JP5812467B2 - Oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with unsaturated carbonyl 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 an unsaturated carbonyl group and a method for producing the same.

  In the fields of industrial and consumer equipment and electrical products, synthetic resins have advantages over other materials in terms of processability, chemical resistance, weather resistance, electrical properties and mechanical strength. Therefore, the amount used has increased in recent years. However, since synthetic resins have the property of being easily combusted, application of a flame retardant is required, and in recent years, the required performance has gradually increased. For this reason, resin compositions used for encapsulants and substrates for electronic components such as LSIs, such as epoxy resin compositions, are flame retardant and contain halogen-containing compounds, halogen-containing compounds and antimony oxide, etc. A mixture with an antimony compound is added as a general flame retardant. However, a resin composition containing such a flame retardant is used during combustion or molding. May generate halogen-based gas that may cause environmental pollution. In addition, since halogen-based gas may interfere with the electrical and mechanical properties of electronic components, recently, halogen-based gas is generated as a flame retardant for synthetic resins during combustion and molding. Difficult non-halogen materials such as metal hydrate flame retardants such as aluminum hydroxide and magnesium hydroxide, phosphate esters, condensed phosphate esters, phosphate amides, ammonium polyphosphates and phosphazenes Phosphorus flame retardants are frequently used.

  Among these, metal hydrate flame retardants exhibit a flame retardant effect because the endothermic reaction of dehydration pyrolysis and the accompanying water release occur in a temperature range that overlaps the thermal decomposition and combustion start temperature of the synthetic resin. However, in order to enhance the effect, it is necessary to add a large amount to the resin composition. For this reason, the molded article of the resin composition containing this type of flame retardant has a drawback that the mechanical strength is impaired. On the other hand, among phosphoric flame retardants, phosphoric acid ester and condensed phosphoric acid ester types have a plastic effect, so if they are added in a large amount to the resin composition in order to increase flame retardancy, resin molded products There are disadvantages such as a decrease in mechanical strength. In addition, phosphate esters, phosphate amides, ammonium polyphosphates, and aluminum phosphinates are easily hydrolyzed, so resin molded products that require mechanical and electrical long-term reliability. It is practically difficult to use in manufacturing materials. In contrast, phosphazene-based flame retardants have a smaller plastic effect and hydrolyzability than other phosphorus-based flame retardants, and can increase the amount added to the resin composition. Thus, it is being widely used as an effective flame retardant for synthetic resins. However, when the amount of the phosphazene-based flame retardant added to the resin composition is increased, the reliability of the resin molded product at a high temperature may be lowered. Specifically, in the case of a thermoplastic resin-based resin composition, the phosphazene-based flame retardant is likely to bleed out (elution) from the resin molded body at a high temperature, and the thermosetting resin-based resin composition. In this case, deformation such as blistering occurs in the resin molded product at a high temperature, and when the resin molded product is used in the electric / electronic field such as a laminated substrate, a short circuit due to deformation may occur.

  Therefore, phosphazene flame retardants have been studied for improving the reliability (high temperature reliability) of resin molded products at high temperatures. As an example, Patent Documents 6 to 8 include acryloyloxy group. Alternatively, a phosphazene compound having a methacryloyloxy group and a polymer using the same are disclosed. This type of phosphazene-based flame retardant can be used alone as a thermosetting resin because the acryloyloxy group or methacryloyloxy group has polymerizability, and is also a monomer component for resin molding. It can also be used as a part. The polymer of the phosphazene compound and the polymer obtained by using the phosphazene compound as a part of the monomer have good high temperature reliability of the molded product, and have flame retardancy due to the phosphazene compound. Therefore, it is expected to be used as a resin material for products such as electric and electronic parts. However, a resin molded body made of this type of polymer is insufficient in terms of flame retardancy required as an essential effect, and is also insufficient in mechanical properties (particularly a high glass transition point).

  On the other hand, in electronic devices used in the field of information communication in recent years, since the capacity and speed of signals have been increased, there is a printed wiring board that has excellent high-frequency characteristics and can cope with a higher number of layers by increasing the number of wires. Is required. 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. Known as printed wiring boards having excellent dielectric properties are those in which the end of polyphenylene ether (PPE) is modified with (meth) acrylate and a cured product of the resin composition is used as an insulating layer (Patent Documents 9 to 11). ing. This printed wiring board has a lower dielectric constant and dielectric loss tangent than those using an insulating layer made of a normal (meth) acrylate resin composition, and has improved dielectric properties, but it has poor flame retardancy. It is enough.

JP 2000-103939 A JP 2004-83671 A JP 2004-210849 A JP 2005-248134 A JP 2007-45916 A JP 2001-335678 A JP-A-8-193091 JP 2008-78209 A JP 2003-252833 A JP 2003-252983 A JP 2004-59645 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 comprise a resin composition containing a novel phosphazene compound having a reactive group, particularly an oligo (phenyleneoxy) group modified with an unsaturated carbonyl group. It has been found that the molded product exhibits excellent flame retardancy while maintaining excellent electrical characteristics and high temperature reliability.

  The oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group of the present invention is represented by the following (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.
Group A1: An aryloxy group having 6 to 20 carbon atoms, which may be substituted with at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group.
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. At least one group selected from a group and an aryl group is a group selected from an aryl group having 6 to 20 carbon atoms which may be substituted, and at least one is an oligo (phenyleneoxy) represented by the following formula (3) It is a group.

In the formula (3), q represents an integer of 1 to 50 (excluding 1) , Y is an acryloyloxy group or a methacryloyl group, E ^{6 to} E ⁹ are each an independent substituent, and a hydrogen atom , An alkyl group having 1 to 6 carbon atoms and an alkenyl group, and an aryl group having 6 to 20 carbon atoms in which at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group and an aryl group may be substituted. The group to be selected.

  In the oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with this unsaturated carbonyl group, preferred A2 group is modified with an oligo (methylphenyleneoxy) group-substituted phenyleneoxy group or unsaturated carbonyl group modified with an unsaturated carbonyl group. Oligo (dimethylphenyleneoxy) group-substituted phenyleneoxy group, oligo (methylphenylene) group-substituted methylphenyleneoxy group modified with unsaturated carbonyl group, oligo (dimethylphenylene) group-substituted methylphenyleneoxy group modified with unsaturated carbonyl group, An oligo (methylphenyleneoxy) group-substituted dimethylphenyleneoxy group modified with an unsaturated carbonyl group and an oligo (dimethylphenyleneoxy) group-substituted dimethylphenyleneoxy group modified with an unsaturated carbonyl group Is one Kutomo. The oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group is preferably a compound in which n in formula (1) is 1 or 2.

  The oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group of the present invention preferably has 1 to (2n + 2) A2 groups out of (2n + 4) A in formula (1). is there. Further, the oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group of the present invention includes, for example, 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 an unsaturated carbonyl group according to the present invention, and represents an oligo (phenylene) represented by the following formula (4): A step of reacting an oxy) group-containing cyclic phosphazene compound with acrylic acid, methacrylic acid or a derivative thereof.

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: an aryloxy group having 6 to 20 carbon atoms in which at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group may be substituted.
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. At least one group selected from a group and an aryl group is a group selected from an aryl group having 6 to 20 carbon atoms which may be substituted, and at least one is an oligo (phenyleneoxy) represented by the following formula (6) 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, and are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms and an alkenyl. And a group selected from an aryl group having 6 to 20 carbon atoms, and at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group may be substituted.

  The resin composition according to the present invention contains one or more oligo (phenyleneoxy) group-containing cyclic phosphazene compounds modified with the unsaturated carbonyl group of the present invention.

  The resin composition according to the present invention contains a resin component and an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with the unsaturated carbonyl 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, bismaleimide resin, benzoxazine resin, oxetane resin, cyanide. It is at least one selected from the group consisting of acid ester resins and bismaleimide-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 an unsaturated carbonyl group of the present invention has a specific structure as described above, it is used in a resin composition for forming a resin molding. In this case, the electrical characteristics, in particular, 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 an unsaturated carbonyl group of the present invention includes the steps as described above, it is modified with an unsaturated carbonyl group having a specific structure according to the present invention. An oligo (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 unsaturated carbonyl group of the present invention as a flame retardant, it exhibits practical flame retardancy, A resin molded body that can achieve a low dielectric constant and a low dielectric loss tangent and is excellent in high temperature reliability can be obtained.

  Since the resin molded body of the present invention is composed of the resin composition of the present invention, it exhibits practical flame retardancy, can achieve low dielectric constant and low dielectric loss tangent in 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 compounds modified with unsaturated carbonyl groups
The oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl 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, the oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group of the present invention is a resin component when a compound having a smaller n in formula (1) is used in the 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, a particularly preferable oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group is an oligo (phenylene) modified with an unsaturated carbonyl group having cyclotriphosphazene (trimer) in which n is 1. An oxy) group-containing cyclic phosphazene compound and an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group having a cyclotetraphosphazene (tetramer) in which n is 2. The oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl 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; In the aryloxy group, at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group may be substituted.

  Examples of such aryloxy groups include phenoxy group, methylphenoxy group, dimethylphenoxy group, ethylphenoxy group, ethylmethylphenoxy group, diethylphenoxy group, n-propylphenoxy group, isopropylphenoxy group, isopropylmethylphenoxy group, Isopropylethylphenoxy group, diisopropylphenoxy group, n-butylphenoxy group, sec-butylphenoxy group, tert-butylphenoxy group, n-pentylphenoxy group, n-hexylphenoxy group, ethenylphenoxy group, 1-propenylphenoxy group, 2-propenylphenoxy group, isopropenylphenoxy group, 1-butenylphenoxy group, sec-butenylphenoxy group, 1-pentenylphenoxy group, 1-hexenylphenoxy group, Nirufenokishi group, naphthyloxy group, and an anthryl group and phenanthryloxy groups and the like. Of these, phenoxy group, methylphenoxy group, dimethylphenoxy group, diethylphenoxy group, 2-propenylphenoxy group, phenylphenoxy group and naphthyloxy group are preferable, and phenoxy group, methylphenoxy group, dimethylphenoxy group and naphthyloxy group are particularly preferable. preferable.

[Group A2]
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. At least one group selected from a group and an aryl group is a group selected from an aryl group having 6 to 20 carbon atoms which may be substituted, and at least one is an oligo (phenyleneoxy) represented by the following formula (3) It is a group.

In formula (3), q represents an integer of 1 to 50, Y represents an unsaturated carbonyloxy group selected from acryloyloxy and methacryloyloxy groups, and E ^{6 to} E ⁹ each represents an independent substituent. And at least one group selected from a hydrogen atom, an alkyl group and an alkenyl group having 1 to 6 carbon atoms, and an alkyl group, an alkenyl group and an aryl group having 1 to 6 carbon atoms may be substituted. A group selected from aryl groups of

  The repeating number q of the phenyleneoxy group of the oligo (phenyleneoxy) group modified with the unsaturated carbonyl group represented by the formula (3) is 1 to 50, but the resin component used and the required flame retardancy are It can be appropriately selected depending on the degree. For example, when the resin component used is easy to burn, the oligo (phenyleneoxy) group-substituted cyclic phosphazene compound modified with an unsaturated carbonyl group used together has a small number of repeating phenyleneoxy groups (small q) Can be selected to increase the phosphorus content, while if the resin component used is difficult to burn, select the one having a large number of repeating phenyleneoxy groups (the one with a large q) to lower the phosphorus content. The flame retardancy of the resin composition can be adjusted as appropriate.

