JP5768274B2 - Oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with glycidyl group 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 an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group and a method for producing the same.

  Synthetic resins are superior to other materials in terms of processability, chemical resistance, weather resistance, electrical properties, mechanical strength, etc., so industrial and consumer equipment and electrical products It is widely used in the field and its usage is increasing. Among the synthetic resins, there are those having the property of being easily combusted, that is, a flammable synthetic resin, and an attempt has been made to impart flame retardancy by adding a flame retardant. As the flame retardant used for this purpose, a halogen-containing compound or a mixture of a halogen-containing compound and an antimony compound such as antimony oxide is generally known. 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 deteriorate the electrical characteristics and mechanical characteristics of the electronic component. Therefore, recently, as a flame retardant for a flammable synthetic resin, a non-halogen-based material that does not easily generate a halogen-based gas during combustion or molding, for example, metal hydration such as aluminum hydroxide and magnesium hydroxide. 2. Description of the Related Art Physical flame retardants and phosphoric flame retardants such as phosphate ester, condensed phosphate ester, phosphate amide, ammonium polyphosphate, phosphinate, and phosphazene 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 with the thermal decomposition and combustion start temperature of the synthetic resin. However, in order to enhance the effect, it is necessary to add a large amount to the resin composition. For this reason, the molded article of the resin composition containing this type of flame retardant has a drawback that the mechanical strength is impaired. On the other hand, among phosphorus-based flame retardants, phosphate ester-based and condensed phosphate ester-based flame retardants have a plastic effect. Therefore, when a large amount is added to the resin composition in order to increase flame retardancy, resin molding There are disadvantages such as a decrease in the mechanical strength of the product. In addition, phosphate ester, phosphate amide, polyphosphate ammonium and phosphinate flame retardants are easily hydrolyzed, making resin molded products that require mechanical and electrical long-term reliability. It is practically difficult to use in materials for use. In contrast, phosphazene-based flame retardants have a lower plasticity and hydrolyzability than other phosphorus-based flame retardants, so that the amount added to the resin composition can be increased. It is being widely used as a flame retardant.

  However, when the amount of the phosphazene flame retardant added to the resin composition is increased, there is a possibility that the reliability (high temperature reliability) of the resin molded product at a high temperature is impaired. Specifically, in the case of a thermoplastic resin-based resin composition, the phosphazene-based flame retardant is likely to bleed out (elute) from the resin molded body at a high temperature, and the thermosetting resin-based resin composition In such a case, deformation such as blistering occurs in the resin molded product at a high temperature, and when the resin molded product is used in the electric / electronic field such as a laminated substrate, a short circuit due to deformation may occur.

  Therefore, phosphazene-based flame retardants have been studied for improving high-temperature reliability. As an example, Patent Documents 1 to 4 include phosphazene-based flame retardants having a reactive group such as a hydroxy group and the like. An epoxy resin composition and a polyimide resin composition were 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. Some of them are insufficient in terms of the essential effects that are difficult to effectively increase, and they also impair the mechanical properties (particularly high glass transition temperatures) of resin molded products. .

  In recent years, electronic devices used in the field of information and communication have been increasing in capacity and speed of signals, so there is a printed wiring board that has excellent high-frequency characteristics and can cope with high-layering by increasing the number of wires. It is requested. In such a printed wiring board, in order to maintain reliability in a high frequency region from the MHz band to the GHz band, good dielectric characteristics, specifically, a dielectric constant (ε) and a dielectric loss tangent (tan δ) are low. I need it. As a printed wiring board having excellent dielectric properties, a printed wiring board using a thermosetting resin composition in which polyphenylene ether (PPE) is blended in an epoxy resin is used as an insulating layer is known. This printed wiring board is superior in dielectric properties compared to those using an insulating layer made of a normal epoxy resin composition, but other expensive high-frequency board materials such as polytetrafluoroethylene (PTFE) Compared with fluorine resin, bismaleimide / triazine resin (BT resin), polyimide resin, etc., there is a problem that the heat resistance and flame retardancy of the insulating layer portion are inferior. Then, in order to achieve the flame retardance requested | required in a practical area in an insulating layer, the example which added the phosphazene type flame retardant to the above-mentioned thermosetting resin composition is reported (patent documents 5, 6). However, in this case, there is a possibility that deterioration of the high temperature reliability may be caused, for example, a bleedout of the flame retardant occurs in the insulating layer.

  On the other hand, an epoxy resin composition using an epoxy resin and a compound in which the terminal of a polyphenylene ether oligomer is modified with an epoxy group, and examples have been reported (Patent Documents 7 to 8). In addition, the dielectric loss tangent is low and the electrical characteristics can be improved, but the flame retardancy is insufficient.

JP 2003-302751 A JP 2003-342339 A JP 2004-143465 A JP 2006-117545 A JP 2009-78209 A JP 2009-108144 A JP 2003-238655 A JP 2009-46631 A

  An object of the present invention is to effectively improve the flame retardancy of a resin molded body, and the resin molded body has low electrical properties, in particular, low dielectric constant (ε) and dielectric loss tangent (tan δ), and high temperature reliability. It is to realize a high phosphazene compound.

  As a result of repeated studies to solve the above-mentioned problems, the present inventors have prepared a resin composition using an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group, and the resin composition comprises the resin composition. It has been found that the molded product exhibits excellent electrical characteristics, and at the same time, is excellent in flame retardancy and high temperature reliability.

  The oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group of the present invention is represented by the following formula (1).

In formula (1), n represents an integer of 1 to 6, 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: 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.
Group A2: a group selected from the group consisting of an oligo (phenyleneoxy) group-substituted phenyloxy group represented by the following formula (2).

In formula (2), E ^{1 to} E ⁵ are each an independent substituent, and are a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an alkyl group having 1 to 6 carbon atoms, alkenyl. a group selected from at least one aryl group having 6 to 20 carbon atoms optionally substituted by a group selected from the group and aryl group, and at least one has been modified with a glycidyl group represented by the following formula (3) An oligo (phenyleneoxy) group.

In the formula (3), q represents an integer of 1 to 50 (excluding 1) , and E ^{6 to} E ⁹ are each an independent substituent, which is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and alkenyl. group shown, and the alkyl group having 1 to 6 carbon atoms, a group selected from at least one aryl group having 6 to 20 carbon atoms optionally substituted by a group selected from an alkenyl group and an aryl group.

  In the oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with glycidyl group, preferred A2 group is oligo (methylphenyleneoxy) group-substituted phenyleneoxy group modified with glycidyl group, oligo (methylphenyleneoxy) modified with glycidyl group ) Group-substituted methylphenyleneoxy group, oligo modified with glycidyl group (methylphenyleneoxy) group substituted dimethylphenyleneoxy group, oligo modified with glycidyl group (dimethylphenyleneoxy) group substituted phenyleneoxy group, oligo modified with glycidyl group ( A dimethylphenyleneoxy) group-substituted methylphenyleneoxy group and an oligo (dimethylphenyleneoxy) group-substituted dimethylphenyleneoxy group modified with a glycidyl group.The oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group is preferably a compound in which n in the formula (1) is 1 or 2.

The oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group of the present invention preferably has 1 (2n + 2) A2 groups out of (2n + 4) A in formula (1). Furthermore, the oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group of the present invention preferably contains two or more compounds having different n in the formula (1).

  The production method of the present invention relates to a method for producing an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group according to the present invention, and represents an oligo (phenyleneoxy) group represented by the following formula (4): A step of reacting the containing cyclic phosphazene compound with epihalohydrin.

In the formula (4), m represents an integer of 1 to 6, G represents a group selected from the group consisting of the following G1 group and G2 group, and at least one is a G2 group.
G1 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.
G2 group: a group selected from the group consisting of an oligo (phenyleneoxy) group-substituted phenyloxy group represented by the following formula (5).

In formula (5), E ^{10 to} E ¹⁴ are each an independent substituent, and are a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an alkyl group having 1 to 6 carbon atoms, alkenyl. oligo is a radical selected from at least one aryl group having 6 to 20 carbon atoms optionally substituted by a group selected from the group and aryl group, and at least one is represented by the following formula (6) (phenyleneoxy) It is a group.

In the formula (6), t represents an integer of 1 to 50 (excluding 1) , and E ^{15 to} E ¹⁸ are each an independent substituent, which is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and alkenyl. And a group selected from an aryl group having 6 to 20 carbon atoms which may be substituted with a group and at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group and an aryl group.

  The resin composition according to the present invention contains a resin component and an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group of the present invention.

  The resin component used here is, for example, epoxy resin, polyphenylene ether resin, polyamide resin, polyamideimide resin, polyetherimide resin, polyimide resin, polysulfone resin, phenoxy resin, cresol novolac resin, cyanate ester resin and bismaleimide- It is at least one selected from the group consisting of cyanate ester resins.

  The resin molded product of the present invention is composed of the resin composition of the present invention. Moreover, the electronic component of the present invention uses the resin molded body of the present invention.

  Since the oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group of the present invention has a specific structure as described above, it is used in a resin composition for forming a resin molded body. In the electrical characteristics, a low dielectric constant and a low dielectric loss tangent can be achieved, and the flame retardancy of the resin molding can be effectively enhanced without impairing the reliability at high temperatures.

  Since the method for producing an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group of the present invention includes the specific steps as described above, an oligo modified with a glycidyl group having a specific structure according to the present invention. A (phenyleneoxy) group-containing cyclic phosphazene compound can be produced.

  Since the resin composition of the present invention contains the oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with the glycidyl group of the present invention as a flame retardant, it exhibits practical flame retardancy, and has a low dielectric constant in its electrical characteristics and A resin molded body that can achieve a low dielectric loss tangent and is excellent in high-temperature reliability can be obtained.

  Since the resin molded body of the present invention comprises the resin composition of the present invention, it exhibits practical flame retardancy, can achieve a low dielectric constant and a low dielectric loss tangent in its electrical characteristics, and is excellent in high temperature reliability. .

The figure which shows the analysis result of the gel permeation chromatography in Example 1. FIG.

Oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with glycidyl group
The oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group of the present invention is represented by the following formula (1).

  In the formula (1), n represents an integer of 1 to 6. However, in the oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group of the present invention, a compound having a smaller n in formula (1) is used as a resin component when used in a resin composition described later. High compatibility. For this reason, n in the formula (1) is preferably an integer of 1 to 4, particularly preferably 1 or 2. That is, as the oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with this glycidyl group, an oligo (phenyleneoxy) group modified with a glycidyl group having a cyclotriphosphazene (trimer) in which n is 1 is particularly preferable. And an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group having a cyclotetraphosphazene (tetramer) in which n is 2. The oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group 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 group and A2 group. However, at least one of A is A2 group.

[A1 group]
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 A2]
A group selected from the group consisting of an oligo (phenyleneoxy) group-substituted phenyloxy group represented by the following formula (2).

In formula (2), E ^{1 to} E ⁵ are each an independent substituent, and are a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an alkyl group having 1 to 6 carbon atoms, alkenyl. oligo is a radical selected from at least one aryl group having 6 to 20 carbon atoms optionally substituted by a group selected from the group and aryl group, and at least one is represented by the following formula (3) (phenyleneoxy) It is a group.

In formula (3), q shows the integer of 1-50. E ^{6 to} E ⁹ are each an independent substituent selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms and an alkenyl group, and an alkyl group having 1 to 6 carbon atoms, an alkenyl group and an aryl group. a group also selected from aryl groups having 6 to 20 carbon atoms substituted with at least one group.

  The repeating number q of the phenyleneoxy group of the oligo (phenyleneoxy) group modified with the glycidyl group represented by the formula (3) is 1 to 50, depending on the resin component used and the degree of flame retardancy required. Can be appropriately selected. For example, if the resin component used is easy to burn, select the oligo (phenyleneoxy) group-substituted cyclic phosphazene compound modified with the glycidyl group used together that has a small number of repeating phenyleneoxy groups (small q) If the resin component used is difficult to burn, it is possible to reduce the phosphorus content by selecting one with a large number of phenyleneoxy group repeats (with a large q). The flame retardancy of the resin composition can be adjusted as appropriate.

