JP2014058691A - Flame retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame retardant resin composition from which a resin molded article having high-temperature reliability and both of enhanced flame retardancy and heat resistance can be formed.SOLUTION: The composition contains a resin component and a cyclic phosphazene compound represented by formula (1), wherein n is an integer of 3-8 and A is a group containing a substituted aryloxy group represented by formula (2), wherein Y is a group selected from a phenylene group, a biphenylene group and a naphthylene group, and Q is an allyloxy group, a dialkylamino group, a diarylamino group or a trimethylsilyloxy group.

Description

  The present invention relates to a flame retardant resin composition, and particularly to a flame retardant resin composition containing a cyclic phosphazene compound.

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

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

JP 2000-103939 A JP 2004-83671 A JP 2004-210849 A JP 2005-8835 A JP 2005-248134 A

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 10 include reactive groups. Disclosed are phosphazene-based flame retardants and resin compositions (for example, epoxy resin compositions and polyimide resin compositions) using the same. This type of phosphazene flame retardant has good compatibility with the resin component, so even if it is added in a large amount to the resin composition, it is difficult to impair the high temperature reliability of the resin molded product. In order to reduce the glass transition temperature of the resin molded product, it is not sufficient in terms of the essential effect that it is difficult to effectively increase the flame retardancy of the resin molded product even if it is increased. In addition, the heat resistance of the resin molded product is impaired.

Japanese Patent Laid-Open No. 6-247989 JP-A-10-259292 JP 2003-302751 A JP 2003-342339 A JP 2004-143465 A

  An object of the present invention is to make it possible to form a resin molded article having high temperature reliability and simultaneously improved in flame retardancy and heat resistance for a flame retardant resin composition using a phosphazene-based flame retardant. There is.

  The inventors of the present invention focused on the cyclic phosphazene compound as a flame retardant mixed with the resin component in the flame retardant resin composition, and further focused on the type of substituent of the cyclic phosphazene compound. A cyclic phosphazene compound substituted with an aryloxy group having an electron donating group (that is, an aprotic electron donating group) having Hammett's substituent constant σp of −0.2 or less and having no active proton is used as a resin component. Since the composition prepared by adding to the resin component has good compatibility between the resin component and the cyclic phosphazene compound, high temperature reliability, that is, to produce a resin molded body in which bleeding out and deformation of the cyclic phosphazene compound are unlikely to occur. In addition, the present inventors have found that this resin molding is excellent in flame retardancy and heat resistance.

  The flame retardant resin composition of the present invention includes a resin component and an aryloxy group having a Hammett substituent constant σp of −0.2 or less and an electron donating group having no active proton as a substituent. And a cyclic phosphazene compound.

  The cyclic phosphazene compound used in this composition is represented by the following formula (1).

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

  In formula (2), Y represents a group selected from the group consisting of a phenylene group, a biphenylene group, and a naphthylene group, Q represents a Hammett's substituent constant σp of −0.2 or less, and has an active proton. An electron donating group, which is an allyloxy group, a dialkylamino group, a diarylamino group or a trimethylsilyloxy group.

  This cyclic phosphazene compound usually comprises the following A1 group and A2 group so that at least one of the halogen atoms of the cyclic phosphonitrile dihalide represented by the following formula (3) is substituted by the following A2 group: It is obtained by substituting with a group selected from the group.

In formula (3), n represents an integer of 3 to 8, and X represents a halogen atom.
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.
A2 group: A substituted aryloxy group represented by the following formula (2).

  In formula (2), Y represents a group selected from the group consisting of a phenylene group, a biphenylene group, and a naphthylene group, Q represents a Hammett's substituent constant σp of −2.0 or less, and has an active proton. An electron donating group, which is an allyloxy group, a dialkylamino group, a diarylamino group or a trimethylsilyloxy group.

  In the cyclic phosphazene compound represented by the formula (1), n is usually 3 or 4.

An example of the cyclic phosphazene compound represented by the formula (1) has A as the following A1 group and A2 group.
A1 group: a group selected from the group consisting of a phenoxy group and a methylphenoxy group.
A2 group: a group in which Y in formula (2) is a phenylene group or a naphthylene group.

  Here, the A2 group is, for example, a group selected from the group consisting of 4-allyloxyphenoxy group, 4- (dimethylamino) phenoxy group, 3- (trimethylsilyloxy) phenoxy group and 4- (trimethylsilyloxy) phenoxy group It is.

  Another example of the cyclic phosphazene compound represented by the formula (1) is one in which all of A are selected from the group consisting of a 4-allyloxyphenoxy group and a 4- (dimethylamino) phenoxy group.

  The resin component used in one embodiment of the composition of the present invention is selected from the group consisting of a modified polyphenylene ether resin, an epoxy resin and a polyimide resin.

  The resin molded body of the present invention is composed of the flame retardant resin composition of the present invention. Moreover, the electrical / electronic component of the present invention uses the resin molded body of the present invention.

  Since the flame retardant resin composition of the present invention is a combination of a cyclic phosphazene compound having an aryloxy group having a specific substituent as described above as a flame retardant with respect to the resin component, high temperature reliability is achieved. It is possible to form a resin molded article that is good and also excellent in flame retardancy and heat resistance.

  Since the resin molded body of the present invention is composed of the flame retardant resin composition of the present invention, the high temperature reliability is good, and at the same time, the flame retardancy and heat resistance are excellent.

  Since the electric / electronic component of the present invention uses the resin molded body of the present invention, the high temperature reliability is good and at the same time, the flame retardancy and heat resistance are excellent.

  The flame retardant resin composition of the present invention contains a resin component and a cyclic phosphazene compound. 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, polylactic acid resin, polyphenylene sulfide, polyether ether ketone, polysulfone, polyarylate, polyether ketone, polyether nitrile, polythioether sulfone, poly Examples include ether sulfones and liquid crystal polymers. As the modified polyphenylene ether, for example, a reactive functional group such as a carboxyl group, an anhydrous dicarboxyl group, an epoxy group, an oxetane group, an amino group, a hydroxy group, an acrylic group, or a methacryl group is grafted on part or all of the polyphenylene ether. Those introduced by some method such as reaction or copolymerization are used.

  A thermoplastic resin can be selected according to the utilization purpose of the flame-retardant resin composition of this invention. For example, 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 liquid crystal polymer.

  On the other hand, specific examples of thermosetting resins that can be used here include polyurethane, phenol resin, melamine resin, urea resin, unsaturated polyester resin, diallyl phthalate resin, silicon resin, maleimide resin, maleimide-cyanate resin, Examples thereof include cyanate ester resins, benzoxazine resins, polybenzimidazoles, polycarbodiimides, and epoxy resins. Among these, the epoxy resin is excellent in strength, electrical characteristics, and adhesiveness, and thus is particularly preferably used in a flame retardant resin composition for various uses including electric and electronic parts.

  A thermosetting resin can be selected according to the utilization purpose of the flame-retardant resin composition of this invention. For example, 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, maleimide resin (particularly bismaleimide resin), cyanate ester resin or epoxy resin as the thermosetting resin.

  In the flame retardant resin composition of the present invention, a heat-resistant resin other than the above-described thermoplastic resin and thermosetting resin can also be used as the resin component. When such a heat resistant resin is used, it is possible to realize a resin molded body in which both flame retardancy and heat resistance are improved more reliably.

  As an example of the heat-resistant resin used as the resin component, a polyimide resin can be exemplified. The flame retardant resin composition containing a polyimide resin as a resin component is excellent in heat resistance, but has a degree of freedom to ensure adhesion depending on the design of the resin. It is particularly preferably used as a material for producing a resin molded body.

  As the polyimide resin, in addition to a completely imidized polyimide resin, a polyamic acid which is a polyimide precursor or a partially imidized polyamic acid can be used. Also, a reactive functional group such as a carboxyl group, an anhydrous dicarboxyl group, an epoxy group, an oxetane group, an amino group, a hydroxy group, an acrylic group or a methacryl group is grafted or copolymerized on a part or all of the polyimide resin. A modified polyimide resin introduced by some method can also be used.

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

The cyclic phosphazene compound used in the flame retardant resin composition of the present invention has an electron donating group having no active proton as a substituent on the aryloxy group. In particular, it is preferable to use a cyclic phosphazene compound having a Hammett's substituent constant σp of −0.2 or less and an aryloxy group having a substituent having no active proton. Hammett's substituent constant σp is described, for example, in Non-Patent Documents 1 and 2 below, and if σp is a negative value and −0.2 or less, it becomes a strong electron-donating substituent.

