JP5137105B2 - Cyanato group-containing cyclic phosphazene compound and process for producing the same - Google Patents

Description

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

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

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

JP 2000-103939 A JP 2004-83671 A JP 2004-210849 A JP 2005-248134 A JP 2007-45916 A

  Therefore, phosphazene-based 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 hydroxyl groups and the like. A phosphazene-based flame retardant having a reactive group, and an epoxy resin composition and a polyimide resin composition using the same are disclosed. This type of phosphazene-based flame retardant is unlikely to impair the high temperature reliability of the resin molded product even when added in a large amount to the resin composition. It is insufficient in terms of the essential effect that it is difficult to effectively increase, and it also impairs the mechanical properties (particularly high glass transition temperature) of the resin molded product.

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

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

  In addition, in computers and information equipment terminals, in order to process a large amount of data at high speed, the frequency of the signal is increasing, but there is a problem that the transmission loss of the electric signal increases as the frequency increases. There is a strong demand for the development of printed wiring boards that can handle high frequencies. Transmission loss in a high-frequency circuit is greatly affected by dielectric loss determined by the dielectric properties of the insulating layer (dielectric) around the wiring. Low dielectric constant and low dielectric loss tangent of printed wiring board substrates (especially insulating resin) tan δ) is required. For example, in devices related to mobile communication, a substrate having a low dielectric loss tangent is strongly desired in order to reduce transmission loss in the quasi-microwave band (1 to 3 GHz) as the signal becomes higher in frequency.

  Furthermore, electronic information devices such as computers are equipped with a high-speed microprocessor having an operating frequency exceeding 1 GHz, and a delay of a high-speed pulse signal on a printed wiring board is a problem. Since the delay time of the signal becomes longer in proportion to the square root of the relative dielectric constant εr of the insulator around the wiring in the printed wiring board, a high-speed computer or the like requires a wiring board substrate having a low dielectric constant.

  Therefore, the phosphazene-based flame retardant needs to make it difficult to impair the dielectric properties of the resin molded product, that is, to achieve a low dielectric constant and a low dielectric loss tangent of the resin molded product.

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

  As a result of repeated research to solve the above-mentioned problems, the inventors of the present invention have a molded article comprising a resin composition containing a novel phosphazene compound having a cyanate group, which exhibits excellent mechanical properties and flame retardancy. At the same time, it was found to be highly reliable at high temperatures and excellent in dielectric properties.

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

In formula (1), n shows the integer of 3-15. A represents a group selected from the group consisting of the following A1, A2 and A3 groups, and at least one is an A3 group.
A1 group: an alkoxy group having 1 to 8 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: 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.
Group A3: a group selected from the group consisting of a cyanatophenyl-substituted phenyloxy group represented by the following formula (2).

式（２）中、Ｘ^１からＸ^８は、それぞれ独立して水素原子、アルキル基若しくはアリール基を示す。）

In formula (2), X ¹ to X ⁸ each independently represents a hydrogen atom, an alkyl group or an aryl group. )

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

  The method for producing a cyanato group-containing cyclic phosphazene compound according to the present invention includes the following step 1, step 2 and step 3.

[Step 1]
Selected from the group consisting of the following E1, E2, and E3 groups such that at least one of the halogen atoms of the cyclic phosphonitrile dihalide represented by the following formula (3) is substituted by the following E3 group: A step of producing a substituted formyl group-containing cyclic phosphonitrile by substitution with a group.

In formula (3), n represents an integer of 3 to 15, and X represents a halogen atom.
E1 group: An alkoxy group having 1 to 8 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.
E2 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.
E3 group: a group selected from the group consisting of a formyl group-substituted phenyloxy group represented by the following formula (4).

[Step 2]
The formyl group (E3 group: formyl group-substituted phenyloxy group) -containing cyclic phosphonitrile substituted product obtained in Step 1 is reacted with a phenol represented by the following formula (5), and represented by the following E4 group. Producing a hydroxyl group-containing cyclic phosphonitrile substitution product.

In formula (5), X ⁹ to X ¹³ each independently represent a hydrogen atom, an alkyl group or an aryl group.
E4 group: a group selected from the group consisting of a hydroxyl group-substituted phenyloxy group represented by the following formula (6).

式（６）中、Ｘ^１からＸ^８は、それぞれ独立して水素原子、アルキル基若しくはアリール基を示す。

In formula (6), X ¹ to X ⁸ each independently represent a hydrogen atom, an alkyl group or an aryl group.

[Step 3]
A step of reacting the cyclic phosphonitrile-substituted product having a hydroxyl group obtained in Step 2 with cyanogen halide.

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

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

  The resin molded body of the present invention is composed of the resin composition of the present invention or a polymer of the polymerizable composition of the present invention.

  Since the cyanato group-containing cyclic phosphazene compound of the present invention has a specific structure as described above, its flame retardancy can be effectively enhanced without impairing the mechanical properties of the resin molded article, High-temperature reliability and dielectric properties of resin moldings are difficult to lose.

  Since the method for producing a cyanato group-containing cyclic phosphazene compound according to the present invention includes Step 1, Step 2 and Step 3 as described above, the cyanate group-containing cyclic phosphazene having the specific structure as described above according to the present invention. Compounds can be produced.

  Since the resin composition of the present invention contains the cyanate group-containing cyclic phosphazene compound of the present invention as a flame retardant, the resin composition exhibits practical mechanical characteristics and flame retardancy, and has high temperature reliability and excellent dielectric characteristics. You can get a body.

  Since the polymerizable composition of the present invention contains the cyanate group-containing cyclic phosphazene compound of the present invention, its polymerization exhibits practical mechanical properties and flame retardancy, and also has high temperature reliability and excellent dielectric properties. A resin molded product can be obtained.

  Since the resin molded body of the present invention is composed of the resin composition of the present invention or a polymer of the polymerizable composition according to the present invention, it exhibits practical mechanical properties and flame retardancy, and has high temperature reliability and dielectric properties. Excellent characteristics.