  Specific examples of the A2 group include glycidyloxy-3-oligo (methylphenyleneoxy) group-substituted phenyloxy group, glycidyloxy-4-oligo (methylphenyleneoxy) group-substituted phenyloxy group, glycidyloxy-3-oligo (methylphenylene) Oxy) group substituted-2-methylphenyloxy group, glycidyloxy-3-oligo (methylphenyleneoxy) group substituted-4-methylphenyloxy group, glycidyloxy-3-oligo (methylphenyleneoxy) group substituted-5-methyl Phenyloxy group, glycidyloxy-4-oligo (methylphenyleneoxy) group-substituted-2-methylphenyloxy group, glycidyloxy-4-oligo (methylphenyleneoxy) group-substituted-3-methylphenyloxy group, glycidyloxy-3 -Oligo (methylphenol Nyleneoxy) group substituted-2-allylphenyloxy group, glycidyloxy-3-oligo (methylphenyleneoxy) group substituted-4-allylphenyloxy group, glycidyloxy-3-oligo (methylphenyleneoxy) group substituted-5-allyl Phenyloxy group, glycidyloxy-4-oligo (methylphenyleneoxy) group-substituted-2-allylphenyloxy group, glycidyloxy-4-oligo (methylphenyleneoxy) group-substituted-3-allylphenyloxy group, glycidyloxy-3 -Oligo (methylphenyleneoxy) group substitution-4-phenylphenyloxy group, glycidyloxy-3-oligo (methylphenyleneoxy) group substitution-5-phenylphenyloxy group, glycidyloxy-4-oligo (methylphenyleneoxy) group Substituted-3-fe Ruphenyloxy group, glycidyloxy-3-oligo (methylphenyleneoxy) group-substituted-2,4-dimethylphenyloxy group, glycidyloxy-3-oligo (methylphenyleneoxy) group-substituted-2,5-dimethylphenyloxy group Glycidyloxy-4-oligo (methylphenyleneoxy) group-substituted-2,3-dimethylphenyloxy group, glycidyloxy-4-oligo (methylphenyleneoxy) group-substituted-2,5-dimethylphenyloxy group, glycidyloxy- 4-oligo (methylphenyleneoxy) group-substituted-3,5-dimethylphenyloxy group, glycidyloxy-3-oligo (methylphenyleneoxy) group-substituted-2,4,5-trimethylphenyloxy group, glycidyloxy-4- Oligo (methylphenyleneoxy) group substitution-2 , 3,5-trimethylphenyloxy group, glycidyloxy-3-oligo (dimethylphenyleneoxy) group-substituted phenyloxy group, glycidyloxy-4-oligo (dimethylphenyleneoxy) group-substituted phenyloxy group, glycidyloxy-3-oligo (Dimethylphenyleneoxy) group substitution-2-methylphenyloxy group, glycidyloxy-3-oligo (dimethylphenyleneoxy) group substitution-4-methylphenyloxy group, glycidyloxy-3-oligo (dimethylphenyleneoxy) group substitution- 5-methylphenyloxy group, glycidyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-2-methylphenyloxy group, glycidyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-3-methylphenyloxy group, glycidyl Oxy-3-oligo (dimethylphenyleneoxy) group-substituted-2-allylphenyloxy group, glycidyloxy-3-oligo (dimethylphenyleneoxy) group-substituted-4-allylphenyloxy group, glycidyloxy-3-oligo (dimethylphenylene) Oxy) group substituted-5-allylphenyloxy group, glycidyloxy-4-oligo (dimethylphenyleneoxy) group substituted-2-allylphenyloxy group, glycidyloxy-4-oligo (dimethylphenyleneoxy) group substituted-3-allyl Phenyloxy group, glycidyloxy-3-oligo (dimethylphenyleneoxy) group substitution-4-phenylphenyloxy group, glycidyloxy-3-oligo (dimethylphenyleneoxy) group substitution-5-phenylphenyloxy group, glycidyloxy-4 -Ori (Dimethylphenyleneoxy) group substituted-3-phenylphenyloxy group, glycidyloxy-3-oligo (dimethylphenyleneoxy) group substituted-2,4-dimethylphenyloxy group, glycidyloxy-3-oligo (dimethylphenyleneoxy) group Substitution-2,5-dimethylphenyloxy group, glycidyloxy-4-oligo (dimethylphenyleneoxy) group substitution-2,3-dimethylphenyloxy group, glycidyloxy-4-oligo (dimethylphenyleneoxy) group substitution-2, 5-dimethylphenyloxy group, glycidyloxy-4-oligo (dimethylphenyleneoxy) group substitution-3,5-dimethylphenyloxy group, glycidyloxy-3-oligo (dimethylphenyleneoxy) group substitution-2,4,5- Trimethylphenyloxy group and group It is at least one selected from the group consisting of lysidyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-2,3,5-trimethylphenyloxy groups.

  As the A2 group, glycidyloxy-3-oligo (methylphenyleneoxy) group-substituted phenyloxy group, glycidyloxy-4-oligo (methylphenyleneoxy) group-substituted phenyloxy group, glycidyloxy-3-oligo (methylphenyleneoxy) ) Group substituted-4-methylphenyloxy group, glycidyloxy-3-oligo (methylphenyleneoxy) group substituted-5-methylphenyloxy group, glycidyloxy-4-oligo (methylphenyleneoxy) group substituted-3-methylphenyl Oxy group, glycidyloxy-3-oligo (methylphenyleneoxy) group-substituted-2,4-dimethylphenyloxy group, glycidyloxy-3-oligo (methylphenyleneoxy) group-substituted-2,5-dimethylphenyloxy group, glycidyl Oxy-4-oligo Methylphenyleneoxy) group-substituted-2,3-dimethylphenyloxy group, glycidyloxy-4-oligo (methylphenyleneoxy) group-substituted-3,5-dimethylphenyloxy group, glycidyloxy-3-oligo (methylphenyleneoxy) Substitution-2,4,5-trimethylphenyloxy group, glycidyloxy-4-oligo (methylphenyleneoxy) group substitution-2,3,5-trimethylphenyloxy group, glycidyloxy-3-oligo (dimethylphenyleneoxy) Group-substituted phenyloxy group, glycidyloxy-4-oligo (dimethylphenyleneoxy) group-substituted phenyloxy group, glycidyloxy-3-oligo (dimethylphenyleneoxy) group-substituted-4-methylphenyloxy group, glycidyloxy-3-oligo (Dimethylphenyle Oxy) group substituted-5-methylphenyloxy group, glycidyloxy-4-oligo (dimethylphenyleneoxy) group substituted-3-methylphenyloxy group, glycidyloxy-3-oligo (dimethylphenyleneoxy) group substituted-2,4 -Dimethylphenyloxy group, glycidyloxy-3-oligo (dimethylphenyleneoxy) group-substituted-2,5-dimethylphenyloxy group, glycidyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-2,3-dimethylphenyloxy Group, glycidyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-3,5-dimethylphenyloxy group, glycidyloxy-3-oligo (dimethylphenyleneoxy) group-substituted-2,4,5-trimethylphenyloxy group, and Glycidyloxy-4-oligo ( Dimethylphenyleneoxy) group-substituted-2,3,5-trimethylphenyloxy group is preferred, and glycidyloxy-4-oligo (methylphenyleneoxy) group-substituted phenyloxy group, glycidyloxy-4-oligo (methylphenyleneoxy) Substituent substitution-3-methylphenyloxy group, glycidyloxy-4-oligo (methylphenyleneoxy) group substitution-2,3-dimethylphenyloxy group, glycidyloxy-4-oligo (methylphenyleneoxy) group substitution-3,5 -Dimethylphenyloxy group, glycidyloxy-4-oligo (methylphenyleneoxy) group-substituted-2,3,5-trimethylphenyloxy group, glycidyloxy-4-oligo (dimethylphenyleneoxy) group-substituted phenyloxy group, glycidyloxy -4-Oligo Le phenylene) group-substituted-3-methylphenyl group, and glycidyl-4-oligo (dimethyl phenylene-oxy) group substituted 3,5-dimethylphenyl group is preferable.

  In formula (1), A includes (2n + 4) A, and at least one of them is an A2 group. Therefore, the oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with the glycidyl group of the present invention represented by the formula (1) can be roughly classified into the following forms.

[Form 1]
All (2n + 4) A's are A2 groups. In this case, all of A may be the same A2 group or two or more A2 groups.

  Preferred as an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group in such a form is an oligo (phenyleneoxy) group-containing cyclotriphosphazene modified with a glycidyl group in which n in formula (1) is 1. Compound, oligo (phenyleneoxy) group-containing cyclotetraphosphazene compound modified with a glycidyl group in which n of formula (1) is 2, oligo (phenyleneoxy) group modified with a glycidyl group in which n of formula (1) is 3 -Containing cyclopentaphosphazene compound and oligo (phenyleneoxy) group-containing cyclohexaphosphazene compound modified with a glycidyl group in which n in formula (1) is 4, wherein all of A is glycidyloxy-3-oligo (methylphenylene) Oxy) group-substituted phenyloxy group, glycidyloxy-4 Oligo (methylphenyleneoxy) group-substituted phenyloxy group, glycidyloxy-3-oligo (methylphenyleneoxy) group-substituted-4-methylphenyloxy group, glycidyloxy-3-oligo (methylphenyleneoxy) group-substituted-5-methyl Phenyloxy group, glycidyloxy-4-oligo (methylphenyleneoxy) group-substituted-3-methylphenyloxy group, glycidyloxy-3-oligo (methylphenyleneoxy) group-substituted-2,4-dimethylphenyloxy group, glycidyloxy -3-Oligo (methylphenyleneoxy) group-substituted-2,5-dimethylphenyloxy group, glycidyloxy-4-oligo (methylphenyleneoxy) group-substituted-2,3-dimethylphenyloxy group, glycidyloxy-4-oligo (Methylphenyleneoxy ) Group-substituted-3,5-dimethylphenyloxy group, glycidyloxy-3-oligo (methylphenyleneoxy) group-substituted-2,4,5-trimethylphenyloxy group, glycidyloxy-4-oligo (methylphenyleneoxy) group Substituted-2,3,5-trimethylphenyloxy group, glycidyloxy-3-oligo (dimethylphenyleneoxy) groupsubstituted phenyloxy group, glycidyloxy-4-oligo (dimethylphenyleneoxy) groupsubstituted phenyloxy group, glycidyloxy- 3-oligo (dimethylphenyleneoxy) group-substituted-4-methylphenyloxy group, glycidyloxy-3-oligo (dimethylphenyleneoxy) group-substituted-5-methylphenyloxy group, glycidyloxy-4-oligo (dimethylphenyleneoxy) Group-substituted-3-methyl Phenyloxy group, glycidyloxy-3-oligo (dimethylphenyleneoxy) group-substituted-2,4-dimethylphenyloxy group, glycidyloxy-3-oligo (dimethylphenyleneoxy) group-substituted-2,5-dimethylphenyloxy group, Glycidyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-2,3-dimethylphenyloxy group, glycidyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-3,5-dimethylphenyloxy group, glycidyloxy-3 -A2 group consisting of oligo (dimethylphenyleneoxy) group-substituted-2,4,5-trimethylphenyloxy group and glycidyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-2,3,5-trimethylphenyloxy group It is a kind of A2 group selected from Of, as well as a two or more kinds of A2 groups selected from the A2 group group. The oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group in this form may be any mixture of these preferable oligo (phenyleneoxy) group-containing cyclic phosphazene compounds modified with a glycidyl group.

[Form 2]
A part (that is, at least one) of (2n + 4) A is an A2 group, and the other A is a group selected from the group consisting of an 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 or two or more kinds of A1 groups may be mixed.

  Preferred as an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group of this form is an oligo (phenyleneoxy) group-containing cyclotriphosphazene compound modified with a glycidyl group in which n in formula (1) is 1. An oligo (phenyleneoxy) group-containing cyclotetraphosphazene compound modified with a glycidyl group in which n in formula (1) is 2, and an oligo (phenyleneoxy) group-containing cyclomodified with a glycidyl group in which n in formula (1) is 3. A pentaphosphazene compound and an oligo (phenyleneoxy) group-containing cyclohexaphosphazene compound modified with a glycidyl group in which n in formula (1) is 4, comprising 1 to (2n + 2) of (2n + 4) A Are preferably A2 groups and any mixtures thereof. This type of oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group is higher in reliability and mechanical properties than the oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group of another embodiment of the present invention. This is advantageous in that a resin molded body with higher mechanical strength (particularly a high glass transition temperature) can be realized.