  Specific examples of A2 group include acryloyloxy-3-oligo (methylphenyleneoxy) group-substituted phenyloxy group, acryloyloxy-4-oligo (methylphenyleneoxy) group-substituted phenyloxy group, acryloyloxy-3-oligo (methylphenylene) Oxy) group substituted-2-methylphenyloxy group, acryloyloxy-3-oligo (methylphenyleneoxy) group substituted-4-methylphenyloxy group, acryloyloxy-3-oligo (methylphenyleneoxy) group substituted-5-methyl Phenyloxy group, acryloyloxy-4-oligo (methylphenyleneoxy) group substitution-2-methylphenyloxy group, acryloyloxy-4-oligo (methylphenyleneoxy) group substitution-3-methylphenyloxy group, acryloyloxy-3 − Rigo (methylphenyleneoxy) group substitution-2-allylphenyloxy group, acryloyloxy-3-oligo (methylphenyleneoxy) group substitution-4-allylphenyloxy group, acryloyloxy-3-oligo (methylphenyleneoxy) group substitution -5-allylphenyloxy group, acryloyloxy-4-oligo (methylphenyleneoxy) group-substituted-2-allylphenyloxy group, acryloyloxy-4-oligo (methylphenyleneoxy) group-substituted-3-allylphenyloxy group, Acryloyloxy-3-oligo (methylphenyleneoxy) group-substituted-4-phenylphenyloxy group, acryloyloxy-3-oligo (methylphenyleneoxy) group-substituted-5-phenylphenyloxy group, acryloyloxy-4-oligo (methylphenol) Renoxy) group substituted-3-phenylphenyloxy group, acryloyloxy-3-oligo (methylphenyleneoxy) group substituted-2,4-dimethylphenyloxy group, acryloyloxy-3-oligo (methylphenyleneoxy) group substituted-2 , 5-dimethylphenyloxy group, acryloyloxy-4-oligo (methylphenyleneoxy) group-substituted-2,3-dimethylphenyloxy group, acryloyloxy-4-oligo (methylphenyleneoxy) group-substituted-2,5-dimethyl Phenyloxy group, acryloyloxy-4-oligo (methylphenyleneoxy) group-substituted-3,5-dimethylphenyloxy group, acryloyloxy-3-oligo (methylphenyleneoxy) group-substituted-2,4,5-trimethylphenyloxy Group, acryloyloxy-4 -Oligo (methylphenyleneoxy) group-substituted-2,3,5-trimethylphenyloxy group, acryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted phenyloxy group, acryloyloxy-4-oligo (dimethylphenyleneoxy) group Substituted phenyloxy group, acryloyloxy-3-oligo (dimethylphenyleneoxy) group substituted-2-methylphenyloxy group, acryloyloxy-3-oligo (dimethylphenyleneoxy) group substituted-4-methylphenyloxy group, acryloyloxy- 3-oligo (dimethylphenyleneoxy) group-substituted-5-methylphenyloxy group, acryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-2-methylphenyloxy group, acryloyloxy-4-oligo (dimethylphenol) Renoxy) group substituted-3-methylphenyloxy group, acryloyloxy-3-oligo (dimethylphenyleneoxy) group substituted-2-allylphenyloxy group, acryloyloxy-3-oligo (dimethylphenyleneoxy) group substituted-4-allyl Phenyloxy group, acryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted-5-allylphenyloxy group, acryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-2-allylphenyloxy group, acryloyloxy-4 -Oligo (dimethylphenyleneoxy) group substitution-3-allylphenyloxy group, acryloyloxy-3-oligo (dimethylphenyleneoxy) group substitution-4-phenylphenyloxy group, acryloyloxy-3-oligo (dimethylphenylene) Xyl) group-substituted-5-phenylphenyloxy group, acryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-3-phenylphenyloxy group, acryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted-2,4 -Dimethylphenyloxy group, acryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted-2,5-dimethylphenyloxy group, acryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-2,3-dimethylphenyloxy Group, acryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-2,5-dimethylphenyloxy group, acryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-3,5-dimethylphenyloxy group, acryloyloxy -3-O Rigo (dimethylphenyleneoxy) group-substituted-2,4,5-trimethylphenyloxy group, acryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-2,3,5-trimethylphenyloxy group, methacryloyloxy-3- Oligo (methylphenyleneoxy) group-substituted phenyloxy group, methacryloyloxy-4-oligo (methylphenyleneoxy) group-substituted phenyloxy group, methacryloyloxy-3-oligo (methylphenyleneoxy) group-substituted-2-methylphenyloxy group, Methacryloyloxy-3-oligo (methylphenyleneoxy) group-substituted-4-methylphenyloxy group, methacryloyloxy-3-oligo (methylphenyleneoxy) group-substituted-5-methylphenyloxy group, methacryloyloxy-4-oligo Tylphenyleneoxy) group substituted-2-methylphenyloxy group, methacryloyloxy-4-oligo (methylphenyleneoxy) group substituted-3-methylphenyloxy group, methacryloyloxy-3-oligo (methylphenyleneoxy) group substituted-2 -Allylphenyloxy group, methacryloyloxy-3-oligo (methylphenyleneoxy) group substitution-4-allylphenyloxy group, methacryloyloxy-3-oligo (methylphenyleneoxy) group substitution-5-allylphenyloxy group, methacryloyloxy -4-Oligo (methylphenyleneoxy) group substituted-2-allylphenyloxy group, methacryloyloxy-4-oligo (methylphenyleneoxy) group substituted-3-allylphenyloxy group, methacryloyloxy-3-oligo (methylphenol) Nyleneoxy) group substituted-4-phenylphenyloxy group, methacryloyloxy-3-oligo (methylphenyleneoxy) group substituted-5-phenylphenyloxy group, methacryloyloxy-4-oligo (methylphenyleneoxy) group substituted-3-phenyl Phenyloxy group, methacryloyloxy-3-oligo (methylphenyleneoxy) group-substituted-2,4-dimethylphenyloxy group, methacryloyloxy-3-oligo (methylphenyleneoxy) group-substituted-2,5-dimethylphenyloxy group, Methacryloyloxy-4-oligo (methylphenyleneoxy) group-substituted-2,3-dimethylphenyloxy group, methacryloyloxy-4-oligo (methylphenyleneoxy) group-substituted-2,5-dimethylphenyloxy group, methacryloyloxy- 4-oligo (methylphenyleneoxy) group-substituted-3,5-dimethylphenyloxy group, methacryloyloxy-3-oligo (methylphenyleneoxy) group-substituted-2,4,5-trimethylphenyloxy group, methacryloyloxy-4- Oligo (methylphenyleneoxy) group substitution-2,3,5-trimethylphenyloxy group, methacryloyloxy-3-oligo (dimethylphenyleneoxy) group substitution phenyloxy group, methacryloyloxy-4-oligo (dimethylphenyleneoxy) group substitution Phenyloxy group, methacryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted-2-methylphenyloxy group, methacryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted-4-methylphenyloxy group, methacryloylio Cy-3-oligo (dimethylphenyleneoxy) group-substituted-5-methylphenyloxy group, methacryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-2-methylphenyloxy group, methacryloyloxy-4-oligo (dimethylphenylene) Oxy) group substituted-3-methylphenyloxy group, methacryloyloxy-3-oligo (dimethylphenyleneoxy) group substituted-2-allylphenyloxy group, methacryloyloxy-3-oligo (dimethylphenyleneoxy) group substituted-4-allyl Phenyloxy group, methacryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted-5-allylphenyloxy group, methacryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-2-allylphenyloxy group, methacrylo Luoxy-4-oligo (dimethylphenyleneoxy) group-substituted-3-allylphenyloxy group, methacryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted-4-phenylphenyloxy group, methacryloyloxy-3-oligo (dimethylphenylene) Oxy) group substituted-5-phenylphenyloxy group, methacryloyloxy-4-oligo (dimethylphenyleneoxy) group substituted-3-phenylphenyloxy group, methacryloyloxy-3-oligo (dimethylphenyleneoxy) group substituted-2,4 -Dimethylphenyloxy group, methacryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted-2,5-dimethylphenyloxy group, methacryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-2,3-dimethyl Phenyloxy group, methacryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-2,5-dimethylphenyloxy group, methacryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-3,5-dimethylphenyloxy group, and It is at least one selected from the group consisting of a methacryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted-2,4,5-trimethylphenyloxy group.

  As the A2 group, acryloyloxy-3-oligo (methylphenyleneoxy) group-substituted phenyloxy group, acryloyloxy-4-oligo (methylphenyleneoxy) group-substituted phenyloxy group, acryloyloxy-3-oligo (methylphenyleneoxy) ) Group substitution-4-methylphenyloxy group, acryloyloxy-3-oligo (methylphenyleneoxy) group substitution-5-methylphenyloxy group, acryloyloxy-4-oligo (methylphenyleneoxy) group substitution-3-methylphenyl Oxy group, acryloyloxy-3-oligo (methylphenyleneoxy) group-substituted-2,4-dimethylphenyloxy group, acryloyloxy-3-oligo (methylphenyleneoxy) group-substituted-2,5-dimethylphenyloxy group, acryloyl Oh Si-4-oligo (methylphenyleneoxy) group-substituted-2,3-dimethylphenyloxy group, acryloyloxy-4-oligo (methylphenyleneoxy) group-substituted-3,5-dimethylphenyloxy group, acryloyloxy-3- Oligo (methylphenyleneoxy) group-substituted-2,4,5-trimethylphenyloxy group, acryloyloxy-4-oligo (methylphenyleneoxy) group-substituted-2,3,5-trimethylphenyloxy group, acryloyloxy-3- Oligo (dimethylphenyleneoxy) group-substituted phenyloxy group, acryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted phenyloxy group, acryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted-4-methylphenyloxy group, Acryloyloxy 3-Oligo (dimethylphenyleneoxy) group substitution-5-methylphenyloxy group, acryloyloxy-4-oligo (dimethylphenyleneoxy) group substitution-3-methylphenyloxy group, acryloyloxy-3-oligo (dimethylphenyleneoxy) Substitution-2,4-dimethylphenyloxy group, acryloyloxy-3-oligo (dimethylphenyleneoxy) group substitution-2,5-dimethylphenyloxy group, acryloyloxy-4-oligo (dimethylphenyleneoxy) group substitution-2 , 3-dimethylphenyloxy group, acryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-3,5-dimethylphenyloxy group, acryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted 2,4,5 -Trimethylphenylo Xyl group, acryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-2,3,5-trimethylphenyloxy group, methacryloyloxy-3-oligo (methylphenyleneoxy) group-substituted phenyloxy group, methacryloyloxy-4- Oligo (methylphenyleneoxy) group substituted phenyloxy group, methacryloyloxy-3-oligo (methylphenyleneoxy) group substituted-4-methylphenyloxy group, methacryloyloxy-3-oligo (methylphenyleneoxy) group substituted-5-methyl Phenyloxy group, methacryloyloxy-4-oligo (methylphenyleneoxy) group-substituted-3-methylphenyloxy group, methacryloyloxy-3-oligo (methylphenyleneoxy) group-substituted-2,4-dimethylphenyloxy group, methacrylate Royloxy-3-oligo (methylphenyleneoxy) group-substituted-2,5-dimethylphenyloxy group, methacryloyloxy-4-oligo (methylphenyleneoxy) group-substituted-2,3-dimethylphenyloxy group, methacryloyloxy-4- Oligo (methylphenyleneoxy) group-substituted-3,5-dimethylphenyloxy group, methacryloyloxy-3-oligo (methylphenyleneoxy) group-substituted-2,4,5-trimethylphenyloxy group, methacryloyloxy-4-oligo Methylphenyleneoxy) group-substituted-2,3,5-trimethylphenyloxy group, methacryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted phenyloxy group, methacryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted phenylo Si group, methacryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted-4-methylphenyloxy group, methacryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted-5-methylphenyloxy group, methacryloyloxy-4- Oligo (dimethylphenyleneoxy) group substituted-3-methylphenyloxy group, methacryloyloxy-3-oligo (dimethylphenyleneoxy) group substituted-2,4-dimethylphenyloxy group, methacryloyloxy-3-oligo (dimethylphenyleneoxy) Substituent substitution-2,5-dimethylphenyloxy group, methacryloyloxy-4-oligo (dimethylphenyleneoxy) group substitution-2,3-dimethylphenyloxy group, methacryloyloxy-4-oligo (dimethylphenyleneoxy) group substitution 3,5-dimethylphenyloxy group, methacryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted-2,4,5-trimethylphenyloxy group and methacryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-2 , 3,5-trimethylphenyloxy group, acryloyloxy-3-oligo (methylphenyleneoxy) group-substituted phenyloxy group, acryloyloxy-4-oligo (methylphenyleneoxy) group-substituted phenyloxy group, acryloyloxy-3 -Oligo (methylphenyleneoxy) group substitution-4-methylphenyloxy group, acryloyloxy-3-oligo (methylphenyleneoxy) group substitution-5-methylphenyloxy group, acryloyloxy-4-oligo (methylphenyleneoxy) Substituted-3-methylphenyloxy group, acryloyloxy-3-oligo (methylphenyleneoxy) group-substituted-2,4-dimethylphenyloxy group, acryloyloxy-3-oligo (methylphenyleneoxy) group-substituted-2,5- Dimethylphenyloxy group, acryloyloxy-4-oligo (methylphenyleneoxy) group-substituted-2,3-dimethylphenyloxy group, acryloyloxy-4-oligo (methylphenyleneoxy) group-substituted-3,5-dimethylphenyloxy group , Acryloyloxy-3-oligo (methylphenyleneoxy) group-substituted-2,4,5-trimethylphenyloxy group, acryloyloxy-4-oligo (methylphenyleneoxy) group-substituted-2,3,5-trimethylphenyloxy group , Acryloyloxy-3-oligo Dimethylphenyleneoxy) group-substituted phenyloxy group, acryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted phenyloxy group, acryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted-4-methylphenyloxy group, acryloyloxy -3-Oligo (dimethylphenyleneoxy) group substitution-5-methylphenyloxy group, acryloyloxy-4-oligo (dimethylphenyleneoxy) group substitution-3-methylphenyloxy group, acryloyloxy-3-oligo (dimethylphenyleneoxy) ) Group-substituted-2,4-dimethylphenyloxy group, acryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted-2,5-dimethylphenyloxy group, acryloyloxy-4-oligo (dimethylphenyleneoxy) Xy) group substitution-2,3-dimethylphenyloxy group, acryloyloxy-4-oligo (dimethylphenyleneoxy) group substitution-3,5-dimethylphenyloxy group, acryloyloxy-3-oligo (dimethylphenyleneoxy) group substitution -2,4,5-trimethylphenyloxy group, acryloyloxy-4-oligo (dimethylphenyleneoxy) group substitution-2,3,5-trimethylphenyloxy group, methacryloyloxy-3-oligo (methylphenyleneoxy) group substitution Phenyloxy group, methacryloyloxy-4-oligo (methylphenyleneoxy) group-substituted phenyloxy group, methacryloyloxy-3-oligo (methylphenyleneoxy) group-substituted-4-methylphenyloxy group, methacryloyloxy-3-oligo (methylphenyle) Oxy) group substitution-5-methylphenyloxy group, methacryloyloxy-4-oligo (methylphenyleneoxy) group substitution-3-methylphenyloxy group, methacryloyloxy-3-oligo (methylphenyleneoxy) group substitution-2,4 -Dimethylphenyloxy group, methacryloyloxy-3-oligo (methylphenyleneoxy) group-substituted-2,5-dimethylphenyloxy group, methacryloyloxy-4-oligo (methylphenyleneoxy) group-substituted-2,3-dimethylphenyloxy Group, methacryloyloxy-4-oligo (methylphenyleneoxy) group-substituted-3,5-dimethylphenyloxy group, methacryloyloxy-3-oligo (methylphenyleneoxy) group-substituted-2,4,5-trimethylphenyloxy group, Methacryloyloxy 4-oligo (methylphenyleneoxy) group-substituted-2,3,5-trimethylphenyloxy group, methacryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted phenyloxy group, methacryloyloxy-4-oligo (dimethylphenyleneoxy) Substituted phenyloxy group, methacryloyloxy-3-oligo (dimethylphenyleneoxy) group substituted-4-methylphenyloxy group, methacryloyloxy-3-oligo (dimethylphenyleneoxy) group substituted-5-methylphenyloxy group, methacryloyloxy -4-Oligo (dimethylphenyleneoxy) group substitution-3-methylphenyloxy group, methacryloyloxy-3-oligo (dimethylphenyleneoxy) group substitution-2,4-dimethylphenyloxy group, methacryloyloxy-3 -Oligo (dimethylphenyleneoxy) group-substituted-2,5-dimethylphenyloxy group, methacryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-2,3-dimethylphenyloxy group, methacryloyloxy-4-oligo (dimethyl) Phenyleneoxy) group substituted-3,5-dimethylphenyloxy group, methacryloyloxy-3-oligo (dimethylphenyleneoxy) group substituted-2,4,5-trimethylphenyloxy group and methacryloyloxy-4-oligo (dimethylphenyleneoxy) The group-substituted-2,3,5-trimethylphenyloxy group is particularly preferred.

