JP6124176B2 - Composition for resin molding - Google Patents

Description

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

  In the fields of industrial and consumer equipment and electrical products, synthetic resins have advantages over other materials in terms of processability, chemical resistance, weather resistance, electrical properties and mechanical strength. Since it has, it is used extensively and the amount of its use is increasing. However, since synthetic resins have the property of being easily combusted, they are required to be provided with flame retardancy, and in recent years, the required performance is gradually increasing. For this reason, resin compositions used for sealants and substrates of electronic parts such as LSIs, for example, epoxy resin compositions, are 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 2005-248134 A JP 2007-45916 A

  Then, the improvement for improving the reliability (high temperature reliability) of the resin molded product under high temperature is examined for the phosphazene flame retardant, and as an example, Patent Documents 6 to 11 have a glycidyl 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. 48-37499 JP-A-3-163090 Japanese Patent Laid-Open No. 6-247989 JP-A-8-193091 JP 2001-335676 A JP 2006-117545 A

  On the other hand, with recent downsizing and higher functionality of electronic devices, printed wiring boards are required to be thin and light and to be capable of high-density wiring. Further, in printed wiring boards, the build-up lamination method having an IVH (Interstitial Via Hole) structure that has a small diameter and connects only necessary layers with non-through holes is rapidly spreading. A heat-resistant resin having a high glass transition temperature (Tg) is required for the insulating layer of the build-up lamination type printed wiring board without using a substrate such as glass cloth. For this reason, even in the phosphazene flame retardant, it is necessary to keep the glass transition temperature of the resin molded product high.

  The object of the present invention is to achieve the synthesis of a phosphazene compound that does not impair the mechanical properties and reliability at high temperatures, and to increase the flame retardancy of the resin molded article without impairing the heat resistance and the high temperature reliability. There is.

  As a result of repeated research to solve the above-mentioned problems, the present inventors have exhibited excellent flame retardancy, which is a molded product composed of a resin molded product composition containing a phosphazene compound having an epoxyethylphenyloxy group, At the same time, it was found that the mechanical properties and reliability at high temperatures were excellent.

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

In the formula (1), A represents a group selected from the group consisting of the following A1 group and A2 group, and at least one is an A2 group.
A1 group: an aryloxy group having 6 to 20 carbon atoms in which at least one group selected from an alkyl group having 1 to 6 carbon atoms and an aryl group may be substituted.

A2 group: An epoxyethylphenyloxy group represented by the following formula (2).

  In this epoxyethylphenyloxy group-containing cyclic phosphazene compound, for example, in formula (1), 1 to 6 of 6 A are A2 groups, and the remaining A is a phenoxy group.

  The method for producing an epoxyethylphenyloxy group-containing cyclic phosphazene compound according to the present invention includes the following step 1 and step 2.

[Step 1]
All halogen atoms of the cyclic phosphonitrile dihalide represented by the following formula (3) are substituted with a group selected from the group consisting of the following G1 group and G2 group so that at least one is substituted with the following G2 group And a step of producing a substituted styryloxy group-containing cyclic phosphonitrile.

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

[Step 2]
A step of oxidizing the styryloxy group-containing cyclic phosphonitrile substitute obtained in Step 1 with an oxidizing agent to produce an epoxyethylphenyloxy group-containing cyclic phosphonitrile substitute.

The composition for a resin molded body of the present invention is an epoxyethylphenyloxy group-containing cyclic phosphazene compound of the present invention, at least one resin component selected from the group consisting of a thermoplastic resin component and a thermosetting resin component (carboxyl group or Except for alicyclic olefin polymers having an acid anhydride group) . Examples of the resin component include epoxy resin, polyimide resin, bismaleimide resin, cyanate ester resin, phenol resin, bismaleimide-cyanate ester resin, polyester resin, and modified polyphenylene ether resin.

  The polymerizable composition of the present invention contains the epoxyethylphenyloxy group-containing cyclic phosphazene compound of the present invention.

  The resin molded body of the present invention is obtained by curing the resin molded body composition of the present invention or the polymerizable composition of the present invention.

  The electronic component of the present invention uses the resin molded body of the present invention.

  Since the epoxyethylphenyloxy group-containing cyclic phosphazene compound of the present invention has the specific structure as described above, it can effectively enhance its flame retardancy without impairing the mechanical properties of the resin molded product. In addition, it is difficult to impair the high temperature reliability of the resin molded body.

  Since the method for producing an epoxyethylphenyloxy group-containing cyclic phosphazene compound according to the present invention includes the steps 1 and 2 as described above, the epoxyethylphenyloxy group having the specific structure as described above according to the present invention. Containing cyclic phosphazene compounds can be produced.

  The composition for a resin molded body and the polymerizable composition of the present invention contain the epoxyethylphenyloxy group-containing cyclic phosphazene compound of the present invention as a flame retardant, and thus exhibit practical mechanical properties and flame retardancy, and also have a high temperature. A highly reliable resin molded body can be obtained.

  Since the resin molded body of the present invention is composed of the resin molded body composition and the polymerizable composition of the present invention, it exhibits practical mechanical properties and flame retardancy, and has high temperature reliability.

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

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

[A1 group]
An aryloxy group having 6 to 20 carbon atoms; In the aryloxy group, at least one group selected from an alkyl group having 1 to 6 carbon atoms and an aryl group may be substituted.

  Examples of such aryloxy groups include phenoxy group, methylphenoxy group, dimethylphenoxy group, ethylphenoxy group, ethylmethylphenoxy group, diethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, isopropylmethylphenoxy group, Isopropylethylphenoxy group, diisopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-pentylphenoxy group, n-hexylphenoxy group, phenylphenoxy group, naphthyloxy group, anthryloxy Groups and phenanthryloxy groups. Of these, phenoxy group, methylphenoxy group, dimethylphenoxy group, diethylphenoxy group, phenylphenoxy group and naphthyloxy group are preferable, and phenoxy group, methylphenoxy group, dimethylphenoxy group and naphthyloxy group are particularly preferable.

[Group A2]
An epoxyethylphenyloxy group represented by the following formula (2).

  In the formula (1), 6 A are included, and at least one of them is an A2 group. Accordingly, the epoxyethylphenyloxy group-containing cyclic phosphazene compound of the present invention represented by the formula (1) can be roughly divided into the following forms [A] and [B].

[Form A]
All 6 A's are A2 groups.

  The epoxyethylphenyloxy group-containing cyclic phosphazene compound having such a form is an epoxyethylphenyloxy group-containing cyclotriphosphazene compound, which is an epoxyethylphenyloxy group in which all of A in the formula (1) are A2 groups. It is.

[Form B]
A part (namely, at least one) of the six As is an A2 group, and the other A is a group selected from the A1 group. In this case, all of A other than the A2 group may be the same A1 group, or two or more kinds of A1 groups may be mixed.

Whether 1 to 6 of 6 A are A2 groups should be confirmed by ¹ H-NMR analysis of an epoxyethylphenyloxy group-containing cyclic phosphazene compound or an intermediate in its production process. Can do.