  Specific examples of such a preferred oligo (phenyleneoxy) group-containing phosphazene compound modified with a glycidyl group include an oligo (phenyleneoxy) group-containing cyclotriphosphazene compound modified with a glycidyl group in which n in formula (1) is 1. , An oligo (phenyleneoxy) group-containing cyclotetraphosphazene compound modified with a glycidyl group in which n in formula (1) is 2, and an oligo (phenyleneoxy) group modified with a glycidyl group in which n in formula (1) is 3 A cyclopentaphosphazene compound and an oligo (phenyleneoxy) group-containing cyclohexaphosphazene compound modified with a glycidyl group in which n in formula (1) is 4, wherein A is an A2 group glycidyloxy-3-oligo (methyl) Phenyloxy group substituted with phenyloxy group and A1 group In combination with a group, glycidyloxy-4-oligo (methylphenyleneoxy) group which is an A2 group, a combination of a phenyloxy group substituted with a phenoxy group which is an A1 group, glycidyloxy-3-oligo which is an A2 group (Methylphenyleneoxy) group-substituted 4-methylphenyloxy group in combination with A1 group phenoxy group, A2 group glycidyloxy-3-oligo (methylphenyleneoxy) group-substituted-5-methylphenyloxy A combination of a group and a phenoxy group which is an A1 group, a combination of a glycidyloxy-4-oligo (methylphenyleneoxy) group which is an A2 group and a 3-methylphenyloxy group and a phenoxy group which is an A1 group A2 group glycidyloxy-3-oligo (methyl phenylene o A) A combination of a group-substituted-2,4-dimethylphenyloxy group and a phenoxy group which is an A1 group, a glycidyloxy-3-oligo (methylphenyleneoxy) group-substituted-2,5-dimethylphenyl which is an A2 group A combination of an oxy group and a phenoxy group that is an A1 group, a glycidyloxy-4-oligo (methylphenyleneoxy) group-substituted-2,3-dimethylphenyloxy group that is an A2 group, and a phenoxy group that is an A1 group Combination, glycidyloxy-4-oligo (methylphenyleneoxy) group-substituted-3,5-dimethylphenyloxy group as A2 group and phenoxy group as A1 group, glycidyloxy- as A2 group 3-oligo (methylphenyleneoxy) group-substituted-2,4,5-tomethylphenyloxy group Combination of phenoxy group which is A1 group, combination of glycidyloxy-4-oligo (methylphenyleneoxy) group substituted-2,3,5-trimethylphenyloxy group which is A2 group and phenoxy group which is A1 group , Glycidyloxy-3-oligo (dimethylphenyleneoxy) group-substituted phenyloxy group as A2 group and phenoxy group as A1 group, glycidyloxy-4-oligo (dimethylphenyleneoxy) as A2 group ) Group-substituted phenyloxy group in combination with A1 group phenoxy group, A2 group glycidyloxy-3-oligo (dimethylphenyleneoxy) group-substituted 4-methylphenyloxy group and A1 group phenoxy group In combination with glycidyloxy-3-A2 group Rigo (dimethylphenyleneoxy) group substituted-5-methylphenyloxy group in combination with A1 group phenoxy group, A2 group glycidyloxy-4-oligo (dimethylphenyleneoxy) group substituted-3-methylphenyl A combination of an oxy group and a phenoxy group that is an A1 group, a glycidyloxy-3-oligo (dimethylphenyleneoxy) group-substituted-2,4-dimethylphenyloxy group that is an A2 group, and a phenoxy group that is an A1 group Combination, A2 group glycidyloxy-3-oligo (dimethylphenyleneoxy) group-substituted-2,5-dimethylphenyloxy group and A1 group phenoxy group, A2 group glycidyloxy- 4-oligo (dimethylphenyleneoxy) group-substituted-2,3-dimethyl Combination of ruphenyloxy group and phenoxy group which is A1 group, 4-glycidyloxy-oligo (dimethylphenyleneoxy) group-substituted-3,5-dimethylphenyloxy group which is A2 group and phenoxy group which is A1 group In combination with 3-glycidyloxy-oligo (dimethylphenyleneoxy) group-substituted-2,4,5-trimethylphenyloxy group as A2 group and phenoxy group as A1 group, A combination of a certain glycidyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-2,3,5-trimethylphenyloxy group and a phenoxy group that is an A1 group, a glycidyloxy-3-oligo that is an A2 group (methyl) Phenyleneoxy) group-substituted phenyloxy group and A1 group methylphenoxy group Glycidyloxy-4-oligo (methylphenyleneoxy) group-substituted phenyloxy group as A2 group and methylphenoxy group as A1 group, glycidyloxy-3-oligo as A2 group (Methylphenyleneoxy) group substituted-4-methylphenyloxy group and A1 group methylphenoxy group combined, A2 group glycidyloxy-3-oligo (methylphenyleneoxy) group substituted-5-methylphenyl A combination of an oxy group and a methylphenoxy group that is an A1 group, a glycidyloxy-4-oligo (methylphenyleneoxy) group-substituted 3-methylphenyloxy group that is an A2 group, and a methylphenoxy group that is an A1 group Combination, glycidyloxy-3-oligo which is A2 group Methylphenyleneoxy) group-substituted 2,4-dimethylphenyloxy group and A1 group methylphenoxy group, A2 group glycidyloxy-3-oligo (methylphenyleneoxy) group-substituted-2,5 -A combination of a dimethylphenyloxy group and a methylphenoxy group that is an A1 group, a glycidyloxy-4-oligo (methylphenyleneoxy) group that is an A2 group, a 2,3-dimethylphenyloxy group and an A1 group A combination of a methylphenoxy group, a combination of a glycidyloxy-4-oligo (methylphenyleneoxy) group-substituted 3,5-dimethylphenyloxy group as an A2 group and a methylphenoxy group as an A1 group, A2 Group glycidyloxy-3-oligo (methylphenyleneoxy) A combination of a substituted-2,4,5-trimethylphenyloxy group and a methylphenoxy group which is an A1 group, a glycidyloxy-4-oligo (methylphenyleneoxy) group substituted-2,3,5-group which is an A2 group A combination of a trimethylphenyloxy group and a methylphenoxy group that is A1 group, a combination of a glycidyloxy-3-oligo (dimethylphenyleneoxy) group-substituted phenyloxy group that is A2 group and a methylphenoxy group that is A1 group A2 group glycidyloxy-4-oligo (dimethylphenyleneoxy) group-substituted phenyloxy group and A1 group methylphenoxy group, A2 group glycidyloxy-3-oligo (dimethylphenyleneoxy) ) Group-substituted 4-methylphenyloxy group and A1 group In combination with a methylphenoxy group, in combination with a glycidyloxy-3-oligo (dimethylphenyleneoxy) group that is an A2 group and a methylphenoxy group that is an A1 group, an A2 group Glycidyloxy-4-oligo (dimethylphenyleneoxy) group-substituted 3-methylphenyloxy group and A1 group methylphenoxy group, A2 group glycidyloxy-3-oligo (dimethylphenyleneoxy) ) Group-substituted-2,4-dimethylphenyloxy group and A1 group methylphenoxy group, A2 group glycidyloxy-3-oligo (dimethylphenyleneoxy) group-substituted-2,5-dimethylphenyl group Combination of oxy group and A1 group methylphenoxy group Glycidyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-2,3-dimethylphenyloxy group as A2 group and methylphenoxy group as A1 group, glycidyloxy as A2 group -4-Oligo (dimethylphenyleneoxy) group-substituted 3,5-dimethylphenyloxy group and A1 group methylphenoxy group, A2 group glycidyloxy-3-oligo (dimethylphenyleneoxy) group Combination of substituted-2,4,5-trimethylphenyloxy group and methylphenoxy group which is A1 group, glycidyloxy-4-oligo (dimethylphenyleneoxy) group substituted-2,3,5-group which is A2 group Combination of trimethylphenyloxy group and methylphenoxy group which is A1 group The and the like, and any mixture thereof.

Of these, an oligo (phenyleneoxy) group-containing cyclotriphosphazene compound modified with a glycidyl group in which n in formula (1) is 1, and an oligo (phenyleneoxy) modified with a glycidyl group in which n in formula (1) is 2 Group-containing cyclotetraphosphazene compound, oligo (phenyleneoxy) group-containing cyclopentaphosphazene compound modified with a glycidyl group in which n in formula (1) is 3, oligo modified with a glycidyl group in which n in formula (1) is 4 (Phenyleneoxy) group-containing cyclohexaphosphazene compound, wherein A is a combination of a glycidyloxy-4-oligo (methylphenyleneoxy) group-substituted phenyloxy group which is an A2 group and a phenoxy group which is an A1 group, A2 group glycidyloxy-4-oligo (methylphenyleneoxy) group-substituted-3 Combination of methylphenyloxy group and phenoxy group which is A1 group, glycidyloxy-4-oligo (methylphenyleneoxy) group which is A2 group, substituted 2,3-dimethylphenyloxy group and phenoxy group which is A1 group In combination with glycidyloxy-4-oligo (methylphenyleneoxy) group-substituted-3,5-dimethylphenyloxy group as A2 group and phenoxy group as A1 group, glycidyl as A2 group Oxy-4-oligo (methylphenyleneoxy) group substituted-2,3,5-trimethylphenyloxy group in combination with A1 group phenoxy group, A2 group glycidyloxy-4-oligo (dimethylphenyleneoxy) ) Combination of group-substituted phenyloxy group and A1 group phenoxy group Glycidyloxy-4-oligo (dimethylphenyleneoxy) group-substituted 3-methylphenyloxy group and A1 group phenoxy group, A2 group glycidyloxy-4- Oligo (dimethylphenyleneoxy) group-substituted-2,3-dimethylphenyloxy group and A1 group phenoxy group, A2 group glycidyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-3, Combination of 5-dimethylphenyloxy group and phenoxy group which is A1 group, glycidyloxy-4-oligo (dimethylphenyleneoxy) group substituted-2,3,5-trimethylphenyloxy group and A1 group which is A2 group In combination with a phenoxy group which is glycidyloxy-4 which is an A2 group -Oligo (methylphenyleneoxy) group-substituted phenyloxy group and A1 group methylphenoxy group in combination, A2 group glycidyloxy-4-oligo (methylphenyleneoxy) group-substituted-3-methylphenyloxy group And a combination of a methylphenoxy group which is an A1 group, a glycidyloxy-4-oligo (methylphenyleneoxy) group-substituted-2,3-dimethylphenyloxy group which is an A2 group, and a methylphenoxy group which is an A1 group Combination, glycidyloxy-4-oligo (methylphenyleneoxy) group-substituted-3,5-dimethylphenyloxy group which is A2 group and methylphenoxy group which is A1 group, glycidyloxy which is A2 group -4-Oligo (methylphenyleneoxy) group substitution-2,3, -Combination of trimethylphenyloxy group and methylphenoxy group which is A1 group, Combination of glycidyloxy-4-oligo (dimethylphenyleneoxy) group substituted phenyloxy group which is A2 group and methylphenoxy group which is A1 group Glycidyloxy-4-oligo (dimethylphenyleneoxy) group-substituted 3-methylphenyloxy group and A1 group methylphenoxy group, A2 group glycidyloxy-4- Oligo (dimethylphenyleneoxy) group substitution-2,3-dimethylphenyloxy group and A1 group methylphenoxy group combination, A2 group glycidyloxy-4-oligo (dimethylphenyleneoxy) group substitution-3 , 5-dimethylphenyloxy group and A1 group Combination with methylphenoxy group, combination of glycidyloxy-4-oligo (dimethylphenyleneoxy) group substituted-2,3,5-trimethylphenyloxy group which is A2 group and methylphenoxy group which is A1 group And any mixtures thereof are more preferred.

  In particular, an oligo (phenyleneoxy) group-containing cyclotriphosphazene compound modified with a glycidyl group in which n of formula (1) is 1, and an oligo (phenyleneoxy) group modified with a glycidyl group in which n of formula (1) is 2. Containing cyclotetraphosphazene compound, oligo (phenyleneoxy) group-containing cyclopentaphosphazene compound modified with a glycidyl group wherein n in formula (1) is 3, oligo modified with a glycidyl group where n in formula (1) is 4 ( A phenyleneoxy) group-containing cyclohexaphosphazene compound, wherein A is a combination of a glycidyloxy-4-oligo (dimethylphenyleneoxy) group-substituted phenyloxy group which is an A2 group and a phenoxy group which is an A1 group, A2 Group glycidyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-3 Combination of methylphenyloxy group and phenoxy group which is A1 group, glycidyloxy-4-oligo (dimethylphenyleneoxy) group which is A2 group-2,3-dimethylphenyloxy group and phenoxy group which is A1 group In combination with glycidyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-3,5-dimethylphenyloxy group as A2 group and phenoxy group as A1 group, glycidyl as A2 group Oxy-4-oligo (dimethylphenyleneoxy) group substituted-2,3,5-trimethylphenyloxy group and A1 group phenoxy group, A2 group glycidyloxy-4-oligo (dimethylphenyleneoxy) ) Group-substituted phenyloxy group and A1 group methylphenoxy , Glycidyloxy-4-oligo (dimethylphenyleneoxy) group-substituted 3-methylphenyloxy group which is A2 group and methylphenoxy group which is A1 group, glycidyloxy which is A2 group -4-Oligo (dimethylphenyleneoxy) group substituted-2,3-dimethylphenyloxy group and A1 group methylphenoxy group, A2 group glycidyloxy-4-oligo (dimethylphenyleneoxy) group Combination of substituted-3,5-dimethylphenyloxy group and methylphenoxy group which is A1 group, glycidyloxy-4-oligo (dimethylphenyleneoxy) group substituted-2,3,5-trimethylphenyl which is A2 group Combination of oxy group and methylphenoxy group which is A1 group And any mixtures thereof are preferred.

  The oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group of the present invention usually has a number average molecular weight of 1,000 to 10,000. If the number average molecular weight exceeds 10,000, the phosphorus content decreases, which may make it difficult to impart sufficient flame retardancy to the resin molded body described later. Conversely, when the number average molecular weight is less than 1,000, the oligo (phenyleneoxy) group of the oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group may not be sufficiently substituted. A resin molded body described later has a high dielectric constant and dielectric loss tangent, and may not exhibit good electrical characteristics.

Method for producing oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with glycidyl group The oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with glycidyl group of the present invention is a specific oligo (phenyleneoxy) group-containing cyclic phosphazene compound. And epihalohydrin can be produced by reaction. Hereinafter, typical manufacturing methods will be described.

(Specific oligo (phenyleneoxy) group-containing cyclic phosphazene compounds)
The oligo (phenyleneoxy) group-containing cyclic phosphazene compound used in the production method of the present invention is represented, for example, by the following formula (4).

  In formula (4), m shows the integer of 1-6. G represents a group selected from the group consisting of the following G1 group and G2 group. However, at least one of (2m + 4) G is G2 group. Accordingly, there are two types of oligo (phenyleneoxy) group-containing cyclic phosphazene compounds represented by formula (4): those in which all of G is a G2 group and those having both G1 group and G2 group as G.

G1 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.
G2 group: a group selected from the group consisting of an oligo (phenyleneoxy) group-substituted phenyloxy group represented by the following formula (5).

