃ ) ₂ ) ₂ (OC ₆ H ₅ ) ₄ ]. [N ₃ = P ₃ (OC ₆ H ₄ —SO ₂ —C ₆ H ₄ OCH (CH ₃ ) ₂ ) ₃ (OC ₆ H ₅ ) ₃ ], [N ₃ = P ₃ (OC ₆ H ₄ —SO 2) _2- C ₆ H ₄ OCH (CH ₃ ) ₂ ) ₄ (OC ₆ H ₅ ) ₂ ], the average composition of which is [N═P (OC ₆ H ₄ —SO ₂ —C ₆ H ₄ OCH ( it was confirmed that _{CH 3) 2) 0.90 (OC} 6 H 5) 1.10] _3.

[Step 2: Deprotecting group step]
In a 1 liter flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube, 122.9 g (0.30 unit mol) of the product obtained in Step 1 and 450 ml of acetic acid were charged. On the other hand, 218.5 g (0.81 mol) of a 30% hydrobromic acid / acetic acid solution was added dropwise at 5 to 10 ° C. over 1 hour in a nitrogen atmosphere, and then stirred and aged at 50 ° C. for 16 hours. After completion of the reaction, the reaction solution is concentrated to distill off excess hydrobromic acid and acetic acid. The residue is dissolved by adding 300 ml of methyl isobutyl ketone (MIBK) and 200 ml of water, and then placed in a separatory funnel. The organic layer was separated. When this organic layer was washed with water three times and MIBK was distilled off, 102.6 g (yield: 92%) of a light brown solid product was obtained. This product did not show a clear melting point due to the glassy solid. The analysis result of this product was as follows.

¹ H-NMR spectrum (in heavy acetone, δ, ppm):
Phenyl C—H 6.8 to 7.3 (9H), 7.7 to 7.9 (4H)
◎ ³¹ P-NMR spectrum (in heavy acetone, δ, ppm):
Trimer (P = N) ₃ 9.6
◎ CHNP elemental analysis:
Theoretical value C: 56.2%, H: 3.7%, N: 3.8%, P: 8.3%
Measured value C: 56.0%, H: 3.9%, N: 3.8%, P: 8.1%
◎ Hydroxyl equivalent:
375 g / eq. (Theoretical value 372 g / eq.)

From the above analysis results, the product obtained in this process is the _{[N = P (OC 6 H} 4 -SO 2 -C 6 H 4 OH) 0.90 (OC 6 H 5) 1.10] 3 It was confirmed.

Example 3 (Production of hydroxyl group-containing cyclic phosphazene compound according to Form 1)
[Step 1: Production of substituted cyclic phosphonitriles by method 1-A above]
In a 5 liter flask equipped with a stirrer, thermometer, reflux condenser, water separator and nitrogen inlet tube, 50.0 g (0.60 mol) of 48% NaOH aqueous solution, 70.1 g (0 .60 mol), 3,000 ml of toluene, and 348.4 g (1.20 mol) of 4′-allyloxyphenylsulfonyl-4-phenol. This was stirred and heated under a nitrogen atmosphere, and water in the flask was removed by azeotropic dehydration (recovered water: about 84 ml) to prepare a sodium / potassium salt of 4′-allyloxyphenylsulfonyl-4-phenol. To this was added dropwise a toluene solution of hexachlorocyclotriphosphazene [58.0 g (0.50 unit mol) of hexachlorocyclotriphosphazene, 300 ml of toluene] with stirring at 20-25 ° C. over 1 hour, and then under reflux (108 ° C.). The reaction was carried out with stirring for 8 hours. After completion of the reaction, 1,000 ml of water was added to the reaction solution to dissolve the contents, and the organic layer was separated using a separatory funnel. This organic layer was washed twice with 5% aqueous NaOH solution, then neutralized with 2% nitric acid, and further washed three times with water. After toluene was distilled off, 286.1 g (yield) of a white solid product was obtained. Rate: 92%). The melting point (melting peak temperature) of this product was 164 ° C. The analysis result of this product was as follows.

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

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

[Step 2: Deprotecting group step]
A 2 liter flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube was charged with 187.1 g (0.30 unit mol) of the product obtained in Step 1 and 1,000 ml of acetic acid under a nitrogen atmosphere. Then, 323.6 g (1.20 mol) of a 30% hydrobromic acid / acetic acid solution was added dropwise at 5 to 10 ° C. over 2 hours, followed by stirring and aging at 50 ° C. for 8 hours. After completion of the reaction, the reaction solution is concentrated to distill off excess hydrobromic acid and acetic acid. After adding and dissolving 500 ml of MIBK and 500 ml of water, the organic layer is separated using a separatory funnel. did. When this organic layer was washed with water three times and MIBK was distilled off, 141.9 g (yield: 87%) of a white solid product was obtained. This product did not show a clear melting point due to the glassy solid. The analysis result of this product was as follows.

¹ H-NMR spectrum (in heavy acetone, δ, ppm):
Phenyl C—H 7.0 to 7.2 (8H), 7.8 to 8.0 (8H), —OH 9.5 (2H)
◎ ³¹ P-NMR spectrum (in heavy acetone, δ, ppm):
Trimer (P = N) ₃ 8.5
◎ CHNP elemental analysis:
Theoretical value C: 53.0%, H: 3.3%, N: 2.6%, P: 5.7%
Measured value C: 52.8%, H: 3.6%, N: 2.5%, P: 5.6%
◎ Hydroxyl equivalent:
270 g / eq. (Theoretical value 272 g / eq.)