“Some Relations between Reaction Rates Equilibrium Constants”, Hammett, L .; P. , Chemical Reviews, 17: 125-136 (1935) “A survey of Hammett substituent constants and resonance and Field parameters”, Hansch, C .; Leo, A .; Taft, R .; W. , Chemical Reviews, 91: 165-195 (1991).

  Hammett's substituent constant σp is −0.2 or less, but when a cyclic phosphazene compound containing an aryloxy group having a substituent having an active proton is used, the phosphazene compound exhibits reactivity with the resin component. It becomes difficult to obtain a resin molded article excellent in heat resistance and high temperature reliability. Thus, for example, monoalkylamino groups such as methylamino group, ethylamino group and butylamino group, arylamino groups such as anilino group, and hydroxy group, hydroxyamino group, amino group, hydrazide group, ureido group and 1-aziridinyl Although the Hammett substituent constant σp of the group or the like is −0.2 or less, the cyclic phosphazene compound containing an aryloxy group having a substituent having an active proton is excluded from the cyclic phosphazene compound used in the present invention.

  In the flame retardant resin composition of the present invention, one kind of such cyclic phosphazene compounds may be used, or two or more kinds thereof may be used in combination.

  A thing preferable as a cyclic phosphazene compound used by this invention is represented by following formula (1), for example.

  In the formula (1), n represents an integer of 3 to 8, preferably an integer of 3 to 6, and particularly preferably 3 or 4. Accordingly, particularly preferred cyclic phosphazene compounds are aryloxycyclotriphosphazene (trimer) with n = 3 and aryloxycyclotetraphosphazene (tetramer) with n = 4. The cyclic phosphazene compound used in the present invention may be a mixture of two or more different n.

  In the formula (1), A represents a group selected from the group consisting of the following A1 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, t-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, phenyl Phenoxy group, naphthyloxy group, and an anthryl group and phenanthryloxy groups and the like. Of these, a phenoxy group, a methylphenoxy group, a dimethylphenoxy group, a diethylphenoxy group, a 2-propenylphenoxy group, a phenylphenoxy group, and a naphthyloxy group are preferable, and a phenoxy group, a methylphenoxy group, a dimethylphenoxy group, and a naphthyloxy group are further included. Preferable are phenoxy group and methylphenoxy group.

[Group A2]
A substituted aryloxy group represented by the following formula (2).

  In formula (2), Y represents a group selected from the group consisting of a phenylene group, a biphenylene group, and a naphthylene group, Q represents a Hammett's substituent constant σp of −0.2 or less, and has an active proton. No substituents.

  Examples of Q include methoxy group, ethoxy group, n-propoxy group, isopropoxy group, n-butoxy group, allyloxy group and other alkoxy groups, dialkylamino group, diarylamino group, trimethylsilyloxy group, and t-butyl group. Can be mentioned.

  In Y, two or more Q may be substituted. In this case, one or more of Q may be substituted for two or more, and two or more of Q may be substituted for two or more. Further, the substitution position of Q in Y is not limited to the para position. Furthermore, in Y, other substituents may be substituted together with Q. In this case, the other substituent may have a Hammett's substituent constant σp of more than −0.2, but preferably has no active proton.

Preferred as the substituted aryloxy group represented by the formula (2) is one in which Y is a phenylene group or a naphthylene group. Specific examples of such a substituted aryloxy group include 2-methoxyphenoxy group, 3-methoxyphenoxy group, 4-methoxyphenoxy group, 2-ethoxyphenoxy group, 3-ethoxyphenoxy group, 4-ethoxyphenoxy group, 2 -(N-propoxy) phenoxy group, 3- (n-propoxy) phenoxy group, 4- (n-propoxy) phenoxy group, 2- (isopropoxy) phenoxy group, 3- (isopropoxy) phenoxy group, 4- ( Isopropoxy) phenoxy group, 2- (n-butoxy) phenoxy group, 3- (n-butoxy) phenoxy group, 4- (n-butoxy) phenoxy group, 2-allyloxyphenoxy group, 3-allyloxyphenoxy group, 4-allyloxyphenoxy group, 4- (2-methoxyphenyl) phenoxy group, 4- (3-methyl Xylphenyl) phenoxy group, 4- (4-methoxyphenyl) phenoxy group, 4- (2-ethoxyphenyl) phenoxy group, 4- (3-ethoxyphenyl) phenoxy group, 4- (4-ethoxyphenyl) phenoxy group, 4 -[2- (n-propoxy) phenyl] phenoxy group, 4- [3- (n-propoxy) phenyl] phenoxy group, 4- [4- (n-propoxy) phenyl] phenoxy group, 4- (2-iso Propoxyphenyl) phenoxy group, 4- (3-isopropoxyphenyl) phenoxy group, 4- (4-isopropoxyphenyl) phenoxy group, 4- [2- (n-butoxy) phenyl] phenoxy group, 4- [3- (N-butoxy) phenyl] phenoxy group, 4- [4- (n-butoxy) phenyl] phenoxy group, 4- (2-allyloxy) Siphenyl) phenoxy group, 4- (3-allyloxyphenyl) phenoxy group, 4- (4-allyloxyphenyl) phenoxy group, 4-methoxy-1-naphthyloxy group, 5-methoxy-1-naphthyloxy group, 4 -Ethoxy-1-naphthyloxy group, 5-ethoxy-1-naphthyloxy group, 4- (n-propoxy) -1-naphthyloxy group, 5- (n-propoxy) -1-naphthyloxy group, 4-iso Propoxy-1-naphthyloxy group, 5-isopropoxy-1-naphthyloxy group, 4- (n-butoxy) -1-naphthyloxy group, 5- (n-butoxy) -1-naphthyloxy group, 4-allyloxy -1-naphthyloxy group, 5-allyloxy-1-naphthyloxy group, 4-methoxy-2-naphthyloxy group, 6-methoxy-2-naphthyl Ruoxy group, 4-ethoxy-2-naphthyloxy group, 6-ethoxy-2-naphthyloxy group, 4- (n-propoxy) -2-naphthyloxy group, 6- (n-propoxy) -2-naphthyloxy group 4-isopropoxy-2-naphthyloxy group, 6-isopropoxy-2-naphthyloxy group, 4- (n-butoxy) -2-naphthyloxy group, 6- (n-butoxy) -2-naphthyloxy group , Alkoxy group-substituted aryloxy groups such as 4-allyloxy-2-naphthyloxy group and 6-allyloxy-2-naphthyloxy group, 2- (dimethylamino) phenoxy group, 3- (dimethylamino) phenoxy group, 4- ( Dimethylamino) phenoxy group, 4- [2- (dimethylamino) phenyl] phenoxy group, 4- [3- (dimethylamino) phenyl] Enoxy group, 4- [4- (dimethylamino) phenyl] phenoxy group, 4- (dimethylamino) -1-naphthyloxy group, 5- (dimethylamino) -1-naphthyloxy group, 4- (dimethylamino)- Dimethylamino group-substituted arylloxy groups such as 2-naphthyloxy group and 6- (dimethylamino) -2-naphthyloxy group, 2- (diphenylamino) phenoxy group, 3- (diphenylamino) phenoxy group, 4- ( Diphenylamino) phenoxy group, 4- [2- (diphenylamino) phenyl] phenoxy group, 4- [3- (diphenylamino) phenyl] phenoxy group, 4- [4- (diphenylamino) phenyl] phenoxy group, 4- (Diphenylamino) -1-naphthyloxy group, 5- (diphenylamino) -1-naphthyloxy group Diphenylamino group-substituted aryloxy groups such as 4- (diphenylamino) -2-naphthyloxy group and 6- (diphenylamino) -2-naphthyloxy group, 2- (trimethylsilyloxy) phenoxy group, 3- (trimethylsilyloxy) Phenoxy group, 4- (trimethylsilyloxy) phenoxy group, 4- [2- (trimethylsilyloxy) phenyl] phenoxy group, 4- [3- (trimethylsilyloxy) phenyl] phenoxy group, 4- [4- (trimethylsilyloxy) phenyl ] Phenoxy group, 4- (trimethylsilyloxy) -1-naphthyloxy group, 5- (trimethylsilyloxy) -1-naphthyloxy group, 4- (trimethylsilyloxy) -2-naphthyloxy group and 6- (trimethylsilyloxy)- 2-Naphtilo Trioxysilyloxy group-substituted aryloxy groups such as xy group, 2- (t-butyl) phenoxy group, 3- (t-butyl) phenoxy group, 4- (t-butyl) phenoxy group, 4- [2- ( t-butyl) phenyl] phenoxy group, 4- [3- (t-butyl) phenyl] phenoxy group, 4- [4- (t-butyl) phenyl] phenoxy group, 4- (t-butyl) -1-naphthyl T-butyl groups such as oxy group, 5- (t-butyl) -1-naphthyloxy group, 4- (t-butyl) -2-naphthyloxy group and 6- (t-butyl) -2-naphthyloxy group Examples include substituted aryloxy groups.