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

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

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

[A1 group]
An alkoxy group having 1 to 8 carbon atoms; In the alkoxy 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 alkoxy groups include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, n-pentyloxy, and n-hexyloxy. Group, n-heptyloxy group, n-octyloxy group, ethenyloxy group, 1-propenyloxy group, 2-propenyloxy group, isopropenyloxy group, 3-butenyloxy group, 2-methyl-2-propenyloxy group, 4 -Pentenyloxy group, 2-hexenyloxy group, 1-propyl-2-butenyloxy group, 5-octenyloxy group, benzyloxy group, 2-phenylethoxy group and the like can be mentioned. Among these, a methoxy group, an ethoxy group, an n-propoxy group, a 2-propenyloxy group and a benzyloxy group are preferable, and an ethoxy group and an n-propoxy group are particularly preferable.

[Group A2]
An aryloxy group having 6 to 20 carbon atoms; 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 A3]
A group selected from the group consisting of a cyanatophenyl-substituted phenyloxy group represented by the following formula (2).

式（２）中、Ｘ^１からＸ^８は、それぞれ独立して水素原子、アルキル基若しくはアリール基を示すが、好ましくは、水素原子、メチル基、ターシャリーブチル基、フェニル基等の炭素数１〜６のアルキル基若しくはフェニル基である。

In formula (2), X ¹ to X ⁸ each independently represent a hydrogen atom, an alkyl group or an aryl group, but preferably have 1 carbon atom such as a hydrogen atom, a methyl group, a tertiary butyl group or a phenyl group. It is an alkyl group of 6 or a phenyl group.

  Specific examples of the cyanatophenyl-substituted phenyloxy group represented by the formula (2) include bis (2′-cyanatophenyl) methyl-2-phenyloxy group and bis (3′-cyanatophenyl) methyl-2. -Phenyloxy group, bis (4'-cyanatophenyl) methyl-2-phenyloxy group, (2'-cyanatophenyl) (3'-cyanatophenyl) methyl-2-phenyloxy group, (2'- (Cyanatophenyl) (4′-cyanatophenyl) methyl-2-phenyloxy group, (3′-cyanatophenyl) (4′-cyanatophenyl) methyl-2-phenyloxy group, bis (2′-si Anatophenyl) methyl-3-phenyloxy group, bis (3′-cyanatophenyl) methyl-3-phenyloxy group, bis (4′-cyanatophenyl) methyl-3-phenyl Xyl group, (2′-cyanatophenyl) (3′-cyanatophenyl) methyl-3-phenyloxy group, (2′-cyanatophenyl) (4′-cyanatophenyl) methyl-3-phenyloxy group , (3′-cyanatophenyl) (4′-cyanatophenyl) methyl-3-phenyloxy group, bis (2′-cyanatophenyl) methyl-4-phenyloxy group, bis (3′-cyanatophenyl) ) Methyl-4-phenyloxy group, bis (4′-cyanatophenyl) methyl-4-phenyloxy group, (2′-cyanatophenyl) (3′-cyanatophenyl) methyl-4-phenyloxy group, (2′-cyanatophenyl) (4′-cyanatophenyl) methyl-4-phenyloxy group, (3′-cyanatophenyl) (4′-cyanatophenyl) methyl-4-phenyl Nyloxy group, bis (2′-cyanato-5′-methylphenyl) methyl-2-phenyloxy group, bis (2′-methyl-5′-cyanatophenyl) methyl-2-phenyloxy group, (2′- Cyanato-5′-methylphenyl) (2′-methyl-5′-cyanatophenyl) methyl-2-phenyloxy group, bis (2′-cyanato-5′-methylphenyl) methyl-3-phenyloxy group, Bis (2′-methyl-5′-cyanatophenyl) methyl-3-phenyloxy group, (2′-cyanato-5′-methylphenyl) (2′-methyl-5′-cyanatophenyl) methyl-3 -Phenyloxy group, bis (2'-cyanato-5'-methylphenyl) methyl-4-phenyloxy group, bis (2'-methyl-5'-cyanatophenyl) methyl-4-pheny Ruoxy group, (2′-cyanato-5′-methylphenyl) (2′-methyl-5′-cyanatophenyl) methyl-4-phenyloxy group, bis (2′-cyanato-3 ′, 5′-dimethyl) Phenyl) methyl-2-phenyloxy group, bis (2 ′, 4′-dimethyl-3′-cyanatophenyl) methyl-2-phenyloxy group, bis (2 ′, 6′-dimethyl-3′-cyanato) Phenyl) methyl-2-phenyloxy group, (2′-cyanato-3 ′, 5′-dimethylphenyl) (2 ′, 4′-dimethyl-3′-cyanatophenyl) methyl-2-phenyloxy group, 2′-cyanato-3 ′, 5′-dimethylphenyl) (2 ′, 6′-dimethyl-3′-cyanatophenyl) methyl-2-phenyloxy group, (2 ′, 4′-dimethyl-3′- Cyanatophenyl (2 ′, 6′-dimethyl-3′-cyanatophenyl) methyl-2-phenyloxy group, bis (2′-cyanato-3 ′, 5′-dimethylphenyl) methyl-3-phenyloxy group, bis ( 2 ′, 4′-dimethyl-3′-cyanatophenyl) methyl-3-phenyloxy group, bis (2 ′, 6′-dimethyl-3′-cyanatophenyl) methyl-3-phenyloxy group, (2 '-Cyanato-3', 5'-dimethylphenyl) (2 ', 4'-dimethyl-3'-cyanatophenyl) methyl-3-phenyloxy group, (2'-cyanato-3', 5'-dimethyl Phenyl) (2 ′, 6′-dimethyl-3′-cyanatophenyl) methyl-3-phenyloxy group, (2 ′, 4′-dimethyl-3′-cyanatophenyl) (2 ′, 6′-dimethyl) -3'-Sianatov Nyl) methyl-3-phenyloxy group, bis (2′-cyanato-3 ′, 5′-dimethylphenyl) methyl-4-phenyloxy group, bis (2 ′, 4′-dimethyl-3′-cyanatophenyl) ) Methyl-4-phenyloxy group, bis (2 ′, 6′-dimethyl-3′-cyanatophenyl) methyl-4-phenyloxy group, (2′-cyanato-3 ′, 5′-dimethylphenyl) ( 2 ′, 4′-dimethyl-3′-cyanatophenyl) methyl-4-phenyloxy group, (2′-cyanato-3 ′, 5′-dimethylphenyl) (2 ′, 6′-dimethyl-3′- Cyanatophenyl) methyl-4-phenyloxy group, (2 ′, 4′-dimethyl-3′-cyanatophenyl) (2 ′, 6′-dimethyl-3′-cyanatophenyl) methyl-4-phenyloxy Group, bis ( 2′-cyanato-5′-tert-butylphenyl) methyl-2-phenyloxy group, bis (2′-tert-butyl-5′-cyanatophenyl) methyl-2-phenyloxy group, (2′-cyanato) -5′-tert-butylphenyl) (2′-tert-butyl-5′-cyanatophenyl) methyl-2-phenyloxy group, bis (2′-cyanato-5′-tert-butylphenyl) methyl-3 -Phenyloxy group, bis (2'-tert-butyl-5'-cyanatophenyl) methyl-3-phenyloxy group, (2'-cyanato-5'-tert-butylphenyl) (2'-tert-butyl) -5'-cyanatophenyl) methyl-3-phenyloxy group, bis (2'-cyanato-5'-tert-butylphenyl) methyl-4-phenylo Si group, bis (2′-tert-butyl-5′-cyanatophenyl) methyl-4-phenyloxy group, (2′-cyanato-5′-tert-butylphenyl) (2′-tert-butyl-5) '-Cyanatophenyl) methyl-4-phenyloxy group, bis (2'-cyanato-5'-phenylphenyl) methyl-2-phenyloxy group, bis (2'-phenyl-5'-cyanatophenyl) methyl 2-phenyloxy group or (2′-cyanato-5′-phenylphenyl) (2′-phenyl-5′-cyanatophenyl) methyl-2-phenyloxy group, bis (2′-cyanato-5′-) Phenylphenyl) methyl-3-phenyloxy group, bis (2′-phenyl-5′-cyanatophenyl) methyl-3-phenyloxy group or (2′-cyanana) -5′-phenylphenyl) (2′-phenyl-5′-cyanatophenyl) methyl-3-phenyloxy group, bis (2′-cyanato-5′-phenylphenyl) methyl-4-phenyloxy group, bis (2'-phenyl-5'-cyanatophenyl) methyl-4-phenyloxy group or (2'-cyanato-5'-phenylphenyl) (2'-phenyl-5'-cyanatophenyl) methyl-4- It is a phenyloxy group.