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

Example 4 (Production of hydroxyl group-containing cyclic phosphazene compound according to Form 2)
[Step 1: Production of substituted cyclic phosphonitriles by method 2-D above]
In a 1 liter flask equipped with a stirrer, thermometer, reflux condenser, water separation receiver and nitrogen inlet tube, 58.4 g (0.50 mol) of 48% KOH aqueous solution, 450 ml of chlorobenzene and 47.1 g of phenol ( 0.50 mol) was charged. This was stirred and heated under a nitrogen atmosphere, and water in the flask was removed by azeotropic dehydration (recovered water: about 39 ml) to prepare a potassium potassium salt. The slurry solution was cooled to 20 ° C., and 200 ml of THF was charged to make a uniform solution.

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

  Next, a THF solution of hexachlorocyclotriphosphazene [58.0 g (0.50 unit mol), THF 200 ml] of hexachlorocyclotriphosphazene was placed in a 3 liter flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube. The phenol potassium salt solution was added dropwise with stirring at 5 ° C. over 10 hours, and the stirring reaction was carried out at 25 ° C. for 5 hours. Subsequently, the potassium salt solution of 4′-allyloxyphenylsulfonyl-4-phenol was added dropwise to the reaction solution over 1 hour at 25 ° C. with stirring, and the stirring reaction was performed under reflux (86 ° C.) for 10 hours. . After completion of the reaction, the reaction solution was concentrated to about 1,000 ml, and after adding 600 ml of chlorobenzene and 600 ml of water to dissolve the contents, the organic layer was separated using a separatory funnel. This organic layer was washed twice with 5% NaOH aqueous solution, then neutralized with 2% sulfuric acid, further washed with water three times, and chlorobenzene was distilled off to obtain a pale yellow solid product. 207.1 g (yield: 96%) was obtained. This product did not show a clear melting point due to the glassy solid. The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
_{-CH 2 - 4.6 (2H),} = CH 2 5.3~5.4 (2H), - CH = 6.0 (1H), phenyl CH 6.8~7.2 (9H), 7.8-8.0 (4H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 8.5
◎ CHNP elemental analysis:
Theoretical value C: 58.9%, H: 4.2%, N: 3.2%, P: 7.2%
Measured value C: 58.7%, H: 4.4%, N: 3.1%, P: 7.0%
◎ Residual chlorine analysis:
<0.01%
◎ TOF-MS (m / z):
1087,1283,1480

From the above analysis results, the product obtained in this step is [N ₃ = P ₃ (OC ₆ H ₄ —SO ₂ —C ₆ H ₄ OCH ₂ CH═CH ₂ ) ₂ (OC ₆ H ₅ ) ₄ ]. [N ₃ = P ₃ (OC ₆ H ₄ —SO ₂ —C ₆ H ₄ OCH ₂ CH═CH ₂ ) ₃ (OC ₆ H ₅ ) ₃ ], [N ₃ = P ₃ (OC ₆ H ₄ —SO 2) _2- C ₆ H ₄ OCH ₂ CH═CH ₂ ) ₄ (OC ₆ H ₅ ) ₂ ], the average composition of which is [N═P (OC ₆ H ₄ —SO ₂ —C ₆ H ₄ OCH _2]. CH ₌ CH ₂₎ was confirmed to be _{1.02 (OC 6 H 5) 0.98} ] 3.

[Step 2: Deprotecting group step]
A 1 liter flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube was charged with 129.4 g (0.30 unit mol) of the product obtained in Step 1 and 500 ml of acetic acid, and 30% under a nitrogen atmosphere. 161.8 g (0.60 mol) of a% hydrobromic acid / acetic acid solution was added dropwise at 5 to 10 ° C. over 2 hours, followed by stirring and aging at 50 ° C. for 8 hours. After completion of the reaction, the reaction solution is concentrated to distill off excess hydrobromic acid and acetic acid. After adding 400 ml of MIBK and 400 ml of water to the residue and dissolving, the organic layer is separated using a separatory funnel. did. The organic layer was washed three times with water and MIBK was distilled off to obtain 99.6 g (yield: 85%) of a tan solid product. This product did not show a clear melting point due to the glassy solid. The analysis result of this product was as follows.

¹ H-NMR spectrum (in heavy acetone, δ, ppm):
Phenyl C—H 6.8 to 7.2 (9H), 7.2 to 7.8 (4H), —OH 9.5 (1H)
◎ ³¹ P-NMR spectrum (in heavy acetone, δ, ppm):
Trimer (P = N) ₃ 9.5
◎ CHNP elemental analysis:
Theoretical value C: 55.7%, H: 3.6%, N: 3.6%, P: 7.9%
Measured value C: 55.5%, H: 3.7%, N: 3.5%, P: 7.7%
◎ Hydroxyl equivalent:
394 g / eq. (Theoretical value 391 g / eq.)