  In the 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 unsaturated carbonyl 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-substituted cyclic phosphazene compound modified with an unsaturated carbonyl group in such a form is an oligo (phenyleneoxy) group modified with an unsaturated carbonyl group in which n in formula (1) is 1. Containing cyclotriphosphazene compound, oligo (phenyleneoxy) group-containing cyclotetraphosphazene compound modified with an unsaturated carbonyl group wherein n in formula (1) is 2, unsaturated carbonyl group wherein n in formula (1) is 3 A modified oligo (phenyleneoxy) group-containing cyclopentaphosphazene compound and an oligo (phenyleneoxy) group-containing cyclohexaphosphazene compound modified with an unsaturated carbonyl group in which n in formula (1) is 4, wherein all of A are , Acryloyloxy-3-oligo (methylphenyleneoxy) group-substituted phenyl Oxy group, acryloyloxy-4-oligo (methylphenyleneoxy) group substituted phenyloxy group, acryloyloxy-3-oligo (methylphenyleneoxy) group substituted-4-methylphenyloxy group, acryloyloxy-3-oligo (methylphenylene) Oxy) group substituted-5-methylphenyloxy group, acryloyloxy-4-oligo (methylphenyleneoxy) group substituted-3-methylphenyloxy group, acryloyloxy-3-oligo (methylphenyleneoxy) group substituted-2,4 -Dimethylphenyloxy group, acryloyloxy-3-oligo (methylphenyleneoxy) group-substituted-2,5-dimethylphenyloxy group, acryloyloxy-4-oligo (methylphenyleneoxy) group-substituted-2,3-dimethylphenyloxy Group Royloxy-4-oligo (methylphenyleneoxy) group-substituted-3,5-dimethylphenyloxy group, acryloyloxy-3-oligo (methylphenyleneoxy) group-substituted-2,4,5-trimethylphenyloxy group, acryloyloxy- 4-oligo (methylphenyleneoxy) group-substituted-2,3,5-trimethylphenyloxy group, acryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted phenyloxy group, acryloyloxy-4-oligo (dimethylphenyleneoxy) Substituent substituted phenyloxy group, acryloyloxy-3-oligo (dimethylphenyleneoxy) group substituted-4-methylphenyloxy group, acryloyloxy-3-oligo (dimethylphenyleneoxy) group substituted-5-methylphenyloxy group, acryloylio Xyl-4-oligo (dimethylphenyleneoxy) group-substituted-3-methylphenyloxy group, acryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted-2,4-dimethylphenyloxy group, acryloyloxy-3-oligo ( Dimethylphenyleneoxy) group-substituted-2,5-dimethylphenyloxy group, acryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-2,3-dimethylphenyloxy group, acryloyloxy-4-oligo (dimethylphenyleneoxy) Substituent substitution-3,5-dimethylphenyloxy group, acryloyloxy-3-oligo (dimethylphenyleneoxy) group substitution-2,4,5-trimethylphenyloxy group, acryloyloxy-4-oligo (dimethylphenyleneoxy) group substitution -2,3,5-G Methylphenyloxy group, methacryloyloxy-3-oligo (methylphenyleneoxy) group-substituted phenyloxy group, methacryloyloxy-4-oligo (methylphenyleneoxy) group-substituted phenyloxy group, methacryloyloxy-3-oligo (methylphenyleneoxy) Substituent substitution-4-methylphenyloxy group, methacryloyloxy-3-oligo (methylphenyleneoxy) group substitution-5-methylphenyloxy group, methacryloyloxy-4-oligo (methylphenyleneoxy) group substitution-3-methylphenyloxy Group, methacryloyloxy-3-oligo (methylphenyleneoxy) group-substituted-2,4-dimethylphenyloxy group, methacryloyloxy-3-oligo (methylphenyleneoxy) group-substituted-2,5-dimethylphenyloxy Group, methacryloyloxy-4-oligo (methylphenyleneoxy) group-substituted-2,3-dimethylphenyloxy group, methacryloyloxy-4-oligo (methylphenyleneoxy) group-substituted-3,5-dimethylphenyloxy group, methacryloyloxy -3-Oligo (methylphenyleneoxy) group substituted-2,4,5-trimethylphenyloxy group, methacryloyloxy-4-oligo (methylphenyleneoxy) group substituted-2,3,5-trimethylphenyloxy group, methacryloyloxy -3-Oligo (dimethylphenyleneoxy) group-substituted phenyloxy group, methacryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted phenyloxy group, methacryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted-4-methylphenol Nyloxy group, methacryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted-5-methylphenyloxy group, methacryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-3-methylphenyloxy group, methacryloyloxy-3- Oligo (dimethylphenyleneoxy) group-substituted-2,4-dimethylphenyloxy group, methacryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted-2,5-dimethylphenyloxy group, methacryloyloxy-4-oligo (dimethylphenylene) Oxy) group-substituted-2,3-dimethylphenyloxy group, methacryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-3,5-dimethylphenyloxy group, methacryloyloxy-3-oligo (dimethylphenylene) 1 type selected from the group A2 consisting of xyl) -substituted 2,4,5-trimethylphenyloxy and methacryloyloxy-4-oligo (dimethylphenyleneoxy) -substituted-2,3,5-trimethylphenyloxy And those that are two or more A2 groups selected from the A2 group. The oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group in this form is an arbitrary mixture of these preferred oligo (phenyleneoxy) group-containing cyclic phosphazene compounds modified with an unsaturated carbonyl group. May be.

[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 an unsaturated carbonyl group of this form is an oligo (phenyleneoxy) group-containing cyclophosphazene compound modified with an unsaturated carbonyl group where n is 1 in formula (1). Triphosphazene compound, oligo (phenyleneoxy) group-containing cyclotetraphosphazene compound modified with an unsaturated carbonyl group in which n in formula (1) is 2, modified with an unsaturated carbonyl group in which n in formula (1) is 3 An oligo (phenyleneoxy) group-containing cyclopentaphosphazene compound and an oligo (phenyleneoxy) group-containing cyclohexaphosphazene compound modified with an unsaturated carbonyl group in which n in formula (1) is 4, comprising (2n + 4) A Of which 1 to (2n + 2) are A2 groups and any mixtures thereof Preferred. The oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group of this kind is higher in temperature than the oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group of another embodiment of the present invention. This is advantageous in that a resin molded body having more excellent reliability and mechanical strength (particularly high glass transition temperature) can be realized.