  Preferred examples of the A3 group include bis (2′-cyanatophenyl) methyl-3-phenyloxy group, bis (4′-cyanatophenyl) methyl-3-phenyloxy group, and (2′-cyanatophenyl). ) (4′-cyanatophenyl) methyl-3-phenyloxy group, bis (2′-cyanatophenyl) methyl-4-phenyloxy group, bis (4′-cyanatophenyl) methyl-4-phenyloxy group , (2′-cyanatophenyl) (4′-cyanatophenyl) methyl-4-phenyloxy group, bis (2′-cyanato-5′-methylphenyl) methyl-3-phenyloxy group, bis (2 ′ -Methyl-5'-cyanatophenyl) methyl-3-phenyloxy group, (2'-cyanato-5'-methylphenyl) (2'-methyl-5'-cyanatophenyl) Til-3-phenyloxy group, bis (2'-cyanato-5'-methylphenyl) methyl-4-phenyloxy group, bis (2'-methyl-5'-cyanatophenyl) methyl-4-phenyloxy group , (2′-cyanato-5′-methylphenyl) (2′-methyl-5′-cyanatophenyl) methyl-4-phenyloxy group, bis (2′-cyanato-5′-tert-butylphenyl) methyl -3-phenyloxy group, bis (2'-tert-butyl-5'-cyanatophenyl) methyl-3-phenyloxy group, (2'-cyanato-5'-tert-butylphenyl) (2'-tert -Butyl-5'-cyanatophenyl) methyl-3-phenyloxy group, bis (2'-cyanato-5'-tert-butylphenyl) methyl-4-phenyloxy Bis (2′-tert-butyl-5′-cyanatophenyl) methyl-4-phenyloxy group, (2′-cyanato-5′-tert-butylphenyl) (2′-tert-butyl-5′- Cyanatophenyl) methyl-4-phenyloxy group, bis (2'-cyanato-5'-phenylphenyl) methyl-3-phenyloxy group, bis (2'-phenyl-5'-cyanatophenyl) methyl-3 -Phenyloxy group, (2'-cyanato-5'-phenylphenyl) (2'-phenyl-5'-cyanatophenyl) methyl-3-phenyloxy group, bis (2'-cyanato-5'-phenylphenyl) ) Methyl-4-phenyloxy group, bis (2′-phenyl-5′-cyanatophenyl) methyl-4-phenyloxy group or (2′-cyanato-5′-f) Enylphenyl) (2'-phenyl-5'-cyanatophenyl) methyl-4-phenyloxy group.

  Of these, bis (2′-cyanatophenyl) methyl-4-phenyloxy group, bis (4′-cyanatophenyl) methyl-4-phenyloxy group, (2′-cyanatophenyl) (4′-cyl Anatophenyl) methyl-4-phenyloxy group, bis (2′-cyanato-5′-phenylphenyl) methyl-4-phenyloxy group, bis (2′-phenyl-5′-cyanatophenyl) methyl-4- A phenyloxy group or a (2′-cyanato-5′-phenylphenyl) (2′-phenyl-5′-cyanatophenyl) methyl-4-phenyloxy group is particularly preferred.