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

Example 5 (Production of hydroxyl group-containing cyclic phosphazene compound according to Form 1)
[Step 1: Production of substituted cyclic phosphonitriles by method 1-A above]
152.0 g (1.30 mol) of 48% aqueous KOH solution, 2,000 ml of toluene and 4′-benzyl in a 3 liter flask equipped with a stirrer, thermometer, reflux condenser, water separator and nitrogen inlet 442.5 g (1.30 mol) of oxyphenylsulfonyl-4-phenol was charged. This was stirred and heated in a nitrogen atmosphere, and water in the flask was removed by azeotropic dehydration (recovered water: about 102 ml) to prepare a potassium salt of 4′-benzyloxyphenylsulfonyl-4-phenol. The slurry solution was cooled to 20 ° C. and charged with 400 ml of THF to obtain a uniform solution.

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

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

From the above analysis results, the product obtained in this step is _{[N = P (OC 6 H} 4 -SO 2 -C 6 H 4 OCH 2 C 6 H 5) 2] 3 and [N = P (OC ₆ it was confirmed that _{H 4 -SO 2 -C 6 H 4} OCH 2 C 6 H 5) 2] _4.

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

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

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

Example 6 (Production of hydroxyl group-containing cyclic phosphazene compound according to Form 2)
[Step 1: Production of substituted cyclic phosphonitrile by method 2-C above]
In a 3 liter flask equipped with a stirrer, thermometer, reflux condenser, water separator and nitrogen inlet, 41.7 g (0.50 mol) of 48% aqueous NaOH, 1,200 ml of toluene and 4′-benzyl 170.2 g (0.50 mol) of oxyphenylsulfonyl-4-phenol was charged. This was stirred and heated under a nitrogen atmosphere, and the water in the flask was removed by azeotropic dehydration (recovered water: about 30 ml) to prepare a 4′-benzyloxyphenylsulfonyl-4-phenol sodium salt. The slurry solution was cooled to 20 ° C., and 600 ml of THF was charged to make a uniform solution.

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

  Next, a THF solution of hexachlorocyclotriphosphazene [58.0 g of hexachlorocyclotriphosphazene (0.50 unit mol), 300 ml of THF] was placed in a 5-liter flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube. The sodium salt solution of 4′-benzyloxyphenylsulfonyl-4-phenol was added dropwise at 5 ° C. over 6 hours with stirring, and the stirring reaction was carried out at 25 ° C. for 4 hours. Subsequently, the potassium salt solution of phenol was added dropwise to the reaction solution at 25 ° C. over 1 hour with stirring, and the stirring reaction was performed under reflux (103 ° C.) for 2 hours. After completion of the reaction, the reaction solution was concentrated to about 1,000 ml, and after adding 200 ml of toluene and 400 ml of water to dissolve the contents, the organic layer was separated using a separatory funnel. This organic layer was washed twice with 5% NaOH aqueous solution, then neutralized with 2% sulfuric acid, and further washed with water three times, and then toluene was distilled off to obtain a light yellow solid product 201. 0.1 g (yield: 87%) was obtained. This product did not show a clear melting point due to the glassy solid. The analysis result of this product was as follows.

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

From the above analysis results, the product obtained in this step is _{[N 3 = P 3 (OC} 6 H 4 -SO 2 -C 6 H 4 OCH 2 C 6 H 5) 2 (OC 6 H 5) 4] , [N ₃ = P ₃ (OC ₆ H ₄ —SO ₂ —C ₆ H ₄ OCH ₂ C ₆ H ₅ ) ₃ (OC ₆ H ₅ ) ₃ ], [N ₃ = P ₃ (OC ₆ H ₄ —SO _2- C ₆ H ₄ OCH ₂ C ₆ H ₅ ) ₄ (OC ₆ H ₅ ) ₂ ], the average composition of which is [N═P (OC ₆ H ₄ —SO ₂ —C ₆ H ₄ OCH _2]. it was confirmed that _{C 6 H 5) 0.95 (OC} 6 H 5) 1.05] _3.

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

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

From the above analysis results, the product obtained in this process is the _{[N = P (OC 6 H} 4 -SO 2 -C 6 H 4 OH) 0.95 (OC 6 H 5) 1.05] 3 It was confirmed.

Example 7 (Production of hydroxyl group-containing cyclic phosphazene compound according to Form 2)
[Step 1: Production of substituted cyclic phosphonitriles by method 2-D above]
In a 1 liter flask equipped with a stirrer, thermometer, reflux condenser, water separator and nitrogen inlet tube, 41.7 g (0.50 mol) of 48% NaOH aqueous solution, 250 ml of toluene and 47.1 g of phenol (0 .50 mol) was charged. This was stirred and heated under a nitrogen atmosphere, and water in the flask was removed by azeotropic dehydration (recovered water: about 29 ml) to prepare a sodium salt of phenol. The slurry solution was cooled to 20 ° C., and 200 ml of THF was charged to make a uniform solution.