  Specific examples of the epoxyethylphenyloxy group-containing cyclic phosphazene compound having such a form are epoxyethylphenyloxy group-containing cyclotriphosphazene compounds, wherein A in the formula (1) is an A2 group. A combination of a phenoxy group as an A1 group, a combination of an epoxyethylphenyloxy group as an A2 group and a methylphenoxy group as an A1 group, an epoxyethylphenyloxy group as an A2 group and an A1 group A combination of a certain dimethylphenoxy group, a combination of an epoxyethylphenyloxy group which is an A2 group and an ethylphenoxy group which is an A1 group, an epoxyethylphenyloxy group which is an A2 group and an ethylmethylphenoxy which is an A1 group In combination with a group, A2 group epoxyethyl A combination of a phenyloxy group and a diethylphenoxy group which is an A1 group, a combination of an epoxyethylphenyloxy group which is an A2 group and an n-propylphenoxy group which is an A1 group, an epoxyethylphenyloxy group which is an A2 group In combination with isopropylphenoxy group as A1 group, in combination with epoxyethylphenyloxy group as A2 group and isopropylmethylphenoxy group as A1 group, epoxyethylphenyloxy group as A2 group and A1 group In combination with isopropylethylphenoxy group which is A2, epoxyethylphenyloxy group which is A2 group and diisopropylphenoxy group which is A1 group, epoxyethylphenyloxy group which is A2 group and n which is A1 group -In combination with butylphenoxy groups A combination of an epoxyethylphenyloxy group that is an A2 group and a sec-butylphenoxy group that is an A1 group, a combination of an epoxyethylphenyloxy group that is an A2 group and a tert-butylphenoxy group that is an A1 group, A combination of an epoxyethylphenyloxy group which is an A2 group and an n-pentylphenoxy group which is an A1 group, a combination of an epoxyethylphenyloxy group which is an A2 group and an n-hexylphenoxy group which is an A1 group, A combination of an epoxyethylphenyloxy group as an A2 group and a phenylphenoxy group as an A1 group, a combination of an epoxyethylphenyloxy group as an A2 group and a naphthyloxy group as an A1 group, an A2 group Combination of epoxyethylphenyloxy group and anthryloxy group which is A1 group And a combination of an epoxyethylphenyloxy group that is an A2 group and a phenanthryloxy group that is an A1 group, and any mixture thereof.

Of these, an epoxyethylphenyloxy group-containing cyclotriphosphazene compound, wherein A in the formula (1) is a combination of an epoxyethylphenyloxy group that is an A2 group and a phenoxy group that is an A1 group, A combination of an epoxyethylphenyloxy group and a methylphenoxy group which is an A1 group, a combination of an epoxyethylphenyloxy group which is an A2 group and a dimethylphenoxy group which is an A1 group, an epoxyethylphenyl which is an A2 group A combination of an oxy group and a diethylphenoxy group which is an A1 group, a combination of an epoxyethylphenyloxy group which is an A2 group and a phenylphenoxy group which is an A1 group, an epoxyethylphenyloxy group which is an A2 group and A1 In combination with the radical naphthyloxy group and any of these Compounds are preferred.

  In particular, an epoxyethylphenyloxy group-containing cyclotriphosphazene compound, wherein A in the formula (1) is a combination of an epoxyethylphenyloxy group that is an A2 group and a phenoxy group that is an A1 group, and is an A2 group Combination of epoxyethylphenyloxy group and methylphenoxy group which is A1 group, Combination of epoxyethylphenyloxy group which is A2 group and dimethylphenoxy group which is A1 group, Epoxyethylphenyloxy which is A2 group A combination of a group with a naphthyloxy group which is an A1 group and any mixtures thereof are preferred.

Production method of epoxyethylphenyloxy group-containing cyclic phosphazene compound The epoxyethylphenyloxy group-containing cyclic phosphazene compound of the present invention can be produced by the following method.

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

  In the formula (3), X represents a halogen atom, preferably a fluorine atom or a chlorine atom.

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

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

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

  A preferable example of the cyclic phosphonitrile dihalide used in this production method is hexafluorocyclotriphosphazene or hexachlorocyclotriphosphazene.

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

[Compound B1]
Phenols having 6 to 20 carbon atoms.
In this phenol, at least one group selected from an alkyl group having 1 to 6 carbon atoms and an aryl group may be substituted.

  Examples of such phenols include phenol, cresol, dimethylphenol, ethylphenol, ethylmethylphenol, diethylphenol, n-propylphenol, isopropylphenol, isopropylmethylphenol, isopropylethylphenol, diisopropylphenol, n-butylphenol, Examples include sec-butylphenol, tert-butylphenol, n-pentylphenol, n-hexylphenol, phenylphenol, naphthol, anthranol, and phenanthranol. Among these, phenol, cresol, dimethylphenol, diethylphenol, phenylphenol and naphthol are preferable, and phenol, cresol, dimethylphenol and naphthol are particularly preferable.

[Compound B2]
4-ethenylphenol represented by the following formula (5).

  In the method for producing an epoxyethylphenyloxy group-containing cyclic phosphazene compound of the present invention, first, the cyclic phosphonitrile dihalide represented by the above formula (3) is reacted with only the above compounds B1 and B2 or B2. To produce a cyclic phosphazene compound by replacing all halogen atoms of the cyclic phosphonitrile dihalide with a group selected from the group consisting of the following G1 group and G2 group so that at least one is substituted with the following G2 group: (Step 1).

[G1 group]
An aryloxy group having 6 to 20 carbon atoms, wherein at least one group selected from an alkyl group having 1 to 6 carbon atoms and an aryl group may be substituted.
This group is substituted with the halogen atom of the cyclic phosphonitrile dihalide represented by the formula (3) by the compound B1, and corresponds to the aforementioned A1 group.

[G2 group]
A styryloxy group represented by the following formula (4).

この基は、化合物Ｂ２により式（３）で表される環状ホスホニトリルジハライドのハロゲン原子と置換されるものである。

This group is substituted with the halogen atom of the cyclic phosphonitrile dihalide represented by the formula (3) by the compound B2.

  In this production process, the type of the epoxyethylphenyloxy group-containing cyclic phosphazene compound to be produced, that is, the case of producing the epoxyethylphenyloxy group-containing cyclic phosphazene compound according to the above-mentioned form A and the epoxyethyl according to the above-mentioned form B In the case of producing a phenyloxy group-containing cyclic phosphazene compound, compounds B1 to B2 are appropriately selected and used. Specifically, it is as follows.

[When producing an epoxyethylphenyloxy group-containing cyclic phosphazene compound of form A]
In this case, the cyclic phosphonitrile dihalide is reacted with the compound B2, and all of the halogen atoms (hereinafter sometimes referred to as active halogen atoms) of the cyclic phosphonitrile dihalide are substituted with the G2 group derived from the compound B2. As a method of reacting the cyclic phosphonitrile dihalide with the compound B2 and substituting all the active halogen atoms of the cyclic phosphonitrile dihalide with the G2 group, any of the following methods can be employed.