Specific examples of such a preferable phosphazene compound containing an oligo (phenyleneoxy) group modified with an unsaturated carbonyl group include an oligo (phenyleneoxy) group modified with an unsaturated carbonyl group where n in formula (1) is 1. Cyclotriphosphazene compound, oligo (phenyleneoxy) group-containing cyclotetraphosphazene compound modified with an unsaturated carbonyl group in which n in formula (1) is 2, modified with an unsaturated carbonyl group in which n in formula (1) is 3 Oligo (phenyleneoxy) group-containing cyclopentaphosphazene compound and oligo (phenyleneoxy) group-containing cyclohexaphosphazene compound modified with an unsaturated carbonyl group wherein n in formula (1) is 4, wherein A is an A2 group Acryloyloxy-3-oligo (methylphenyleneoxy) group-substituted phenyl A combination of an oxy group and a phenoxy group which is an A1 group, a combination of an acryloyloxy-4-oligo (methylphenyleneoxy) group-substituted phenyloxy group which is an A2 group and a phenoxy group which is an A1 group, A2 Acryloyloxy-3-oligo (methylphenyleneoxy) group-substituted 4-methylphenyloxy group which is a group and phenoxy group which is A1 group, acryloyloxy-3-oligo (methylphenyleneoxy) which is A2 group ) Group-substituted-5-methylphenyloxy group in combination with A1 group phenoxy group, A2-group acryloyloxy-4-oligo (methylphenyleneoxy) group-substituted-3-methylphenyloxy group and A1 group In combination with a phenoxy group which is Iroxy-3-oligo (methylphenyleneoxy) group-substituted 2,4-dimethylphenyloxy group and A1 group phenoxy group, A2 group acryloyloxy-3-oligo (methylphenyleneoxy) group A combination of a substituted-2,5-dimethylphenyloxy group and a phenoxy group which is an A1 group, an acryloyloxy-4-oligo (methylphenyleneoxy) group which is an A2 group, and a substituted 2,3-dimethylphenyloxy group Combination of phenoxy group which is A1 group, combination of acryloyloxy-4-oligo (methylphenyleneoxy) group substituted-3,5-dimethylphenyloxy group which is A2 group and phenoxy group which is A1 group , A2 group acryloyloxy-3-oligo (methylphenyleneo Xyl) group-substituted-2,4,5-trimethylphenyloxy group in combination with A1 group phenoxy group, A2 group acryloyloxy-4-oligo (methylphenyleneoxy) group-substituted-2,3 Combination of 5-trimethylphenyloxy group and A1 group phenoxy group, combination of A2 group acryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted phenyloxy group and A1 group phenoxy group A2 group acryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted phenyloxy group and A1 group phenoxy group combination, A2 group acryloyloxy-3-oligo (dimethylphenyleneoxy) Group-substituted 4-methylphenyloxy group and A1 group pheno A combination of cis group, A2 group acryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted 5-methylphenyloxy group and A1 group phenoxy group, A2 group acryloyl Oxy-4-oligo (dimethylphenyleneoxy) group substitution-Through combination of 3-methylphenyloxy group and A1 group phenoxy group, A2 group acryloyloxy-3-oligo (dimethylphenyleneoxy) group substitution- Combination of 2,4-dimethylphenyloxy group and phenoxy group which is A1 group, acryloyloxy-3-oligo (dimethylphenyleneoxy) group which is A2 group-2,5-dimethylphenyloxy group and A1 group In combination with a phenoxy group which is Iroxy-4-oligo (dimethylphenyleneoxy) group substituted-2,3-dimethylphenyloxy group in combination with A1 group phenoxy group, A2 group acryloyloxy-4-oligo (dimethylphenyleneoxy) group Combination of substituted-3,5-dimethylphenyloxy group and phenoxy group which is A1 group, acryloyloxy-3-oligo (dimethylphenyleneoxy) group substituted-2,4,5-trimethylphenyloxy which is A2 group A combination of a phenoxy group as an A1 group, an acryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-2,3,5-trimethylphenyloxy group as an A2 group, and a phenoxy group as an A1 group; Acryloyloxy-3-oligo which is A2 group Combination of (methylphenyleneoxy) group-substituted phenyloxy group and methylphenoxy group which is A1 group, acryloyloxy-4-oligo (methylphenyleneoxy) group-substituted phenyloxy group which is A2 group and methyl which is A1 group A combination of phenoxy group, A2 group acryloyloxy-3-oligo (methylphenyleneoxy) group-substituted 4-methylphenyloxy group and A1 group of methylphenoxy group, A2 group Acrylyloxy-3-oligo (methylphenyleneoxy) group-substituted 5-methylphenyloxy group and A1 group methylphenoxy group, A2 group acryloyloxy-4-oligo (methylphenyleneoxy) group Substituted-3-methylphenyloxy group and A1 In combination with a methylphenoxy group that is A2, in combination with an acryloyloxy-3-oligo (methylphenyleneoxy) group-substituted 2,4-dimethylphenyloxy group that is an A2 group and a methylphenoxy group that is an A1 group A2 group acryloyloxy-3-oligo (methylphenyleneoxy) group-substituted-2,5-dimethylphenyloxy group and A1 group methylphenoxy group in combination, A2 group acryloyloxy-4- Oligo (methylphenyleneoxy) group substituted-2,3-dimethylphenyloxy group and A1 group methylphenoxy group combined, A2 group acryloyloxy-4-oligo (methylphenyleneoxy) group substituted-3 , 5-Dimethylphenyloxy group and methyl group which is A1 group A combination of a xy group, a combination of an acryloyloxy-3-oligo (methylphenyleneoxy) group substituted-2,4,5-trimethylphenyloxy group as an A2 group and a methylphenoxy group as an A1 group, A2 group acryloyloxy-4-oligo (methylphenyleneoxy) group substituted-2,3,5-trimethylphenyloxy group in combination with A1 group methylphenoxy group, A2 group acryloyloxy-3 -Oligo (dimethylphenyleneoxy) group-substituted phenyloxy group and A1 group methylphenoxy group in combination, A2 group acryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted phenyloxy group and A1 group In combination with a certain methylphenoxy group, A2 group Acryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted 4-methylphenyloxy group and A1 group methylphenoxy group, A2 group acryloyloxy-3-oligo (dimethylphenyleneoxy) Group-substituted-5-methylphenyloxy group and A1 group methylphenoxy group, A2 group acryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-3-methylphenyloxy group and A1 group In combination with methylphenoxy group which is A2, in combination with acryloyloxy-3-oligo (dimethylphenyleneoxy) group substituted-2,4-dimethylphenyloxy group which is A2 group and methylphenoxy group which is A1 group , A2 group is acryloyloxy-3-o A combination of a go (dimethylphenyleneoxy) group-substituted-2,5-dimethylphenyloxy group and a methylphenoxy group that is an A1 group, an acryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted that is an A2 group , 3-dimethylphenyloxy group and A1 group methylphenoxy group, A2 group acryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-3,5-dimethylphenyloxy group and A1 group In combination with a methylphenoxy group which is A2, a combination of acryloyloxy-3-oligo (dimethylphenyleneoxy) group substituted-2,4,5-trimethylphenyloxy group which is an A2 group and a methylphenoxy group which is an A1 group Acryloyloxy-4-oligo which is A2 group Dimethylphenyleneoxy) group-substituted 2,3,5-trimethylphenyloxy group and A1 group methylphenoxy group, A2 group methacryloyloxy-3-oligo (methylphenyleneoxy) group-substituted phenyloxy A combination of a group and a phenoxy group that is an A1 group, a combination of a methacryloyloxy-4-oligo (methylphenyleneoxy) group-substituted phenyloxy group that is an A2 group and a phenoxy group that is an A1 group, A combination of a certain methacryloyloxy-3-oligo (methylphenyleneoxy) group-substituted 4-methylphenyloxy group and a phenoxy group that is A1 group, a methacryloyloxy-3-oligo (methylphenyleneoxy) group that is A2 group Substituted 5-methylphenyloxy group and A A combination of a phenoxy group as one group, a methacryloyloxy-4-oligo (methylphenyleneoxy) group-substituted 3-methylphenyloxy group as an A2 group and a phenoxy group as an A1 group, A2 Methacryloyloxy-3-oligo (methylphenyleneoxy) group-substituted 2,4-dimethylphenyloxy group and A1 group phenoxy group, A2 group methacryloyloxy-3-oligo (methyl) Phenyleneoxy) group-substituted 2,5-dimethylphenyloxy group and A1 group phenoxy group, A2 group methacryloyloxy-4-oligo (methylphenyleneoxy) group-substituted-2,3-dimethyl Combination of phenyloxy group and phenoxy group which is A1 group A combination of a methacryloyloxy-4-oligo (methylphenyleneoxy) group substituted-3,5-dimethylphenyloxy group which is an A2 group and a phenoxy group which is an A1 group, a methacryloyloxy-3-oligo which is an A2 group (Methylphenyleneoxy) group-substituted-2,4,5-trimethylphenyloxy group and A1 group phenoxy group, A2 group methacryloyloxy-4-oligo (methylphenyleneoxy) group-substituted-2 , 3,5-trimethylphenyloxy group and A1 group phenoxy group, A2 group methacryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted phenyloxy group and A1 group phenoxy group Methacryloyloxy- which is a combination of A2 A combination of an oligo (dimethylphenyleneoxy) group-substituted phenyloxy group and a phenoxy group that is A1, a methacryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted 4-methylphenyloxy group that is an A2 group; A combination with a phenoxy group which is an A1 group, a combination of a methacryloyloxy-3-oligo (dimethylphenyleneoxy) group which is an A2 group with a 5-methylphenyloxy group and a phenoxy group which is an A1 group, A2 Methacryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted 3-methylphenyloxy group and A1 group phenoxy group, A2 group methacryloyloxy-3-oligo (dimethylphenyleneoxy) ) Group-substituted-2,4-dimethylthio A combination of a phenyloxy group and a phenoxy group which is an A1 group, a methacryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted-2,5-dimethylphenyloxy group which is an A2 group, and a phenoxy group which is an A1 group Combination, A2 group methacryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-2,3-dimethylphenyloxy group and A1 group phenoxy group, A2 group methacryloyloxy- 4-Oligo (dimethylphenyleneoxy) group substitution-3,5-dimethylphenyloxy group and A1 group phenoxy group in combination, A2 group methacryloyloxy-3-oligo (dimethylphenyleneoxy) group substitution- 2,4,5-trimethylphenyloxy group and A1 In combination with a phenoxy group, and in combination with a methacryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-2,3,5-trimethylphenyloxy group as an A2 group and a phenoxy group as an A1 group , A2 group methacryloyloxy-3-oligo (methylphenyleneoxy) group substituted phenyloxy group and A1 group methylphenoxy group, A2 group methacryloyloxy-4-oligo (methylphenyleneoxy) A combination of a group-substituted phenyloxy group and a methylphenoxy group which is an A1 group, a methacryloyloxy-3-oligo (methylphenyleneoxy) group which is an A2 group, a methylphenoxy which is a 4-methylphenyloxy group and an A1 group In combination with the group, A2 group Methacryloyloxy-3-oligo (methylphenyleneoxy) group-substituted-5-methylphenyloxy group and A1 group methylphenoxy group, A2 group methacryloyloxy-4-oligo (methylphenyleneoxy) A combination of a group-substituted-3-methylphenyloxy group and a methylphenoxy group that is an A1 group, a methacryloyloxy-3-oligo (methylphenyleneoxy) group-substituted-2,4-dimethylphenyloxy group that is an A2 group, and A combination with a methylphenoxy group which is an A1 group, a combination of a methacryloyloxy-3-oligo (methylphenyleneoxy) group substituted-2,5-dimethylphenyloxy group which is an A2 group and a methylphenoxy group which is an A1 group Methacryloyloxy which is A2 group -4-oligo (methylphenyleneoxy) group-substituted-2,3-dimethylphenyloxy group and A1 group methylphenoxy group, A2 group methacryloyloxy-4-oligo (methylphenyleneoxy) group Combination of substituted-3,5-dimethylphenyloxy group and methylphenoxy group which is A1 group, methacryloyloxy-3-oligo (methylphenyleneoxy) group substituted-2,4,5-trimethylphenyl which is A2 group Combination of oxy group and methylphenoxy group which is A1 group, methacryloyloxy-4-oligo (methylphenyleneoxy) group substituted-2,3,5-trimethylphenyloxy group which is A2 group and methyl which is A1 group Combination with phenoxy group, methacryloyloxy which is A2 group -3-Oligo (dimethylphenyleneoxy) group-substituted phenyloxy group and A1 group methylphenoxy group, A2 group methacryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted phenyloxy group and A1 A combination with a methylphenoxy group which is a group, a combination of a methacryloyloxy-3-oligo (dimethylphenyleneoxy) group which is an A2 group with a 4-methylphenyloxy group and a methylphenoxy group which is an A1 group, Methacryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted 5-methylphenyloxy group and A1 group methylphenoxy group, A2 group methacryloyloxy-4-oligo (dimethyl) Phenyleneoxy) group substitution -A combination of a methylphenyloxy group and a methylphenoxy group that is an A1 group, a methacryloyloxy-3-oligo (dimethylphenyleneoxy) group that is an A2 group, a 2,4-dimethylphenyloxy group and an A1 group A combination of a methylphenoxy group, a combination of a methacryloyloxy-3-oligo (dimethylphenyleneoxy) group-substituted-2,5-dimethylphenyloxy group which is an A2 group and a methylphenoxy group which is an A1 group, A2 Methacryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-2,3-dimethylphenyloxy group as a group and methylphenoxy group as A1 group, methacryloyloxy-4-oligo as A2 group ( Dimethylphenyleneoxy) group-substituted-3,5-di Combination of methylphenyloxy group and methylphenoxy group which is A1 group, methacryloyloxy-3-oligo (dimethylphenyleneoxy) group which is A2 group-substituted 2,4,5-trimethylphenyloxy group and A1 group In combination with a certain methylphenoxy group, in combination with a methacryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-2,3,5-trimethylphenyloxy group that is an A2 group and a methylphenoxy group that is an A1 group And any mixtures thereof.