Among these specific examples, those in which Y is a phenylene group are more preferable, and 3-methoxyphenoxy group, 4-methoxyphenoxy group, 3-ethoxyphenoxy group, 4-ethoxyphenoxy group, 3- (n- Propoxy) phenoxy group, 4- (n-propoxy) phenoxy group, 3- (isopropoxy) phenoxy group, 4- (isopropoxy) phenoxy group, 3- (n-butoxy) phenoxy group, 4- (n-butoxy) Phenoxy group, 3-allyloxyphenoxy group, 4-allyloxyphenoxy group, 4- (4-methoxyphenyl) phenoxy group, 4- (4-ethoxyphenyl) phenoxy group, 4- [4- (n-propoxy) phenyl ] Phenoxy group, 4- [4-isopropoxyphenyl] phenoxy group, 4- [4- (n-butoxy) phenyl] Alkoxy group-substituted phenyloxy groups such as phenoxy group and 4- (4-allyloxyphenyl) phenoxy group, 3- (dimethylamino) phenoxy group, 4- (dimethylamino) phenoxy group and 4- [4- (dimethylamino) Dimethylamino group-substituted phenyloxy groups such as phenyl] phenoxy group, trimethylsilyloxy groups such as 3- (trimethylsilyloxy) phenoxy group, 4- (trimethylsilyloxy) phenoxy group and 4- [4- (trimethylsilyloxy) phenyl] phenoxy group Substituted phenyloxy group or t-butyl group-substituted phenyloxy such as 3- (t-butyl) phenoxy group, 4- (t-butyl) phenoxy group and 4- [4- (t-butyl) phenyl] phenoxy group Groups and the like are more preferable.

  In particular, 3-methoxyphenoxy group, 4-methoxyphenoxy group, 3-ethoxyphenoxy group, 4-ethoxyphenoxy group, 3- (n-propoxy) phenoxy group, 4- (n-propoxy) phenoxy group, 4-allyloxy Phenoxy group, 4- (dimethylamino) phenoxy group, 3- (trimethylsilyloxy) phenoxy group, 4- (trimethylsilyloxy) phenoxy group, 3- (t-butyl) phenoxy group and 4- (t-butyl) phenoxy group preferable.

  In the formula (1), 2n of A are included, and at least one of them is an A2 group. Therefore, the cyclic phosphazene compounds represented by the formula (1) can be roughly classified into the following forms.

[Form 1]
All 2n A's are A2 groups. In this case, all of A may be the same A2 group or two or more A2 groups. For example, an aryloxycyclotriphosphazene compound in which n is 3 in formula (1), an aryloxycyclotetraphosphazene compound in which n is 4 in formula (1), an aryloxycyclopentapentane in which n is 5 in formula (1) A phosphazene compound and an aryloxycyclohexaphosphazene compound wherein n in formula (1) is 6, wherein all of A is one kind of A2 group, all of A is two or more kinds of A2 groups, and Mention may be made of any mixture of these.

  The A2 group in the cyclic phosphazene compound of this form is usually 3-methoxyphenoxy group, 4-methoxyphenoxy group, 3-ethoxyphenoxy group, 4-ethoxyphenoxy group, 3- (n-propoxy) phenoxy group, 4- ( n-propoxy) phenoxy group, 4-allyloxyphenoxy group, 4- (4-methoxyphenyl) phenoxy group, 4- (dimethylamino) phenoxy group, 4- [4- (dimethylamino) phenyl] phenoxy group, 3- Those selected from the group consisting of (trimethylsilyloxy) phenoxy group, 4- (trimethylsilyloxy) phenoxy group, 3- (t-butyl) phenoxy group and 4- (t-butyl) phenoxy group are preferred, and 3-methoxyphenoxy Group, 3-ethoxyphenoxy group, 3- (n-propoxy) phenoxy group Group, 4-methoxyphenoxy group, 4-ethoxyphenoxy group, 4- (n-propoxy) phenoxy group, 4-allyloxyphenoxy group, 4- (dimethylamino) phenoxy group, 3- (t-butyl) phenoxy group and Those selected from the group consisting of 4- (t-butyl) phenoxy groups are particularly preferred.

[Form 2]
A part (ie, at least one) of 2n A's is an A2 group, and the other A is an A1 group. Here, when two or more of A are A2 groups, each A2 group may be the same or two or more different ones. In addition, A other than the A2 group may all be the same A1 group, or two or more A1 groups.

  The preferred cyclic phosphazene compounds of this form are those in which 2 to (2n-2) of 2n A are A2 groups. In particular, an aryloxycyclotriphosphazene compound in which n in formula (1) is 3; an aryloxycyclotetraphosphazene compound in which n is 4 in formula (1); an aryloxycyclopentaene in which n is 5 in formula (1) A phosphazene compound and an aryloxycyclohexaphosphazene compound in which n in formula (1) is 6, wherein 2 out of 2n A to (2n-2) are A2 groups, and any mixture thereof It is. Such a cyclic phosphazene compound is advantageous in that a resin composition superior in moldability can be realized as compared with other cyclic phosphazene compounds.

  In addition, it can be confirmed by TOF-MS analysis of a cyclic phosphazene compound or an intermediate in the production process thereof, whether 2 to (2n-2) of 2n A are A2 groups.

Specific examples of the cyclic phosphazene compound having such a form include an aryloxycyclotriphosphazene compound in which n in the formula (1) is 3, an aryloxycyclotetraphosphazene compound in which n in the formula (1) is 4, 1) an aryloxycyclopentaphosphazene compound in which n is 5 or an aryloxycyclohexaphosphazene compound in which n is 6 in formula (1), wherein A is an A2 group 3-methoxyphenoxy group and an A1 group A combination of a 3-methoxyphenoxy group as an A2 group and a methylphenoxy group as an A1 group, a 4-methoxyphenoxy group as an A2 group, and a phenoxy group as an A1 group Combination of 4-methoxyphenoxy group which is A2 group and methylphenoxy group which is A1 group A combination of 3-ethoxyphenoxy group which is A2 group and a phenoxy group which is A1 group, a combination of 3-ethoxyphenoxy group which is A2 group and methylphenoxy group which is A1 group, A2 group 4-ethoxyphenoxy group and A1 group phenoxy group, A2 group 4-ethoxyphenoxy group and A1 group methylphenoxy group, A2 group 3- ( n-propoxy) a combination of phenoxy group and A1 group phenoxy group, a combination of A2 group 3- (n-propoxy) phenoxy group and A1 group methylphenoxy group, A2 group Combination of 4- (n-propoxy) phenoxy group and phenoxy group which is A1 group, 4- (n-propoxy) phenoxy group which is A2 group and In combination with a methylphenoxy group that is one group, in a combination of a 4-allyloxyphenoxy group that is an A2 group and a phenoxy group that is an A1 group, a 4-allyloxyphenoxy group that is an A2 group and an A1 group A combination with a certain methylphenoxy group, a combination of 4- (4-methoxyphenyl) phenoxy group which is an A2 group and a phenoxy group which is an A1 group, 4- (4-methoxyphenyl) phenoxy which is an A2 group A combination of a group and a methylphenoxy group which is an A1 group, a combination of a 4- (dimethylamino) phenoxy group which is an A2 group and a phenoxy group which is an A1 group, a 4- (dimethylamino) which is an A2 group Combination of phenoxy group and methylphenoxy group which is A1 group, 4- [4- (dimethylamino) phenyl] phenoxy group which is A2 group In combination with a phenoxy group which is an A1 group, a combination of 4- [4- (dimethylamino) phenyl] phenoxy group which is an A2 group and a methylphenoxy group which is an A1 group, 3- Combination of (trimethylsilyloxy) phenoxy group and phenoxy group which is A1 group, combination of 3- (trimethylsilyloxy) phenoxy group which is A2 group and methylphenoxy group which is A1 group, 4 which is A2 group -A combination of (trimethylsilyloxy) phenoxy group and A1 group phenoxy group, a combination of A2 group 4- (trimethylsilyloxy) phenoxy group and A1 group methylphenoxy group, A2 group Combination of 3- (t-butyl) phenoxy group and A1 group phenoxy group, 3- (t Butyl) phenoxy group and A1 group methylphenoxy group, A2 group 4- (t-butyl) phenoxy group and A1 group phenoxy group combination, and A2 group 4- Examples include a combination of a (t-butyl) phenoxy group and a combination of a methylphenoxy group which is an A1 group.