<Method Aa>
A cyclic phosphonitrile dihalide is reacted with an alkali metal salt of compound B2.
In the case of this method, the amount of the alkali metal salt of compound B2 is usually preferably set to 1.0 to 2.0 equivalents of the amount of the active halogen atom of the cyclic phosphonitrile dihalide, and 1.05 to 1 More preferably, it is set to 5 equivalents. When the amount used is less than 1.0 equivalent, a part of the active halogen atom remains, and the target epoxyethylphenyloxy group-containing cyclic phosphazene compound may not exhibit the required effect. On the other hand, if the amount used exceeds 2.0 equivalents, it may be difficult to separate and purify the reaction product, which is uneconomical.

<Method Ab>
Cyclic phosphonitrile dihalide and compound B2 are reacted in the presence of a base that captures hydrogen halide.
In the case of this method, the amount of compound B2 used is preferably set to 1.0 to 2.0 equivalents, preferably 1.05 to 1.5 equivalents, of the amount of the active halogen atom of the cyclic phosphonitrile dihalide. Is more preferable. When the amount used is less than 1.0 equivalent, a part of the active halogen atom remains, and the target epoxyethylphenyloxy 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 equivalent, a part of the active halogen atom remains, and the target epoxyethylphenyloxy group-containing cyclic phosphazene compound may not exhibit the required effect. On the other hand, if the amount used exceeds 2.1 equivalents, it may be difficult to separate and purify the reaction product, which is uneconomical.

[When producing an epoxyethylphenyloxy group-containing cyclic phosphazene compound of Form B]
In this case, the compound B2 and at least one of the compounds B1 are reacted with the cyclic phosphonitrile dihalide, and a part of the active halogen atoms of the cyclic phosphonitrile dihalide is substituted with the G2 group derived from the compound B2. And all of the other remaining active halogen atoms are replaced with at least one of the G1 groups derived from compound B1. As a method for this, any of the following methods can be adopted.

<Method Ba>
The cyclic phosphonitrile dihalide is reacted with an alkali metal salt of compound B2 and at least one alkali metal salt of compound B1 to replace all active halogen atoms. In the said mixture, the ratio of the alkali metal salt of compound B2 can be suitably set according to the kind of epoxy ethyl phenyloxy group containing cyclic phosphazene compound to manufacture.

  In the case of this method, the amount of the above mixture used is preferably set to 1.0 to 2.0 equivalents of the amount of active halogen atoms of the cyclic phosphonitrile dihalide, and is set to 1.05 to 1.3 equivalents. More preferably. When the amount used is less than 1.0 equivalent, a part of the active halogen atom remains, and the target epoxyethylphenyloxy group-containing cyclic phosphazene compound may not exhibit the required effect. On the other hand, if the amount used exceeds 2.0 equivalents, it may be difficult to separate and purify the reaction product, which is uneconomical.

<Method B-b>
The cyclic phosphonitrile dihalide is reacted with a mixture of compound B2 and at least one of the compounds B1 in the presence of a base that captures hydrogen halide to replace all active halogen atoms. In the said mixture, the ratio of compound B2 can be suitably set according to the kind of epoxy ethyl phenyloxy group containing cyclic phosphazene compound to manufacture.

  In the case of this method, the amount of the above mixture used is preferably set to 1.0 to 2.0 equivalents of the amount of active halogen atoms of the cyclic phosphonitrile dihalide, and is set to 1.05 to 1.3 equivalents. More preferably. When the amount used is less than 1.0 equivalent, a part of the active halogen atom remains, and the target epoxyethylphenyloxy 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 equivalent, a part of the active halogen atom remains, and the target epoxyethylphenyloxy group-containing cyclic phosphazene compound may not exhibit the required effect. On the other hand, if the amount used exceeds 2.1 equivalents, it may be difficult to separate and purify the reaction product, which is uneconomical.

<Method Bc>
First, compound B2 is reacted with cyclic phosphonitrile dihalide to obtain a partially substituted product in which part of the active halogen atom of cyclic phosphonitrile dihalide is substituted with G2 group derived from compound B2 (first step). Next, at least one compound of the compound B1 is reacted with the partial substitution product thus obtained, and all the remaining active halogen atoms are substituted with the G1 group derived from the compound B1 (second step).

  The first step of this method may be carried out by reacting an alkali metal salt of compound B2 with a cyclic phosphonitrile dihalide, or captures a hydrogen halide of compound B2 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 alkali metal salt of compound B1 with the partially substituted product obtained in the first step, or with respect to the partially substituted product obtained in the first step. May be reacted in the presence of a base that captures the hydrogen halide.

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

  The first step of this method may be carried out by reacting an alkali metal salt of Compound B1 with a cyclic phosphonitrile dihalide, or captures the hydrogen halide of Compound B1 with respect to the cyclic phosphonitrile dihalide. The reaction may be performed in the presence of a base. Further, the second step may be carried out by reacting the alkali metal salt of compound B2 with the partially substituted product obtained in the first step, or with respect to the partially substituted product obtained in the first step. May be reacted in the presence of a base that captures the hydrogen halide.

  In general, the alkali metal salt used in each of the above methods is preferably a lithium salt, a sodium salt, a potassium salt, or a cesium salt. In particular, sodium salt and potassium salt are preferable. Such an alkali metal salt is a dehydrogenation reaction between the compounds B1 and B2 and metal lithium, metal sodium, or metal potassium, or the compounds B1 to B2 and lithium hydroxide, sodium hydroxide, potassium hydroxide, or the like. It can be obtained by a dehydration reaction from a mixture with an alkali metal hydroxide.

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

  The reaction of the above-mentioned cyclic phosphonitrile dihalide and the compounds B1 to B2 can be carried out without solvent for any of the above-mentioned methods, and can also be carried out using a solvent. When a solvent is used, the type of the solvent is not particularly limited as long as it does not adversely affect the reaction. Usually, diethyl ether, tetrahydrofuran (THF), 1,4-dioxane, 1,2- Ether systems such as dimethoxyethane, butyl methyl ether, diisopropyl ether, 1,2-diethoxyethane and diphenyl ether, aromatic hydrocarbon systems such as benzene, toluene, chlorobenzene, nitrobenzene, xylene, ethylbenzene and isopropylbenzene, chloroform and methylene chloride Halogenated hydrocarbons such as pentane, hexane, cyclohexane, heptane, octane, nonane, undecane and dodecane, etc., heterocyclic aromatic hydrocarbons such as pyridine, tertiary amines and cyanide Conversion Is preferably used an organic solvent -based like. Of these, ether-based organic solvents having an ether bond in the molecule and high solubility of the compounds B1 to B2 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 with the compounds B1 and B2 can be set as appropriate depending on any of the above-mentioned methods or considering the thermal stability of the reaction product. . However, when the reaction is carried out using a solvent, it is usually preferable to set the reaction temperature in a temperature range from −20 ° C. to the boiling point of the solvent. On the other hand, when carrying out the reaction without solvent, the reaction temperature is usually preferably set in the range of 40 to 200 ° C.

  In addition, the epoxy ethylphenyloxy group-containing cyclic phosphazene compound of the present invention is a compound according to the above-mentioned form B, particularly one in which one to five of the six As in the formula (1) are A2 groups. In such a case, it is preferable to employ the above-mentioned method Bc or Method Bd.