  Of these, an oligo (phenyleneoxy) group-containing cyclotriphosphazene compound modified with an unsaturated carbonyl group in which n in formula (1) is 1, and an oligo modified with an unsaturated carbonyl group in which n is 2 in formula (1) (Phenyleneoxy) group-containing cyclotetraphosphazene compound, oligo (phenyleneoxy) group-containing cyclopentaphosphazene compound modified with an unsaturated carbonyl group where n is 3 in formula (1), n in formula (1) is 4 An oligo (phenyleneoxy) group-containing cyclohexaphosphazene compound modified with an unsaturated carbonyl group, wherein A is an A2 group acryloyloxy-4-oligo (methylphenyleneoxy) group-substituted phenyloxy group and an A1 group Combination with phenoxy group, A2 group acryloyloxy-4-oligo (methyl Enyleneoxy) group-substituted 3-methylphenyloxy group and A1 group phenoxy group, A2 group acryloyloxy-4-oligo (methylphenyleneoxy) group-substituted-2,3-dimethylphenyloxy group And a combination of a phenoxy group which is an A1 group, a combination of an acryloyloxy-4-oligo (methylphenyleneoxy) group which is an A2 group, a 3,5-dimethylphenyloxy group and a phenoxy group which is an A1 group A2 group acryloyloxy-4-oligo (methylphenyleneoxy) group-substituted-2,3,5-trimethylphenyloxy group in combination with A1 group phenoxy group, A2 group acryloyloxy- 4-oligo (dimethylphenyleneoxy) group-substituted phenyloxy group A combination of a phenoxy group that is an A1 group, a combination of an acryloyloxy-4-oligo (dimethylphenyleneoxy) group that is an A2 group and a 3-methylphenyloxy group and a phenoxy group that is an A1 group, A2 Acryloyloxy-4-oligo (dimethylphenyleneoxy) group substituted-2,3-dimethylphenyloxy group as a group and phenoxy group as A1 group, acryloyloxy-4-oligo as dimethyl group (dimethyl) Phenyleneoxy) group-substituted 3,5-dimethylphenyloxy group and A1 group phenoxy group, A2 group acryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-2,3,5 -Combination of trimethylphenyloxy group and phenoxy group which is A1 group A2 group acryloyloxy-4-oligo (methylphenyleneoxy) group-substituted phenyloxy group and A1 group methylphenoxy group, A2 group acryloyloxy-4-oligo (methyl) Phenyleneoxy) group-substituted 3-methylphenyloxy group and A1 group methylphenoxy group, A2 group acryloyloxy-4-oligo (methylphenyleneoxy) group-substituted-2,3-dimethylphenyl Combination of oxy group and methylphenoxy group which is A1 group, acryloyloxy-4-oligo (methylphenyleneoxy) group substituted with A2 group-3,5-dimethylphenyloxy group and methylphenoxy group which is A1 group In combination with acryloyloxy which is A2 group -4-oligo (methylphenyleneoxy) group-substituted-2,3,5-trimethylphenyloxy group and A1 group methylphenoxy group, A2 group acryloyloxy-4-oligo (dimethylphenyleneoxy) ) A combination of a group-substituted phenyloxy group and a methylphenoxy group that is an A1 group, an acryloyloxy-4-oligo (dimethylphenyleneoxy) group that is an A2 group, and a methyl that is an A1 group. A combination of phenoxy group, A2 group acryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-2,3-dimethylphenyloxy group and A1 group methylphenoxy group, A2 group Acryloyloxy-4-oligo (dimethylpheny Noxy) group substituted-3,5-dimethylphenyloxy group and A1 group methylphenoxy group, A2 group acryloyloxy-4-oligo (dimethylphenyleneoxy) group substituted-2,3,5 A combination of a trimethylphenyloxy group and a methylphenoxy group that is an A1 group, a combination of a methacryloyloxy-4-oligo (methylphenyleneoxy) group that is an A2 group and a phenoxy group that is an A1 group Methacryloyloxy-4-oligo (methylphenyleneoxy) group-substituted 3-methylphenyloxy group which is A2 group and phenoxy group which is A1 group, methacryloyloxy-4-oligo which is A2 group ( Methylphenyleneoxy) group-substituted-2,3-dimethylpheny A combination of a ruoxy group and a phenoxy group that is an A1 group, a methacryloyloxy-4-oligo (methylphenyleneoxy) group-substituted-3,5-dimethylphenyloxy group that is an A2 group, and a phenoxy group that is an A1 group Combination, methacryloyloxy-4-oligo (methylphenyleneoxy) group-substituted-2,3,5-trimethylphenyloxy group which is A2 group and phenoxy group which is A1 group, methacryloyl which is A2 group Combination of oxy-4-oligo (dimethylphenyleneoxy) group-substituted phenyloxy group and phenoxy group which is A1 group, methacryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-3-methylphenyl group which is A2 group Combination of oxy group and phenoxy group which is A1 group , Methacryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted 2,3-dimethylphenyloxy group as A2 group and phenoxy group as A1 group, methacryloyloxy-4 as A2 group -Oligo (dimethylphenyleneoxy) group substitution-3,5-dimethylphenyloxy group and A1 group phenoxy group, A2 group methacryloyloxy-4-oligo (dimethylphenyleneoxy) group substitution-2 , 3,5-trimethylphenyloxy group and A1 group phenoxy group, A2 group methacryloyloxy-4-oligo (methylphenyleneoxy) group-substituted phenyloxy group and A1 group methylphenoxy group In combination with methacryloyl which is A2 group Oxy-4-oligo (methylphenyleneoxy) group substitution-3-methylphenyloxy group and A1 group methylphenoxy group, A2 group methacryloyloxy-4-oligo (methylphenyleneoxy) group substitution A combination of a 2,3-dimethylphenyloxy group and a methylphenoxy group that is A1, a methacryloyloxy-4-oligo (methylphenyleneoxy) group-substituted 3,5-dimethylphenyloxy group that is an A2 group, and A combination with a methylphenoxy group that is an A1 group, a methacryloyloxy-4-oligo (methylphenyleneoxy) group-substituted-2,3,5-trimethylphenyloxy group that is an A2 group, and a methylphenoxy group that is an A1 group Methacryloyloxy-4 which is A2 group -Oligo (dimethylphenyleneoxy) group-substituted phenyloxy group and A1 group methylphenoxy group, A2 group methacryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-3-methylphenyloxy group And a combination of a methylphenoxy group that is an A1 group, a methacryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted 2,3-dimethylphenyloxy group that is an A2 group, and a methylphenoxy group that is an A1 group Combination, methacryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-3,5-dimethylphenyloxy group which is A2 group and methylphenoxy group which is A1 group, methacryloyloxy which is A2 group -4-oligo (dimethylphenyle Oxy) group substituted -2,3,5 ones and any mixture thereof in combination with methylphenoxy group a trimethylphenyl group and A1 groups are more preferred.

  In particular, an oligo (phenyleneoxy) group-containing cyclotriphosphazene compound modified with an unsaturated carbonyl group in which n in formula (1) is 1, an oligo modified with an unsaturated carbonyl group in which n in formula (1) is 2 ( (Phenyleneoxy) group-containing cyclotetraphosphazene compound, oligo (phenyleneoxy) group-containing cyclopentaphosphazene compound modified with an unsaturated carbonyl group in which n is 3 in formula (1), n in formula (1) is 4 Oligo (phenyleneoxy) group-containing cyclohexaphosphazene compound modified with a saturated carbonyl group, wherein A is an A2 group acryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted phenyloxy group and an A1 group phenoxy In combination with a group, acryloyloxy-4-oligo (dimethyl) which is an A2 group Enyleneoxy) group-substituted 3-methylphenyloxy group and A1 group phenoxy group, A2 group acryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-2,3-dimethylphenyloxy group And a combination of the phenoxy group which is the A1 group, a combination of the acryloyloxy-4-oligo (dimethylphenyleneoxy) group which is the A2 group-3,5-dimethylphenyloxy group and the phenoxy group which is the A1 group A2 group acryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-2,3,5-trimethylphenyloxy group and A1 group phenoxy group, A2 group acryloyloxy- 4-oligo (dimethylphenyleneoxy) group-substituted phenylo A combination of a silyl group and a methylphenoxy group which is an A1 group, an acryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted 3-methylphenyloxy group which is an A2 group, and a methylphenoxy group which is an A1 group Combination, A2 group acryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-2,3-dimethylphenyloxy group and A1 group methylphenoxy group, A2 group acryloyloxy -4-Oligo (dimethylphenyleneoxy) group-substituted 3,5-dimethylphenyloxy group and A1 group methylphenoxy group, A2 group acryloyloxy-4-oligo (dimethylphenyleneoxy) group Substituted-2,3,5-trimethylphenyloxy group and A1 A combination of a methylphenoxy group as a group, a combination of a methacryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted phenyloxy group as an A2 group and a phenoxy group as an A1 group, a methacryloyloxy as an A2 group -4-Oligo (dimethylphenyleneoxy) group substitution -3-A combination of methylphenyloxy group and A1 group phenoxy group, A2 group methacryloyloxy-4-oligo (dimethylphenyleneoxy) group substitution-2 , 3-dimethylphenyloxy group and A1 group phenoxy group, A2 group methacryloyloxy-4-oligo (dimethylphenyleneoxy) group substituted-3,5-dimethylphenyloxy group and A1 group In combination with some phenoxy group, A2 Methacryloyloxy-4-oligo (dimethylphenyleneoxy) group substituted-2,3,5-trimethylphenyloxy group and A1 group phenoxy group, methacryloyloxy-4-oligo group A2 Dimethylphenyleneoxy) group-substituted phenyloxy group and A1 group methylphenoxy group, A2 group methacryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted 3-methylphenyloxy group and A1 group In combination with a methylphenoxy group which is A2, in combination with a methacryloyloxy-4-oligo (dimethylphenyleneoxy) group-substituted-2,3-dimethylphenyloxy group which is an A2 group and a methylphenoxy group which is an A1 group , Methacryloyloxy which is A2 group -4-Oligo (dimethylphenyleneoxy) group substituted-3,5-dimethylphenyloxy group and A1 group methylphenoxy group, A2 group methacryloyloxy-4-oligo (dimethylphenyleneoxy) group A combination of a substituted-2,3,5-trimethylphenyloxy group with a methylphenoxy group which is an A1 group, and an arbitrary mixture thereof are preferable.

  The oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group of the present invention preferably 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. On the other hand, when the number average molecular weight is less than 1,000, the oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group may not be sufficiently substituted. The dielectric constant and dielectric loss tangent may be high, and good electrical characteristics may not be exhibited.

Method for producing oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with unsaturated carbonyl group The oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with unsaturated carbonyl group of the present invention is a specific oligo (phenyleneoxy) group. It can be produced by reacting the containing cyclic phosphazene compound with acrylic acid, methacrylic acid or derivatives thereof. 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 this production is, for example, represented 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 a G2 group. Accordingly, there are two types of oligo (phenyleneoxy) group-containing cyclic phosphazene compounds represented by the formula (4): those in which all G are G2 groups, and those in which both G1 groups and G2 groups are provided as G.

G1 group: an aryloxy group having 6 to 20 carbon atoms in which at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group may be substituted.
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. At least one group selected from a group and an aryl group is a group selected from an aryl group having 6 to 20 carbon atoms which may be substituted, and at least one is an oligo (phenyleneoxy) represented by the following formula (6) 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 It is a group selected from an aryl group having 6 to 20 carbon atoms in which at least one group selected from 1 to 6 alkyl groups, alkenyl groups and aryl groups may be substituted.