  Among them, an aryloxycyclotriphosphazene compound in which n is 3 in formula (1), an aryloxycyclotetraphosphazene compound in which n is 4 in formula (1), and an aryloxycyclophosphine compound in which n is 5 in formula (1) A pentaphosphazene compound, an aryloxycyclohexaphosphazene compound wherein n in formula (1) is 6, wherein A is a combination of a 3-methoxyphenoxy group which is an A2 group and a phenoxy group which is an A1 group, A2 A combination of a 3-methoxyphenoxy group which is a group and a methylphenoxy group which is an A1 group, a combination of a 4-methoxyphenoxy group which is an A2 group and a phenoxy group which is an A1 group, a 4-group which is an A2 group Combination of methoxyphenoxy group and methylphenoxy group which is A1 group, 3-ethoxyphenoxy group which is A2 group and A A combination of a phenoxy group as a group, a combination of a 3-ethoxyphenoxy group as an A2 group and a methylphenoxy group as an A1 group, a 4-ethoxyphenoxy group as an A2 group and a phenoxy group as an A1 group A combination of 4-ethoxyphenoxy group which is A2 group and methylphenoxy group which is A1 group, 3- (n-propoxy) phenoxy group which is A2 group and phenoxy group which is A1 group A combination of 3- (n-propoxy) phenoxy group which is A2 group and methylphenoxy group which is A1 group, 4- (n-propoxy) phenoxy group which is A2 group and A1 group A combination with a phenoxy group, a combination of a 4- (n-propoxy) phenoxy group which is an A2 group and a methylphenoxy group which is an A1 group, A A combination of a 4-allyloxyphenoxy group that is a group and a phenoxy group that is an A1 group, a combination of a 4-allyloxyphenoxy group that is an A2 group and a methylphenoxy group that is an A1 group, and an A2 group Combination of 4- (dimethylamino) phenoxy group and A1 group phenoxy group, combination of A2 group 4- (dimethylamino) phenoxy group and A1 group methylphenoxy group, A2 group A combination of a 4- (trimethylsilyloxy) phenoxy group and a phenoxy group that is an A1 group, a combination of a 4- (trimethylsilyloxy) phenoxy group that is an A2 group and a methylphenoxy group that is an A1 group, an A2 group 4- (t-butyl) phenoxy group and A1 group phenoxy group, A2 group 4- (t- Preferred are combinations of (butyl) phenoxy groups with methylphenoxy groups which are A1 groups, as well as any mixtures thereof.

Of these, more preferred are an A2 group in which Y is a phenylene group and Q is selected from the group consisting of an alkoxy group, a dialkylamino group, a trimethylsilyloxy group, and a t-butyl group, and a phenoxy group. In combination with one of the groups and one of the methylphenoxy groups. Particularly, an aryloxycyclotriphosphazene compound in which n in formula (1) is 3 or an aryloxycyclotetraphosphazene compound in which n is 4 in formula (1), wherein A is an A2 group, 3-methoxyphenoxy A combination of a phenoxy group as an A1 group, a combination of a 4-methoxyphenoxy group as an A2 group and a phenoxy group as an A1 group, a 3-ethoxyphenoxy group and an A1 group as an A2 group Combination of phenoxy group, combination of 4-ethoxyphenoxy group which is A2 group and phenoxy group which is A1 group, 3- (n-propoxy) phenoxy group which is A2 group and phenoxy group which is A1 group A combination of 4- (n-propoxy) phenoxy group which is an A2 group and a phenoxy group which is an A1 group, an A2 group A combination of a certain 4-allyloxyphenoxy group and a phenoxy group that is an A1 group, a combination of a 4- (dimethylamino) phenoxy group that is an A2 group and a phenoxy group that is an A1 group, or a group that is an A2 group A combination of a-(trimethylsilyloxy) phenoxy group and a phenoxy group which is an A1 group;
Preference is given to combinations of 4- (t-butyl) phenoxy groups which are A2 groups with phenoxy groups which are A1 groups and any mixtures thereof.

  The above-mentioned cyclic phosphazene compound used in the present invention is usually made from a cyclic phosphonitrile dihalide represented by the following formula (3), and at least one of its halogen atoms is substituted by the above-mentioned A2 group. It can be obtained by substitution with a group selected from the group consisting of the aforementioned A1 group and A2 group.

  Here, as a method for substituting the halogen atom of the cyclic phosphonitrile dihalide with the A1 group and the A2 group, for example, the methods described in the following Non-Patent Documents 3 and 4 can be referred to.

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

  The flame retardant resin composition of the present invention can be prepared by uniformly mixing the above resin component and the cyclic phosphazene compound. Since the above-mentioned cyclic phosphazene compound used here has good compatibility with the resin component, it can be uniformly mixed with the resin component.

  The amount of the cyclic phosphazene compound used in the flame-retardant resin composition of the present invention can be appropriately set according to various conditions such as the type of resin component and the use of the composition of the present invention, but usually in terms of solid content The amount is preferably set to 0.1 to 200 parts, more preferably 0.5 to 100 parts, and still more preferably 1 to 50 parts with respect to 100 parts of the resin component. When the usage-amount of a cyclic phosphazene compound is less than 0.1 part, it may become difficult to obtain the resin molding which shows sufficient flame retardance. Conversely, when the amount of the cyclic phosphazene compound used exceeds 200 parts, the original properties of the resin component are impaired, and it may be difficult to obtain a resin molded product exhibiting the properties due to the resin component.

  The flame-retardant resin composition of the present invention is a range in which the intended physical properties are not impaired in accordance with the use and the type of the resin component in addition to the above-described essential components, that is, the above-described resin component and cyclic phosphazene compound. Various fillers and additives can be blended.

Usable fillers and additives are not particularly limited as long as they are commonly used in the technical field of resin compositions, and are various known ones. Specific examples of the filler include clay, clay, kaolin, bentonite, alumina silicate such as feldspar and mica, magnesium silicate such as talc and talc, calcium silicate (wollastonite), and silicate such as pumice powder. , Natural silica, calcined silica, synthetic silica, amorphous silica, white carbon,
Silica or silicic acid such as aerosil, silica sand, quartz powder and diatomaceous earth, metal oxides such as alumina, titanium oxide, magnesium oxide, molybdenum oxide and zinc oxide, carbonic acid such as calcium carbonate, barium carbonate and magnesium carbonate Salts, sulfates such as barium sulfate and magnesium sulfate, titanates such as potassium titanate and barium titanate, hydroxides such as calcium hydroxide, aluminum hydroxide and magnesium hydroxide, carbons such as carbon black and graphite Zinc compounds such as zinc borate and zinc molybdate, inorganic or organic balloons such as glass balloons, shirasu balloons and phenol balloons, glasses such as glass fibers, glass cloth and glass fine powder, and alumina silica fibers, alumina fibers, Aramid fiber , Mention may be made of alumina fibers, boron fibers, carbon fibers, polyvinyl alcohol fibers, polyester fibers, polytetrafluoroethylene fibers, liquid crystal fibers and PBO (polyparaphenylene benzobisoxazole) fibers such as fibers. Two or more of these fillers may be used in combination.

  Specific examples of additives include ultraviolet absorbers such as hindered amines, benzotriazoles and benzophenones, antioxidants such as hindered phenols, phosphorus, sulfur and hydrazides, phosphate esters, condensed phosphorus Phosphate such as acid ester, phosphoric acid amide, phosphoric acid amide ester, ammonium phosphate, aluminum phosphinate and red phosphorus, nitrogenous materials such as melamine, melamine cyanurate, melam, melem, melon and succinoguanamine, silicone based materials, Various flame retardants such as bromine and chlorinated paraffin, flame retardant aids such as antimony trioxide, coupling agents such as silane and titanium, dyes, pigments, colorants, leveling agents, rheology control agents, pigment dispersants , Polymerization inhibitor, repellency inhibitor, antifoaming agent, mold release agent and charging Mention may be made of the stopping agents, and the like.