In formula (5), E ^{10 to} E ¹⁴ are each an independent substituent, and are a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an alkyl group having 1 to 6 carbon atoms, alkenyl. oligo is a radical selected from at least one aryl group having 6 to 20 carbon atoms optionally substituted by a group selected from the group and aryl group, and at least one is represented by the following formula (6) (phenyleneoxy) It is a group.

In the formula (6), t represents an integer of 1 to 50, E ^{15 to} E ¹⁸ are each an independent substituent, and are a hydrogen atom, an alkyl group and an alkenyl group having 1 to 6 carbon atoms, and a carbon number 1-6 alkyl group, a group selected from at least one aryl group having 6 to 20 carbon atoms optionally substituted by a group selected from an alkenyl group and an aryl group.

  The oligo (phenyleneoxy) group-containing cyclic phosphazene compound represented by the formula (4) used in the production method of the present invention can be produced by various methods. Hereinafter, typical manufacturing methods will be described.

<Manufacturing method P-1>
In this production method, a specific hydroxy group-containing cyclic phosphazene compound and a specific polyphenylene ether are redistributed in the presence of a radical initiator to produce a corresponding oligo (phenyleneoxy) group-containing cyclic phosphazene compound. It is.

(Specific hydroxy group-containing cyclic phosphazene compounds)
The specific hydroxy group-containing cyclic phosphazene compound used in this production method is represented by the following formula (7).

  In formula (7), k shows the integer of 1-6. Q represents a group selected from the group consisting of the following Q1 group and Q2 group. However, at least one of (2k + 4) Q is a Q2 group. Therefore, there are two types of hydroxy group-containing cyclic phosphazene compounds represented by formula (7): those in which all Qs are Q2 groups and those having both Q1 groups and Q2 groups as Q.

Q1 group: alkyl group having 1 to 6 carbon atoms, optionally substituted with at least one group selected from an alkenyl group and an aryl group, an aryloxy group having 6 to 20 carbon atoms.

  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.

  Q2 group: a group selected from the group consisting of a hydroxy-substituted phenyloxy group represented by the following formula (8).

In formula (8), L ^{1 to} L ⁵ are each an independent substituent, at least one of which is a hydroxyl group, and the remainder is selected from a hydrogen atom or an alkyl group, alkenyl group and aryl group having 1 to 6 carbon atoms. Group.

Examples of such a hydroxyl group-substituted aryloxy group include a 3-hydroxyphenoxy group,
4-hydroxyphenoxy group, 2-methyl-3-hydroxyphenoxy group, 4-methyl-3-hydroxyphenoxy group, 5-methyl-3-hydroxyphenoxy group, 2-methyl-4-hydroxyphenoxy group, 3-methyl- 4-hydroxyphenoxy group, 2,4-dimethyl-3-hydroxyphenoxy group, 2,5-dimethyl-3-hydroxyphenoxy group, 2,3-dimethyl-4-hydroxyphenoxy group, 3,5-dimethyl-4- Hydroxyphenoxy group, 2-ethyl-3-hydroxyphenoxy group, 4-ethyl-3-hydroxyphenoxy group, 5-ethyl-3-hydroxyphenoxy group, 2-ethyl-4-hydroxyphenoxy group, 3-ethyl-4- Hydroxyphenoxy group, 4-phenyl-3-hydroxyphenoxy group, 5-phenyl Examples include 3-hydroxyphenoxy group, 3-phenyl-4-hydroxyphenoxy group, 4-allyl-3-hydroxyphenoxy group, 5-allyl-3-hydroxyphenoxy group, and 3-allyl-4-hydroxyphenoxy group. . Among these, 4-hydroxyphenoxy group, 2-methyl-4-hydroxyphenoxy group, 3-methyl-4-hydroxyphenoxy group, 2,3-dimethyl-4-hydroxyphenoxy group, 3,5-dimethyl-4-hydroxy Preferred are phenoxy, 2-ethyl-4-hydroxyphenoxy, 3-ethyl-4-hydroxyphenoxy, 3-phenyl-4-hydroxyphenoxy and 3-allyl-4-hydroxyphenoxy, especially 4-hydroxy Phenoxy group, 3-methyl-4-hydroxyphenoxy group and 3,5-dimethyl-4-hydroxyphenoxy group are preferred.

  The production method of such a hydroxy group-containing cyclic phosphazene is described in various documents and patents, for example, Non-Patent Documents 1 and 2 and Patent Documents 9 to 11. It can be manufactured according to these methods.

PHOSPHAZENES, A WORLDWIDE INSIGHT, M.C. GLERIA, R.M. DE JAEGER, 2004, NOVA SCIENCE PUBLISHERS INC. Company Alessandro Medici, Giancarlo Fantin, Paola Pedrini, Mario Gleria, and Francesco Minto, Macromolecules, 25 (10), 2569, 1992 JP 58-219190 A JP 2007-153747 A JP 2010-37240 A

  Examples of such a hydroxy group-containing cyclic phosphazene compound include, for example, a hydroxy group-containing cyclotriphosphazene compound in which k in formula (7) is 1, a hydroxy group-containing cyclotetraphosphazene compound in which k in formula (7) is 2, 7) a hydroxy group-containing cyclopentaphosphazene compound in which k is 3, and a hydroxy group-containing cyclohexaphosphazene compound in which k in formula (7) is 4, wherein all of Q corresponding to [Form 1] are 3 -Hydroxyphenoxy group, all of Q are 4-hydroxyphenoxy groups, all of Q are 3-methyl-4-hydroxyphenoxy groups, and all of Q are 3,5-dimethyl-4-hydroxyphenoxy groups And a 3-hydroxyphenoxy group corresponding to [Form 2], wherein Q is a Q2 group, and A phenoxy group that is one group, a 3-hydroxyphenoxy group that is Q2 group and a methylphenoxy group that is Q1 group, a 3-hydroxyphenoxy group that is Q2 group and a dimethylphenoxy group that is Q1 group Q-group of 3-hydroxyphenoxy group and Q1-group of naphthyloxy group, Q-group of Q2-4-hydroxyphenoxy group and Q1-group of phenoxy group, Q-group of Q2 4-hydroxyphenoxy group and Q1 group methylphenoxy group, Q is Q2 group 4-hydroxyphenoxy group and Q1 group dimethylphenoxy group, Q is Q2 group 4-hydroxyphenoxy group A naphthyloxy group that is a Q1 group and a 3-methyl-4-hydroxyphenoxy group that is a Q2 group and a Q1 group A phenoxy group, a 3-methyl-4-hydroxyphenoxy group in which Q is a Q2 group and a methylphenoxy group in which a Q1 group is present, a 3-methyl-4-hydroxyphenoxy group and a Q1 group in which Q is a Q2 group A dimethylphenoxy group, a 3-methyl-4-hydroxyphenoxy group in which Q is a Q2 group and a naphthyloxy group in which a Q1 group is present, a 3,5-dimethyl-4-hydroxyphenoxy group in which Q is a Q2 group And Q1 group, phenoxy group, Q is Q2 group 3,5-dimethyl-4-hydroxyphenoxy group and Q1 group methylphenoxy group, Q is Q2 group 3,5-dimethyl- 4-hydroxyphenoxy group and Q1 group dimethylphenoxy group, Q is Q2 group 3,5-dimethyl-4-hydroxyphenoxy group and Q1 group Of the naphthyloxy group and any mixtures thereof. Among these, a hydroxy group-containing cyclotriphosphazene compound in which k in formula (7) is 1, a hydroxy group-containing cyclotetraphosphazene compound in which k is 2 in formula (7), and a hydroxy group-containing cyclohexane in which k is 3 in formula (7). A pentaphosphazene compound corresponding to the [form 1], wherein all of Q are 4-hydroxyphenoxy groups, all of Q are 3-methyl-4-hydroxyphenoxy groups, and all of Q are 3 , 5-dimethyl-4-hydroxyphenoxy group, and those corresponding to [Form 2], wherein Q is a Q2-group of 4-hydroxyphenoxy group and Q1 group of phenoxy group, Q is Q2 group 4-hydroxyphenoxy group and Q1 group methylphenoxy group, and Q is Q2-group 4-hydroxyphenoxy group and Q1 group A dimethylphenoxy group, a 3-methyl-4-hydroxyphenoxy group in which Q is a Q2 group and a phenoxy group in which a Q1 group is present, a 3-methyl-4-hydroxyphenoxy group and a Q1 group in which Q is a Q2 group A certain methylphenoxy group, a 3-methyl-4-hydroxyphenoxy group in which Q is a Q2 group and a dimethylphenoxy group in which a Q1 group is present, a 3,5-dimethyl-4-hydroxyphenoxy group in which Q is a Q2 group And Q1 group, phenoxy group, Q is Q2 group 3,5-dimethyl-4-hydroxyphenoxy group and Q1 group methylphenoxy group, Q is Q2 group 3,5-dimethyl- Preferred are those having a 4-hydroxyphenoxy group and a dimethylphenoxy group which is a Q1 group, and any mixture thereof. A xyl group-containing cyclotriphosphazene compound and a hydroxy group-containing cyclotetraphosphazene compound in which k in formula (7) is 2, wherein Q is a 4-hydroxyphenoxy group corresponding to [Form 1], In addition, corresponding to [Form 2], Q is a 4-hydroxyphenoxy group having a Q2 group and a phenoxy group having a Q1 group, and 4-methylphenoxy group having a Q2 group and a methyl having a Q1 group A phenoxy group, a 3-methyl-4-hydroxyphenoxy group in which Q is a Q2 group and a phenoxy group in which a Q1 group is present, a 3,5-dimethyl-4-hydroxyphenoxy group and a Q1 group in which Q is a Q2 group Preference is given to those of the phenoxy group and any mixtures thereof.

(Specific polyphenylene ethers)
The specific polyphenylene ethers used in this production method are those represented by the following formula (9).

In the formula (9), r represents an integer of 30 to 1,000. L ^{5 to} L ⁸ are groups selected from a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 20 carbon atoms. An aryl group having 6 to 20 carbon atoms, 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.

  Specific examples of the polyphenylene ethers represented by the formula (9) include poly (methylphenylene) ethers such as poly (2-methyl-1,4-phenylene) ether, poly (2,6) as homopolymers thereof. -Poly (dimethylphenylene) ethers such as dimethyl-1,4-phenylene) ether, poly (methylethylphenylene) ethers such as poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly ( Poly (diethylphenylene) ethers such as 2,6-diethyl-1,4-phenylene) ether, poly (ethylpropylphenylene) such as poly (2-ethyl-6-n-propyl-1,4-phenylene) ether Poly (dipropylphenylene) ethers such as ethers and poly (2,6-n-propyl-1,4-phenylene) ether , Poly (methylpropylphenylene) ethers such as poly (2-methyl-6-n-propyl-1,4-phenylene) ether, poly (2-methyl-6-n-butyl-1,4-phenylene) Poly (methylbutylphenylene) ethers such as ether, poly (methylisopropylphenylene) ethers such as poly (2-methyl-6-isopropyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-) Homogeneous such as poly (ethyl isopropyl phenylene) ethers such as 1,4-phenylene) ether and poly (methyl hydroxyethyl phenylene) ethers such as poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether Polymers. Further, as a copolymer having a phenylene ether structure as a main monomer unit, a copolymer of 2,6-dimethylphenol and o-cresol, 2,6-dimethylphenol and 2,3,6-trimethylphenol, and and a copolymer with o-cresol.

  Among them, poly (methylphenylene) ethers such as poly (2-methyl-1,4-phenylene) ether and poly (dimethylphenylene) ethers such as poly (2,6-dimethyl-1,4-phenylene) ether , Poly (methylethylphenylene) ethers such as poly (2-methyl-6-ethyl-1,4-phenylene) ether, and poly (diethyl) such as poly (2,6-diethyl-1,4-phenylene) ether Phenylene) ethers and copolymers of 2,6-dimethylphenol with 2,3,6-trimethylphenol and o-cresol are preferred, and poly (methyl) such as poly (2-methyl-1,4-phenylene) ether Poly (dimethylphenylene) such as phenylene) ethers and poly (2,6-dimethyl-1,4-phenylene) ether Ethers are particularly preferred.

  Specific polyphenylene ethers include functional groups such as 2- (dialkylaminomethyl) -6-methylphenylene ether units and 2- (N-alkyl-N-phenylaminomethyl) -6-methylphenylene ether units. Polyphenylene ethers containing a phenylene ether unit having a partial structure can also be used. These polyphenylene ethers may be used in combination with the polyphenylene ether represented by the formula (9).

  Furthermore, as specific polyphenylene ethers, as long as they do not inhibit the redistribution reaction in the presence of a radical initiator, some or all of the polyphenylene ethers are epoxy groups, amino groups, hydroxyl groups, mercapto groups, Modified polyphenylene ethers functionalized with carboxyl groups or silyl groups can also be used. Two or more of these may be used in combination. The method for producing the functionalized modified polyphenylene ether is not particularly limited as long as the effects of the present invention can be obtained. For example, it can be produced by reacting polyphenylene ethers with an unsaturated carboxylic acid or a functional derivative thereof by melt-kneading in the presence or absence of a radical initiator. Moreover, it can also manufacture by dissolving polyphenylene ether, unsaturated carboxylic acid, and its functional derivative in the organic solvent in the presence or absence of radical initiation, and making it react under a solution.