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

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

  Specific examples of the cyanato group-containing cyclic phosphazene compound having such a form include a cyanato group-containing cyclotriphosphazene compound in which n in the formula (1) is 3, and a cyanate group-containing cyclotetrazane in which n in the formula (1) is 4. A phosphazene compound, a cyanato group-containing cyclopentaphosphazene compound in which n in formula (1) is 5 and a cyanato group-containing cyclohexaphosphazene compound in which n in formula (1) is 6, wherein all of A are bis (2 '-Cyanatophenyl) methyl-4-phenyloxy group, bis (4'-cyanatophenyl) methyl-4-phenyloxy group, (2'-cyanatophenyl) (4'-cyanatophenyl) methyl-4 -Phenyloxy group, bis (2'-cyanato-5'-phenylphenyl) methyl-4-phenyloxy group, bis (2'-phenyl-5) -Cyanatophenyl) methyl-4-phenyloxy group or (2'-cyanato-5'-phenylphenyl) (2'-phenyl-5'-cyanatophenyl) methyl-4-phenyloxy group And those in which all of A are two or more A3 groups selected from the A3 group, and any mixtures thereof.

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

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

  In addition, it is confirmed by TOF-MS analysis of cyanate group-containing cyclic phosphazene compounds or intermediates in the production process thereof whether 1 to (2n-2) of 2n A are A3 groups or not. Can do.

  Specific examples of the cyanato group-containing cyclic phosphazene compound having such a form include a cyanato group-containing cyclotriphosphazene compound in which n in the formula (1) is 3, and a cyanate group-containing cyclotetrazane in which n in the formula (1) is 4. A phosphazene compound, a cyanato group-containing cyclopentaphosphazene compound in which n in formula (1) is 5 or a cyanato group-containing cyclohexaphosphazene compound in which n is 6 in formula (1), wherein A is a bis group Combination of (2′-cyanatophenyl) methyl-4-phenyloxy group and n-propoxy group which is A1 group, bis (2′-cyanatophenyl) methyl-4-phenyloxy group which is A3 group In combination with phenoxy group which is A2 group, bis (2′-cyanatophenyl) methyl-4-phenyloxy group which is A3 group and A3 group In combination with a methylphenoxy group which is a group, in combination with a bis (4′-cyanatophenyl) methyl-4-phenyloxy group which is an A3 group and an n-propoxy group which is an A1 group, A combination of a certain bis (4′-cyanatophenyl) methyl-4-phenyloxy group and a phenoxy group that is an A2 group, a bis (4′-cyanatophenyl) methyl-4-phenyloxy group that is an A3 group In combination with a methylphenoxy group which is an A2 group, (2′-cyanatophenyl) (4′-cyanatophenyl) methyl-4-phenyloxy group which is an A3 group, and n-propoxy which is an A1 group A combination of a group with (2′-cyanatophenyl) (4′-cyanatophenyl) methyl-4-phenyloxy group which is an A3 group and a phenoxy group which is an A2 group A combination of (2′-cyanatophenyl) (4′-cyanatophenyl) methyl-4-phenyloxy group which is an A3 group and a methylphenoxy group which is an A2 group, an A3 group Combination of bis (2′-cyanato-5′-phenylphenyl) methyl-4-phenyloxy group and n-propoxy group which is A1 group, bis (2′-cyanato-5′-phenyl) which is A3 group A combination of a phenyl) methyl-4-phenyloxy group and a phenoxy group which is an A2 group, a bis (2′-cyanato-5′-phenylphenyl) methyl-4-phenyloxy group which is an A3 group and an A2 group In combination with a certain methylphenoxy group, bis (2′-phenyl-5′-cyanatophenyl) methyl-4-phenyloxy group which is an A3 group and n-propoxy which is an A1 group A combination of cis group, a combination of bis (2′-phenyl-5′-cyanatophenyl) methyl-4-phenyloxy group which is an A3 group and a phenoxy group which is an A2 group, an A3 group Combination of bis (2′-phenyl-5′-cyanatophenyl) methyl-4-phenyloxy group and methylphenoxy group which is A2 group, A3 group (2′-cyanato-5′-phenylphenyl) ) (2′-Phenyl-5′-cyanatophenyl) methyl-4-phenyloxy group in combination with A1 group n-propoxy group, A3 group (2′-Cyanato-5′-phenyl) (Phenyl) (2′-phenyl-5′-cyanatophenyl) methyl-4-phenyloxy group and a phenoxy group which is an A2 group or an A3 group (2′-cyanato-5 - it can be exemplified phenyl) (2'-phenyl-5'-cyanatophenyl) that in combination with methylphenoxy group is methyl-4-phenyl group and A2 groups and any mixture thereof.

  Among these, a cyanato group-containing cyclotriphosphazene compound in which n in formula (1) is 3, a cyanato group-containing cyclotetraphosphazene compound in which n in formula (1) is 4, and a cyanato in which n in formula (1) is 5 A bis (2′-cyanatophenyl) methyl-4-phenyloxy group-containing cyclopentaphosphazene compound, a cyanato group-containing cyclohexaphosphazene compound in which n in the formula (1) is 6, wherein A is an A3 group A combination of a group and a phenoxy group which is an A2 group, a combination of a bis (2′-cyanatophenyl) methyl-4-phenyloxy group which is an A3 group and a methylphenoxy group which is an A2 group, an A3 group A combination of a bis (4′-cyanatophenyl) methyl-4-phenyloxy group which is a phenoxy group which is an A2 group, a bis (4′- A combination of anatophenyl) methyl-4-phenyloxy group and a methylphenoxy group which is A2 group, (2′-cyanatophenyl) (4′-cyanatophenyl) methyl-4-phenyloxy which is A3 group A combination of a phenoxy group which is an A2 group, a (2′-cyanatophenyl) (4′-cyanatophenyl) methyl-4-phenyloxy group which is an A3 group, and a methylphenoxy which is an A2 group In combination with a group, bis (2′-cyanato-5′-phenylphenyl) methyl-4-phenyloxy group as an A3 group and a phenoxy group as an A2 group, bis ( Combination of 2'-cyanato-5'-phenylphenyl) methyl-4-phenyloxy group and A2 group methylphenoxy group, A3 group bis (2 ' Phenyl-5'-cyanatophenyl) methyl-4-phenyloxy group in combination with phenoxy group which is A2 group, bis (2'-phenyl-5'-cyanatophenyl) methyl-4 which is A3 group -A combination of a phenyloxy group and a methylphenoxy group which is an A2 group, (2'-cyanato-5'-phenylphenyl) (2'-phenyl-5'-cyanatophenyl) methyl-4 which is an A3 group A combination of a phenyloxy group and a phenoxy group which is an A2 group or an A3 group (2'-cyanato-5'-phenylphenyl) (2'-phenyl-5'-cyanatophenyl) methyl-4- A combination of a phenyloxy group and a methylphenoxy group which is an A2 group and any mixture thereof are preferred.