  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: an aryloxy group having 6 to 20 carbon atoms in which at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group may be substituted.

  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, an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group. Group.

Examples of such a hydroxyl group-substituted aryloxy group include 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- Til-4-hydroxyphenoxy group, 4-phenyl-3-hydroxyphenoxy group, 5-phenyl-3-hydroxyphenoxy group, 3-phenyl-4-hydroxyphenoxy group, 4-allyl-3-hydroxyphenoxy group, 5- An allyl-3-hydroxyphenoxy group and a 3-allyl-4-hydroxyphenoxy group can be mentioned. 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 Phenoxy group, 2-ethyl-4-hydroxyphenoxy group, 3-ethyl-4-hydroxyphenoxy group, 3-phenyl-4-hydroxyphenoxy group and 3-allyl-4-hydroxyphenoxy group are preferable, 4-hydroxyphenoxy group 3-methyl-4-hydroxyphenoxy group and 3,5-dimethyl-4-hydroxyphenoxy group are particularly 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 12 to 14. 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 certain 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- A 4-hydroxyphenoxy group and a dimethylphenoxy group which is a Q1 group, a 3,5-dimethyl-4-hydroxyphenoxy group where Q is a Q2 group, and a Q1 group And those mixtures of any of these there naphthyloxy group. 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 methylphenoxy group, a 3-methyl-4-hydroxyphenoxy group where Q is a Q2 group and a dimethylphenoxy group which is a Q1 group, a 3,5-dimethyl-4-hydroxyphenoxy group where 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 of 4-hydroxyphenoxy group and Q1 group of dimethylphenoxy group and any mixture thereof. A thio group-containing cyclotriphosphazene compound and a hydroxy group-containing cyclotetraphosphazene compound wherein k in formula (7) is 2, wherein all of Q corresponding to [Form 1] are 4-hydroxyphenoxy groups, 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 Those of the phenoxy group and any mixtures thereof are preferred.

(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. In the aryl group having 6 to 20 carbon atoms, at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group may be substituted.

  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 reacting the above-mentioned specific hydroxyl group-containing cyclic phosphazene compound with 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 Rophenol, 2-ethyl-6-phenylphenol, 2-phenylphenol, 2,6-diphenylphenol, 2,6-bis (4-fluorophenyl) phenol, 2-methyl-6-tolylphenol and 2,6- Examples include ditolylphenol. 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 production method P-1 in an aromatic hydrocarbon solvent in the presence of a phase transfer catalyst such as aqueous sodium hydroxide and tetrabutylammonium hydrogen sulfate and air. It can also be produced by reacting a hydroxy group-containing cyclic phosphazene compound similar to that used with a halophenol compound.

  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 unsaturated carbonyl group)
The oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group is selected from the oligo (phenyleneoxy) group-containing cyclic phosphazene compound obtained by the above-mentioned production method, acrylic acid, methacrylic acid and derivatives thereof. It can be produced by reacting with at least one kind of compound.

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

The reaction temperature at the time of reacting the above-mentioned oligo (phenyleneoxy) group-containing cyclic phosphazene compound with acrylic acid, methacrylic acid or a derivative thereof depends on any of the above-mentioned methods, or the thermal stability of the reaction product. It can be set as appropriate in consideration. However, when reacting using a solvent, it is usually preferable to set the reaction temperature within the temperature range from -20 ° C to the boiling point of the solvent. On the other hand, when the reaction is carried out without a solvent, the reaction temperature is preferably set in the range of 40 to 200 ° C.

  The oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with the target unsaturated carbonyl group obtained by the reaction of such an oligo (phenyleneoxy) group-containing cyclic phosphazene compound with acrylic acid or methacrylic acid or a derivative thereof is , Filtration, solvent extraction, column chromatography, reprecipitation, and the like, and can be isolated and purified from the reaction system.

Resin Composition The resin composition of the present invention comprises a flame retardant comprising a oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group of the present invention and a resin component. As the flame retardant comprising an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group of the present invention, one type of flame retardant may be used, or two or more types may be used in combination. As the resin component, various thermoplastic resins or thermosetting resins can be used. These resin components may be natural or synthetic.

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

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

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

  In the resin composition of the present invention, the amount of flame retardant comprising an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group depends on various conditions such as the type of resin component and the use of the resin composition. In general, it is preferably set to 0.1 to 50 parts by weight, and preferably set to 0.5 to 40 parts by weight with respect to 100 parts by weight of the resin component in terms of solid content. More preferably, it is more preferably set to 1 to 30 parts by weight. When the amount of the flame retardant comprising an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group is less than 0.1 parts by weight, the resin molded article comprising the resin composition is sufficiently flame retardant. May not be indicated. On the other hand, if it exceeds 50 parts by weight, the original properties of the resin component may be impaired, and a resin molded product having such properties may not be obtained.

  Moreover, the resin composition of this invention can mix | blend various additives in the range which does not impair the target physical property according to the kind of resin component, the use of a resin composition, etc. 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, phosphinate salt, phosphorus flame retardants such as ammonium phosphate and red phosphorus, melamine, melamine cyanurate, melam, melem, melon and Nitrogen flame retardants such as succinoguanamine, silicone flame retardants, flame retardants such as bromine flame retardants, flame retardant aids such as antimony trioxide, anti-dripping agents such as polytetrafluoroethylene (PTFE), benzotriazole UV absorbers such as, 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 , Photosensitizer, thickener, lubricant, defoamer, leveling agent, brightener, heavy It may be mentioned inhibitor, thixotropic agents, plasticizers and antistatic agents.

  Furthermore, the resin composition of the present invention is at least selected from a polymerizable material group consisting of a thermopolymerizable monomer, a thermopolymerizable oligomer, a photopolymerizable monomer, a photopolymerizable oligomer, a radiation polymerizable monomer, and a radiation polymerizable oligomer. One polymerizable material may be further included. In this case, the resin composition of the present invention is heated and irradiated with ultraviolet rays by a polymerization action of these polymerizable materials and a flame retardant comprising an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with the unsaturated carbonyl group of the present invention. It can be cured by irradiation with energy rays such as electromagnetic waves such as visible rays and electron beams such as electron beams.

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

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

  When the above-mentioned epoxy resin is used as the resin component (hereinafter sometimes referred to as “epoxy resin composition”), a flame retardant comprising an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group of the present invention is provided. The proportion of the epoxy resin composition is preferably 0.1 to 80% by weight, and more preferably 0.5 to 70% by weight. When the proportion of the flame retardant comprising an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group is less than 0.1% by weight, the resin molded article comprising the epoxy resin composition is sufficiently flame retardant. May not be indicated. On the other hand, if it exceeds 80% by weight, the original properties of the epoxy resin component may be impaired, and a resin molded product having such properties may not be obtained.

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

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

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

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

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

Polymerizable composition The polymerizable composition of the present invention contains a flame retardant comprising an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group of the present invention. Two or more flame retardants composed of an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group may be used.

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

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

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

  Furthermore, the polymerizable composition of the present invention may contain a known reactive diluent or additive as necessary. Although the reactive diluent which can be utilized is not specifically limited, For example, aliphatic alkyl glycidyl ethers, such as butyl glycidyl ether, 2-ethylhexyl glycidyl ether, and allyl glycidyl ether, glycidyl methacrylate, and tertiary carboxylic acid glycidyl ester And alkyl glycidyl esters such as styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, ps-butylphenyl glycidyl ether, and nonylphenyl glycidyl ether. These reactive diluents may be used alone or in combination of two or more. On the other hand, the thing similar to what is used in the resin composition of this invention can be used.

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

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

EXAMPLES The present invention will be specifically described below with reference to examples and 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, (PNA ₂ ) for general formula (1), and (PNG ₂ ) for general formula (4). ). In the general formula (7), when Q 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 the examples include ¹ H-NMR spectrum and ³¹ P-NMR spectrum measurement, CHN elemental analysis, IR spectrum measurement, chlorine by potentiometric titration using silver nitrate after alkali melting. It was identified based on the results of elemental (residual chlorine) analysis, phosphorus elemental analysis by ICP-AES after microwave wet decomposition, and TOF-MS analysis. In addition, 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 was measured by the following method.

  Hydroxyl equivalent (g / eq .: mass g of resin containing 1 equivalent of hydroxy group) is obtained by dissolving a oligo (phenyleneoxy) group-containing cyclic phosphazene compound in chloroform and then adding a methanol solution of 0.1N tetraethylammonium hydroxide. After vigorous stirring, 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.

Synthesis Example 1 (Oligo according to Form 2 (Production of phenyleneoxy group-containing cyclic phosphazene compound))
An average composition of [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ OH) _2.1 (OC ₆ H ₅ ) _3] was added to a 3 liter four-necked flask equipped with a thermometer, a stirrer and a condenser. _.9 ] hydroxy group-containing cyclic phosphazene compound (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. Then, benzoyl peroxide (20 g, 0.082 mol) was added thereto 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.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.0-2.2 (267H), 6.3-6.6 (89H), 6.7-7.3 (19H)
◎ ³¹ P-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 structure of the product obtained in this step is [N ₃ P ₃ {OC ₆ H ₂ (CH ₃ ) ₂ (OC ₆ H ₂ (CH ₃ ) ₂ ) _20.2 OH} _{2 .1} (OC ₆ H ₅ ) _3.9 ] was confirmed to be a cyclic phosphazene compound.

Synthesis Example 2 (Production of oligo (phenyleneoxy) group-containing cyclic phosphazene compound according to form 2)
An average composition of [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) ₂ OH) _2.1 (OC _6] was added to a 3 liter four-necked flask equipped with a thermometer, a stirrer, an air introduction tube and a cooling tube. H ₅ ) _3.9 ] hydroxy group-containing 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) was added and heated to 40 ° C. 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 stopping the reaction by adding ethylenediaminetetraacetic acid, 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.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.0-2.2 (137H), 6.3-6.6 (46H), 6.7-7.3 (20H)
◎ ³¹ P-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 has a composition of [N ₃ P ₃ {OC ₆ H ₂ (CH ₃ ) ₂ (OC ₆ H ₂ (CH ₃ ) ₂ ) _9.9 OH} _{2. .1} (OC ₆ H ₅ ) _3.9 ] was confirmed to be a cyclic phosphazene compound.

Synthesis Example 3 (Production of oligo (phenyleneoxy) group-containing cyclic phosphazene compound according to form 2)
Hydroxyl group-containing with an average composition of [N ₃ P ₃ (OC ₆ H ₂ (CH ₃ ) OH) _2.0 (OC ₆ H ₅ ) _4.0 ] instead of the hydroxy group-containing phosphazene compound used in Synthesis Example 1 Except for using the cyclic phosphazene compound (100 g, 0.40 unit mol), the same operation as in Synthesis Example 1 was performed 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.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.0 to 2.2 (244H), 6.3 to 6.6 (85H), 6.7 to 7.3 (20H),
◎ ³¹ P-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 has a composition of [N ₃ P ₃ {OC ₆ H ₃ (CH ₃ ) (OC ₆ H ₂ (CH ₃ ) ₂ ) _20.9 OH} _{2. 0} (OC ₆ H ₅ ) _4.0 ] was confirmed to be a cyclic phosphazene compound.

Synthesis Example 4 (Production of oligo (phenyleneoxy) group-containing cyclic phosphazene compound according to form 2)
Hydroxy having a mean composition of [N ₃ P ₃ (OC ₆ H ₄ OH) _2.2 (OC ₆ H ₅ ) _3.8 ] in a 3 liter four-necked flask equipped with a thermometer, stirrer and condenser. A group-containing cyclic phosphazene compound (50 g, 0.21 unit mol), a 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 the internal temperature A solution of 4-bromo-2,6-xylenol (638 g, 3.17 mol) in toluene (1,200 mL) was added dropwise at 20 to 40 ° C. 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%).

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.0-2.2 (125H), 6.3-6.6 (50H), 6.7-7.3 (19H)
◎ ³¹ P-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 has a composition of [N ₃ P ₃ {OC ₆ H ₄ (OC ₆ H ₂ (CH ₃ ) ₂ ) _9.5 OH} _2.2 (OC ₆ H ₅ ) _3.8 ] was confirmed to be a cyclic phosphazene compound.