  Here, when adopting Method Bc, first, an ether solvent solution or an aromatic hydrocarbon solvent solution of cyclic phosphonitrile dihalide is prepared. Then, with respect to this solvent solution, an ether solvent solution or an aromatic hydrocarbon solvent solution of an alkali metal salt of compound B2 or an ether solvent solution or an aromatic hydrocarbon system of compound B2 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 G2 group derived from B2 is produced. Next, an ether solvent solution or an aromatic hydrocarbon solvent solution of an alkali metal salt of compound B1 or a compound B1 and a hydrogen halide is added to the ether solvent solution or aromatic hydrocarbon solvent solution of the partially substituted product. An ether solvent solution or an aromatic hydrocarbon solvent solution with a base for trapping is usually added at a temperature of 0 to 50 ° C. over 3 to 24 hours, and at a temperature from 0 ° C. to the boiling point of the solvent. React and replace all remaining active halogen atoms with G1 groups from compound B1.

  On the other hand, when adopting Method Bd, first, an ether solvent solution or an aromatic hydrocarbon solvent solution of cyclic phosphonitrile dihalide is prepared. Then, an ether solvent solution or an aromatic hydrocarbon solvent solution of an alkali metal salt of the compound B1 or an ether solvent solution or an aromatic hydrocarbon system of the compound B1 and a base that captures hydrogen halide is added to the solvent solution. 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 G1 group derived from B1 is produced. Next, an ether solvent solution or an aromatic hydrocarbon solvent solution of an alkali metal salt of compound B2 or a compound B2 and a hydrogen halide is added to the ether solvent solution or aromatic hydrocarbon solvent solution of the partially substituted product. An ether solvent solution or an aromatic hydrocarbon solvent solution with a base for trapping is usually added at a temperature of 0 to 50 ° C. over 3 to 24 hours, and at a temperature from 0 ° C. to the boiling point of the solvent. React and replace all remaining active halogen atoms with G2 groups from compound B2.

  Next, in the production method of the present invention, the cyclic phosphazene compound having a styryloxy group obtained in the above-mentioned step 1 is oxidized with an oxidizing agent to produce an epoxyethylphenyloxy group-containing cyclic phosphazene compound (step 2). Thereby, the target epoxy ethyl phenyloxy group containing cyclic phosphazene compound is obtained.

  Methods for oxidizing the styryloxy group of the G2 group to produce an epoxyethylphenyloxy group-containing cyclic phosphazene compound are described in various documents, for example, Non-Patent Documents 3 to 5 as described below.

COMPREHENSIVEORGANIC SYNTHESIS VOL. 7, OXIDATION, BARRY. M.M. By TOST, published in 1991, ELSEVIER H. Hibert, P.M. Burt, ORG. SYNTH. 1928, VOL. 8, 102 5th edition, Experimental Chemistry Course, Volume 17, 2004, Maruzen Co., Ltd.

  The oxidizing agents that can be used in the method of the present invention are all oxidizing agents known for oxidation as described in the above non-patent literature. The oxidizing agent can be used either in pure form or in the form of a mixture thereof, but is preferably used in pure form. The oxidizing agents used are, for example, inorganic or organic peroxides, adducts of hydrogen peroxide, hydrogen peroxide and urea, peroxo complexes of transition metals, peroxo compounds and organic acids and / or inorganic acids and / or Lewis acids, These are organic peracids, inorganic peracids, mixtures with dioxiranes, or mixtures of these oxidizing agents. Moreover, an oxygen-added enzyme (oxygenase) can also be used.

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

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

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

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

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

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

  The production method of the present invention includes the type and amount of styryloxy group and oxidant used in the cyclic phosphonitrile-substituted product having a styryloxy group, the presence or absence of a reaction solvent, and the epoxyethylphenyloxy-containing cyclic phosphonitrile substitution to be obtained. It can be appropriately selected from a wide range according to various conditions such as physical properties and uses of the body. The equivalent amount of the cyclic phosphonitrile substituent having a styryloxy group to the oxidizing agent relative to the styryloxy group depends particularly on the reactivity of the cyclic phosphonitrile substituent having a styryloxy group and the oxidizing agent used. The equivalent of the oxidizing agent with respect to the styryloxy group of the cyclic phosphazene compound having a styryloxy group can usually be selected from the range of 1-10. Preferably it is 1.05-3.5, More preferably, it is 1.2-2.5.

  The production method of the present invention, that is, the method of producing an epoxyethylphenyloxy group-containing cyclic phosphazene compound by oxidizing a cyclic phosphonitrile substituted product having a styryloxy group with an oxidizing agent, The reaction can be carried out without a solvent, or can be carried out using a solvent. When a solvent is used, the type of the solvent is not particularly limited as long as it does not adversely affect the reaction. Usually, a halogenated hydrocarbon compound (dichloromethane, chloroform, 1,2-dichloroethane or 1 , 1,2,2-tetrachloroethane), paraffinic compounds (hexane, pentane or ligroin), ether compounds (diethyl ether), acid amide compounds (N, N-dimethylformamide), nitrile compounds (acetonitrile), Carbon disulfide, nitroaliphatic compounds (nitromethane) and nitroaromatic compounds (nitrobenzene) or mixtures of the aforementioned solvents can be used. Of these, it is particularly preferable to use a halogenated hydrocarbon compound.

  In the production of the present invention, that is, in the production of an epoxyethylphenyloxy group-containing cyclic phosphazene compound by oxidizing a cyclic phosphonitrile substituted product having a styryloxy group with an oxidizing agent, Alternatively, if it is necessary to take out the intermediate styryloxy group-containing cyclic phosphonitrile substitution product depending on the production conditions, it can be isolated and purified from the reaction system by usual methods such as filtration, solvent extraction, column chromatography and recrystallization. Can do.

Resin Molded Composition The resin molded article composition of the present invention comprises the epoxyethylphenyloxy group-containing cyclic phosphazene compound of the present invention and a resin component.

  In the resin molded body composition of the present invention, one type of epoxyethylphenyloxy group-containing cyclic phosphazene compound of the present invention may be used, or two or more types may be used in combination. As the resin component, various thermoplastic resins or thermosetting resins can be used. These resin components may be natural or synthetic.

  Specific examples of the thermoplastic resin that can be used here include polyethylene, polyisoprene, polybutadiene, chlorinated polyethylene, polyvinyl chloride, styrene resin, impact-resistant polystyrene, acrylonitrile-styrene resin (AS resin), and acrylonitrile-butadiene-. Styrene resin (ABS resin), methyl methacrylate-butadiene-styrene resin (MBS resin), methyl methacrylate-acrylonitrile-butadiene-styrene resin (MABS resin), acrylonitrile-acrylic rubber-styrene resin (AAS resin), polymethyl acrylate, poly Methyl methacrylate, polycarbonate, polyphenylene ether, modified polyphenylene ether, aliphatic polyamide, aromatic polyamide, polyethylene terephthalate, polypropylene Polyester resins such as 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. In addition, when using the composition for resin molded bodies of the present invention as a material for casings and parts for electronic equipment applications, in particular, OA equipment, AV equipment, communication equipment, and home appliances, a polyester resin as a thermoplastic resin, It is preferable to use ABS resin, polycarbonate, modified polyphenylene ether, polyamide or the like.