  The flame-retardant resin composition of the present invention is a material for producing various resin molded articles, for example, paints such as powder paints, electrodeposition paints and PCM (pre-coated metal) paints, adhesives, sealing materials, It can be used as a material for manufacturing molding materials, composite materials, laminates, sealing materials, and the like. And various resin moldings made of such a material using the flame retardant resin composition of the present invention, for example, a coating film or a molded product, include a resin component and a cyclic phosphazene compound in the flame retardant resin composition. Excellent compatibility and resistance to bleed-out of cyclic phosphazene compounds, not only excellent high-temperature reliability, but also excellent flame retardancy and high glass transition temperature, which also excels in heat resistance It becomes a thing.

  For this reason, the flame-retardant resin composition of the present invention is used for various manufacturing materials for various electrical parts and electronic parts, such as semiconductor sealing materials, circuit boards (particularly for metal-clad laminates and printed wiring boards). Substrate) material, adhesive for printed wiring board, adhesive sheet for printed wiring board, insulating circuit protective film for printed wiring board, conductive paste for printed wiring board, sealing for multilayer printed wiring board It is particularly preferably used as a stopper, an interlayer insulating material for a multilayer substrate, an insulating adhesive material, a circuit protective agent, a coverlay film, a cover ink, and the like. And the electrical / electronic component using the resin molding formed using such various production materials has excellent high-temperature reliability and at the same time, excellent flame retardancy and heat resistance.

EXAMPLES The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited by these. Of the following examples, examples other than Examples 5, 6, 8, 13, 14, 16, 21, 22, 22, 24, 29, 30 and 32 are experimental examples.
In the following, “unit” in “unit mol” means the smallest structural unit of a cyclic phosphazene compound, for example, (PNA ₂ ) for general formula (1) and (PNX ₂ ) for general formula (3). means. In the general formula (3), when X is chlorine, its 1 unit mol is 115.87 g. In the following, unless otherwise specified, “%” and “parts” mean “% by weight” and “parts by weight”, respectively.

The phosphazene compounds obtained in the synthesis examples and reference examples were prepared by measuring ¹ H-NMR spectrum and ³¹ P-NMR spectrum, analyzing chlorine element (residual chlorine) by potentiometric titration using silver nitrate after alkali melting, and TOF. -Identified based on the results of MS analysis.

Synthesis Example 1 (Production of cyclic phosphazene compound according to Form 2)
Oily sodium hydride (151 g, 6.3 mol) from which oil was completely removed by washing with heptane was charged into a 5 liter flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube. To this was added a solution of hexachlorocyclotriphosphazene (348 g, 3.0 unit mol) in tetrahydrofuran (700 mL) and cooled to 0 ° C., and then 3-methoxyphenol (247 g, 2.0 mol) and p-cresol (454 g, 4. 2 mol) in tetrahydrofuran (700 mL) was added dropwise over 1 hour and stirred at reflux for 5 hours. Toluene (500 mL) and water (700 mL) were added to the reaction solution, and the mixture was separated. The organic layer was washed twice with a saturated aqueous sodium chloride solution, dehydrated and dried over anhydrous magnesium sulfate, and the solvent was distilled off. 788 g (yield: 97%) of a viscous product was obtained. The analysis result of this product was as follows.

¹ H-NMR spectrum (300 MHz, CDCl ₃ , δ, ppm):
2.1 (12H, s), 3.7 (6H, s), 6.6-7.3 (24H)
◎ ³¹ P-NMR spectrum (120 MHz, CDCl ₃ , δ, ppm):
9.4-10.1
◎ MS (LDI-TOF) m / z:
825, 810, 793
◎ Residual chlorine analysis:
<0.01%

From the above analysis results, product obtained in this _{step, [N 3 P 3 (OC} 6 H 4 OMe) (OC 6 H 4 Me) 5], [N 3 P 3 (OC 6 H 4 OMe) ₂ (OC ₆ H ₄ Me) ₄ ] and [N ₃ P ₃ (OC ₆ H ₄ OMe) ₃ (OC ₆ H ₄ Me) ₃ ], the average composition of which is [N ₃ P ₃ (OC ₆ H ₄ OMe) _2.0 (OC ₆ H ₄ Me) _4.0 ] was confirmed to be a mixture of cyclic phosphazene compounds.

Synthesis Example 2 (Production of cyclic phosphazene compound according to Form 1)
48% aqueous NaOH (550 g, 6.6 mol), toluene (1,000 mL) and 4-methoxy in a 5 liter flask equipped with stirrer, thermometer, reflux condenser, water separator and nitrogen inlet. Phenol (681 g, 6.3 mol) was charged. This was stirred and heated under a nitrogen atmosphere, water in the flask was removed by azeotropic dehydration to prepare sodium 4-methoxyphenoxide, and then this slurry solution was cooled to 40 ° C.

To this slurry solution was added hexachlorocyclotriphosphazene (348 g, 3.0 units).
mol) and refluxed for 6 hours. After completion of the reaction, the reaction solution was washed 4 times with 5% NaOH aqueous solution. This was neutralized with 2% nitric acid and separated, and the organic layer was dehydrated and dried over anhydrous magnesium sulfate, and then the solvent was distilled off to obtain 857 g (yield: 98%) of a white solid product. It was. The analysis result of this product was as follows.

¹ H-NMR (300 MHz, CDCl ₃ , δ, ppm):
3.7 (18H, s), 6.6 (12H, d), 6.7 (12H, d)
◎ ³¹ P-NMR (120 MHz, CDCl ₃ , δ, ppm):
9.9
◎ MS (LDI-TOF) m / z:
874
◎ Residual chlorine analysis:
<0.01%

From the above analysis results, it was confirmed that the product obtained in this step was a cyclic phosphazene compound having a structure of [N ₃ P ₃ (OC ₆ H ₄ OMe) ₆ ].

Synthesis Example 3 (Production of cyclic phosphazene compound according to Form 1)
By using a chlorocyclophosphazene oligomer mixture (348 g, 3.0 unit mol) represented by the molecular formula [PNCl ₂ ] _n instead of hexachlorocyclotriphosphazene, where n is 3 to 8, the same operation as in Synthesis Example 2 is performed. 840 g (yield: 96%) of a white solid product was obtained. The analysis result of this product was as follows.

¹ H-NMR (300 MHz, CDCl ₃ , δ, ppm):
3.7 (6H, m), 6.6-6.7 (8H, m)
◎ ³¹ P-NMR (120 MHz, CDCl _3, δ, ppm):
-17.3 (hexamer), -16.9 (pentamer), -11.2 (tetramer), 9.9 (trimer)
◎ MS (LDI-TOF) m / z:
1748, 1456, 1165, 874
◎ Residual chlorine analysis:
<0.01%

From the above analysis results, it was confirmed that the product obtained in this step was a mixture of cyclic phosphazene compounds having a composition of [NP (OC ₆ H ₄ OMe) ₂ ] _n , where n is 3 to 8. .

Synthesis Example 4 (Production of cyclic phosphazene compound according to Form 2)
By using a mixture of 4-methoxyphenol (248 g, 2.0 mol) and phenol (395 g, 4.2 mol) instead of 4-methoxyphenol (681 g, 6.3 mol), the same operation as in Synthesis Example 2 was performed. 737 g (yield: 98%) of a slightly yellow viscous product was obtained. The analysis result of this product was as follows.

¹ H-NMR (300 MHz, CDCl ₃ , δ, ppm):
3.7 (6H, m), 6.6-7.0 (28H, m)
◎ ³¹ P-NMR (120 MHz, CDCl _3, δ, ppm):
9.3-10.0
◎ MS (LDI-TOF) m / z:
784,754,724
◎ Residual chlorine analysis:
<0.01%

From the above analysis results, the products obtained in this step are [N ₃ P ₃ (OC ₆ H ₄ OMe) (OPh) ₅ ], [N ₃ P ₃ (OC ₆ H ₄ OMe) ₂ (OPh) ₄ ] and [N ₃ P ₃ (OC ₆ H ₄ OMe) ₃ (OPh) ₃ ], the average composition of which is [N ₃ P ₃ (OC ₆ H ₄ OMe) _2.0 (OPh) _{4. 0} ] was confirmed to be a mixture of cyclic phosphazene compounds.