(Production of oligo (phenyleneoxy) group-containing cyclic phosphazene compounds)
The oligo (phenyleneoxy) group-containing cyclic phosphazene compound can be produced by redistributing the above-mentioned specific hydroxyl group-containing cyclic phosphazene compound and the above-mentioned specific polyphenylene ether in the presence of a radical initiator. .

  In this reaction, polyphenylene ethers are radicalized by a radical initiator, and the radicalized polymer chain is cleaved by a redistribution reaction to generate activated oligophenylene ether. This oligophenylene ether reacts with the hydroxy group of the hydroxy group-containing cyclic phosphazene compound. Thereby, the target oligo (phenyleneoxy) group containing cyclic phosphazene compound can be obtained.

  The type of the radical initiator used here is not particularly limited. For example, various organic peroxides, azo compounds such as azobisisobutyronitrile and azobisisovaleronitrile, and 2, Examples thereof include 3-dimethyl-2,3-diphenylbutane (for example, “Biscumyl”, a trade name of Nippon Oil & Fat Co., Ltd.). Among these, it is preferable to use an organic peroxide.

  Preferred organic peroxides include, for example, peroxyesters, dialkyl peroxides, hydroperoxides, diacyl peroxides, peroxydicarbonates, peroxyketals, and silyl peroxides.

  Examples of peroxyesters include cumyl peroxyneodecanate, 1,1,3,3-tetramethylbutylperoxyneodecanate, 1-cyclohexyl-1-methylethylperoxynoedecanoate, and tert-hexyl. Peroxyneodecanoate, tert-butyl peroxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 2,5-dimethyl-2,5-di (2- Ethylhexanoylperoxy) hexane, 1-cyclohexyl-1-methylethylperoxy-2-ethylhexanoate, L-hexylperoxy-2-ethylhexanoate, L-butylperoxy-2-ethylhexanoate Tert-butyl peroxyisobutyrate, 1,1-bis (tert-butyl -Oxy) cyclohexane, tert-hexyl peroxyisopropyl monocarbonate, tert-butyl peroxylaurate, 2,5-dimethyl-2,5-di (m-toluoyl peroxy) hexane tert-butyl peroxyisopropyl monocarbonate, Examples thereof include tert-butyl peroxy-2-ethylhexyl monocarbonate, tert-hexyl peroxybenzoate, and tert-butyl peroxyacetate.

Examples of the dialkyl peroxide include α, α′-bis (tert-butylperoxy-m-isopropyl) benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy). Examples include hexyne-3,2,5-dimethyl-2,5-di (tert-butylperoxy) hexane and tert-butylcumyl peroxide.

Examples of the hydroperoxide include diisopropylbenzene hydroperoxide and cumene hydroperoxide.

Examples of the diacyl peroxide include isobutyl peroxide, di-tert-butyl peroxide, 2,4-dichlorobenzoyl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, lauroyl peroxide, Examples include stearoyl peroxide, succinic peroxide, benzoyl peroxide and benzoyl peroxide.

Examples of the peroxydicarbonate include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, bis (4-tert-butylcyclohexyl) peroxydicarbonate, di-2-ethoxymethoxydicarbonate, di ( 2-ethylhexyl peroxy) dicarbonate, dimethoxybutyl peroxydicarbonate, di (3-methyl-3-methoxybutylperoxy) dicarbonate, and the like.

Examples of the peroxyketal include 1,1-bis (tert-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (tert-hexylperoxy) cyclohexane, 1,1-bis ( tert-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1- (tert-butylperoxy) cyclododecane, 2,2-bis (tert-butylperoxy) decane, and the like. .

Examples of the silyl peroxide include tert-butyltrimethylsilyl peroxide, bis (tert-butyl) dimethylsilyl peroxide, tert-butyltrivinylsilyl peroxide, bis (tert-butyl) divinylsilyl peroxide, tris (tert- Examples thereof include butyl) vinylsilyl peroxide, tert-butyltriallylsilyl peroxide, bis (tert-butyl) diallylsilyl peroxide, and tris (tert-butyl) allylsilyl peroxide.

Among these, benzoyl peroxide, dicumyl peroxide, tert-butylcumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di (tert-butylperoxy) are particularly preferable. ) Hexin-3,2,5-dimethyl-2,5-di (tert-butyl) hexane and α, α′-bis (tert-butylperoxy-m-isopropyl) benzene.

In addition, although an organic peroxide can be used independently, respectively, 2 or more types can also be used together.

In this reaction, the amount of the hydroxy group-containing cyclic phosphazene compound used is preferably set to 1 to 300 parts by weight with respect to 100 parts by weight of the polyphenylene ethers. When the amount of the hydroxy group-containing phosphazene compound exceeds 300 parts by weight, the number average molecular weight of the oligophenylene ether produced decreases because the redistribution reaction proceeds too much, and the desired oligo (phenyleneoxy) group-containing cyclic phosphazene There is a possibility that a compound, that is, an oligo (phenyleneoxy) group-containing cyclic phosphazene compound having a predetermined G2 group cannot be obtained. Conversely, when the amount of the hydroxy group-containing cyclic phosphazene compound used is less than 1 part by weight, the redistribution reaction does not proceed sufficiently, so that the resulting oligo (phenyleneoxy) group-containing cyclic phosphazene compound, that is, a predetermined G2 An oligo (phenyleneoxy) group-containing cyclic phosphazene compound having a group may not be obtained.

  Moreover, it is preferable to set the usage-amount of a radical initiator to 1-30 weight part with respect to 100 weight part of polyphenylene ethers. When the usage-amount of a radical initiator exceeds 30 weight part, it is a redistribution reaction. The number average molecular weight of the oligophenylene ether produced decreases due to excessive progress of the oligo (phenyleneoxy) group-containing cyclic phosphazene compound, that is, the oligo (phenyleneoxy) group-containing cyclic phosphazene compound having a predetermined G2 group. It may not be obtained. Conversely, when the amount of radical initiator used is less than 1 part by weight, the number average molecular weight of the oligophenylene ether produced increases because the redistribution reaction does not proceed sufficiently, and the desired oligo (phenyleneoxy) group There is a possibility that a containing cyclic phosphazene compound, that is, an oligo (phenyleneoxy) group-containing cyclic phosphazene compound having a predetermined G2 group cannot be obtained.

  This reaction can usually be performed in a solvent, and it is preferable to set the reaction temperature to 80 to 120 ° C. and the reaction time to 10 to 180 minutes. As the solvent, for example, aromatic hydrocarbon solvents such as toluene, benzene and xylene, chloroform and the like can be used.

  In this production method, polyphenylene ethers (homopolymers) are generated due to the above-mentioned redistribution reaction, and a trace amount thereof may be mixed into the oligo (phenyleneoxy) group-containing cyclic phosphazene compound. Even if such polyphenylene ethers are mixed, the epoxidation reaction described later can be used without any problem, but if there is a problem, it is preferable to remove the polyphenylene ether and use it. Methods for removing polyphenylene ethers mixed in oligo (phenyleneoxy) group-containing phosphazene compounds include, for example, ultrafiltration based on molecular weight differences, fractional precipitation based on solubility differences, and molecules based on vapor pressure differences Examples thereof include distillation.

<Manufacturing method P-2>
The oligo (phenyleneoxy) group-containing cyclic phosphazene compound of the present invention can be produced by the above production method P-1, but can be produced based on a general production method of a polyphenylene ether resin. In this method, a hydroxy group-containing cyclic phosphazene compound similar to that used in Production Method P-1 in an aromatic hydrocarbon solvent or a mixed solvent of an aromatic hydrocarbon and an alcohol, and the following monovalent phenol compound: Is subjected to oxidative polymerization in the presence of a complex catalyst containing copper, manganese or cobalt, whereby the desired oligo (phenyleneoxy) group-containing cyclic phosphazene compound can be produced.

  The monohydric phenol compound used here is capable of forming a predetermined G2 group by reaction with a hydroxy group of a hydroxy group-containing cyclic phosphazene compound and oxidative polymerization. For example, o-cresol, 2,6-dimethyl Phenol, 2,3,6-trimethylphenol, 2-ethylphenol, 2-methyl-6-ethylphenol, 2,6-diethylphenol, 2-n-propylphenol, 2-ethyl-6-n-propylphenol, 2-methyl-6-chlorophenol, 2-methyl-6-bromophenol, 2-methyl-6-isopropylphenol, 2-methyl-6-n-propylphenol, 2-ethyl-6-bromophenol, 2-ethyl -6-butylphenol, 2,6-di-n-propylphenol, 2-ethyl-6-alkyl Lophenol 2-ethyl-6-phenylphenol, 2-phenylphenol, 2,6-diphenylphenol, 2,6-bis (4-fluorophenyl) phenol, 2-methyl-6-tolylphenol and 2,6-di Examples include tolylphenol. Two or more of these phenol compounds can be used in combination.

  Examples of amines used for oxidative polymerization include diisopropylamine, di-sec-butylamine, di-tert-butylamine, di-tert-allylamine, dicyclopentylamine, dicyclohexylamine, diphenylamine, p, p′-. Ditolylamine, m, m′-ditolylamine, ethyl-tert-butylamine, N, N′-di-tert-butylethylenediamine, methylcyclohexylamine, methylphenylamine, triethylamine, methyldiethylamine, n-butyldimethylamine, benzyldimethylamine, Examples include phenyldimethylamine, N, N-dimethyl-p-toluidine, triphenylamine, N, N-dimethylpiperazine, pyridine, methylpyridine and 2,6-dimethylpyridine. It is possible. Two or more of these amines can be used in combination.

  This production method produces an oligo (phenyleneoxy) group-containing phosphazene compound having a higher purity than the above-mentioned method because there is a low possibility that polyphenylene ethers and the like are mixed into the oligo (phenyleneoxy) group-containing cyclic phosphazene compound. be able to.

<Manufacturing method P-3>
The oligo (phenyleneoxy) group-containing cyclic phosphazene compound of the present invention is produced in the presence of a phase transfer catalyst such as aqueous sodium hydroxide and tetrabutylammonium hydrogen sulfate and air in an aromatic hydrocarbon solvent. It can also be produced by reacting a hydroxy group-containing cyclic phosphazene compound similar to that used in the above and a halophenol compound described below.

  The halophenol compound used here is capable of forming a predetermined A2 group by reaction with a hydroxy group of a hydroxy group-containing cyclic phosphazene compound and oxidative polymerization, such as 4-bromo-2-methylphenol or 4- Mention may be made of bromo-2,6-dimethylphenol. Two or more halophenol compounds can be used in combination.

  In this production method, since there is a low possibility that polyphenylene ethers and the like are mixed into the target oligo (phenyleneoxy) group-containing cyclic phosphazene compound, an oligo (phenyleneoxy) group having a higher purity than production method P-1. Containing cyclic phosphazene compounds can be produced.

(Method for producing oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with glycidyl group)
The oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group is obtained by reacting the oligo (phenyleneoxy) group-containing cyclic phosphazene compound obtained by the above-described production method with epihalohydrin in the presence of a base. Can be manufactured.

  Examples of the epihalohydrin used herein include epichlorohydrin, epibromohydrin, and epiiodohydrin, and epichlorohydrin is particularly preferable.

  The base used here is not particularly limited, and examples thereof include alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide, triethylamine, trimethylamine, diisopropylethylamine, pyridine and 4-dimethylamino. Mention may be made of aliphatic or aromatic amines such as pyridine, alkali metal carbonates such as potassium carbonate and potassium carbonate, and metal hydrides such as sodium hydride. Of these, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, triethylamine and pyridine are preferred.

  The oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group of the present invention can be produced by selecting the above-mentioned epihalohydrin or the like and a base. Hereinafter, typical manufacturing methods will be described.

<Manufacturing method G-1>
This is a production method in which an oligo (phenyleneoxy) group-containing cyclic phosphazene compound and an epihalohydrin are reacted. In this case, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide as a base is added to the mixture of the oligo (phenyleneoxy) group-containing phosphazene compound and epihalohydrin, or the reaction (dehalogenation is performed). (Ring-closing reaction with hydrogen). The reaction temperature is preferably set to 20 to 120 ° C. The reaction time is usually preferably set to 1 to 10 hours.

  In the case of this method, the amount of epihalohydrin used is usually preferably set in the range of 1.1 to 20 equivalents relative to 1 equivalent of the hydroxyl group of the oligo (phenyleneoxy) group-containing cyclic phosphazene compound. Incidentally, as the amount of epihalohydrin used increases, the resulting oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group becomes closer to the theoretical structure. The production | generation of the secondary hydroxy group produced by reaction with a hydroxyl group and an epoxy group can be suppressed. From this, it is more preferable that the addition amount of epihalohydrin is set in the range of 2.5 to 20 equivalents with respect to 1 equivalent of hydroxy group of the oligo (phenyleneoxy) group-containing cyclic phosphazene compound.

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

<Manufacturing method G-2>
In this production method, first, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide and tetramethylbenzylammonium chloride is used as a catalyst for a mixture of an oligo (phenyleneoxy) group-containing cyclic phosphazene compound and epihalohydrin. It is added and reacted under the conditions of 50 to 150 ° C. to once produce a halohydrin etherified product (Step A). The reaction time in this step is not particularly limited, but usually it is preferably set to 1 to 5 hours.