  On the other hand, in a 3 liter flask equipped with a stirrer, a thermometer, a reflux condenser, a water separator and a nitrogen inlet tube, 87.7 g (0.75 mol) of a 48% KOH aqueous solution, 1500 ml of toluene and 4 ′ -238.8 g (0.75 mol) of benzyloxyphenylisopropylidene-4-phenol was charged. This was stirred and heated under a nitrogen atmosphere, and water in the flask was removed by azeotropic dehydration (recovered water: about 59 ml) to prepare a potassium salt of 4'-benzyloxyphenylisopropylidene-4-phenol. The slurry solution was cooled to 20 ° C., and 500 ml of THF was charged to make a uniform solution.

  Next, a THF solution of hexachlorocyclotriphosphazene [58.0 g (0.50 unit mol), THF 500 ml] of hexachlorocyclotriphosphazene was placed in a 5-liter flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube. The sodium salt solution of the phenol was added dropwise at 5 ° C. over 6 hours with stirring, and the stirring reaction was carried out at 25 ° C. for 2 hours. Subsequently, the potassium salt solution of 4′-benzyloxyphenylisopropylidene-4-phenol was added dropwise to the reaction solution over 1 hour at 25 ° C. with stirring, and the stirring reaction was performed under reflux (85 ° C.) for 14 hours. went. After completion of the reaction, the reaction solution was concentrated to about 1,000 ml, 500 ml of toluene and 1,000 ml of water were added to dissolve the contents, and then the organic layer was separated using a separatory funnel. This organic layer was washed twice with 5% NaOH aqueous solution, then neutralized with 2% sulfuric acid, and further washed with water three times, and then toluene was distilled off to obtain a brown solid product 221. 9 g (yield: 96%) was obtained. This product did not show a clear melting point due to the glassy solid. The analysis result of this product was as follows.

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

From the above analysis results, the product obtained in this step is [N ₃ = P ₃ (OC ₆ H ₄ —C (CH ₃ ) ₂ —C ₆ H ₄ OCH ₂ C ₆ H ₅ ) ₂ (OC ₆ H _{5) 4], [N 3} = P 3 (OC 6 H 4 -C (CH 3) 2 -C 6 H 4 OCH 2 C 6 H 5) 3 (OC 6 H 5) 3], [N 3 = P ₃ (OC ₆ H ₄ —C (CH ₃ ) ₂ —C ₆ H ₄ OCH ₂ C ₆ H ₅ ) ₄ (OC ₆ H ₅ ) ₂ ], the average composition of which is [N = P (OC ₆ it was confirmed that _{H 4 -C (CH 3) 2} -C 6 H 4 OCH 2 C 6 H 5) 1.03 (OC 6 H 5) 0.97] _3.

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

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

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

Example 8 (Production of hydroxyl group-containing cyclic phosphazene compound according to Form 2)
[Step 1: Production of substituted cyclic phosphonitriles by method 2-A above]
500 ml 1,2-dimethoxyethane (DME) and 44.0 g (1.10 mol) 60% NaH / oil under nitrogen atmosphere in a 3 liter flask equipped with stirrer, thermometer, reflux condenser and nitrogen inlet Was charged. Under stirring, p-cresol and 1,3,3-trimethyl-1- (4-benzyloxyphenyl) indan-6-ol (45%) and 1,3,3-trimethyl-1- (4-bidro DME solution of a mixture with xylphenyl) -6-benzyloxyindane (55%) [p-cresol 54.1 g (0.50 mol), 1,3,3-trimethyl-1- (4-benzyloxyphenyl) indane 6-ol 96.7 g (0.27 mol), 1,3,3-trimethyl-1- (4-bidoxyphenyl) -6-benzyloxyindane 118.8 g (0.33 mol), DME 1,000 ml] After dropwise addition over 2 hours at 5 ° C. or lower, the mixture was stirred at 50 ° C. for 2 hours to prepare a sodium salt of the p-cresol and the indane derivative.

  Next, a DME solution of cyclophosphazene [46.4 g (0.40 unit mol) of hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, in a 3 liter flask equipped with a stirrer, a thermometer, a reflux condenser and a nitrogen inlet tube. 5.8 g (0.05 unit mol), decachlorocyclopentaphosphazene 2.9 g (0.025 unit mol), dodecachlorocyclohexaphosphazene 1.7 g (0.015 unit mol), macrocycle greater than tetradecachlorocycloheptaphosphazene 1.2 g (0.01 unit mol), DME 500 ml], sodium salt solution of p-cresol and indane derivative was added dropwise at 25 ° C. over 1 hour with stirring, and stirred under reflux (75 ° C.). The reaction was carried out for 8 hours. After completion of the reaction, the reaction solution was concentrated to about 1,000 ml, 500 ml of toluene and 500 ml of water were added to dissolve the contents, and the organic layer was separated using a separatory funnel. The organic layer was washed twice with 5% NaOH aqueous solution, then neutralized with 2% sulfuric acid, and further washed with water three times. After removing DME and toluene, a yellow solid product was obtained. 228.4 g (yield: 89%) was obtained. This product did not show a clear melting point due to the glassy solid. The analysis result of this product was as follows.