  In particular, a cyanato group-containing cyclotriphosphazene compound in which n in formula (1) is 3 or a cyanato group-containing cyclotetraphosphazene compound in which n is 4 in formula (1), wherein A is a bis ( Combination of 2'-cyanatophenyl) methyl-4-phenyloxy group and phenoxy group which is A2 group, bis (2'-cyanatophenyl) methyl-4-phenyloxy group which is A3 group and A2 group In combination with a methylphenoxy group that is A3, bis (4′-cyanatophenyl) methyl-4-phenyloxy group that is an A3 group and a phenoxy group that is an A2 group, bis ( 4'-cyanatophenyl) methyl-4-phenyloxy group and A2 group methylphenoxy group in combination, A3 group (2'-cyanatophenyl) 4'-cyanatophenyl) methyl-4-phenyloxy group and a combination of phenoxy group which is A2 group or (2'-cyanatophenyl) (4'-cyanatophenyl) methyl- which is A3 group Preferred are combinations of 4-phenyloxy groups with methylphenoxy groups which are A2 groups and any mixtures thereof.

Method for Producing Cyanato Group-Containing Cyclic Phosphazene Compound The cyanato group-containing cyclic phosphazene compound of the present invention can be produced by the following method.

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

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

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

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

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

  Preferred examples of the cyclic phosphonitrile dihalide used in this production method include hexafluorocyclotriphosphazene (where n is 3), octafluorocyclotetraphosphazene (where n is 4), decafluorocyclopentaphosphazene (n 5), dodecafluorocyclohexaphosphazene (where n is 6), a mixture of hexafluorocyclotriphosphazene and octafluorocyclotetraphosphazene, a mixture of cyclic phosphonitrile difluorides where n is 3 to 15, hexachlorocyclo Triphosphazene (n is 3), octachlorocyclotetraphosphazene (n is 4), decachlorocyclopentaphosphazene (n is 5), dodecachlorocyclohexaphosphazene (n is 6), hexa Rollo is Cyclotriphosphazene a mixture of cyclic phosphonate nitrile dichloride mixtures and n is 3 to 15 and octa-chloro cyclotetrasiloxane phosphazene like. Of these, hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, a mixture of hexachlorocyclotriphosphazene and octachlorocyclotetraphosphazene, and a mixture of cyclic phosphonitrile dichloride having n of 3 to 15 are more preferable, hexachlorocyclotriphosphazene, hexachloro Particular preference is given to mixtures of cyclotriphosphazene and octachlorocyclotetraphosphazene and mixtures of cyclic phosphonitrile dichlorides with n of 3 to 15.

  Moreover, the following compound B1, compound B2, and compound B3 are prepared as a compound made to react with the above-mentioned cyclic phosphonitrile dihalide.

[Compound B1]
Alcohols having 1 to 8 carbon atoms.
In these alcohols, 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 alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol, n-pentanol, n-hexanol, n-heptanol, and n-octanol. , Vinyl alcohol, 1-propen-1-ol, 2-propen-1-ol (allyl alcohol), 1-methyl-1-ethen-1-ol, 3-buten-1-ol, 2-methyl-2- Examples include propen-1-ol, 4-penten-1-ol, 2-hexen-1-ol, 2-hepten-4-ol, 5-octen-1-ol, benzyl alcohol, and phenethyl alcohol. Among these, methanol, ethanol, n-propanol, allyl alcohol and benzyl alcohol are preferable, and ethanol and n-propanol are particularly preferable.

[Compound B2]
Phenols having 6 to 20 carbon atoms.
In these phenols, 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 phenols include phenol, cresol, dimethylphenol, ethylphenol, ethylmethylphenol, diethylphenol, n-propylphenol, isopropylphenol, isopropylmethylphenol, isopropylethylphenol, diisopropylphenol, n-butylphenol, sec-butylphenol, tert-butylphenol, n-pentylphenol, n-hexylphenol, vinylphenol, 1-propenylphenol, 2-propenylphenol, isopropenylphenol, 1-butenylphenol, sec-butenylphenol, 1-pentenyl Phenol, 1-hexenylphenol, phenylphenol, naphthol, anthranol and phenanthate Mention may be made of the Nord and the like. Among these, phenol, cresol, dimethylphenol, diethylphenol, 2-propenylphenol, phenylphenol and naphthol are preferable, and phenol, cresol, dimethylphenol and naphthol are particularly preferable.

[Compound B3]
Formylphenols represented by the following formula (7).

このようなホルミルフェノール類としては、例えば、２−ホルミルフェノール、３−ホルミルフェノールおよび４−ホルミルフェノール等を挙げることができる。このうち、３−ホルミルフェノールおよび４−ホルミルフェノールが好ましく、４−ホルミルフェノールが特に好ましい。

Examples of such formylphenols include 2-formylphenol, 3-formylphenol, and 4-formylphenol. Of these, 3-formylphenol and 4-formylphenol are preferable, and 4-formylphenol is particularly preferable.