  Next, for example, a solid or aqueous solution of an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide is added as a base to the halohydrin etherified product formed in Step A, and dehydrated at a temperature of 20 to 120 ° C. A ring-closing reaction with hydrogen halide is performed (step B). The reaction time in this step is not particularly limited, but usually it is preferably set to 1 to 10 hours.

  In step B, the ring closure reaction by dehydrohalogenation proceeds smoothly, alcohols such as methanol, ethanol, isopropanol and butanol, ketones such as acetone and methyl ethyl ketone, ethers such as tetrahydrofuran and dioxane, dimethyl sulfone and A solvent such as an aprotic polar solvent such as dimethyl sulfoxide is preferably added to the reaction system. The amount of the aprotic polar solvent used is usually preferably set to 5 to 100% by weight and more preferably set to 10 to 60% by weight with respect to the amount of epihalohydrin. On the other hand, solvents other than aprotic polar solvents, for example, aliphatic or aromatic hydrocarbons such as hexane, toluene and xylene and halogen solvents such as chloroform, dichloromethane and chlorobenzene can be used. The amount is usually preferably set to 5 to 50% by weight based on the amount of epihalohydrin used.

  The reaction liquid of Step B is usually distilled off of epihalohydrin and other added solvents under heating and reduced pressure at 110 to 250 ° C. and a pressure of 10 hPa or less after washing with water or without washing with water. The resulting oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group is dissolved again in a solvent such as toluene or methyl isobutyl ketone, and an alkali metal such as sodium hydroxide or potassium hydroxide is dissolved in the solution. It is preferable to complete the ring closure reaction by adding an aqueous solution of hydroxide. By such an operation, an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group with a small residual amount of hydrolyzable halogen can be obtained.

  When such an operation is performed, the amount of alkali metal hydroxide used is usually 1 mol of hydrolyzable halogen atoms remaining in the oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group. It is preferable to set to 0.5-10 mol, and it is more preferable to set to 1.2-5.0 mol. The reaction temperature is preferably set to 50 to 120 ° C., and the reaction time is preferably set to 0.5 to 3 hours. In this treatment, a phase transfer catalyst such as a quaternary ammonium salt or crown ether can be added for the purpose of improving the reaction rate. In this case, the amount of the phase transfer catalyst used is 0.1 to 3.3 with respect to the oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group. It is preferably set to 0% by weight.

  The oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group, after the reaction is completed, the produced salt is removed by a method such as filtration or washing with water, and a solvent such as toluene or methyl butyl ketone is removed under heating and reduced pressure. Obtained by distilling off.

  The oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with the target glycidyl group obtained by the above-described production methods G-1 and G-2 is used for ordinary filtration, solvent extraction, column chromatography, reprecipitation and the like. It can be isolated and purified from the reaction system by a purification method.

Resin Composition The resin composition of the present invention comprises the oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with the glycidyl group of the present invention and a resin component.

  In the resin composition of the present invention, as the oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group of the present invention, one kind may be used, or two or more kinds, that is, the aforementioned Such an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with two or more glycidyl groups 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. 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 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 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, and insulating materials such as Si substrates or SiC substrates. When used as a material, conductive material, and surface protection material, polyurethane, phenol resin, bismaleimide resin, cyanate ester resin, bismaleimide-cyanate ester resin, polyimide resin, epoxy resin, or the like is used as the thermosetting resin. Is preferred.

  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 oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group can be appropriately set according to various conditions such as the type of the resin component and the use of the resin composition. However, it is usually preferably set to 0.1 to 200 parts by weight, more preferably 0.5 to 100 parts by weight, with respect to 100 parts by weight of the resin component in terms of solid content. More preferably, it is set to parts by weight. When the amount of the oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group is less than 0.1 parts by weight, the resin molded body made of the resin composition may not exhibit sufficient flame retardancy. . 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 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. 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 fibers, 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 mold release agents such as paraffin, chlorine Paraffin, phosphate ester, condensed phosphate ester, phosphate amide, phosphate amide ester, phosphinate salt, phosphorus flame retardants such as ammonium phosphate and red phosphorus, melamine, melamine cyanurate, melam, melem, melon and succino Nitrogen flame retardants such as guanamine, silicone flame retardants and flame retardants such as bromine flame retardants, flame retardant aids such as antimony trioxide, anti-dripping agents such as polytetrafluoroethylene (PTFE), benzotriazole, etc. UV absorbers, hindered phenols, antioxidants such as styrenated phenols, photopolymerization initiators such as thioxanthones, fluorescent brighteners such as stilbene derivatives, curing agents, dyes, pigments, colorants, light stabilizers, light Sensitizer, thickener, lubricant, defoamer, leveling agent, brightener, polymerization inhibitor, thixo Imparting agent, and a plasticizer as well as antistatic agents.

  Furthermore, the resin composition 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 resin composition of the present invention is used for materials for electric and electronic fields, specifically, sealants and substrates for electronic components such as LSI, the resin components include epoxy resins, polyimide resins, and 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 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-described epoxy resin is used as the resin component (hereinafter, such a resin composition may be referred to as “epoxy resin composition”), the oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group of the present invention Is preferably 0.1 to 80% by weight, and more preferably 0.5 to 70% by weight in the epoxy resin composition. When the proportion of the oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group is less than 0.1% by weight, the resin molded body made of the resin composition may not exhibit sufficient flame retardancy. . On the other hand, if it exceeds 80% by weight, the original properties of the resin component may be impaired, and a resin molded product having such properties may not be obtained.

  The epoxy resin composition usually contains a curing agent. The type of curing agent is not particularly limited as long as it is used as a curing agent for epoxy resins. For example, polyamine curing agents such as aliphatic polyamines, aromatic polyamines, and polyamide polyamines, hexahydrophthalic anhydride. And acid anhydride curing agents such as methyltetrahydrophthalic anhydride, phenolic curing agents such as phenol novolac, phosphazene compounds having a hydroxy group, Lewis acids such as boron trifluoride and their salts, and dicyandiamides be able to. 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. The reactive diluent that can be used is not particularly limited, but examples thereof include aliphatic alkyl glycidyl ethers such as butyl glycidyl ether, 2-ethylhexyl glycidyl ether, and allyl glycidyl ether, glycidyl methacrylate, and glycidyl tertiary carboxylate. Examples thereof include alkyl glycidyl esters such as esters, aromatic alkyl glycidyl ethers such as styrene oxide and phenyl glycidyl ether, cresyl glycidyl ether, p-s-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 oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group of the present invention is stably held in the cured product because the glycidyloxy group reacts with the resin component. Therefore, it is difficult to impair the high temperature reliability of the cured product. In addition, the oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group of the present invention increases its flame retardancy without impairing the mechanical properties (particularly the glass transition temperature) of such a cured product. Can do. 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.

  According to the resin composition of the present invention, a cured product having a low dielectric constant and dielectric loss tangent can be obtained. Therefore, 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 film, conductive paste for printed wiring board, sealing agent for multilayer printed wiring board, circuit protective agent, cover lay film, cover ink), etc. are particularly suitable as materials for manufacturing electrical and electronic parts. .

Polymerizable composition The polymerizable composition of the present invention contains an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group of the present invention. The oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group used here may be two or more kinds. In addition to the oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group of the present invention, this polymerizable composition is, for example, an epoxy resin, a polyimide resin modified to impart thermoplasticity or solvent solubility (preferably Has functional groups that react with and bond to glycidyloxy groups, such as carboxyl groups, epoxy groups, hydroxy groups and amino groups, polyimides, polyamideimides, polyetherimides, polyesterimides, polycarbodiimides, maleimide resins and maleimides. Reactive functional groups such as carboxyl groups, epoxy groups, hydroxy groups, amino groups, and anhydrous dicarboxyl groups on part or all of polyphenylene ethers (polyimide resins such as cyanate ester resins) and modified polyphenylene ethers , Those that have been introduced by any method such as grafting reaction or copolymerization) is used. Two or more kinds of these resin components can be used in combination. 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 resin composition.

  Furthermore, this polymerizable composition is used to improve the reactivity of the oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group of the present invention with the epoxy resin, polyimide resin, modified polyphenylene ether, and the like. In addition, a catalyst may be included. The catalyst usable here is, for example, in the case of an epoxy resin, usually the same as the curing agent mentioned in the description of the epoxy resin composition, 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 novolak, phosphazenes having a glycidyloxy group different from those of the present invention Compounds, Lewis acids such as boron trifluoride and their salts and dicyandiamides, imidazole compounds such as 2-methylimidazole and 2-ethylimidazole, tertiary amine compounds such as 2- (dimethylaminomethyl) phenol , Triphenylphos Fin compounds and the like, and the like.

  In the polymerizable composition comprising an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group of the present invention and an epoxy resin, the amount of these catalysts used is 0.01 to 1 equivalent of the epoxy group of the epoxy resin. It is preferably set to be ˜15 equivalents, and more preferably set to be 0.1 to 7 equivalents.

  The polymerizable composition of the present invention can be obtained by uniformly mixing required components. This polymerizable composition usually undergoes a polymerization reaction between the oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group when heated and the above-mentioned epoxy resin, polyimide resin, modified polyphenylene ether, and the like. A polymer is formed. In the case where an epoxy resin is used, this polymer is changed from a liquid to a cured product (resin molded product) depending on the number of reactive groups. The obtained polymer is substantially composed of a polymer of oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group of the present invention, so that it has excellent flame retardancy and high temperature reliability, and has a glass transition temperature. Since it is high, it has excellent mechanical properties. 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 and 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 comparative examples, but the present invention is not limited by these. In the following, “unit” in “unit mol” means the smallest structural unit of the cyclic phosphazene compound, for example, (PNA2) for general formula (1) and (PNG2) for general formula (4). means. In the general formula (7), when X is chlorine, its 1 unit mol is 115.87 g. In the following, unless otherwise specified, “%” and “parts” mean “% by weight” and “parts by weight”, respectively.

  The phosphazene compounds obtained in the synthesis examples and examples were measured by 1H-NMR spectrum and 31P-NMR spectrum, CHN elemental analysis, IR spectrum measurement, and chlorine element (potentiometric titration using silver nitrate after alkali melting) It was identified based on the results of analysis of residual chlorine), analysis of phosphorus element by ICP-AES after microwave wet decomposition, and TOF-MS analysis. Further, the hydroxyl group equivalent of the hydroxy group-containing cyclic phosphazene compound is determined according to JIS K0070-1992 “Testing methods for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponified product of chemical products”. It measured according to the neutralization titration method of the measuring method, and the value of hydroxyl value mgKOH / g was determined as the hydroxyl equivalent g / eq. Converted to. Furthermore, the molecular weight (number average molecular weight) is determined according to JIS K7252-2008 “How to determine the average molecular weight and molecular weight distribution of polymers by plastic-size exclusion chromatography”, Waters Gel Permeation Chromatography “2695”, Tosoh Corporation Using a company-made column “TSKgel Super HZM-M” (two) and a Waters differential refractometer (DRI detector: trade name “2414”) at 40 ° C. under conditions of 0.25 mL / min of tetrahydrofuran It was measured. Here, the molecular weight of the substance to be measured is a calibration curve prepared using six types of standard polystyrene (molecular weights 1110,000, 397,000, 98,900, 17,100, 5,870 and 1,010). Calculated from

  Moreover, the hydroxyl equivalent of the oligo (phenyleneoxy) group-containing cyclic phosphazene compound and the epoxy equivalent of the oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a glycidyl group were measured by the following methods.

(1) Hydroxyl equivalent The hydroxyl equivalent (g / eq .: mass g of resin containing 1 equivalent of a hydroxy group) is obtained by dissolving an oligo (phenyleneoxy) group-containing cyclic phosphazene compound in chloroform, and then adding 0.1N tetraethylammonium hydroxide. After adding vigorously methanol solution, the absorbance at 318 nm was measured. It was determined from the difference in absorbance between when 0.1 M tetraethylammonium hydroxide in methanol was added and when it was not added.

(2) 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”.

Synthesis Example 1 (Oligo according to Form 2 (Production of phenyleneoxy group-containing cyclic phosphazene compound))
Hydroxy group-containing cyclic phosphazene compound having an average composition of [N3P3 (OC6H2 (CH3) 2OH) 2.1 (OC6H5) 3.9] in a 3 liter four-necked flask equipped with a thermometer, a stirrer and a condenser ( 100 g, 0.38 unit mol), polyphenylene ether (670 g, number average molecular weight: 17,000) and toluene (2,000 mL) manufactured by Asahi Kasei Chemicals Co., Ltd. and toluene (2,000 mL) are added, and the mixture is heated and dissolved at 90 ° C. Benzoyl (20 g, 0.082 mol) was added and reacted at 90 ° C. for 1 hour. And the precipitate obtained by throwing this reaction mixture into methanol (6,000 mL) was separated by filtration. The precipitate was washed with methanol (1,200 mL) and then dried under reduced pressure to obtain 744 g of an oligo (phenyleneoxy) group-containing cyclic phosphazene compound (yield 96.6%). The yield was calculated by assuming that 100% of the polyphenylene ether was redistributed to the hydroxy group-containing cyclic phosphazene compound. The analysis results of the obtained oligo (phenyleneoxy) group-containing cyclic phosphazene compound are as follows.