¹ H-NMR spectrum (in heavy acetone, δ, ppm):
_{-CH 3 1.0~1.6 (12H), -} CH 2 - 2.1~2.4 (2H), - CH 2 - 5.0 (2H), phenyl CH from 6.8 to 7. 9 (11H)
◎ ³¹ P-NMR spectrum (in heavy acetone, δ, ppm):
Trimer _{(P =} N) 3 9.5, tetramer _(P = N) 4 -12.4, V. hexamer _(P = N) 5,6 -17.0, heptamer or more ( P = N) _≧ 7−18.0 to −23.0
◎ CHNP elemental analysis:
Theoretical value C: 75.5%, H: 6.4%, N: 2.7%, P: 6.0%
Measured value C: 75.2%, H: 6.6%, N: 2.7%, P: 5.8%
◎ Residual chlorine analysis:
<0.01%

From the above analysis results, product obtained in this process _{[N = P (OC 6 H} 4 -Indane-OCH 2 C 6 H 5) 1.05 (OC 6 H 4 CH 3) 0.95] n and it was confirmed to be _{[n = P (O-Indane} -C 6 H 4 OCH 2 C 6 H 5) 0.98 (OC 6 H 4 CH 3) 1.02] mixture of n.

[Step 2: Deprotecting group step]
In a 3 liter flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube, 154.0 g (0.30 unit mol) of the product obtained in Step 1 and 1,000 ml of toluene were charged. To this was added dropwise 120.1 g (0.60 mol) of trimethylsilane iodide at 5 to 10 ° C. over 10 hours under a nitrogen atmosphere, and the mixture was stirred at 25 to 30 ° C. for 12 hours. After completion of the reaction, the reaction solution was poured into 1,000 ml of water, and the organic layer was separated using a separatory funnel. This organic layer was washed with water three times, and toluene was distilled off to obtain 113.9 g (yield: 90%) of a yellow solid product. This product did not show a clear melting point due to the glassy solid. The analysis result of this product was as follows.

¹ H-NMR spectrum (in heavy acetone, δ, ppm):
_{-CH 3 1.0~1.6 (12H), -} CH 2 - 2.1~2.4 (2H), - CH 2 - 5.0 (2H), phenyl CH from 6.8 to 7. 9 (11H)
◎ ³¹ P-NMR spectrum (in heavy acetone, δ, ppm):
Trimer _{(P =} N) 3 9.5, tetramer _(P = N) 4 -12.4, V. hexamer _(P = N) 5,6 -17.0, heptamer or more ( P = N) _≧ 7−18.0 to −23.0
◎ CHNP elemental analysis:
Theoretical value C: 71.6%, H: 6.3%, N: 3.3%, P: 7.3%
Measured value C: 70.2%, H: 6.2%, N: 3.3%, P: 7.1%
◎ Hydroxyl equivalent:
418 g / eq. (Theoretical value 422 g / eq.)

From the above analysis results, product obtained in this process _{[N = P (OC 6 H} 4 -Indane-OH) 1.05 (OC 6 H 4 CH 3) 0.95] n and [N = P was confirmed to be _{(O-Indane-C 6 H} 4 OH) 0.98 (OC 6 H 4 CH 3) 1.02] mixture of n.

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

Examples 9 to 17 and Comparative Examples 2 and 3 (Preparation of resin composition)
Epicoat 1001 which is a bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd .: epoxy equivalent 456 g / eq., Solid content of resin 70%) 651 parts, YDCN-704P which is a cresol novolac epoxy resin (manufactured by Toto Kasei Co., Ltd .: Manufactured in Examples 1-3, 5, 7, and 8 with respect to 300 parts of epoxy equivalent 210 g / eq., Resin solid content 70%), 361 parts of aluminum hydroxide and 0.9 part of 2-ethyl-4-methylimidazole. The hydroxyl group-containing cyclic phosphazene compound or the cyclic phosphazene compound produced in Comparative Example 1 and BRG-558 (manufactured by Showa Polymer Co., Ltd .: hydroxyl group equivalent 106 g / eq., Resin solid content 70%) as a novolak type phenol resin 1 is added at a ratio shown in FIG. Added methyl ether (PGM) a resin solid content of 65% epoxy resin varnish was prepared.

  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 MPa for 100 minutes to obtain a glass epoxy laminated plate having a thickness of 1/16 inch.

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

(Combustion quality)
Based on Underwriters Laboratories Inc.'s UL-94 standard vertical combustion test, V-0, V depending on the total combustion time at the 10th flame contact and the presence or absence of cotton ignition by dripping at the time of combustion. -1, V-2 and non-standard four stages. The evaluation criteria are shown below. The flame retardancy level decreases in the order of V-0>V-1>V-2> non-standard.

V-0: All the following conditions are satisfied.
(A) The total extinguishing time after 10 times of flame contact is within 50 seconds, 5 test pieces twice each.
(B) The test piece was fired twice for each of the five test pieces, and the flame-out time after each contact was within 5 seconds.
(C) There is no ignition of the absorbent cotton under 300 mm due to the drop in all the test pieces.
(D) Growing after the second flame contact is within 30 seconds for all specimens.
(E) All specimens are not framing to the clamp.

V-1: All the following conditions are satisfied.
(A) The total extinguishing time after a total of 10 flame contact times is less than 250 seconds, 5 test pieces twice each.
(B) Flame test was performed twice for each of five test pieces, and the flame extinguishing time after each flame contact was within 30 seconds.
(C) There is no ignition of the absorbent cotton under 300 mm due to the drop in all the test pieces.
(D) For all specimens, the glowing after the second flame contact is within 60 seconds.
(E) All specimens are not framing to the clamp.