  In the process for producing a cyanato group-containing cyclic phosphazene compound of the present invention, first, the cyclic phosphonitrile dihalide is reacted with the cyclic phosphonitrile dihalide represented by the above formula (3) and the above-mentioned compounds B1 to B3. Are substituted with a group selected from the group consisting of the following E1, E2 and E3 groups so that at least one of them is substituted with the following E3 group to produce a cyclic phosphonitrile substituted product (step) 1).

[E1 group]
The C1-C8 alkoxy group in which the at least 1 sort (s) chosen from a C1-C6 alkyl group, an alkenyl group, and an aryl group may be substituted.
This group is substituted with a halogen atom by the compound B1, and corresponds to the A1 group described above.

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

[E3 group]
A group selected from the group consisting of a formyl group-substituted phenyloxy group represented by the following formula (4).

この基は、化合物Ｂ３によりハロゲン原子と置換されるものである。

This group is substituted with a halogen atom by the compound B3.

  In this production process, the type of cyanato group-containing cyclic phosphazene compound to be produced, that is, the case where the cyanate group-containing cyclic phosphazene compound according to the above-described form A is produced, and the cyanate group-containing cyclic phosphazene compound according to the above-described form B are produced. When selected, compounds B1 to B3 are appropriately selected and used. Specifically, it is as follows.

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

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

<Method Ab>
Cyclic phosphonitrile dihalide and compound B3 are reacted in the presence of a base that captures hydrogen halide.
In the case of this method, the amount of compound B3 used is preferably set to 1.0 to 2.0 equivalents, preferably 1.05 to 1.3 equivalents, of the amount of the active halogen atom of the cyclic phosphonitrile dihalide. Is more preferable. When the amount used is less than 1.0 equivalent, a part of the active halogen atom remains, and the target cyanato group-containing cyclic phosphazene compound may not exhibit the required effect. On the other hand, if the amount used exceeds 2.0 equivalents, it may be difficult to separate and purify the reaction product, which is uneconomical. The amount of the base used is preferably set to 1.1 to 2.1 equivalents, more preferably 1.1 to 1.4 equivalents, of the amount of active halogen atoms in the cyclic phosphonitrile dihalide. . When the amount used is less than 1.1 equivalents, a part of the active halogen atoms may remain, and the intended cyanato group-containing cyclic phosphazene compound may not exhibit the required effect. On the other hand, if the amount used exceeds 2.1 equivalents, it may be difficult to separate and purify the reaction product, which is uneconomical.

[When producing a cyanato group-containing cyclic phosphazene compound of Form B]
In this case, at least one of compound B3 and at least one compound of compound B1 and compound B2 are reacted with cyclic phosphonitrile dihalide, and a part of the active halogen atoms of cyclic phosphonitrile dihalide is reacted. Is substituted with E3 group derived from compound B3, and all of the remaining other active halogen atoms are replaced with at least one group of E1 group derived from compound B1 and E2 group derived from compound B2. As a method for this, any of the following methods can be adopted.

<Method Ba>
A cyclic phosphonitrile dihalide is reacted with a mixture of an alkali metal salt of compound B3 and an alkali metal salt of at least one of compound B1 and compound B2 to replace all active halogen atoms. In the said mixture, the ratio of the alkali metal salt of compound B3 can be suitably set according to the kind of cyanato group containing cyclic phosphazene compound to manufacture.

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

<Method B-b>
A cyclic phosphonitrile dihalide is reacted with a mixture of compound B3 and at least one of compound B1 and compound B2 in the presence of a base that captures hydrogen halide to replace all active halogen atoms. To do. In the said mixture, the ratio of compound B3 can be suitably set according to the kind of cyanato group containing cyclic phosphazene compound to manufacture.

  In the case of this method, the amount of the above mixture used is preferably set to 1.0 to 2.0 equivalents of the amount of active halogen atoms of the cyclic phosphonitrile dihalide, and is set to 1.05 to 1.3 equivalents. More preferably. When the amount used is less than 1.0 equivalent, a part of the active halogen atom remains, and the target cyanato group-containing cyclic phosphazene compound may not exhibit the required effect. On the other hand, if the amount used exceeds 2.0 equivalents, it may be difficult to separate and purify the reaction product, which is uneconomical. The amount of the base used is preferably set to 1.1 to 2.1 equivalents, more preferably 1.1 to 1.4 equivalents, of the amount of active halogen atoms in the cyclic phosphonitrile dihalide. . When the amount used is less than 1.1 equivalents, a part of the active halogen atoms may remain, and the intended cyanato group-containing cyclic phosphazene compound may not exhibit the required effect. On the other hand, if the amount used exceeds 2.1 equivalents, it may be difficult to separate and purify the reaction product, which is uneconomical.

<Method Bc>
First, compound B3 is reacted with cyclic phosphonitrile dihalide to obtain a partially substituted product in which a part of the active halogen atom of cyclic phosphonitrile dihalide is substituted with E3 group derived from compound B3 (first step). Next, at least one of compound B1 and compound B2 is reacted with the obtained partially substituted product, and all of the remaining active halogen atoms are converted into E1 group derived from compound B1 and E2 derived from compound B2. Substitution with at least one of the groups (second step).

  The first step of this method may be carried out by reacting an alkali metal salt of compound B3 with a cyclic phosphonitrile dihalide, or captures a hydrogen halide of compound B3 with respect to the cyclic phosphonitrile dihalide. The reaction may be performed in the presence of a base. In addition, the second step may be carried out by reacting the partially substituted product obtained in the first step with an alkali metal salt of at least one of the compounds B1 and B2, or the first step. The partially substituted product obtained in (1) may be reacted with at least one of compound B1 and compound B2 in the presence of a base that captures hydrogen halide.

<Method Bd>
First, at least one of compound B1 and compound B2 is reacted with cyclic phosphonitrile dihalide, and a part of the active halogen atom of cyclic phosphonitrile dihalide is converted into E1 group derived from compound B1 and compound B2. A partially substituted product substituted with at least one of the derived E2 groups is obtained (first step). Next, compound B3 is reacted with the partially substituted product thus obtained, and all of the remaining active halogen atoms are substituted with E3 group derived from compound B3 (second step).