1H-NMR spectrum (in heavy chloroform, δ, ppm):
2.0-2.2 (267.1H), 6.3-6.6 (89.0H), 6.7-7.3 (19.5H)
◎ 31P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) 3 9.5 to 10.0
◎ Hydroxyl equivalent 2,800 g / eq. (Theoretical value 2,825 g / eq.)
◎ Gel permeation chromatography:
Number average molecular weight 5,900

  The analysis result of gel permeation chromatography is shown in FIG. In the figure, the peak of polyphenylene ether was detected at a retention time of 24.5 minutes before the start of the reaction, and the peak of a hydroxy group-containing cyclic phosphazene compound was detected at a retention time of 30.4 minutes. On the other hand, 1 hour after the start of the reaction, no peak was detected at retention times 24.5 and 30.4 minutes, and a single peak was detected at retention time 25.8 minutes. The final product (the precipitate obtained by the reaction was filtered and washed) was detected as a single peak at 25.9 minutes.

  From the above analysis results, the product obtained in this step is a cyclic phosphazene whose structure is [N3P3 {OC6H2 (CH3) 2 (OC6H2 (CH3) 2) 20.2OH} 2.1 (OC6H5) 3.9]. It was confirmed to be a compound.

Synthesis Example 2 (Production of oligo (phenyleneoxy) group-containing cyclic phosphazene compound according to form 2)
Hydroxy group having an average composition of [N3P3 (OC6H2 (CH3) 2OH) 2.1 (OC6H5) 3.9] in a 3 liter four-necked flask equipped with a thermometer, stirrer, air inlet tube and condenser tube Add cyclic phosphazene compound (100 g, 0.38 unit mol), copper (I) chloride (3.4 g, 0.034 mol), dibutylamine (200 g, 1.55 mol) and nitrobenzene (1,500 mL) to 40 ° C. Heated. While blowing air, a solution of 2,6-xylenol (366.5 g, 3.00 mol) in nitrobenzene (1,000 mL) was added dropwise over 6 hours, and then reacted at 40 ° C. for 24 hours. After adding ethylenediaminetetraacetic acid aqueous solution to stop the reaction, the reaction mixture was concentrated under reduced pressure. The concentrated residue was poured into methanol (6,000 mL), and the resulting precipitate was filtered off. The precipitate was washed with methanol (1,200 mL) and then dried under reduced pressure to obtain 375 g of an oligo (phenyleneoxy) group-containing cyclic phosphazene compound (yield 88.6%). The analysis results of the obtained oligo (phenyleneoxy) group-containing cyclic phosphazene compound are as follows.

1H-NMR spectrum (in heavy chloroform, δ, ppm):
2.0-2.2 (267.1H), 6.3-6.6 (89.0H), 6.7-7.3 (19.5H)
◎ 31P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) 3 9.5 to 10.0
◎ Hydroxyl equivalent 1,500 g / eq. (Theoretical value 1,564 g / eq.)
◎ Gel permeation chromatography:
Number average molecular weight 3,300

  From the above analysis results, the product obtained in this step is a cyclic phosphazene whose composition is [N3P3 {OC6H2 (CH3) 2 (OC6H2 (CH3) 2) 9.9OH} 2.1 (OC6H5) 3.9]. It was confirmed to be a compound.

Synthesis Example 3 (Production of oligo (phenyleneoxy) group-containing cyclic phosphazene compound according to form 2)
A hydroxy group-containing cyclic phosphazene compound (100 g, 0.40 unit mol) having an average composition of [N3P3 (OC6H2 (CH3) OH) 2.0 (OC6H5) 4.0] instead of the hydroxy group-containing phosphazene compound used in Synthesis Example 1 ) Was used in the same manner as in Synthesis Example 1 to obtain 744 g of an oligo (phenyleneoxy) group-containing cyclic phosphazene compound (yield 96.6%). The analysis results of the obtained oligo (phenyleneoxy) group-containing cyclic phosphazene compound are as follows.

1H-NMR spectrum (in heavy chloroform, δ, ppm):
2.0 to 2.2 (243.6H), 6.3 to 6.6 (85.2H), 6.7 to 7.3 (20.0H),
◎ 31P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) 3 9.6-10.0
◎ Hydroxyl equivalent 2,900 g / eq. (Theoretical value 2,804 g / eq.)
◎ Gel permeation chromatography Number average molecular weight 5,800

  Similar to Synthesis Example 1, the peak of the hydroxy group-containing cyclic phosphazene compound disappeared 1 hour after the start of the reaction, and the peak of the charged polyphenylene ether changed to the low molecular weight side to become a single peak.

  From the above analysis results, the product obtained in this step is a cyclic phosphazene compound whose composition is [N3P3 {OC6H3 (CH3) (OC6H2 (CH3) 2) 20.9OH} 2.0 (OC6H5) 4.0]. It was confirmed that.

Synthesis Example 4 (Production of oligo (phenyleneoxy) group-containing cyclic phosphazene compound according to form 2)
Hydroxy group-containing cyclic phosphazene compound having an average composition of [N3P3 (OC6H4OH) 2.2 (OC6H5) 3.8] (50 g, 0.00 g) in a 3 liter four-necked flask equipped with a thermometer, a stirrer and a condenser. 21 unit mol), 10% aqueous potassium hydroxide solution (3,750 mL, 6.68 mol) and potassium ferricyanide (395 g, 1.2 mol) and toluene (1,000 mL) were charged, and 4-bromo-2 at an internal temperature of 20 to 40 ° C. , 6-xylenol (638 g, 3.17 mol) in toluene (1,200 mL) was added dropwise over 3 hours. The reaction mixture was stirred at the same temperature for 1 hour and then transferred to a separatory funnel to separate the aqueous layer. After the organic layer was concentrated, the residue was poured into methanol (5,000 g), and the resulting precipitate was filtered off. The precipitate was washed with methanol (1,000 g) and dried under reduced pressure to obtain an oligo (phenyleneoxy) group-containing cyclic phosphazene compound (396 g, yield 92.1%).

1H-NMR spectrum (in heavy chloroform, δ, ppm):
2.0-2.2 (125H), 6.3-6.6 (50H), 6.7-7.3 (19H)
◎ 31P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) 3 9.6-10.0
◎ Hydroxyl equivalent 1,500 g / eq. (Theoretical value 1,473 g / eq.)
◎ Gel permeation chromatography:
Number average molecular weight 3,240

  From the above analysis results, the product obtained in this step is a cyclic phosphazene compound whose composition is [N3P3 {OC6H4 (OC6H2 (CH3) 2) 9.5OH} 2.2 (OC6H5) 3.8]. It was confirmed.

Synthesis Example 5 (Production of oligo (phenyleneoxy) group-containing cyclic phosphazene compound according to Form 1)
Similar to Synthesis Example 1 except that the hydroxy group-containing cyclic phosphazene compound (100 g, 0.38 unit mol) having an average composition of [N3P3 (OC6H4OH) 6] was used instead of the hydroxy group-containing phosphazene compound used in Synthesis Example 1. To obtain 744 g of an oligo (phenyleneoxy) group-containing cyclic phosphazene compound (yield 96.6%). The analysis results of the obtained oligo (phenyleneoxy) group-containing cyclic phosphazene compound are as follows.

1H-NMR spectrum (in heavy chloroform, δ, ppm):
2.0-2.2 (252.0H), 6.3-6.6 (108.0H)
◎ 31P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) 3 9.6-10.0
◎ Hydroxyl equivalent 1,000 g / eq. (Theoretical value 972 g / eq.)
◎ Gel permeation chromatography:
Number average molecular weight 5,840

  Similar to Synthesis Example 1, the peak of the hydroxy group-containing cyclic phosphazene compound disappeared 1 hour after the start of the reaction, and the peak of the charged polyphenylene ether changed to the low molecular weight side to become a single peak.

  From the above analysis results, it was confirmed that the product obtained in this step was a cyclic phosphazene compound having a composition of [N3P3 {OC6H4 (OC6H2 (CH3) 2) 7.0OH} 6].

Synthesis Example 6 (Production of oligo (phenyleneoxy) group-containing cyclic phosphazene compound according to Form B)
A synthesis example except that the hydroxy group-containing cyclic phosphazene compound (100 g, 0.38 unit mol) having an average composition of [NP (OC6H4OH) (OC6H5CH3)] n was used instead of the hydroxy group-containing phosphazene compound used in Synthesis Example 1. In the same manner as in Example 1, 740 g of an oligo (phenyleneoxy) group-containing cyclic phosphazene compound was obtained (yield 96.1%). The analysis results of the obtained oligo (phenyleneoxy) group-containing cyclic phosphazene compound are as follows.

1H-NMR spectrum (in heavy chloroform, δ, ppm):
2.0-2.2 (241.6H), 6.3-6.6 (89.3H), 6.7-7.3 (19.0H)
◎ 31P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) 3 9.6-10.0
◎ Hydroxyl equivalent 1,900 g / eq. (Theoretical value 1,967 g / eq.)
◎ Gel permeation chromatography:
Number average molecular weight 7,100

  Similar to Synthesis Example 1, the peak of the hydroxy group-containing cyclic phosphazene compound disappeared 1 hour after the start of the reaction, and the peak of the charged polyphenylene ether changed to the low molecular weight side to become a single peak.

  From the above analysis results, it was confirmed that the product obtained in this step was a cyclic phosphazene compound having a composition of [NP {OC6H4 (OC6H2 (CH3) 2) 14.2OH} (OC6H4CH3)] n.

Synthesis Example 7 (Production of phenoxy group fully substituted cyclic phosphazene compound)
PHOSPHORUS-NITROGEN COMPOUNDS, H.P. R. [N = P (OC6H5) 2] using a mixture of 81% hexachlorocyclotriphosphazene and 19% octachlorocyclotetraphosphazene according to the method described in ALLCOCK, 1972, page 151, ACADEMIC PRESS. ] And [N = P (OC6H5) 2] 4 (white solid / melting point: 65-112 ° C.).

Example 1 (Production of oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with glycidyl group according to Form 2)
In a 1 liter four-necked flask equipped with a thermometer and a stirrer, an oligo (phenyleneoxy) group-containing cyclic phosphazene compound produced in Synthesis Example 1 (100 g, 0.05 unit mol), epichlorohydrin in a nitrogen stream (200 g, 2.16 mol) and N, N-dimethylformamide (100 mL) were charged, and sodium hydroxide (1.7 g, 0.04 mol) was added to the stirring solution, followed by dehydration and reflux for 3 hours. After completion of the reaction, N, N-dimethylformamide and unreacted epichlorohydrin were distilled off by concentration under reduced pressure, and methyl isobutyl ketone (MIBK) (300 mL) was added and dissolved, followed by washing with water three times. The MIBK layer was concentrated under reduced pressure and dried under reduced pressure at 120 ° C. to obtain 101.0 g (yield: 99.3%) of the product. The analysis result of this product was as follows.

1H-NMR spectrum (in heavy chloroform, δ, ppm):
2.0-2.2 (265H), 2.6-2.9 (4H), 3.1-3.6 (6H), 6.3-6.6 (89H), 6.7-7. 3 (19H)
◎ 31P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) 3 9.6-10.0
◎ Epoxy equivalent:
2,800 g / eq.

  From the above analysis results, the product obtained in this step has a glycidyl group whose structure is [N3P3 {OC6H2 (CH3) 2 (OC6H2 (CH3) 2) 20.2OCH2CHOCH2} 2.1 (OC6H5) 3.9]. It was confirmed that it was an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with 1.

Example 2 (Production of oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with glycidyl group according to Form 2)
In a 1 liter four-necked flask equipped with a thermometer and a stirrer, an oligo (phenyleneoxy) group-containing cyclic phosphazene compound produced in Synthesis Example 2 (100 g, 0.09 unit mol), epichlorohydrin in a nitrogen stream (200 g, 2.16 mol) and N, N-dimethylformamide (100 mL) were charged, and sodium hydroxide (3.2 g, 0.08 mol) was added to the stirred place and refluxed for 3 hours. After completion of the reaction, N, N-dimethylformamide and unreacted epichlorohydrin were distilled off by concentration under reduced pressure, and MIBK (300 mL) was added and dissolved, followed by washing with water three times. The MIBK layer was concentrated under reduced pressure and dried under reduced pressure at 120 ° C. to obtain 101.3 g (yield: 97.8%) of product. The analysis result of this product was as follows.

1H-NMR spectrum (in heavy chloroform, δ, ppm):
2.0-2.2 (138H), 2.6-2.9 (4H), 3.1-3.6 (6H), 6.3-6.6 (46H), 6.7-7. 3 (19H)
◎ 31P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) 3 9.6-10.0
◎ Epoxy equivalent:
1,600 g / eq.

  From the above analysis results, the product obtained in this step has a glycidyl group whose structure is [N3P3 {OC6H2 (CH3) 2 (OC6H2 (CH3) 2) 9.9OCH2CHOCH2} 2.1 (OC6H5) 3.9]. It was confirmed that it was an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with 1.

Example 3 (Production of oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with glycidyl group according to Form 2)
In a 1 liter four-necked flask equipped with a thermometer and a stirrer, an oligo (phenyleneoxy) group-containing cyclic phosphazene compound produced in Synthesis Example 3 (100 g, 0.05 unit mol), epichlorohydrin in a nitrogen stream (200 g, 2.16 mol) and N, N-dimethylformamide (100 mL) were charged, and sodium hydroxide (1.6 g, 0.04 mol) was added to the stirred place and refluxed for 3 hours. After completion of the reaction, N, N-dimethylformamide and unreacted epichlorohydrin were distilled off by concentration under reduced pressure, and MIBK (300 mL) was added and dissolved, followed by washing with water three times. The MIBK layer was concentrated under reduced pressure and dried under reduced pressure at 120 ° C. to obtain 100.6 g (yield: 98.9%) of the product. The analysis result of this product was as follows.