V-2: All the following conditions are satisfied.
(A) The total extinguishing time after a total of 10 flame contact times is less than 250 seconds, 5 test pieces twice each.
(B) Flame test was performed twice for each of five test pieces, and the flame extinguishing time after each flame contact was within 30 seconds.
(C) At least one of the five test pieces is ignited on the absorbent cotton under 300 mm by the drop.
(D) For all specimens, the glowing after the second flame contact is within 60 seconds.
(E) All specimens are not framing to the clamp.

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

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

  As is clear from Table 1, the glass epoxy laminates (resin molded bodies) made of the resin compositions of Examples 9 to 17 are superior in flame retardancy to those of Comparative Examples 2 and 3, and have a glass transition. Since the temperature is high, the mechanical properties are excellent, and the bleedout of the cyclic phosphazene compound evaluated by heat resistance is not substantially observed.

Examples 18 to 24 and Comparative Examples 4 and 5 (Preparation of resin composition)
10 parts ESCN-195XL (manufactured by Sumitomo Chemical Co., Ltd .: epoxy equivalent 200 g / eq.), 100 parts spherical fused silica (manufactured by Tatsumori Co., Ltd .: average particle size 20 μm), carnauba wax (Toa Kasei) Co., Ltd.) and 0.5 parts of DBU (1,8-diazabicyclo (5,4,0) undecene-7) were prepared in Examples 1-3, 5, 7 or 8. A hydroxyl group-containing cyclic phosphazene compound or the cyclic phosphazene compound produced in Comparative Example 1 and a phenol novolac resin DL-92 (Maywa Kasei Co., Ltd .: phenolic hydroxyl group equivalent 110) are blended in the proportions shown in Table 2 at room temperature. Mixed. And this was knead | mixed at 90-95 degreeC, Then, it cool-pulverized and manufactured the molding material. The molded product made of this molding material was evaluated for flammability and high temperature storage reliability. The evaluation method is as follows. The results are shown in Table 2.

(Combustion quality)
The molding material is transferred into a mold heated to 175 ° C. and post-cured for 8 hours, and a molded product (sealed product) 5 inches long, 0.5 inches wide and 1/32 inches thick. Got. About this molded article, flammability was evaluated based on the UL-94 standard vertical combustion test as in Examples 9 to 17 and Comparative Examples 2 and 3.

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

  As is apparent from Table 2, the molding materials of Examples 18 to 24 can form resin molded articles having excellent flame retardancy and high temperature storage reliability as compared with those of Comparative Examples 4 and 5.

Synthesis Example 1 (Synthesis of soluble polyimide resin)
In a 3 liter glass flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube, 277.7 g (0.95 mol) of 1,3-bis (3-aminophenoxy) benzene and 3,3 ′ -Dihydroxy-4,4'-diaminobiphenyl (10.7 g, 0.05 mol) and N, N-dimethylformamide (DMF) (700 ml) were charged and dissolved under stirring in a nitrogen atmosphere. Next, the solution in the flask was stirred under a nitrogen atmosphere, and a DMF solution of 4,4 ′-(4,4′-isopropylidenediphenoxy) bisphthalic anhydride (IPBP) [IPBP 520.5 g (1.00 mol) , DMF1,100 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 750 g of a soluble polyimide resin. Obtained.

Synthesis Example 2 (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 were added. 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, with stirring at a reaction temperature of 40 ° C. 2,8.6 g (0.48 mol) of 2,6-dimethylphenol was added dropwise over 2 hours while bubbling air at 2 liters / minute, and then bubbling air at 2 liters / minute for 1 hour. Stirring was performed. And the ethylenediaminetetraacetic acid disodium dihydrogen aqueous solution was added to this, and reaction was stopped. Thereafter, washing was performed 3 times with a 3% hydrochloric acid aqueous solution, followed by further washing with ion-exchanged water. The resulting solution was concentrated and further dried under reduced pressure to obtain 101.3 g of a bifunctional PPE oligomer having hydroxyl groups at both ends. This oligomer has a number average molecular weight of 860, a weight average molecular weight of 1,150, and a hydroxyl group equivalent of 455 g / eq. Met.

Example 25 (Preparation of resin composition)
In Example 2, 20.0 g of the soluble polyimide resin obtained in Synthesis Example 1 and 25.0 g of a dicyclopentadiene-based epoxy resin (trade name “HP7200”: Epoxy equivalent 277 g / eq. Of Dainippon Ink & Chemicals, Inc.) 33.8 g of the produced cyclic phosphazene compound (hydroxyl equivalent: 375 g / eq.) And 0.3 g of 2-ethyl-4-methylimidazole (trade name “2E4MZ” of Shikoku Kasei Co., Ltd.) as a curing accelerator are added to dioxolane. It melt | dissolved and the resin solution (resin composition) was obtained.