  The first step of this method may be carried out by reacting cyclic phosphonitrile dihalide with an alkali metal salt of at least one of compound B1 and compound B2, or for cyclic phosphonitrile dihalide. Alternatively, at least one of compound B1 and compound B2 may be reacted in the presence of a base that captures hydrogen halide. In addition, the second step may be carried out by reacting the alkali metal salt of compound B3 with the partial substituent obtained in the first step, or with respect to the partial substituent obtained in the first step. Compound B3 may be reacted in the presence of a base that captures hydrogen halide.

  In general, the alkali metal salt used in each of the above methods is preferably a lithium salt, a sodium salt, a potassium salt, or a cesium salt. In particular, sodium salt and potassium salt are preferable. Such an alkali metal salt is a dehydrogenation reaction between the compounds B1 to B3 and metal lithium, metal sodium or metal potassium, or the compounds B1 to B3 and lithium hydroxide, sodium hydroxide, potassium hydroxide or the like. It can be obtained by a dehydration reaction from a mixture with an alkali metal hydroxide.

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

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

  The reaction temperature at the time of reacting the above-mentioned cyclic phosphonitrile dihalide and the compounds B1 to B3 can be set as appropriate depending on any of the above-mentioned methods or considering the thermal stability of the reaction product. . However, when the reaction is carried out using a solvent, it is usually preferable to set the reaction temperature in a temperature range from −20 ° C. to the boiling point of the solvent. On the other hand, when carrying out the reaction without solvent, the reaction temperature is usually preferably set in the range of 40 to 200 ° C.

  In addition, as the cyanato group-containing cyclic phosphazene compound of the present invention, those according to the above-mentioned form B, particularly those in which 1 to (2n-2) of 2n A in formula (1) are A3 groups are produced. In this case, it is preferable to adopt the above-mentioned method Bc or Method Bd.

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

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

  In the production method of the present invention, next, the E3 group of the substituted cyclic phosphonitrile having a formyl group obtained in the above-mentioned step 1 is reacted with a phenol represented by the following formula (5), A hydroxyl group-containing cyclic phosphonitrile substitution product represented by E4 group is produced (step 2).

式（５）中、Ｘ^９からＸ^１３は、それぞれ独立して水素原子、アルキル基若しくはアリール基を示す。
これらは後述の化合物Ｂ４に該当する。

In formula (5), X ⁹ to X ¹³ each independently represent a hydrogen atom, an alkyl group or an aryl group.
These correspond to the compound B4 described later.

[E4 group]
A group selected from the group consisting of a hydroxyl group-containing phenyloxy group represented by the following formula (6).

式（６）中、Ｘ^１からＸ^８は、それぞれ独立して水素原子、アルキル基若しくはアリール基を示す。
この基は、化合物Ｂ４とホルミル基を有する環状ホスホニトリル置換体のＥ３基とを反応され得られる。

In formula (6), X ¹ to X ⁸ each independently represent a hydrogen atom, an alkyl group or an aryl group.
This group can be obtained by reacting compound B4 with the E3 group of the substituted cyclic phosphonitrile having a formyl group.

[Compound B4]
Examples of the phenols represented by the above formula (5) include phenol, 2-methylphenol, 3-methylphenol, 4-methylphenol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2, Examples include 5-dimethylphenol, 2,6-dimethylphenol, 2,3,5-trimethylphenol, 4-tert-butylphenol, 2-phenylphenol and 4-phenylphenol. Among these, phenol, 4-methylphenol, 2,6-dimethylphenol, 4-tert-butylphenol and 4-phenylphenol are preferable, and phenol, 4-methylphenol and 4-phenylphenol are particularly preferable. Two or more of these can be used in combination.

  A method for producing a hydroxyl group-containing cyclic phosphonitrile substituted product represented by the E4 group by reacting the formyl group portion of the E3 group with the above-described phenols is described in various documents, for example, the following non-patent Documents 3 and 4 describe.

"Phenolic resin", issued by Plastic Age Co., Ltd., 1987, PHENOLIC RESINS: CHEMISTRY, APPLICATIONS, STANDARDIZATION, SAFETY AND ECOLOGY, A. GARDZIELLA, L.G. A. PILATO, A.I. By Knop, published in 2000, SPRINGER

  As described in these documents, as a method for reacting the formyl group portion of E3 group with phenols, a method of reacting formyl group with phenols under acidic or neutral conditions is known. A timely acidic catalyst can be used. As the acidic catalyst that can be used here, any known catalyst can be used, for example, inorganic acids such as hydrochloric acid, sulfuric acid, and sulfonic acid, organic acids such as oxalic acid and acetic acid, Lewis acids, zinc acetate, lead acetate, and naphthenic acid. Examples thereof include divalent metal salts such as zinc, and among these, hydrochloric acid, organic acids and the like are preferable. Further, by using zinc acetate or the like, a high-ortho type compound having a high bond ratio at the ortho-position to the phenol nucleus of the methylene bond can also be produced. The amount of the acidic catalyst used is not particularly limited, and the type and amount of the cyclic phosphonitrile substituent having a formyl group to be used, the presence or absence of a reaction solvent, the physical properties and applications of the hydroxyl group-containing cyclic phosphonitrile substituent to be obtained, etc. However, it is preferably set to 0.001 to 5 equivalents relative to the equivalent of formyl group of the cyclic phosphonitrile substituted product having a formyl group to be used. More preferably, it is set to ˜1 equivalent.

  The substituted cyclic phosphonitrile having the desired hydroxyl group obtained by reaction with such phenols is isolated and purified from the reaction system by usual methods such as filtration, solvent extraction, column chromatography and recrystallization. can do.

  In the production method of the present invention, next, the cyclic phosphonitrile-substituted product having a hydroxyl group obtained in the above-mentioned step 2 is reacted with cyanogen halide, and the —OH group portion of the E3 group formed in the step 2 is reacted. Convert to —OCN group (step 3). Thereby, the target cyanato group containing cyclic phosphazene compound is obtained.