1H-NMR spectrum (in heavy chloroform, δ, ppm):
2.0-2.2 (257H), 2.6-2.9 (4H), 3.1-3.6 (6H), 6.3-6.6 (89H), 6.7-7. 3 (20H)
◎ 31P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) 3 9.6-10.0
◎ Epoxy equivalent:
2,980 g / eq.

  From the above analysis results, the product obtained in this step has a glycidyl group of [N3P3 {OC6H2 (CH3) (OC6H2 (CH3) 2) 20.9OCH2CHOCH2} 2.1 (OC6H5) 3.9]. It was confirmed that this was a modified oligo (phenyleneoxy) group-containing cyclic phosphazene compound.

Example 4 (Production of oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with glycidyl group according to Form 2)
In a 1 liter four-necked flask equipped with a thermometer and a stirrer, an oligo (phenyleneoxy) group-containing cyclic phosphazene compound produced in Synthesis Example 3 (100 g, 0.09 unit mol), epichlorohydrin was added in a nitrogen stream. (200 g, 2.16 mol) and N, N-dimethylformamide (100 mL) were charged, and sodium hydroxide (3.2 g, 0.08 mol) was added to the stirred place and refluxed for 3 hours. After completion of the reaction, N, N-dimethylformamide and unreacted epichlorohydrin were distilled off by concentration under reduced pressure, and MIBK (300 mL) was added and dissolved, followed by washing with water three times. The MIBK layer was concentrated under reduced pressure and dried under reduced pressure at 120 ° C. to obtain 102.5 g (yield: 98.9%) of product. The analysis result of this product was as follows.

1H-NMR spectrum (in heavy chloroform, δ, ppm):
2.0-2.2 (125H), 2.6-2.9 (5H), 3.1-3.6 (7H), 6.3-6.6 (46H), 6.7-7. 3 (20H)
◎ 31P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) 3 9.6-10.0
◎ Epoxy equivalent:
1540 g / eq.

  From the above analysis results, the product obtained in this step has an oligo structure modified with a glycidyl group of [N3P3 {OC6H4 (OC6H2 (CH3) 2) 9.5OCH2CHOCH2} 2.2 (OC6H5) 3.8]. It was confirmed that it was a (phenyleneoxy) group-containing cyclic phosphazene compound.

Example 5 (Production of oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with glycidyl group according to Form 1)
In a 1 liter four-necked flask equipped with a thermometer and a stirrer, an oligo (phenyleneoxy) group-containing cyclic phosphazene compound produced in Synthesis Example 5 (100 g, 0.05 unit mol), epichlorohydrin in a nitrogen stream (200 g, 2.16 mol) and N, N-dimethylformamide (100 mL) were charged, and sodium hydroxide (4.8 g, 0.12 mol) was added to the stirred place and refluxed for 3 hours. After completion of the reaction, N, N-dimethylformamide and unreacted epichlorohydrin were distilled off by concentration under reduced pressure, and MIBK (300 mL) was added and dissolved, followed by washing with water three times. The MIBK layer was concentrated under reduced pressure and dried under reduced pressure at 120 ° C. to obtain 105.7 g (yield: 99.2%) of the product. The analysis result of this product was as follows.

1H-NMR spectrum (in heavy chloroform, δ, ppm):
2.0-2.2 (252H), 2.6-2.9 (12H), 3.1-3.6 (18H), 6.3-6.6 (108H)
◎ 31P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) 3 9.6-10.0
◎ Epoxy equivalent:
1,050 g / eq.

  From the above analysis results, the product obtained in this step has an oligo (phenyleneoxy) group-containing cyclic phosphazene modified with a glycidyl group of [N3P3 {OC6H4 (OC6H2 (CH3) 2) 7.0OCH2CHOCH2} 6]. It was confirmed to be a compound.

Example 6 (Production of oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with glycidyl group according to Form B)
An oligo (phenyleneoxy) group-containing cyclic phosphazene compound produced in Synthesis Example 6 (100 g, 0.05 unit mol), epichlorohydrin was placed in a 1-liter four-necked flask equipped with a thermometer and a stirrer under a nitrogen stream. (200 g, 2.16 mol) and N, N-dimethylformamide (100 mL) were charged, and sodium hydroxide (1.6 g, 0.04 mol) was added to the stirred place and refluxed for 3 hours. After completion of the reaction, N, N-dimethylformamide and unreacted epichlorohydrin were distilled off by concentration under reduced pressure, and MIBK (300 mL) was added and dissolved, followed by washing with water three times. The MIBK layer was concentrated under reduced pressure and dried under reduced pressure at 120 ° C. to obtain 102.5 g (yield: 98.9%) of product. The analysis result of this product was as follows.

1H-NMR spectrum (in heavy chloroform, δ, ppm):
2.0-2.2 (91H), 2.6-2.9 (2H), 3.1-3.6 (3H), 6.3-6.6 (33H)
◎ 31P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) 3 9.6-10.0
◎ Epoxy equivalent:
2,010 g / eq.

  From the above analysis results, the product obtained in this step has an oligo (phenyleneoxy) group modified with a glycidyl group of [NP {OC6H4 (OC6H2 (CH3) 2) 14.2OCH2CHOCH2} (OC6H4CH3)] n. It was confirmed that it was a containing cyclic phosphazene compound.

Examples 7-12
Bisphenol A type epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name “Epicron 850S”: epoxy equivalent 180), polyphenylene ether resin having a number average molecular weight (Mn) of about 19,000 (manufactured by Asahi Kasei Chemicals Corporation) and table The oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with the glycidyl group shown in 1 was blended with toluene at the ratio shown in Table 1, and stirred for 30 minutes in an oil bath heated to 70 ° C. to uniformly dissolve. Furthermore, the toluene was removed by heating in an oil bath at 140 ° C. for 2 hours, and then the toluene was completely removed by drying under reduced pressure for 2 hours in an environment of 140 ° C. and 1 mmHg or less using a vacuum concentrator.

  The obtained mixture was kept at 110 ° C., and 1 part of diaminodiphenylmethane as a curing agent and 0.1 part of 2-ethyl-4-methylimidazole as a curing accelerator were added. The mixture was sufficiently stirred for 1 minute while being heated, and then poured into a mold. Then, after curing with a hot press machine in order of 100 ° C., 0 MPa for 2 minutes, 130 ° C., 1 MPa for 2 minutes, and 180 ° C., 3 MPa for 10 minutes, take out from the mold and finally cure at 180 ° C. for 3 hours. Thus, a test piece was prepared in accordance with the following evaluation items. Table 1 shows the results of evaluating the flame retardancy, dielectric properties, high-temperature reliability, and bending strength of the obtained test pieces. The evaluation results are as follows.

(Flame retardance)
Based on UL-94 standard vertical combustion test of Underwriters' Laboratories Inc., using test pieces with a length of 125 mm, a width of 12.5 mm and a thickness of 1.5 mm It was classified into V-0, V-1, V-2, and non-standard four-stage flame retardant classes according to the combustion time and the presence or absence of cotton ignition by droppings during combustion. V-0 is the highest evaluation, and the evaluation decreases in the order of V-1, V-2, and non-standard.

(High temperature reliability: Pressure cooker test, temperature 121 ° C., pressure 0.2 MPa)
A test piece having a length of 15 mm, a width of 15 mm, and a thickness of 3 mm was placed in a polytetrafluoroethylene container having a capacity of 15 mL together with 5 mL of distilled water, and the container was further sealed in a steel container. After leaving the steel container at 121 ° C. for 100 hours, the test piece was taken out and the appearance change was observed. The criteria for evaluation are as follows.

○: No change in appearance due to bleeding out of cyclic phosphazene compound, and high temperature reliability.
X: There is a change in appearance due to bleeding out of the cyclic phosphazene compound, and there is no high temperature reliability.

(Dielectric properties)
With respect to a test piece having a length of 50 mm, a width of 50 mm, and a thickness of 2.0 mm, the relative dielectric constant and dielectric loss tangent at a frequency of 1 GHz were measured in accordance with JIS C2138 “Measurement method of relative dielectric constant and dielectric loss tangent”.

(Bending strength)
About the test piece of length 100mm, width 20mm, and thickness 0.5mm, both ends were held by hand and bending strength (mechanical strength) was evaluated on the following reference | standard by repeating 180 degree | times bending 20 times.

○: No cracking occurred.
×: Cracking occurred.

According to Table 1, the resin compositions of Examples 7 to 12 exhibit excellent flame retardancy, high temperature reliability and bending strength, and are excellent in electrical characteristics due to their low dielectric constant and dielectric loss tangent.

Claims (10)

An oligo (phenyleneoxy) group-substituted cyclic phosphazene compound modified with a glycidyl group, represented by the following formula (1).


(In Formula (1), n shows the integer of 1-6, A shows group selected from the group which consists of following A1 group and A2 group, and at least one is A2 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 aryloxy group having 6 to 20 carbon atoms.
A2 group: a group selected from the group consisting of an oligo (phenyleneoxy) group-substituted phenyloxy group modified with a glycidyl group represented by the following formula (2).


In formula (2), E ^{1 to} E ⁵ are each an independent substituent, and are a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an alkyl group having 1 to 6 carbon atoms, alkenyl. a group selected from at least one aryl group having 6 to 20 carbon atoms optionally substituted by a group selected from the group and aryl group, and at least one has been modified with a glycidyl group represented by the following formula (3) An oligo (phenyleneoxy) group.


In the formula (3), q represents an integer of 1 to 50 (excluding 1) , and E ^{6 to} E ⁹ are each an independent substituent, which is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and alkenyl. group shown, and the alkyl group having 1 to 6 carbon atoms, a group selected from at least one aryl group having 6 to 20 carbon atoms optionally substituted by a group selected from an alkenyl group and an aryl group. )   Oligo (methylphenyleneoxy) group-modified phenyleneoxy group modified with glycidyl group, Oligo (methylphenyleneoxy) group-substituted methylphenyleneoxy group modified with glycidyl group, Oligo (methylphenyleneoxy) modified with glycidyl group Oligo (dimethylphenyleneoxy) group-modified oligophenylene modified with glycidyl group, oligo (dimethylphenyleneoxy) group modified with glycidyl group, and oligo (dimethylphenyleneoxy) group modified with glycidyl group The oligo (phenyleneoxy) group-substituted cyclic phosphazene compound modified with a glycidyl group according to claim 1, which is at least one selected from the group consisting of a phenyleneoxy) group-substituted dimethylphenyleneoxy group. N is 1 or 2 of the formula (1), according to claim 1 or 2 oligos modified with a glycidyl group as described in (phenylene) group substituted cyclic phosphazene compound.   In formula (1), 1 to (2n + 2) of (2n + 4) A are A2 groups, and oligo (phenyleneoxy) group substitution modified with a glycidyl group according to any one of claims 1 to 3 Cyclic phosphazene compounds.   The oligo (phenyleneoxy) group-substituted cyclic phosphazene compound modified with a glycidyl group according to any one of claims 1 to 4, which contains two or more compounds having different n in formula (1). A method for producing an oligo (phenyleneoxy) group-substituted cyclic phosphazene compound modified with a glycidyl group according to claim 1,
A step of reacting an oligo (phenyleneoxy) group-substituted cyclic phosphazene compound represented by the following formula (4) with an epihalohydrin,
A method for producing an oligo (phenyleneoxy) group-substituted cyclic phosphazene compound modified with a glycidyl group.


(In the formula (4), m represents an integer of 1 to 6, G represents a group selected from the group consisting of the following G1 group and G2 group, and at least one is a G2 group.
G1 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.
G2 group: a group selected from the group consisting of an oligo (phenyleneoxy) group-substituted phenyloxy group represented by the following formula (5).


In formula (5), E ^{10 to} E ¹⁴ are each an independent substituent, and are a hydrogen atom, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an alkyl group having 1 to 6 carbon atoms, alkenyl. oligo is a radical selected from at least one aryl group having 6 to 20 carbon atoms optionally substituted by a group selected from the group and aryl group, and at least one is represented by the following formula (6) (phenyleneoxy) It is a group.


In the formula (6), t represents an integer of 1 to 50 (excluding 1) , and E ^{15 to} E ¹⁸ are each an independent substituent, which is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, and alkenyl. group shown, and the alkyl group having 1 to 6 carbon atoms, a group selected from at least one aryl group having 6 to 20 carbon atoms optionally substituted by a group selected from an alkenyl group and an aryl group. ) A resin component;
An oligo (phenyleneoxy) group-substituted cyclic phosphazene compound modified with a glycidyl group according to any one of claims 1 to 5;
A resin composition comprising:   The resin component is an epoxy resin, polyphenylene ether resin, polyamide resin, polyamideimide resin, polyetherimide resin, polyimide resin, polysulfone resin, phenoxy resin, bismaleimide resin, cyanate ester resin, and bismaleimide-cyanate ester resin. The resin composition according to claim 7, which is at least one selected from the group consisting of: The resin molding which consists of a resin composition of Claim 7 or 8.   The electronic component using the resin molding of Claim 9.