  On the other hand, specific examples of the thermosetting resin usable here include polyurethane, phenol resin, melamine resin, urea resin, unsaturated polyester resin, diallyl phthalate resin, silicone resin, maleimide resin, cyanate ester resin, maleimide- Examples thereof include cyanate ester resins, benzoxazine resins, polybenzimidazoles, polyimides, polyamideimides, polyetherimides, polyesterimides, polycarbodiimides, and epoxy resins. In addition, polyimide resins such as polyimide, polyamideimide, polyetherimide, polyesterimide, polycarbodiimide, maleimide resin, and maleimide-cyanate resin are used to improve the workability and adhesiveness. The thing to which solubility was provided may be sufficient. In addition, the resin molded body composition of the present invention is used for electronic parts, in particular, sealing materials for various IC elements, substrate materials for wiring boards, insulating materials such as interlayer insulating materials and insulating adhesive materials, Si substrates or SiC substrates. When used as insulating materials, conductive materials, and surface protection materials such as polyurethane, phenolic resin, bismaleimide resin, cyanate ester resin, bismaleimide-cyanate resin, polyimide resin or epoxy resin Etc. are preferably used.

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

  In the resin molded body composition of the present invention, the amount of the epoxyethylphenyloxy 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, Usually, it is preferably 0.1 to 200 parts by weight, more preferably 0.5 to 100 parts by weight, and more preferably 1 to 50 parts by weight with respect to 100 parts by weight of the resin component in terms of solid content. It is more preferable to set. When the usage-amount of an epoxy ethyl phenyloxy 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 composition for resin moldings may not show sufficient flame retardance. On the other hand, if it exceeds 200 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 composition for resin moldings 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. Available additives include, for example, natural silica, calcined silica, synthetic silica, amorphous silica, white carbon, alumina, aluminum hydroxide, magnesium hydroxide, calcium silicate, calcium carbonate, zinc borate, zinc stannate, oxidation Titanium, zinc oxide, molybdenum oxide, zinc molybdate, natural mica, synthetic mica, aerosil, kaolin, clay, talc, calcined kaolin, calcined clay, calcined talc, wollastonite, short glass fiber, glass fine powder, hollow glass and Inorganic fillers such as potassium titanate, organic fibers such as aramid fibers or polyparaphenylene benzbisoxazole fibers, surface treatment agents for fillers such as silane coupling agents, waxes, fatty acids and their metal salts, acid amides and Release agents such as paraffin, phosphoric acid Phosphorus flame retardants such as tellurium, condensed phosphate ester, phosphate amide, phosphate amide ester, ammonium phosphate, phosphinate, red phosphorus, melamine, melamine cyanurate, melam, melem, melon and succinoguanamine Nitrogen flame retardant, chlorine flame retardant such as chlorinated paraffin, silicone flame retardant and flame retardant such as bromine flame retardant, flame retardant auxiliary such as antimony trioxide, dripping polytetrafluoroethylene (PTFE) etc. Inhibitors, UV absorbers such as benzotriazole, antioxidants such as hindered phenol and styrenated phenol, photopolymerization initiators such as thioxanthone, fluorescent brighteners such as stilbene derivatives, curing agents, dyes, pigments, coloring Agent, light stabilizer, photosensitizer, thickener, lubricant, antifoaming agent, leveling agent, brightener, polymerization inhibitor, Shit-imparting agent, and the like plasticizers and antistatic agents.

  Furthermore, the composition for resin moldings of this invention can mix | blend the hardening | curing agent and hardening accelerator of a thermosetting resin as needed. The curing agent and curing accelerator used here are not particularly limited as long as they are generally used, but are usually amine compounds, phenolic compounds, acid anhydrides, imidazoles, and organic metal salts. is there. These can also use 2 or more types together.

  When the composition for a resin molded body 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 includes an epoxy resin, a phenol resin, Polyimide resins, bismaleimide resins, cyanate ester resins, bismaleimide-cyanate ester resins and modified polyphenylene ether resins are preferred.

  The epoxy resin that can be used in the resin molded body composition of the present invention is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule. Specific examples thereof include phenol novolac type epoxy resins, brominated phenol novolak type epoxy resins, orthocresol novolak type epoxy resins, biphenyl novolac type epoxy resins, bisphenol-A novolak type epoxy resins and naphthol novolak type epoxy resins. 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 obtained by reaction of aldehydes with aldehydes , Biphenol type epoxy resin, naphthalene type epoxy resin, cyclopentagen type epoxy resin, alkyl-substituted biphenol type epoxy resin, polyfunctional phenol type epoxy resin Resin, obtained by reaction of phenols such as tris (hydroxyphenyl) methane and epichlorohydrin, obtained by reaction of phenolic epoxy resin, trimethylolpropane, oligopropylene glycol, hydrogenated bisphenol-A and the like with epichlorohydrin Aliphatic epoxy resin, hexahydrophthalic acid, tetrahydrophthalic acid or phthalic acid obtained by reaction of epichlorohydrin or 2-methylepichlorohydrin, glycidyl ester epoxy resin, obtained by reaction of amine such as diaminodiphenylmethane or aminophenol with epichlorohydrin Heterocyclic epoxies obtained by the reaction of polyamines such as glycidylamine epoxy resins and isocyanuric acid with epichlorohydrin Phosphazene compounds having a glycidyl group, an epoxy-modified phosphazene resins, isocyanate modified epoxy resin, cyclic aliphatic epoxy resins and urethane-modified epoxy resins. Among these, phenol novolac type epoxy resins, orthocresol novolac type epoxy resins, bisphenol-A type epoxy resins, biphenol type epoxy resins, biphenyl novolac type epoxy resins, naphthalene type epoxy resins, polyfunctional phenol type epoxy resins and tris (hydroxy) Phenolic epoxy resins obtained by reaction of phenyl) methane with epichlorohydrin are preferred. 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, such a resin composition may be referred to as “epoxy resin composition”), the epoxy resin composition is an epoxyethylphenyloxy group-containing cyclic phosphazene compound of the present invention. In addition, other curing agents may be included. The proportion of the epoxyethylphenyloxy group-containing cyclic phosphazene of the present invention in the total amount of the epoxyethylphenyloxy group-containing cyclic phosphazene compound of the present invention and the other curing agent is preferably 0.1 to 99% by weight, 5 to 90% by weight is more preferable. When the proportion of the epoxyethylphenyloxy group-containing cyclic phosphazene compound is less than 0.1% by weight, the resin molded body made of the resin molded body composition may not exhibit sufficient flame retardancy.

  Other curing agents that can be used in combination with the epoxyethylphenyloxy group-containing cyclic phosphazene compound in the epoxy resin composition are not particularly limited. For example, polyamines such as aliphatic polyamines, aromatic polyamines, and polyamide polyamines. Curing agents, acid anhydride curing agents such as hexahydrophthalic anhydride and methyltetrahydrophthalic anhydride, phenolic curing agents such as phenol novolac and cresol novolac, phosphazene compounds having a glycidyloxy group, Lewis such as boron trifluoride Examples thereof include acids and salts thereof and dicyandiamide (DICY). These may be used alone or in combination of two or more.