Synthesis Example 5 (Production of oligo (phenyleneoxy) group-containing cyclic phosphazene compound according to Form 1)
Hydroxy group-containing cyclic phosphazene compound (100 g, 0.38 unit) having an average composition of [N ₃ P ₃ (OC ₆ H ₄ OH) ₆ ] in a 3 liter four-necked flask equipped with a thermometer, a stirrer and a condenser. mol), polyphenylene ether having a number average molecular weight of 18,000 (Asahi Kasei Chemicals, 670 g), toluene (1,200 mL) and n-propanol (600 mL) were added, and the mixture was heated and dissolved at 90 ° C. After adding benzoyl peroxide (20 g, 0.082 mol) and reacting at 90 ° C. for 60 minutes, the reaction mixture was poured into methanol (6,000 mL), and the resulting precipitate was filtered off. The precipitate was washed with methanol (1,200 mL) and dried under reduced pressure to obtain an oligo (phenyleneoxy) group-containing cyclic phosphazene compound (726 g, yield 94.3%). The yield was calculated by assuming that 100% of the polyphenylene ether was redistributed to the hydroxy group-containing cyclic phosphazene compound.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.0-2.2 (252H), 6.3-6.6 (108H)
◎ ³¹ P-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 5,700

  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 [N ₃ P ₃ {OC ₆ H ₄ (OC ₆ H ₂ (CH ₃ ) ₂ ) _7.0 OH} ₆ ]. It was confirmed that.

Synthesis Example 6 (Production of oligo (phenyleneoxy) group-containing cyclic phosphazene compound according to form 2)
In place of the hydroxy group-containing phosphazene compound used in Synthesis Example 1, an average composition of [NP (OC ₆ H ₄ OH) (OC ₆ H ₅ CH ₃ )] _n hydroxy group-containing cyclic phosphazene compound (100 g, 0.38 unit mol) ) Was used in the same manner as in Synthesis Example 1 to obtain 740 g of an oligo (phenyleneoxy) group-containing cyclic phosphazene compound (yield 96.1%). The analysis results of the obtained oligo (phenyleneoxy) group-containing cyclic phosphazene compound are as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.0-2.2 (242H), 6.3-6.6 (89H), 6.7-7.3 (19H)
◎ ³¹ P-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, the product obtained in this step has a composition of [NP {OC ₆ H ₄ (OC ₆ H ₂ (CH ₃ ) ₂ ) _14.2 OH} (OC ₆ H ₄ CH ₃ )] It was confirmed that this was a cyclic phosphazene compound of _n .

Synthesis Example 7 (Production of phenoxy group fully substituted cyclic phosphazene compound)
PHOSPHORUS-NITROGEN COMPOUNDS, H.P. R. According to the method described in ALLCOCK, 1972, page 151, ACADEMIC PRESS, using a cyclophosphazene mixture of 81% hexachlorocyclotriphosphazene and 19% octachlorocyclotetraphosphazene [N = P (OC ₆ H ₅ ) ₂ ] ₃ and a mixture of [N = P (OC ₆ H ₅ ) ₂ ] ₄ (white solid / melting point: 65-112 ° C.).

Example 1 (Production of oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with unsaturated carbonyl group according to Form 2)
A 1 liter four-necked flask equipped with a thermometer and a stirrer was subjected to an oligo (phenyleneoxy) group-containing cyclic phosphazene compound (100 g, 0.05 unit mol), acrylic acid chloride (prepared in Synthesis Example 1) under a nitrogen stream. 6.8 g, 0.08 mol), 250 g of synthetic zeolite (3A) and methyl ethyl ketone (700 mL) were charged and stirred for 24 hours under reflux. After completion of the reaction, synthetic zeolite was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain 98 g (yield 96%) of an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group. The analysis result of this product was as follows.

◎ IR spectrum (KBr Pellet, cm ⁻¹ )
2737, 1732, 1634, 1171
◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.0-2.2 (267H), 5.9-6.1 (4H), 6.3-6.6 (91H), 6.7-7.3 (19H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.6-10.0

From the above analysis results, the product obtained in this step has a structure of [N ₃ P ₃ {OC ₆ H ₂ (CH ₃ ) ₂ (OC ₆ H ₂ (CH ₃ ) ₂ ) _20.2 OCOCHCH ₂ }. _2.1 (OC ₆ H ₅ ) _3.9 ] was confirmed to be an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group.

Example 2 (Production of oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with unsaturated carbonyl group according to Form 2)
To a 1 liter four-necked flask equipped with a thermometer and a stirrer, an oligo (phenyleneoxy) group-containing cyclic phosphazene compound (100 g, 0.09 unit mol), acrylic acid chloride (prepared in Synthesis Example 2) under a nitrogen stream 12.7 g, 0.14 mol), 250 g of synthetic zeolite (3A) and methyl ethyl ketone (700 mL) were charged and stirred for 24 hours under reflux. After completion of the reaction, synthetic zeolite was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain 98 g (yield 95%) of an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group. The analysis result of this product was as follows.

◎ IR spectrum (KBr Pellet, cm ⁻¹ )
2737, 1732, 1634, 1171
◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.0-2.2 (137H), 5.9-6.1 (4H), 6.3-6.6 (48H), 6.7-7.3 (20H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.6-10.0

From the above analysis results, the product obtained in this step has a structure of [N ₃ P ₃ {OC ₆ H ₂ (CH ₃ ) ₂ (OC ₆ H ₂ (CH ₃ ) ₂ ) _9.9 OCOCHCH ₂ }. _2.1 (OC ₆ H ₅ ) _3.9 ] was confirmed to be an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group.

Example 3 (Production of oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with unsaturated carbonyl group according to Form 2)
A 1 liter four-necked flask equipped with a thermometer and a stirrer was charged with an oligo (phenyleneoxy) group-containing cyclic phosphazene compound (100 g, 0.05 unit mol), acrylic acid chloride (prepared in Synthesis Example 3) under a nitrogen stream. 6.5 g, 0.07 mol), 250 g of synthetic zeolite (3A) and methyl ethyl ketone (700 mL) were charged and stirred for 24 hours under reflux. After completion of the reaction, synthetic zeolite was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain 98 g (yield 97%) of an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group. The analysis result of this product was as follows.

◎ IR spectrum (KBr Pellet, cm ⁻¹ )
2737, 1732, 1634, 1171
◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.0-2.2 (257H), 5.9-6.1 (4H), 6.3-6.6 (90H), 6.7-7.3 (20H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.6-10.0

From the above analysis results, the product obtained in this step has a structure of [N ₃ P ₃ {OC ₆ H ₂ (CH ₃ ) (OC ₆ H ₂ (CH ₃ ) ₂ ) _20.9 OCOCHCH ₂ } _{2. .1} (OC ₆ H ₅ ) _3.9 ] was confirmed to be an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group.

Example 4 (Production of oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with unsaturated carbonyl group according to Form 2)
A 1 liter four-necked flask equipped with a thermometer and a stirrer was subjected to an oligo (phenyleneoxy) group-containing cyclic phosphazene compound (100 g, 0.09 unit mol), acrylic acid chloride (prepared in Synthesis Example 4) under a nitrogen stream. 12.7 g, 0.14 mol), 250 g of synthetic zeolite (3A) and methyl ethyl ketone (700 mL) were charged and stirred for 24 hours under reflux. After completion of the reaction, synthetic zeolite was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain 99 g (yield 96%) of an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group. The analysis result of this product was as follows.

◎ IR spectrum (KBr Pellet, cm ⁻¹ )
2737, 1732, 1634, 1171
◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.0-2.2 (125H), 5.9-6.1 (4H), 6.3-6.6 (53H), 6.7-7.3 (20H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.6-10.0

From the above analysis results, the product obtained in this step has a structure of [N ₃ P ₃ {OC ₆ H ₄ (OC ₆ H ₂ (CH ₃ ) ₂ ) _9.5 OCOCHCH ₂ } _2.2 (OC ₆ H ₅ ) _3.8 ] was confirmed to be an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group.

Example 5 (Production of oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl 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 (100 g, 0.05 unit mol), acrylic acid chloride (prepared in Synthesis Example 5) was added under a nitrogen stream. 19.0 g, 0.21 mol), 250 g of synthetic zeolite (3A) and methyl ethyl ketone (700 mL) were charged and stirred for 24 hours under reflux. After completion of the reaction, the synthetic zeolite was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain 100 g (yield 96%) of an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group. The analysis result of this product was as follows.

◎ IR spectrum (KBr Pellet, cm ⁻¹ )
2737, 1732, 1634, 1171
◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.0-2.2 (252H), 5.9-6.1 (12H), 6.3-6.6 (114H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.6-10.0

From the above analysis results, the product obtained in this step has an unsaturated structure of [N ₃ P ₃ {OC ₆ H ₄ (OC ₆ H ₂ (CH ₃ ) ₂ ) _7.0 OCOCHCH ₂ } ₆ ]. It was confirmed to be an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with a carbonyl group.

Example 6 (Production of oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with unsaturated carbonyl group according to Form 2)
A 1 liter four-necked flask equipped with a thermometer and a stirrer was charged with an oligo (phenyleneoxy) group-containing cyclic phosphazene compound (100 g, 0.05 unit mol), acrylic acid chloride (prepared in Synthesis Example 6) under a nitrogen stream. 10.1 g, 0.11 mol), 250 g of synthetic zeolite (3A) and methyl ethyl ketone (700 mL) were charged and stirred for 24 hours under reflux. After completion of the reaction, synthetic zeolite was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain 99 g (yield 96%) of an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group. The analysis result of this product was as follows.

◎ IR spectrum (KBr Pellet, cm ⁻¹ )
2737, 1732, 1634, 1171
◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.0-2.2 (91H), 5.9-6.1 (2H), 6.3-6.6 (33H), 6.7-7.3 (4H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.6-10.0

From the above analysis results, the product obtained in this step has a structure of [NP {OC ₆ H ₄ (OC ₆ H ₂ (CH ₃ ) ₂ ) _14.6 OCOCHCH ₂ } (OC ₆ H ₄ CH ₃ ). It was confirmed that it was an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group of _n .

Example 7 (Production of oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with unsaturated carbonyl group according to Form 2)
An oligo (phenyleneoxy) modified with an unsaturated carbonyl group was operated in the same manner as in Example 1 except that methacrylic acid chloride (7.9 g, 0.08 mol) was used instead of the acrylic acid chloride used in Example 1. ) 99 g (yield 97%) of a group-containing cyclic phosphazene compound was obtained. The analysis result of this product was as follows.

◎ IR spectrum (KBr Pellet, cm ⁻¹ )
2737, 1732, 1634, 1171
◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
1.9 to 2.2 (273H), 5.6 to 6.2 (4H), 6.3 to 6.6 (91H), 6.7 to 7.3 (19H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.6-10.0

From the above analysis results, the product obtained in this step has the structure [N ₃ P ₃ {OC ₆ H ₂ (CH ₃ ) ₂ (OC ₆ H ₂ (CH ₃ ) ₂ ) _20.2 OCOC (CH ₃₎ was confirmed to be a _{CH 2} 2.1 (OC 6 H} 5) 3.9] oligo (phenylene) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group.

Example 8 (Production of oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with unsaturated carbonyl group according to Form 2)
An oligo (phenyleneoxy) modified with an unsaturated carbonyl group was operated in the same manner as in Example 2 except that methacrylic acid chloride (14.7 g, 0.14 mol) was used instead of the acrylic acid chloride used in Example 2. ) 100 g (yield 96%) of a group-containing cyclic phosphazene compound was obtained. The analysis result of this product was as follows.

◎ IR spectrum (KBr Pellet, cm ⁻¹ )
2737, 1732, 1634, 1171
◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.0-2.2 (143H), 5.6-6.2 (4H), 6.3-6.6 (48H), 6.7-7.3 (20H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.6-10.0

From the above analysis results, the product obtained in this step has the structure [N ₃ P ₃ {OC ₆ H ₂ (CH ₃ ) ₂ (OC ₆ H ₂ (CH ₃ ) ₂ ) _9.9 OCOC (CH ₃₎ was confirmed to be a _{CH 2} 2.1 (OC 6 H} 5) 3.9] oligo (phenylene) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group.