Synthesis Example 5 (Production of cyclic phosphazene compound according to Form 1)
In a 7 liter flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube, a mixture of chlorocyclophosphazene oligomers having a molecular formula of [PNCl ₂ ] _n and n of 3 to 8 (348 g, 3.0 units) mol), potassium carbonate (912 g, 6.6 mol) and acetonitrile (1,600 mL) were charged. And while stirring this, a solution of 4-allyloxyphenol (946 g, 6.3 mol) in acetonitrile (1,300 mL) was added dropwise over 1 hour and stirred at reflux for 8 hours. Toluene (1,000 mL) and water (1,000 mL) were added to the reaction solution for liquid separation, and the organic layer was washed twice with saturated brine, dehydrated and dried over anhydrous magnesium sulfate, and then the solvent was distilled off. 950 g (yield: 92%) of a slightly yellow solid product was obtained. The analysis result of this product was as follows.

¹ H-NMR (300 MHz, CDCl ₃ , δ, ppm):
4.5 (4H, d), 5.3-5.4 (4H, m), 6.0 (2H, m), 6.6-7.1 (8H)
◎ ³¹ P-NMR (120 MHz, CDCl _3, δ, ppm):
-17.2 (hexamer), -16.8 (pentamer), -11.2 (tetramer), 9.8 (trimer)
◎ MS (LDI-TOF) m / z:
1716, 1373, 1030
◎ Residual chlorine analysis:
<0.01%

From the above analysis results, the product obtained in this step is a mixture of cyclic phosphazene compounds having a composition of [NP (OC ₆ H ₄ OCH ₂ CH═CH ₂ ) ₂ ] _n , where n is 3 to 8. I confirmed that there was.

Synthesis Example 6 (Production of cyclic phosphazene compound according to Form 1)
In a 5 liter flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube, a thin slice of sodium metal (145 g, 6.3 mol) and tetrahydrofuran (500 mL) were charged. To this was added dropwise a solution of 4- (dimethylamino) phenol (864 g, 6.3 mol) in tetrahydrofuran (1,000 mL) at 30 ° C. over 1 hour, stirred for 2 hours, and then octachlorocyclotetraphosphazene (348 g, 3 (0.0 unit mol) in tetrahydrofuran (700 mL) was further added dropwise over 1 hour, and stirring was continued for 4 hours. Methanol (50 mL) was added to the reaction mixture, and the mixture was stirred for 1 hour. Toluene (500 mL) and water (1,000 mL) were added for liquid separation, and the organic layer was washed twice with saturated brine and washed with anhydrous magnesium sulfate. When the solvent was distilled off after dehydration and drying, 886 g (yield: 93%) of a slightly yellow viscous product was obtained. The analysis result of this product was as follows.

¹ H-NMR (300 MHz, CDCl ₃ , δ, ppm):
2.8 (48H, s), 6.5-6.6 (32H, m)
◎ ³¹ P-NMR (120 MHz, CDCl ₃ , δ, ppm):
-11.4
◎ MS (LDI-TOF) m / z
1270
◎ Residual chlorine analysis <0.01%

From the above analysis results, it was confirmed that the product obtained in this step was a cyclic phosphazene compound having a structure of [N ₄ P ₄ (OC ₆ H ₄ NMe ₂ ) ₈ ].

Synthesis Example 7 (Production of cyclic phosphazene compound according to Form 1)
In a 5 liter flask equipped with a stirrer, thermometer, reflux condenser, water separator and nitrogen inlet tube, 48% KOH aqueous solution (772 g, 6.6 mol), chlorobenzene (1,200 mL) and 4- ( t-Butyl) phenol (1,008 g, 7.2 mol) was charged. This was stirred and heated under a nitrogen atmosphere, water in the flask was removed by azeotropic dehydration to prepare potassium 4- (t-butyl) phenoxide, and then the slurry solution was cooled to 40 ° C.

To the resulting slurry solution was added a chlorocyclophosphazene oligomer mixture (348 g, 3.0 unit mol) represented by molecular formula [PNCl ₂ ] _n , where n is 3 to 8, and refluxed for 18 hours. After completion of the reaction, the reaction mixture was concentrated to 1,800 mL, chloroform (1,000 mL) was added, and the mixture was washed 4 times with 5% NaOH aqueous solution. This was neutralized with 2% nitric acid and separated, and the organic layer was dehydrated and dried over anhydrous magnesium sulfate, and then the solvent was distilled off to obtain 972 g (yield: 94%) of a white solid product. It was. The analysis result of this product was as follows.

¹ H-NMR (300 MHz, CDCl ₃ , δ, ppm):
1.2-1.3 (18H, m), 6.8-7.3 (8H)
◎ ³¹ P-NMR (120 MHz, CDCl ₃ , δ, ppm):
-17.2 (hexamer), -16.8 (pentamer), -11.0 (tetramer), 10.1 (trimer)
◎ MS (LDI-TOF) m / z:
1032, 1374, 1718, 2061
◎ Residual chlorine analysis:
<0.01%

From the above analysis results, it was confirmed that the product obtained in this step was a mixture of cyclic phosphazene compounds having the composition [NP (OC ₆ H ₄ -t-Bu) ₂ ] _n .

Synthesis Example 8 (Production of cyclic phosphazene compound according to form 2)
Hexachlorocyclotriphosphazene (348 g, 3.0 unit mol), 4- (trimethylsilyloxy) phenol (365 g, 2.0 mol) in a 5 liter flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube. Phenol (395 g, 4.2 mol) and tetrahydrofuran (1,000 mL) were charged. Then, a solution of potassium t-butoxide (707 g, 6.3 mol) in tetrahydrofuran (1,000 mL) was added dropwise over 2 hours while stirring at 0 ° C., and the mixture was stirred at 40 ° C. for 2 hours. The reaction solution was washed twice with water and saturated brine, dehydrated and dried over anhydrous magnesium sulfate, and then the solvent was distilled off to obtain 784 g (yield: 90%) of a slightly yellow viscous product. The analysis result of this product was as follows.

¹ H-NMR (300 MHz, CDCl ₃ , δ, ppm):
0.1 (18H, m), 6.5-7.2 (28H, m)
◎ ³¹ P-NMR (120 MHz, CDCl ₃ , δ, ppm):
10.3
◎ MS (LDI-TOF) m / z:
958, 869, 781
◎ Residual chlorine analysis:
<0.01%

From the above analysis results, the products obtained in this step are [N ₃ P ₃ (OC ₆ H ₄ OSiMe ₃ ) (OPh) ₅ ], [N ₃ P ₃ (OC ₆ H ₄ OSiMe ₃ ) ₂ ( OPh) ₄ ] and [N ₃ P ₃ (OC ₆ H ₄ OSiMe ₃ ) ₃ (OPh) ₃ ], the average composition of which is [N ₃ P ₃ (OC ₆ H ₄ OSiMe ₃ ) _2.0 ( OPh) _4.0 ] was confirmed to be a mixture of cyclic phosphazene compounds.

Reference Example 1 (Production of cyclic phosphazene compound)
PHOSPHORUS-NITROGEN COMPOUNDS, H.P. R. According to the method described in ALLCOCK, 1972, 151, ACADEMIC PRESS (Non-Patent Document 3 mentioned above), hexachlorocyclotriphosphazene (348 g, 3.0 unit mol) from [N ₃ P ₃ (OPh ₆ ] A white solid cyclic phosphazene compound represented by the chemical formula of ₆ ] was produced.

Reference Example 2 (Production of cyclic phosphazene compound)
[N ₃ P ₃ (OPh) ₆ ] and a cyclophosphazene mixture (348 g, 3.0 unit mol) composed of 81% hexachlorocyclotriphosphazene and 19% octachlorocyclotetraphosphazene were used in the same manner as in Reference Example 1. A mixture of white solid cyclic phosphazene compounds each represented by the chemical formula of [N ₄ P ₄ (OPh) ₈ ] was obtained.

Reference Example 3 (Production of cyclic phosphazene compound)
The chemical formula of [N ₃ P ₃ (OC ₆ H ₄ CH ₃ ) ₆ ] is the same as in Synthesis Example 2 except that p-cresol (681 g, 6.3 mol) is used instead of 4-methoxyphenol. As a result, a white solid cyclic phosphazene compound was obtained.