  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 molded body composition of the present invention such as the above-described epoxy resin composition can be obtained by uniformly mixing the respective components. When this resin molded body composition is allowed to stand for 1 to 36 hours in a temperature range of about 100 to 250 ° C. according to 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 epoxyethylphenyloxy-containing cyclic phosphazene compound of the present invention reacts with the resin component of the epoxyethylphenyloxy group and is stably held in the cured product. High temperature reliability is difficult to lose. Moreover, the epoxy ethyl phenyloxy group containing cyclic phosphazene compound of this invention can improve the flame retardance, without impairing the mechanical characteristics (especially glass transition temperature) of such hardened | cured material. For this reason, the composition for resin moldings 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.

  According to the resin molded body composition of the present invention, a cured product having a low dielectric constant and dielectric loss tangent can be obtained. Accordingly, the resin molded body composition of the present invention is suitable for semiconductor encapsulation and circuit boards (in particular, metal-clad laminates, printed wiring board substrates, printed wiring board adhesives, printed wiring board adhesive sheets, Insulating circuit protective film for wiring boards, conductive paste for printed wiring boards, sealing agents for multilayer printed wiring boards, circuit protective agents, coverlay films, cover inks, etc. Is preferred.

Polymerizable composition The polymerizable composition of the present invention contains the epoxyethylphenyloxy group-containing cyclic phosphazene compound of the present invention. The epoxyethylphenyloxy group-containing cyclic phosphazene compound used here may be two or more kinds. This polymerizable composition is, for example, an epoxy resin, modified to impart thermoplasticity or solvent solubility, preferably a functional group that reacts and bonds with an epoxyethylphenyloxy group (carboxyl group, epoxy group, hydroxy group, Amino group-containing polyimide resins (polyimide, polyamideimide, polyetherimide, polyesterimide, polycarbodiimide, maleimide resin and maleimide-cyanate resin, etc.) and modified polyphenylene ether (in part or all of polyphenylene ether, A reactive functional group such as a carboxyl group, an epoxy group, a hydroxy group, an amino group, or an anhydrous dicarboxyl group introduced by any method such as a graft reaction or copolymerization). Moreover, this polymeric composition can mix | blend various additives in the range which does not impair the target physical property according to the use etc. Available additives are the same as those mentioned in the description of the epoxy resin composition.

  Further, the polymerizable composition may contain a catalyst for improving the reactivity of the epoxyethylphenyloxy group-containing cyclic phosphazene compound of the present invention, the epoxy resin, the polyimide resin, the modified polyphenylene ether, and the like. The catalyst usable here is, for example, in the case of an epoxy resin, usually the same as those mentioned in the description of the epoxy resin composition described above, that is, polyamines such as aliphatic polyamines, aromatic polyamines and polyamide polyamines. Curing agents, acid anhydride curing agents such as hexahydrophthalic anhydride and methyltetrahydrophthalic anhydride, phenolic curing agents such as phenol novolak and cresol novolac, phosphazene compounds having a glycidyl group, Lewis acids such as boron trifluoride And salts thereof, dicyandiamides, imidazole compounds such as 2-methylimidazole and 2-ethylimidazole, tertiary amine compounds such as 2- (dimethylaminomethyl) phenol, and triphenylphosphine compounds.

  In the polymerizable composition containing the epoxyethylphenyloxy-containing cyclic phosphazene compound of the present invention, the amount of these catalysts used is preferably set to 0.01 to 15 equivalents relative to 1 equivalent of epoxy group. It is more preferable to set 1 to 7 equivalents.

  The polymerizable composition of the present invention can be obtained by uniformly mixing required components. This polymerizable composition usually forms an epoxy ethylphenyloxy-containing cyclic phosphazene compound or an epoxyethylphenyloxy group-containing cyclic phosphazene with the epoxy resin, polyimide resin and modified polyphenylene ether when heated. To do. This polymer is changed from a liquid to a cured product (resin molded product) depending on the number of reactive groups in the polymerization composition. Since the obtained polymer is substantially composed of the polymer of the epoxyethylphenyloxy-containing cyclic phosphazene compound of the present invention, it has excellent flame retardancy and high temperature reliability, and has high mechanical properties due to its high glass transition temperature. Is also excellent. For this reason, the polymerizable composition of the present invention can be used as a material for producing resin moldings used in various fields, for example, for semiconductor encapsulation and circuit boards (in particular, metal-clad laminates, printed wiring board substrates, Adhesive for printed wiring board, adhesive sheet for printed wiring board, insulating circuit protective film for printed wiring board, conductive paste for printed wiring board, sealing agent for multilayer printed wiring board, circuit protective agent, coverlay film, cover Ink) can be widely used as a material for manufacturing electrical / 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. In the following, “unit” in “unit mol” means the smallest structural unit of a cyclic phosphazene compound, for example, (PNA ₂ ) for formula (1) and (PNX ₂ ) for formula (3). means. In the formula (3), when X is chlorine, its 1 unit mol is 115.87 g. In the following, unless otherwise specified, “%” and “parts” mean “% by weight” and “parts by weight”, respectively.
Of the following examples, Examples 1 to 3 are production examples of an epoxyethylphenyloxy group-containing cyclic phosphazene compound, and Examples 4 to 6 are reference examples.

The phosphazene compounds obtained in Examples and the like were identified based on the results of measurement of ¹ H-NMR spectrum and ³¹ P-NMR spectrum and measurement of CHNP elemental analysis. Moreover, the refractive index was measured as a physical-property value of a compound.

Moreover, the physical properties of the resins and cured products thereof according to Examples and Comparative Examples were evaluated by the methods described below.
(1) Epoxy equivalent The epoxy equivalent (g / eq .: mass g of resin containing 1 equivalent of an epoxy group) was measured according to the method defined in JIS K 7236 “How to Determine Epoxy Equivalent of Epoxy Resin”.

Example 1 (Production of epoxyethylphenyloxy group-containing cyclic phosphazene compound according to Form B)
[Step 1: Production of styryloxy group-containing cyclic phosphazene compound by method Bc above]
A 5-liter four-necked flask equipped with a thermometer, stirrer, condenser, and dropping funnel was charged with hexachlorocyclotriphosphazene (173.8 g, 1.50 unit mol) under a nitrogen stream, and toluene (1,950 mL). To dissolve. A solution of sodium 4-ethenylphenoxide (142.1 g, 1.0 mol) in THF (400 mL) was added dropwise thereto over 5 hours, followed by stirring at 25 ° C. for 24 hours. The obtained reaction solution was added to a toluene (1,250 mL) suspension of sodium phenoxide (348.3 g, 3.0 mol) prepared in advance, and then refluxed at 110 ° C. for 3 hours. The reaction mixture was cooled to room temperature, 5% aqueous sodium hydroxide solution (500 mL) was added, and the mixture was transferred to a separatory funnel. After separating the aqueous layer, the toluene layer was washed with a 5% aqueous sodium hydroxide solution (500 mL), neutralized with dilute nitric acid, and washed with water. The toluene layer was concentrated under reduced pressure to obtain 361.6 g (yield: 98.6%) of the product. The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
6.5-7.6 (19.5H), 5.1-6.0 (2H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.6 to 10.3

From the above analysis results, the product _{[N 3 P 3 (OC 6} H 4 CHCH 2) (OC 6 H 5) 5], [N 3 P 3 (OC 6 H 4 CHCH 2) 2 (OC 6 H _{5) 4]} and _{[N 3 P 3 (OC 6} H 4 CHCH 2) is a mixture of _{3 (OC 6 H 5) 3} ], the average composition _{[N 3 P 3 (OC 6} H 4 CHCH 2) 1 _.5 (OC ₆ H ₅ ) _4.5 ] was confirmed to be a cyclic phosphazene compound.