Example 9 (Production of oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with unsaturated carbonyl group according to Form 2)
An oligo (phenyleneoxy) modified with an unsaturated carbonyl group was operated in the same manner as in Example 3 except that methacrylic acid chloride (7.4 g, 0.07 mol) was used instead of the acrylic acid chloride used in Example 3. ) 99 g (yield 97%) of a group-containing cyclic phosphazene compound was obtained. The analysis result of this product was as follows.

◎ IR spectrum (KBr Pellet, cm ⁻¹ )
2737, 1732, 1634, 1171
◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.0-2.2 (263H), 5.6-6.2 (4H), 6.3-6.6 (90H), 6.7-7.3 (20H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.6-10.0

From the above analysis results, the product obtained in this step has the structure [N ₃ P ₃ {OC ₆ H ₂ (CH ₃ ) (OC ₆ H ₂ (CH ₃ ) ₂ ) _20.9 OCOC (CH ₃ ) CH ₂ } _2.1 (OC ₆ H ₅ ) _3.9 ] was confirmed to be an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group.

Example 10 (Production of oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with unsaturated carbonyl group according to Form 2)
An oligo (phenyleneoxy) modified with an unsaturated carbonyl group was operated in the same manner as in Example 4 except that methacrylic acid chloride (14.7 g, 0.14 mol) was used instead of the acrylic acid chloride used in Example 4. ) 100 g (yield 96%) of a group-containing cyclic phosphazene compound was obtained. The analysis result of this product was as follows.

◎ IR spectrum (KBr Pellet, cm ⁻¹ )
2737, 1732, 1634, 1171
◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.0-2.2 (132H), 5.6-6.2 (4H), 6.3-6.6 (53H), 6.7-7.3 (20H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.6-10.0

From the above analysis results, the structure of the product obtained in this step is [N ₃ P ₃ {OC ₆ H ₄ (OC ₆ H ₂ (CH ₃ ) ₂ ) _9.5 OCOC (CH ₃ ) CH ₂ }. _2.2 (OC ₆ H ₅ ) _3.8 ] was confirmed to be an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group.

Example 11 (Production of oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group according to Form 1)
An oligo (phenyleneoxy) modified with an unsaturated carbonyl group was operated in the same manner as in Example 5 except that methacrylic acid chloride (21.9 g, 0.21 mol) was used instead of the acrylic acid chloride used in Example 5. ) 98 g (yield 95%) of a group-containing cyclic phosphazene compound was obtained. The analysis result of this product was as follows.

◎ IR spectrum (KBr Pellet, cm ⁻¹ )
2737, 1732, 1634, 1171
◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.0-2.2 (270H), 5.6-6.2 (12H), 6.3-6.6 (114H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.6-10.0

From the above analysis results, the structure of the product obtained in this step is [N ₃ P ₃ {OC ₆ H ₄ (OC ₆ H ₂ (CH ₃ ) ₂ ) _7.0 OCOC (CH ₃ ) CH ₂ }. ₆ ] was confirmed to be an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group.

Example 12 (Production of oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with unsaturated carbonyl group according to Form 2)
An oligo (phenyleneoxy) modified with an unsaturated carbonyl group was operated in the same manner as in Example 6 except that methacrylic acid chloride (11.6 g, 0.11 mol) was used instead of the acrylic acid chloride used in Example 6. ) 98 g (yield 95%) of a group-containing cyclic phosphazene compound was obtained. The analysis result of this product was as follows.

◎ IR spectrum (KBr Pellet, cm ⁻¹ )
2737, 1732, 1634, 1171
◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
2.0-2.2 (94H), 5.6-6.2 (2H), 6.3-6.6 (33H), 6.7-7.3 (4H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.6-10.0

From the above analysis results, the product obtained in this step has the structure [NP {OC ₆ H ₄ (OC ₆ H ₂ (CH ₃ ) ₂ ) _14.6 OCOC (CH ₃ ) CH ₂ } (OC ₆ H ₄ CH ₃ )] It was confirmed to be an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group of _n .

Examples 13 to 24 (Preparation of resin composition)
Bisphenol A type epoxy resin (Dainippon Ink Chemical Co., Ltd. trade name “Epicron 850S”: epoxy equivalent 180), polyphenylene ether resin (manufactured by Asahi Kasei Chemicals Corporation) having a number average molecular weight (Mn) of about 19,000 The oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group obtained in Examples 1 to 12 was blended with toluene at the ratio shown in Table 1, and stirred for 30 minutes in an oil bath heated to 70 ° C. And evenly dissolved. 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 evaluation items described above. Tables 1 and 2 show the results of evaluation of flame retardancy, dielectric properties, and high temperature reliability 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”.

Comparative Examples 1-2 (Preparation of resin composition)
Resin compositions were obtained in the same manner as in Examples 13 to 24 except that the cyclic phosphazene compound produced in Synthesis Example 7 was used instead of the cyclic phosphazene compound produced in Examples 1 to 12. And this resin composition was shape | molded and hardened in the same method and conditions as Examples 13-24, and the cured resin sheet was obtained. About this resin sheet, the flame retardance, dielectric property, and high temperature reliability were evaluated similarly to Examples 13-24. The results are shown in Table 2.

  According to Table 1 and Table 2, the resin composition of Examples 13-24 showed the outstanding flame retardance and high temperature reliability, and also has the outstanding electrical property.

Synthesis Example 8 (Synthesis of bifunctional PPE oligomer)
In a 2 liter glass flask equipped with a stirrer, thermometer, reflux condenser and air inlet tube, 1.3 g (0.012 mol) of CuCl, 70.7 g (0.55 mol) of di-n-butylamine and 500 ml of methyl ethyl ketone Was stirred at a reaction temperature of 40 ° C., and 45.4 g (0.16 mol) of 4,4 ′-(1-methylethylidene) bis (2,6-dimethylphenol) previously dissolved in 1,000 ml of methyl ethyl ketone. And 58.6 g (0.48 mol) of 2,6-dimethylphenol were added dropwise over 2 hours while bubbling air at 2 liters / minute, and after 1 hour after completion of the dropwise addition, air was bubbled at 2 liters / minute. Stirring was performed while continuing. Ethylenediaminetetraacetic acid dihydrogen disodium aqueous solution was added thereto to stop the reaction. Thereafter, washing was performed 3 times with a 3% hydrochloric acid aqueous solution, followed by further washing with ion-exchanged water. The obtained solution was concentrated and further dried under reduced pressure to obtain 100.9 g of a PPE oligomer having hydroxyl groups at both ends. This oligomer has a number average molecular weight of 860, a weight average molecular weight of 1150, and a hydroxyl group equivalent of 454 g / eq. Met.

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

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

Examples 25-36 (Preparation of resin composition)
45.0 g of PPE oligomer having an acrylate group at both ends obtained in Synthesis Example 8, 15.0 g of the cyclic phosphazene compound obtained in Examples 1 to 12, EO-modified bisphenol A diacrylate (of Shin-Nakamura Chemical Co., Ltd.) Product name “NK Ester A-BPE-10”) 5.0 g, 2,2′-azobisisobutyronitrile (AIBN) 0.5 g and toluene 60 ml were mixed and dissolved, then melted and degassed at 150 ° C. Thus, a resin composition was obtained. This resin composition was molded into a sheet and heated at 200 ° C. for 6 hours. Thereby, a cured resin sheet was obtained. About this resin sheet, it carried out similarly to Examples 13-24, and measured combustibility (flame retardance), high temperature reliability, and an electrical property. The results are shown in Table 3 and Table 4.

Comparative Examples 3 and 4 (Preparation of resin composition)
A resin composition was obtained in the same manner as in Examples 25 to 36 except that the cyclic phosphazene compound produced in Synthesis Example 7 was used instead of the cyclic phosphazene compound produced in Examples 1 to 12. And this resin composition was shape | molded and hardened in the same method and conditions as Examples 25-36, and the cured resin sheet was obtained. About this resin sheet, the flame retardance, dielectric property, and high temperature reliability were evaluated similarly to Examples 25-36. The results are shown in Table 4.

As is clear from Tables 3 and 4, the cured sheets of Examples 25 to 36 are superior in flame retardancy, high temperature reliability, and electrical characteristics as compared with those in Comparative Examples 3 and 4.

Claims (11)

An oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl 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.
Group A1: An aryloxy group having 6 to 20 carbon atoms, which may be substituted with at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group.
Group A2: a group selected from the group consisting of an oligo (phenyleneoxy) group-substituted phenyloxy group modified with an unsaturated carbonyl 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. At least one group selected from a group and an aryl group is a group selected from an aryl group having 6 to 20 carbon atoms which may be substituted, and at least one is an oligo (phenyleneoxy) represented by the following formula (3) It is a group.
In the formula (3), q represents an integer of 1 to 50 (excluding 1) , Y is an unsaturated carbonyloxy group selected from an acryloyloxy group and a methacryloyloxy group, and E ^{6 to} E ⁹ are each independently In which at least one group 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 may be substituted. The group chosen from a C6-C20 aryl group is shown. )   A2 group was modified with an oligo (methylphenyleneoxy) group-substituted phenyleneoxy group modified with an unsaturated carbonyl group, an oligo (methylphenyleneoxy) group-substituted methylphenyleneoxy group modified with an unsaturated carbonyl group, or an unsaturated carbonyl group Oligo (methylphenyleneoxy) group-substituted dimethylphenyleneoxy group, oligo (dimethylphenyleneoxy) group-modified phenyleneoxy group modified with unsaturated carbonyl group, oligo (dimethylphenyleneoxy) group-substituted methylphenyleneoxy modified with unsaturated carbonyl group The oligo (dimethylphenyleneoxy) group modified with an unsaturated carbonyl group according to claim 1, which is at least one selected from the group consisting of a substituted dimethylphenyleneoxy group and an oligo (dimethylphenyleneoxy) group modified with a group and an unsaturated carbonyl group. Oxy) group containing a cyclic phosphazene compound. N is 1 or 2 of the formula (1), according to claim 1 or 2 oligos modified with an unsaturated carbonyl group according to (phenylene) group-containing cyclic phosphazene compound.   The oligo (phenyleneoxy) modified with an unsaturated carbonyl group according to any one of claims 1 to 3, wherein 1 to (2n + 2) of (2n + 4) A in formula (1) is an A2 group. Group-containing cyclic phosphazene compounds.   The oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group according to any one of claims 1 to 4, which contains two or more compounds having different n in formula (1). The process comprising reacting an oligo (phenyleneoxy) group-containing cyclic phosphazene compound represented by the following formula (4) with at least one compound selected from acrylic acid, methacrylic acid and derivatives thereof: The manufacturing method of the oligo (phenyleneoxy) group containing cyclic phosphazene compound modified | denatured by the unsaturated carbonyl group of description.
(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: an aryloxy group having 6 to 20 carbon atoms in which at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group may be substituted.
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. At least one group selected from a group and an aryl group is a group selected from an aryl group having 6 to 20 carbon atoms which may be substituted, and at least one is an oligo (phenyleneoxy) represented by the following formula (6) It is a group.
Wherein (6), t represents an integer (excluding 1) of 1 to ^50, E 15 ^{to E 18} is a independent substituent, a hydrogen atom, an alkyl group and an alkenyl having 1 to 6 carbon atoms And a group selected from an aryl group having 6 to 20 carbon atoms, and at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group may be substituted. )   A resin composition comprising the oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group according to any one of claims 1 to 5 alone or in combination of two or more.   A resin composition comprising a resin component and an oligo (phenyleneoxy) group-containing cyclic phosphazene compound modified with an unsaturated carbonyl group according to any one of claims 1 to 5. The resin component is epoxy resin, polyphenylene ether resin, polyamide resin, polyamideimide resin, polyetherimide resin, polyimide resin, polysulfone resin, phenoxy resin, bismaleimide resin, benzoxazine resin, oxetane resin, cyanate ester resin, and bis The resin composition according to claim 8 , which is at least one selected from the group consisting of maleimide-cyanate resin.   The resin molding which consists of a resin composition in any one of Claim 7 to 9.   The electronic component using the resin molding of Claim 10.