Examples 1-8 and Comparative Examples 1-3
Table 1 shows the cyclic phosphazene compounds obtained in Synthesis Examples 1 to 8 or the cyclic phosphazene compounds obtained in Reference Examples 1 to 3 for 100 parts of polycarbonate resin (trade name “Iupilon S3000” manufactured by Mitsubishi Gas Chemical Co., Ltd.). A resin composition was prepared by adding at the indicated ratio and melt-kneading at 200 to 240 ° C. for 5 minutes. The obtained resin composition was heated and pressed at 190 to 200 ° C. for 10 minutes using a press molding machine to obtain a sheet having a thickness of 1.6 mm. About this sheet | seat (test piece), the UL-94 flame retardance test (vertical combustion test) was implemented, and the thermal deformation temperature (heat resistance) and blooming property (high temperature reliability) were investigated. The evaluation method for each item is as follows. The results are shown in Table 1.

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

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

V-1: All the following conditions are satisfied.
(A) A total of 2 flame extinguishing times after 10 times of flame contact, 2 times each for 5 test pieces
Within 50 seconds.
(B) Flame test was performed twice for each of five test pieces, and the flame extinguishing time after each flame contact was within 30 seconds.
(C) There is no ignition of the absorbent cotton under 300 mm due to the drop in all the test pieces.
(D) For all specimens, the glowing after the second flame contact is within 60 seconds.
(E) All specimens are not framing to the clamp.

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

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

(Blooming properties)
The test piece was heated at 150 ° C. for 6 hours, and the oozing state (leaching state from the inside of the test piece) on the surface of the test piece was visually observed. The criteria for evaluation are as follows.
A: No oozing is observed.
◯: Almost no seepage is seen.
Δ: Some exudation is observed.
X: Significant exudation is observed.

  As is clear from Table 1, the sheets (resin molded bodies) made of the resin compositions of Examples 1 to 8 are superior in flame retardancy and have a high heat distortion temperature compared to those of Comparative Examples 1 to 3. Therefore, it is excellent in heat resistance, and further, blooming is not substantially observed, so that high temperature reliability (bleed out resistance) is also excellent.

Examples 9-16 and Comparative Examples 4-6
651 parts of bisphenol A type epoxy resin (trade name “Epicoat 1001” of Japan Epoxy Resin Co., Ltd .: epoxy equivalent 456 g / eq., Resin solid content 70%), cresol novolac epoxy resin (trade name “YDCN” of Toto Kasei Co., Ltd.) -704P ": 300 parts of epoxy equivalent 210 g / eq., Resin solid content 70%), novolac type phenol resin (trade name" BRG-558 "of Showa Polymer Co., Ltd .: hydroxyl value 106 g / eq., Resin solid content 70 %) The cyclic phosphazene compound obtained in Synthesis Examples 1 to 8 or Reference Examples 1 to 3 was obtained with respect to a mixture of 303 parts, 361 parts of aluminum hydroxide and 0.9 parts of 2-ethyl-4-methylimidazole. Cyclic phosphazene compound was added in the ratio shown in Table 2, and propylene glycol monomethyl as a solvent. The ether (PGM) was added resin solid content of 65 percent of the epoxy resin varnish (resin composition) was prepared.

  Next, the prepared epoxy resin varnish was applied to a glass woven fabric having a thickness of 180 μm and impregnated, and dried at a temperature of 160 ° C. to produce a prepreg. Eight glass woven prepregs having a thickness of 180 μm thus obtained were laminated, and this was heated and pressurized at a temperature of 170 ° C. and a pressure of 4 MPa for 100 minutes to obtain a glass epoxy laminated plate having a thickness of 1.2 mm.

A test piece having a length of 5 inches, a width of 0.5 inches, and a thickness of 1.2 mm was cut out from the glass epoxy laminate, and its combustibility, glass transition temperature (Tg), and high temperature reliability were examined. Here, the flammability was evaluated by a method based on the UL-94 standard vertical combustion test, as in Examples 1 to 8 and Comparative Examples 1 to 3. The glass transition temperature is JIS K 7121-
It was measured by DSC according to 1987 “Method for measuring transition temperature of plastic”. Furthermore, the high temperature reliability was evaluated by treating the test piece at 290 ° C. for 20 minutes and observing a change in appearance. The results are shown in Table 2. In the results of high temperature reliability in Table 2, “Yes” means that there is no bleed out of the cyclic phosphazene compound or the like from the test piece (that is, there is high temperature reliability), and “No” means that the bleed. It means that there is out (that is, there is no high temperature reliability).

  As is clear from Table 2, the glass epoxy laminates (resin molded bodies) made of the resin compositions of Examples 9 to 16 are superior in flame retardancy compared to those made of the resin compositions of Comparative Examples 4 to 6. In addition, since the glass transition temperature is high, it is excellent in heat resistance, and is also excellent in high temperature reliability (bleedout resistance).

Examples 17-24 and Comparative Examples 7-9
278 parts of bisphenol A type epoxy resin (trade name “jER1004” of Japan Epoxy Resin Co., Ltd .: epoxy equivalent 925), 126 parts of cresol novolac epoxy resin (trade name “YDCN-703P” of Toto Kasei Co., Ltd .: 210 equivalent of epoxy) , 106 parts of bisphenol A type novolak resin (trade name “PHENOLITE VH-4170” of Dainippon Ink Chemical Co., Ltd .: hydroxyl value 118), cross-linked styrene butadiene rubber (SBR) having polar functional groups such as hydroxy group and carboxy group 300 parts of particles (trade name “XSK-500” of JSR Corporation: average particle size 0.5 μm), obtained in cyclic phosphazene compounds obtained in Synthesis Examples 1 to 8 in the proportions shown in Table 3 or Reference Examples 1 to 3 Cyclic phosphazene compounds, 2,6-di (t-butyl) -4-me From 3 parts of ruphenol, 200 parts of aluminum hydroxide (trade name “H-421” of Showa Denko KK) and 2 parts of 2-ethyl-4-methylimidazole (trade name “Curesol 2E4MZ” of Shikoku Kasei Kogyo Co., Ltd.) Then, propylene glycol monomethyl ether and methyl ethyl ketone were added as solvents to obtain an adhesive composition (resin composition) having a solid content of 33%.

  Applying the obtained adhesive composition to a polyimide film having a thickness of 25 μm (trade name “Kapton” manufactured by Toray DuPont Co., Ltd.) using a roll coater so that the thickness after drying is 15 μm. It dried and obtained the polyimide film with an adhesive agent. The adhesive composition layer side of this polyimide film with adhesive and the treated surface of the copper foil (thickness 35 μm) are superposed and pressure-bonded with a laminate roll at 120 ° C., and further 3 hours at 100 ° C. and 3 hours at 130 ° C. A flexible copper-clad laminate was prepared by treatment at 160 ° C. for 3 hours. In addition, the obtained adhesive composition is applied to a polypropylene film having a thickness of 40 μm using a roll coater so that the thickness after drying is 50 μm and dried, and the polypropylene film is used as a carrier film. An adhesive film was obtained.

  The adhesive composition layer side of the obtained adhesive film was pressure-bonded to a 125 μm thick polyimide reinforcing plate with a laminate roll at 120 ° C. And the polypropylene film of the carrier film was peeled off, and the film surface of the obtained flexible copper clad laminated board was piled up with respect to the adhesive composition layer. This was heat-pressure bonded at 160 ° C. and 0.5 MPa for 15 minutes to produce a flexible copper-clad laminate with a reinforcing plate for evaluation.

  About the obtained flexible copper clad laminated board with a reinforcement board, a flame retardance and high temperature reliability were evaluated. The flame retardancy is a UL-94 standard vertical combustion test as in Examples 1-8 and Comparative Examples 1-3, with the test piece being the copper foil of the flexible copper-clad laminate with reinforcing plate removed by full etching. It evaluated by the method based on. High temperature reliability was evaluated by solder heat resistance before and after humidification. The solder heat resistance before humidification is the same as that applied to the flame retardancy test, dried by heating at 100 ° C for 60 minutes, and then floated in each solder bath at 260 ° C, 288 ° C and 310 ° C for 20 seconds. Evaluation was made by confirming the presence or absence of changes in appearance (particularly swelling). On the other hand, the solder heat resistance after humidification is to check the presence or absence of changes in appearance (particularly swelling) by humidifying the test piece at 60 ° C. and 85% relative humidity for 1 hour and then floating it in a 260 ° C. solder bath for 1 minute. It was evaluated. The results are shown in Table 3. In each solder heat resistance result, “Yes” indicates that heat resistance and high temperature reliability are present because no change in appearance has occurred, and “No” indicates heat resistance and high temperature reliability because of appearance change. Indicates that there is no.