  The obtained resin solution was cast on the surface of a 125 μm thick PET film (trade name “Therapy HP” from Toyo Metallizing Co., Ltd.). Thereafter, it was heated and dried for 3 minutes at 60 ° C., 80 ° C., 100 ° C., 120 ° C. and 140 ° C. in a hot air oven to obtain a two-layer resin sheet using a PET film as a support. From this two-layer resin sheet, the PET film was peeled and removed to obtain a single-layer resin sheet (thickness before heat curing 50 μm). The obtained resin sheet is sandwiched between 18 μm rolled copper foil (trade name “BHY-22B-T” of Japan Energy Co., Ltd.) so that the resin surface is in contact with the roughened surface of the copper foil, and the temperature is 180 ° C. and the pressure is 3 MPa. After heating and pressing under the conditions of 1 hour, a copper foil laminate (a single layer resin sheet sandwiched between rolled copper foils) was obtained. The thus obtained copper foil laminate having copper foil layers on both sides was evaluated for solder heat resistance. Moreover, the copper foil of the obtained copper foil laminated body was removed by etching, and the cured sheet was obtained. For the obtained cured sheets, combustibility and glass transition temperature were measured in the same manner as in Examples 9 to 17 and Comparative Examples 2 and 3. The results are shown in Table 3. The solder heat resistance evaluation method is as follows.

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

Examples 26 to 28 (Preparation of resin composition)
A resin composition was obtained in the same manner as in Example 25 except that the cyclic phosphazene compound shown in Table 3 was used in the amount shown in the same table in place of the cyclic phosphazene compound produced in Example 2. It was. Using this resin composition, a copper foil laminate and a cured sheet were obtained by the same method and conditions as in Example 25, and the solder heat resistance, glass transition temperature and combustibility were evaluated. The results are shown in Table 3.

Comparative Example 6 (Preparation of resin composition)
Instead of the cyclic phosphazene compound produced in Example 2, 30.0 g of the cyclic phosphazene compound produced in Comparative Example 1 and a phenol novolak type phenol resin (trade name “PSM-4324” of Gunei Chemical Co., Ltd .: hydroxyl group equivalent of 104 g / eq.) A resin composition was obtained in the same manner as in Example 25 except that 9.4 g was used. Using this resin composition, a copper foil laminate and a cured sheet were obtained by the same method and conditions as in Example 25, and the solder heat resistance, glass transition temperature and flame retardancy were evaluated. The results are shown in Table 3.

Example 29 (Preparation of resin composition)
50 g of the soluble polyimide resin obtained in Synthesis Example 1, 28.0 g of 2,2′-bis (4-cyanatophenyl) propane (trade name “BADCy” from Lonza), which is a bisphenol A-based cyanate compound, and an implementation 33.8 g of the cyclic phosphazene compound obtained in Example 2 (hydroxyl equivalent = 375 g / eq.) Was dissolved in dioxolane to obtain a resin solution (resin composition).

  This resin solution was cast on the surface of a 125 μm-thick PET film (trade name “Therapy HP” from Toyo Metallizing Co., Ltd.). Thereafter, it was heated and dried for 3 minutes at 60 ° C., 80 ° C., 100 ° C., 120 ° C. and 140 ° C. in a hot air oven to obtain a two-layer resin sheet using a PET film as a support. From this two-layer resin sheet, the PET film was peeled and removed to obtain a single-layer resin sheet (thickness before heat curing 50 μm). The obtained resin sheet is sandwiched between 18 μm rolled copper foil (trade name “BHY-22B-T” of Japan Energy Co., Ltd.) so that the resin surface is in contact with the roughened surface of the copper foil, temperature 200 ° C., pressure 3 MPa. A copper foil laminate (single layer resin sheet sandwiched between rolled copper foils) was obtained by heating and pressurizing for 1 hour under the above conditions. And about this copper foil laminated body, the solder heat resistance was evaluated by the method similar to Example 25. FIG. Further, the flammability and glass transition temperature of the cured sheet obtained by removing the copper foil of the copper foil laminate by etching were measured in the same manner as in Example 25. The results are shown in Table 4.

Examples 30 to 32 (Preparation of resin composition)
A resin composition was obtained in the same manner as in Example 29 except that the cyclic phosphazene compound shown in Table 4 was used in the compounding amount indicated in the same table instead of the cyclic phosphazene compound produced in Example 2. It was. Using this resin composition, a copper foil laminate and a cured sheet were obtained by the same method and conditions as in Example 29, and the solder heat resistance, glass transition temperature and combustibility were evaluated. The results are shown in Table 4.

Comparative Example 7 (Preparation of resin composition)
Instead of the cyclic phosphazene compound produced in Example 2, 30.0 g of the cyclic phosphazene compound produced in Comparative Example 1 and a phenol novolac type phenol resin (trade name “PSM-4324” of Gunei Chemical Co., Ltd .: hydroxyl group equivalent of 104 g / eq.) A resin composition was obtained in the same manner as in Example 29 except that 9.4 g was used. Using this resin composition, a copper foil laminate and a cured sheet were obtained by the same method and conditions as in Example 29, and the solder heat resistance, glass transition temperature and combustibility were evaluated. The results are shown in Table 4.

Example 33 (Preparation of resin composition)
22.8 g of the bifunctional PPE oligomer obtained in Synthesis Example 2 (hydroxyl equivalent: 455 g / eq), 13.8 g of the cyclic phosphazene compound obtained in Example 1 (hydroxyl equivalent 276 g / eq.), And a bisphenol A type epoxy resin (Product name “Epikote 828” of Japan Epoxy Resin Co., Ltd .: epoxy equivalent 188 g / eq.) 18.8 g was dissolved in dioxolane to obtain a resin solution (resin composition).