[Step 2: Production of epoxyethylphenyloxy group-containing cyclic phosphazene compound by oxidation]
In a 5-liter four-necked flask equipped with a thermometer, a stirrer, and a dropping funnel, a solution of the compound obtained in Step 1 (122.2 g, 0.50 unit mol) in dichloromethane (2,500 mL) and diphosphate diphosphate. Sodium hydride (106.5 g,
0.75 mol) was charged, and a solution of m-chloroperbenzoic acid (86.3 g, 0.50 mol) in dichloromethane (1,000 mL) was added dropwise over 1 hour. To the reaction solution obtained by stirring at 25 ° C. for 3 hours, dichloromethane (1,000 mL), saturated aqueous sodium hydrogen carbonate solution (1,000 mL), and saturated aqueous sodium thiosulfate solution (1,000 mL) were added, and a separatory funnel was added. Moved to. After separating the aqueous layer, the dichloromethane layer was washed with a saturated aqueous sodium hydrogen carbonate solution (1,000 mL) and further washed with water. The dichloromethane layer was concentrated under reduced pressure to obtain 113.7 g of product (yield: 90.0%). The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
6.7 to 7.3 (18.5H), 3.8 (1H), 3.1 (1H), 2.8 (1H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.7 to 10.2.
◎ CHNP elemental analysis:
Theoretical value C: 61.9%, H: 4.4%, N: 5.5%, P: 12.3%
Measured value C: 61.7%, H: 4.5%, N: 5.5%, P: 12.2%
◎ Epoxy equivalent:
498 g / eq.
◎ Refractive index 1.597 (20 ℃)

From the above analysis results, the products obtained in this step are [N ₃ P ₃ (OC ₆ H ₄ CHOCH ₂ ) (OC ₆ H ₅ ) ₅ ], [N ₃ P ₃ (OC ₆ H ₄ CHOCH _2]. ) ₂ (OC ₆ H ₅ ) ₄ ] and [N ₃ P ₃ (OC ₆ H ₄ CHOCH ₂ ) ₃ (OC ₆ H ₅ ) ₃ ], the average composition of which is [N ₃ P ₃ (OC _6). H ₄ CHOCH ₂ ) _1.5 (OC ₆ H ₅ ) _4.5 ] was confirmed to be a 4- (1,2-epoxyethyl) phenoxy group-containing cyclic phosphazene compound.

Example 2 (Production of an epoxyethylphenyloxy group-containing cyclic phosphazene compound according to Form A)
[Step 1: Production of styryloxy group-containing cyclic phosphazene compound by method Ab]
In a 3 liter four-necked flask equipped with a thermometer, stirrer, condenser and dropping funnel, hexachlorocyclotriphosphazene (173.8 g, 1.50 unit mol) and 4-ethenylphenol (396. A solution of 5 g, 3.3 mol) in acetonitrile (1,000 mL) was added. To this, triethylamine (404.8 g, 4.0 mol) was added dropwise over 1 hour, and then heated to reflux for 6 hours. The reaction mixture was cooled to room temperature, concentrated under reduced pressure, toluene (1,000 mL) and 5% aqueous sodium hydroxide solution (500 mL) were added, and the mixture was transferred to a separatory funnel. After separating the aqueous layer, the toluene layer was washed with a 5% aqueous sodium hydroxide solution (500 mL), neutralized with dilute nitric acid, and washed with water. The toluene layer was concentrated under reduced pressure to obtain 418.1 g (yield: 98.4%) of the product.

[Step 2: Production of epoxyethylphenyloxy group-containing cyclic phosphazene compound by oxidation]
The product was obtained by oxidizing the above compound in the same manner as in Step 2 of Example 1. The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
6.7 to 7.2 (18.5H), 3.9 (1H), 3.1 (1H), 2.8 (1H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.7 to 10.2.
◎ CHNP elemental analysis:
Theoretical value C: 61.0%, H: 4.5%, N: 4.4%, P: 9.8%
Measured value C: 61.0%, H: 4.6%, N: 4.4%, P: 9.8%
◎ Epoxy equivalent:
150 g / eq.

From the above analysis results, the product obtained in this step is a 4- (1,2-epoxyethyl) phenoxy group-containing cyclic phosphazene compound of [N ₃ P ₃ (OC ₆ H ₄ CHOCH ₂ ) ₆ ]. It was confirmed.

Example 3 (Production of an epoxyethylphenyloxy group-containing cyclic phosphazene compound according to Form B)
[Step 1: Production of styryloxy group-containing cyclic phosphazene compound by method Bc above]
The product was obtained in the same manner as in Step 1 of Example 1. The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
6.5-7.6 (19.5H), 5.1-6.0 (2H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.6 to 10.3

[Step 2: Production of epoxyethylphenyloxy group-containing cyclic phosphazene compound by oxidation]
To a 3 liter four-necked flask equipped with a thermometer, stirrer, condenser and dropping funnel, a solution of ethenylphenoxyphosphazene (73.34 g, 0.30 unit mol) in dichloromethane (1,500 mL) under a nitrogen stream, Sodium percarbonate (62.8 g,
0.40 mol) was added, and a solution of acetic anhydride (122.51 g, 1.20 mol) in dichloromethane (500 mL) was added dropwise thereto over 1 hour. A saturated aqueous sodium hydrogen carbonate solution (500 mL) and a saturated aqueous sodium thiosulfate aqueous solution (500 mL) were added to the reaction solution obtained by stirring at 40 ° C. for 2 hours, and transferred to a separatory funnel. After separating the aqueous layer, the dichloromethane layer was washed with a saturated aqueous sodium hydrogen carbonate solution (1,000 mL) and further washed with water. The dichloromethane layer was concentrated under reduced pressure to obtain 59.5 g of product (yield: 78.5%). The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
6.7 to 7.3 (18.5H), 3.8 (1H), 3.1 (1H), 2.8 (1H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.7 to 10.2.
◎ CHNP elemental analysis:
Theoretical value C: 61.9%, H: 4.4%, N: 5.5%, P: 12.3%
Measured value C: 61.8%, H: 4.5%, N: 5.5%, P: 12.3%
◎ Epoxy equivalent:
502 g / eq.