  As is clear from Table 3, the flexible copper-clad laminate with a reinforcing plate (resin molded body) formed using the adhesive compositions of Examples 17 to 24 is substantially the same as Comparative Examples 7 to 9 in flame retardancy. Although equivalent, solder heat resistance before and after humidification is better than Comparative Examples 7 to 9, and excellent in heat resistance and high temperature reliability.

Synthesis Example 9 (Synthesis of polyamic acid)
A stirrer, a Dean-Stark tube, a reflux condenser, a 200 ml dropping funnel, and a nitrogen introducing tank were installed in a 300 mL separable flask. In a separable flask of this reactor, 106.7 g of N-methylpyrrolidone, 45.7 g of mesitylene, and 45.8 g of pyromellitic dianhydride (manufactured by Mitsubishi Gas Chemical Co., Inc.) were charged in a nitrogen atmosphere. While stirring it, 12.3 g of terminal aminated polypropylene glycol (trade name “Jeffamine D400” of Huntsman Corporation), 11.3 g of terminal aminated polypropylene glycol (trade name “Jeffamine D230” of Huntsman Corporation) 0 g and 36.8 g of terminal aminated poly (propylene glycol-tetramethylene glycol copolymer) (trade name “Jeffamine XTJ542” from Huntsman Corporation) were added dropwise at an elevated temperature over 1 hour. Thereafter, the internal temperature was raised to 180 ° C., reflux was maintained at 180 ° C. for 4 hours, and then cooled to room temperature. After cooling, 18.6 g of 4,4′-diaminodiphenyl ether (manufactured by JFE Chemical Co., Ltd.) was added. After the addition, stirring was continued in a nitrogen atmosphere for 20 hours to obtain a partially imidized polyamic acid solution having a solid content of 45% by mass.

Synthesis Example 10 (Synthesis of polyamic acid)
In a separable flask of a reactor similar to that used in Synthesis Example 9, N-methylpyrrolidone 106.7 g, mesitylene 45.7 g and biphenyltetracarboxylic dianhydride (manufactured by JFE Chemical Co., Ltd.) 56 were added in a nitrogen atmosphere. 0.0 g was charged. While stirring it, 22.0 g of terminal aminated polypropylene glycol (trade name “Jeffamine D230” of Huntsman Corporation) and terminal aminated poly (propylene glycol-tetramethylene glycol copolymer) (manufactured by Huntsman Corporation) 34.9 g of a trade name “Jeffamine XTJ542”) was added dropwise at an elevated temperature over 1 hour. Thereafter, the internal temperature was raised to 180 ° C., reflux was maintained at 180 ° C. for 4 hours, and then cooled to room temperature. After cooling, 16.4 g of 1,3-bis (3-aminophenoxy) benzene (Mitsui Chemicals) was added. After the addition, stirring was continued in a nitrogen atmosphere for 20 hours to obtain a partially imidized polyamic acid solution having a solid content of 45% by mass.

Examples 25-32 and Comparative Examples 10-12
900 parts of the solution of the polyamic acid (partially imidized polyamic acid) obtained in Synthesis Examples 9 and 10 and the cyclic phosphazene compounds obtained in Synthesis Examples 1 to 8 in the proportions shown in Table 4 or Reference Examples 1 to A mixture composed of the cyclic phosphazene compound obtained in 3 was prepared, and N, N-dimethylacetamide as a solvent was added thereto to obtain a resin composition having a solid content of 50%.

  A 25 μm thick polyethylene terephthalate film (trade name “M5001” manufactured by Toyobo Co., Ltd.) was applied using an applicator and dried to obtain a 25 μm thick dry film. It was. Then, using a vacuum laminator manufactured by Meiki Seisakusho Co., Ltd., copper (12 μm) / polyimide (25 μm) / copper (12 μm) flexible copper-clad laminate (trade name “Neoflex® NFX” by Mitsui Chemicals, Inc.) -2ABEPFE (25T) "The dry film obtained on one side was bonded at 80 ° C for 1 minute at 0.5MPa, under pressure, and then cured by heating at 160 ° C for 1 hour. A flexible copper clad laminate with a cover film was prepared.

  About the obtained flexible copper clad laminated board with a cover film, the flame retardance, the bleed-out property after a humidification test, and the solder heat resistance after humidification were evaluated. The flame retardancy was evaluated by a method based on the following UL-94 flame retardant test (thin vertical combustion test) using a test piece obtained by removing the copper foil of the flexible copper-clad laminate with cover film by double-sided etching. . The bleed-out property after the humidification test is evaluated based on whether or not there is a crystalline precipitate on the surface after humidification at 60 ° C. and a relative humidity of 90% for the same test piece used in the evaluation of flame retardancy. did. For the solder heat resistance after humidification, a test piece similar to that used in the evaluation of flame retardancy was humidified for 1 hour at 60 ° C. and 85% relative humidity, and then floated in a solder bath at 260 ° C. for 1 minute. Evaluation was made by confirming the presence or absence of changes in appearance (particularly swelling). The results are shown in Table 4. In the results of solder heat resistance after humidification, “Yes” indicates that heat resistance and high-temperature reliability are present because no change in appearance has occurred, and “No” indicates heat resistance and high temperature due to appearance change. Indicates no reliability.

(Flame retardancy test)
Based on Underwriters Laboratories Inc.'s UL-94 thin vertical combustion test, VTM-0, VTM, VTM-0, VTM -1, VTM-2 and non-standard four stages. The evaluation criteria are shown below. The flame retardancy level decreases in the order of VTM-0>VTM-1>VTM-2> non-standard.

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

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

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

  As is apparent from Table 4, the flexible copper-clad laminates with cover films of Examples 25 to 32 are substantially equivalent to Comparative Examples 10 to 12 in flame retardancy, but the bleed-out property after the humidification test and after the humidification The solder heat resistance is better than those of Comparative Examples 10 to 12, and is excellent in heat resistance and high temperature reliability.

Claims (9)

A resin component;
A cyclic phosphazene compound having an aryloxy group represented by the following formula (1) and having an electron donating group having a Hammett's substituent constant σp of −0.2 or less and no active proton as a substituent; ,
A flame retardant resin composition.

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

In formula (2), Y represents a group selected from the group consisting of a phenylene group, a biphenylene group, and a naphthylene group, Q represents a Hammett's substituent constant σp of −0.2 or less, and has an active proton. An electron donating group, which is an allyloxy group, a dialkylamino group, a diarylamino group or a trimethylsilyloxy group. ) The cyclic phosphazene compound is selected from the group consisting of the following A1 group and A2 group such that at least one of the halogen atoms of the cyclic phosphonitrile dihalide represented by the following formula (3) is substituted by the following A2 group: The flame-retardant resin composition according to claim 1, which is obtained by substitution with a selected group.

(In formula (3), n represents an integer of 3 to 8, and X represents a halogen atom.)
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.
A2 group: A substituted aryloxy group represented by the following formula (2).

(In Formula (2), Y represents a group selected from the group consisting of a phenylene group, a biphenylene group, and a naphthylene group, and Q represents a Hammett's substituent constant σp of −2.0 or less and an active proton. An electron donating group which does not have an allyloxy group, a dialkylamino group, a diarylamino group or a trimethylsilyloxy group.   The flame retardant resin composition according to claim 1 or 2, wherein the cyclic phosphazene compound has n of 3 or 4 in formula (1). The flame retardant resin composition according to any one of claims 1 to 3, wherein the cyclic phosphazene compound has the following A1 group and A2 group as A in the formula (1).
A1 group: a group selected from the group consisting of a phenoxy group and a methylphenoxy group.
A2 group: a group in which Y in formula (2) is a phenylene group or a naphthylene group.   The A2 group is a group selected from the group consisting of 4-allyloxyphenoxy group, 4- (dimethylamino) phenoxy group, 3- (trimethylsilyloxy) phenoxy group and 4- (trimethylsilyloxy) phenoxy group. The flame-retardant resin composition as described in 2.   4. The cyclic phosphazene compound according to claim 1, wherein all of A in formula (1) are selected from the group consisting of a 4-allyloxyphenoxy group and a 4- (dimethylamino) phenoxy group. The flame-retardant resin composition as described.   The flame-retardant resin composition according to any one of claims 1 to 6, wherein the resin component is selected from the group consisting of a modified polyphenylene ether resin, an epoxy resin, and a polyimide resin.   The resin molding which consists of a flame-retardant resin composition in any one of Claim 1 to 7.   The electrical / electronic component using the resin molding of Claim 8.