  This resin solution was cast on the surface of a 125 μm-thick PET film (trade name “Therapy HP” from Toyo Metallizing Co., Ltd.). Thereafter, it was heated and dried for 3 minutes at 60 ° C., 80 ° C., 100 ° C., 120 ° C. and 140 ° C. in a hot air oven to obtain a two-layer resin sheet using a PET film as a support. The PET film was peeled and removed from the two-layer resin sheet to obtain a single-layer resin sheet (thickness before heat curing was 50 μm). The obtained resin sheet is sandwiched between 18 μm rolled copper foil (trade name “BHY-22B-T” of Japan Energy Co., Ltd.) so that the resin surface is in contact with the roughened surface of the copper foil, and the temperature is 180 ° C. and the pressure is 3 MPa. A copper foil laminate (single layer resin sheet sandwiched between rolled copper foils) was obtained by heating and pressing for 1 hour under the above conditions. And about this copper foil laminated body, the solder heat resistance was evaluated by the method similar to Example 25. FIG. Further, the flammability and glass transition temperature of the cured sheet obtained by removing the copper foil of the copper foil laminate by etching were measured in the same manner as in Example 25. The results are shown in Table 5.

Examples 34 to 36 (Preparation of resin composition)
In place of the cyclic phosphazene compound produced in Example 1, the cyclic phosphazene compound shown in Table 5 was used in the same manner as in Example 33 except that the compounding amount indicated in the table was used to obtain a resin composition. It was. Using this resin composition, a copper foil laminate and a cured sheet were obtained by the same method and conditions as in Example 33, and the solder heat resistance, glass transition temperature and combustibility were evaluated. The results are shown in Table 5.

Comparative Example 8 (Preparation of resin composition)
Instead of the cyclic phosphazene compound and bisphenol A type epoxy resin produced in Example 1, 15.0 g of the cyclic phosphazene compound produced in Comparative Example 1 and bisphenol A type epoxy resin (trade name “Epikote 828, Japan Epoxy Resin Co., Ltd.”) ": Epoxy equivalent 188 g / eq.) A resin composition was obtained in the same manner as in Example 33 except that 9.4 g was used. Using this resin composition, a copper foil laminate and a cured sheet were obtained by the same method and conditions as in Example 33, and the solder heat resistance, glass transition temperature and combustibility were evaluated. The results are shown in Table 5.

Claims (8)

A hydroxyl group-containing cyclic phosphazene compound represented by the following formula (1).

(In the formula (1), n represents an integer of 3 to 15, A represents a group selected from the group consisting of the following A1, A2, and A3 groups, and at least one is an A3 group.
A1 group: alkyl group having 1 to 6 carbon atoms, optionally substituted with at least one group selected from an alkenyl group and an aryl group, an alkoxy group having 1 to 8 carbon atoms.
A2 group: alkyl group having 1 to 6 carbon atoms, optionally substituted with at least one group selected from an alkenyl group and an aryl group, an aryloxy group having 6 to 20 carbon atoms.
A3 group: a hydroxyphenyl-substituted phenyloxy group represented by the following formula (3), a hydroxyphenyl-substituted indanoxy group represented by the following formula (4), and a hydroxyindan-substituted phenyloxy group represented by the following formula (5) A group selected from the group consisting of

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

In Formula (4) and Formula (5), R ¹ and R ² represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, or a phenyl group. )   The hydroxyl group-containing cyclic phosphazene compound according to claim 1, wherein 2 (2n-2) of 2n A's are A3 groups in the formula (1).   The hydroxyl group-containing cyclic phosphazene compound according to claim 1 or 2, wherein n in the formula (1) is 3 or 4.   The hydroxyl group-containing cyclic phosphazene compound according to any one of claims 1 to 3, comprising two or more kinds of hydroxyl group-containing cyclic phosphazene compounds having different n in the formula (1). Selected from the group consisting of the following E1, E2, and E3 groups such that at least one of the halogen atoms of the cyclic phosphonitrile dihalide represented by the following formula (6) is substituted by the following E3 group: Substituting with a group to produce a cyclic phosphonitrile substituent,

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

( Z in Formula (8), Formula (9) and Formula (10) represents a protecting group capable of forming an OH group when eliminated, and Y in Formula (8) represents O, S, SO) ₂ , CH ₂ , CHCH ₃ , C (CH ₃ ) CH ₂ CH ₃ or CO, wherein R ¹ and R ² in formula (9) and formula (10) are a hydrogen atom, an alkyl having 1 to 4 carbon atoms Group, cycloalkyl group or phenyl group.)
Removing the protecting group from the E3 group of the cyclic phosphonitrile substituent;
The manufacturing method of the hydroxyl-group containing cyclic phosphazene compound containing this. A resin component;
The hydroxyl group-containing cyclic phosphazene compound according to any one of claims 1 to 4,
A resin composition comprising:   The resin composition according to claim 6, wherein the resin component is selected from the group consisting of an epoxy resin, a polyimide resin, and a modified polyphenylene ether.   The resin molding which consists of a resin composition of Claim 6 or 7.