From the above analysis results, the products obtained in this step are [N ₃ P ₃ (OC ₆ H ₄ CHOCH ₂ ) (OC ₆ H ₅ ) ₅ ], [N ₃ P ₃ (OC ₆ H ₄ CHOCH _2]. ) ₂ (OC ₆ H ₅ ) ₄ ] and [N ₃ P ₃ (OC ₆ H ₄ CHOCH ₂ ) ₃ (OC ₆ H ₅ ) ₃ ], the average composition of which is [N ₃ P ₃ (OC _6). H ₄ CHOCH ₂ ) _1.5 (OC ₆ H ₅ ) _4.5 ] was confirmed to be a 4- (1,2-epoxyethyl) phenoxy group-containing cyclic phosphazene compound.

Comparative Example 1 (Production of cyclic phosphazene compound)
A cyclic phosphazene having a hydroxy group ([NP ( OC ₆ H ₄ OH) _1.6 (OC ₆ H ₅ ) _0.4 ] ₃ ) (145 g, 0.6 unit mol), epichlorohydrin (148.0 g, 1.6 mol) and methanol (300 mL) are charged. To the stirring site, sodium hydroxide (16.0 g, 0.4 mol) was added and heated under reflux for 1 hour. After completion of the reaction, methanol and unreacted epichlorohydrin were distilled off by concentration under reduced pressure, and 4-methyl-2-pentanone (300 mL) was added and dissolved, followed by washing with water three times. This was concentrated under reduced pressure and dried under reduced pressure at 120 ° C. to obtain 158.5 g (yield: 95.2%) of product. The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.7 (1H), 2.9 (1H), 3.3 (1H), 3.9 (1H), 4.2 (1H), 6.6 to 7.4 (15H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.6 to 10.1
◎ CHNP elemental analysis:
Theoretical value C: 60.3%, H: 4.6%, N: 5.0%, P: 11.2%
Measured value C: 60.4%, H: 4.5%, N: 5.0%, P: 11.2%
◎ Epoxy equivalent:
433 g / eq.

From the above analysis results, the product _{[N 3 P 3 (OC 6} H 4 OC 3 H 5 O) (OC 6 H 5) 5], [N 3 P 3 (OC 6 H 4 OC 3 H 5 O ) ₂ (OC ₆ H ₅ ) ₄ ] and [N ₃ P ₃ (OC ₆ H ₄ OC ₃ H ₅ O) ₃ (OC ₆ H ₅ ) ₃ ], the average composition of which is [N ₃ P ₃ (OC ₆ H ₄ OC ₃ H ₅ O) _1.2 (OC ₆ H ₅ ) _4.8 ].

Examples 4 to 6 (Production of resin molded body)
The epoxyethylphenyloxy group-containing cyclic phosphazene synthesized in Examples 1 to 3 and dicyandiamide were mixed and made uniform in the proportions shown in Table 1, and then poured into a PTFE mold at 160 ° C. for 2 hours at 190 ° C. And cured for 3 hours to produce two types of sheet-like cured products (resin moldings) of 1/16 inch thickness and 5 mm thickness. It was confirmed by the IR spectrum that the cured product had completely lost the absorption of the epoxy group.

Comparative Example 2
A sheet-like cured product was obtained in the same manner as in Examples 4 to 6, except that the cyclic phosphazene compound synthesized in Comparative Example 1 was used instead of the epoxyethylphenyloxy group-containing cyclic phosphazene compound used in Examples 4 to 6. Produced.

  About the obtained sheet-like hardened | cured material, combustibility and heat resistance were measured by 1/16 inch thickness, glass transition temperature was 5 mm thickness, and those results were shown in Table 1. The evaluation method for each item is as follows.

(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 less than 50 seconds, 2 times for each of 5 test pieces.
(B) Flame test was performed twice for each of five test pieces, and the flame extinguishing time after each flame 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 times of flame contact is within 250 seconds, 2 times for each of 5 test pieces.
(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) Growing after the second flame contact is within 60 seconds for all specimens.
(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 times of flame contact is within 250 seconds, 2 times for each of 5 test pieces.
(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) Growing after the second flame contact is within 60 seconds for all specimens.
(E) All specimens are not framing to the clamp.

(Heat-resistant)
The test piece was treated at 288 ° 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.

(Glass transition temperature: Tg)
Using a differential scanning calorimeter DSC-60 (manufactured by Shimadzu Corporation), the glass transition temperature (° C.) was measured according to JIS K 7121 “Method for Measuring Transition Temperature of Plastic”.

Measurement atmosphere: Dry nitrogen atmosphere Measurement temperature: Measurement sample within a range of 35 to 200 ° C .: Cured resin sheet having a width of 9 mm and a length of 40 mm

  As is clear from Table 1, the sheet-like cured products of Examples 4 to 6 have a higher glass transition temperature than that of Comparative Example 2.

Examples 7 to 9, Comparative Example 3 (Preparation of resin molding)
DL-92 (manufactured by Meiwa Kasei Co., Ltd .: phenolic hydroxyl group equivalent 110 g / eq.) 5.5 parts phenolic novolac resin, 100 parts spherical fused silica (manufactured by Tatsumori Co., Ltd .: average particle size 20 μm), carnauba wax ( (Toa Kasei Co., Ltd.) 0.5 parts of triphenylphosphine and 0.5 parts of triphenylphosphine epoxyethylphenyloxy group-containing cyclic phosphazene compound obtained in Examples 1 to 3 or cyclic phosphazene compound obtained in Comparative Example 1 In addition, ESCN-195XL (manufactured by Sumitomo Chemical Co., Ltd .: epoxy equivalent 200 g / eq.), Which is a cresol novolac type epoxy resin, was blended at a ratio shown in Table 2 and mixed at room temperature. The mixture was kneaded at 90 to 95 ° C. and then cooled and pulverized to produce a molding material. This molding material was transferred and injected 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. )

  The molded product was examined for combustibility, heat resistance and glass transition temperature, and the results are shown in Table 2.

  As is apparent from Table 2, the cured products of Examples 7 to 9 comprising the cyclic phosphazene compound having an epoxyethylphenyloxy group of the present invention were compared with Comparative Example 3 comprising a cyclic phosphazene compound having no epoxyethylphenyloxy group. The glass transition temperature is higher than that.

Claims (4)

An epoxyethylphenyloxy group-containing cyclic phosphazene compound represented by the following formula (1) ;
At least one resin component selected from the group consisting of a thermoplastic resin and a thermosetting resin (excluding an alicyclic olefin polymer having a carboxyl group or an acid anhydride group) ;
A resin molded body composition comprising:

(In Formula (1), A shows the group chosen from the group which consists of following A1 group and A2 group, and at least one is A2 group.
A1 group: an aryloxy group having 6 to 20 carbon atoms in which at least one group selected from an alkyl group having 1 to 6 carbon atoms and an aryl group may be substituted.
A2 group: An epoxyethylphenyloxy group represented by the following formula (2).

The epoxy-ethylphenyl group-containing cyclic phosphazene compound, in the formula (1), a 1-6 is A2 groups of the A, those remaining A phenoxy group, resin according to claim 1 Composition for molded article . The resin molding obtained by hardening the composition for resin moldings of Claim 1 or 2 . The electronic component using the resin molding of Claim 3 .