  Methods for converting the —OH group portion of the E3 group into —OCN groups, that is, methods for producing cyanate esters are described in various documents, for example, Non-Patent Documents 5 and 6 as described below.

CHEMISTRY AND TECHNOLOGY OF Cyanate Ester Resins, I.C. By HAMERTON, published in 1994, BLACKIE ACADEMIC & PROFESSIONAL THE CHEMISTRY OF FUNCTIONAL GROUPS. THE CHEMISTRY OF CIANATES AND THEIR THIO DERIVATEVES, S. PATAI, published in 1977, JOHN WILEY & SONS

  As described in these documents, as a method for producing cyanate ester, (1) a method in which cyanogen halide and phenol are reacted in the presence of a tertiary amine, and (2) an alcohol-based or phenol-based compound A method of reacting an alkali metal salt with a cyanogen halide is known. Cyanogen halides usable here include cyanogen chloride and cyanogen bromide. The method for producing these cyanate esters can be selected according to the kind of the substituted cyclic phosphonitrile having a hydroxyl group, its stability, and the like.

  The desired cyanate group-containing cyclic phosphazene compound obtained by the reaction of a cyclic phosphonitrile substituted product having such a hydroxyl group with cyanogen halide is subjected to usual methods such as filtration, solvent extraction, column chromatography and recrystallization. Can be isolated and purified from the reaction system.

Resin Composition The resin composition of the present invention contains the cyanate group-containing cyclic phosphazene compound of the present invention and a resin component.

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

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

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

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

  In the resin composition of the present invention, the amount of the cyanato group-containing cyclic phosphazene compound used can be appropriately set according to various conditions such as the type of the resin component and the use of the resin composition. It is preferable to set to 0.1 to 200 parts by weight with respect to 100 parts by weight of the resin component, more preferably to set to 0.5 to 100 parts by weight, and further preferably to 1 to 50 parts by weight. . When the amount of the cyanato group-containing cyclic phosphazene compound used is less than 0.1 part by weight, the resin molded body made of the resin composition may not exhibit sufficient flame retardancy. On the other hand, if it exceeds 200 parts by weight, the original properties of the resin component may be impaired, and a resin molded product having such properties may not be obtained.

  Moreover, the resin composition of this invention can mix | blend various additives in the range which does not impair the target physical property according to the kind of resin component, the use of a resin composition, etc. Available additives include, for example, natural silica, calcined silica, synthetic silica, amorphous silica, white carbon, alumina, aluminum hydroxide, magnesium hydroxide, calcium silicate, calcium carbonate, zinc borate, zinc stannate, oxidation Titanium, zinc oxide, molybdenum oxide, zinc molybdate, natural mica, synthetic mica, aerosil, kaolin, clay, talc, calcined kaolin, calcined clay, calcined talc, wollastonite, short glass fiber, glass fine powder, hollow glass and Inorganic fillers such as potassium titanate fibers, organic fibers such as aramid fibers or polyparaphenylene benzbisoxazole fibers, surface treatment agents for fillers such as silane coupling agents, waxes, fatty acids and their metal salts, acid amides And mold release agents such as paraffin, phosphorus Ester, condensed phosphate ester, phosphate amide, phosphate amide ester, ammonium phosphate, red phosphorus, chlorinated paraffin, melamine, melamine cyanurate, melam, melem, melon and succinoguanamine Flame retardants, brominated flame retardants, flame retardants such as antimony trioxide, anti-dripping agents such as polytetrafluoroethylene (PTFE), UV absorbers such as benzotriazole, hindered phenols, styrene Antioxidants such as fluorinated phenols, photopolymerization initiators such as thioxanthones, fluorescent brighteners such as stilbene derivatives, curing agents, dyes, pigments, colorants, light stabilizers, photosensitizers, thickeners, lubricants Antifoaming agents, leveling agents, brighteners, polymerization inhibitors, thixotropic agents, plasticizers and antistatic agents. Rukoto can.

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

  When the resin composition of the present invention is used for materials for electric and electronic fields, specifically, sealants and substrates for electronic components such as LSI, the resin components include cyanate ester resins, epoxy resins, polyimides Resins and modified polyphenylene ether resins are preferred.

  The cyanate ester resin that can be used in the resin composition of the present invention is not particularly limited as long as it has two or more cyanato groups in one molecule. Examples of such a cyanate ester resin include a cyanate ester compound and a prepolymer having a triazine ring formed by trimerization of a cyanate group of the cyanate ester compound and having a weight average molecular weight of 500 to 5,000. Can be mentioned.

  Examples of cyanate ester compounds that can be used here include 1,3-dicyanatobenzene, 1,4-dicyanatobenzene, 1,3,5-tricyanatobenzene, 1,3-dicyanatonaphthalene, 1, 4-dicyanatonaphthalene, 1,6-dicyanatonaphthalene, 1,8-dicyanatonaphthalene, 2,6-dicyanatonaphthalene, 2,7-dicyanatonaphthalene, 1,3,6-tricyanatonaphthalene, 4, 4'-dicyanatobiphenyl, 3,3 ', 5,5'-tetramethyl-4,4'-dicyanatobiphenyl, bis (4-cyanatophenyl) methane, bis (4-cyanato-3-methylphenyl) Methane, bis (4-cyanato-3-tert-butylphenyl) methane, bis (4-cyanato-3-iso-propylphenyl) methane, bis (4- Anato-3,5-dimethylphenyl) methane, bis (2-cyanato-3-tert-butyl-5-methylphenyl) methane, bis (4-cyanatophenyl) ethane, bis (4-cyanato-3-methylphenyl) ) Ethane, bis (4-cyanato-3-tert-butylphenyl) ethane, bis (4-cyanato-3-iso-propylphenyl) ethane, bis (4-cyanato-3,5-dimethylphenyl) ethane, bis ( 2-cyanato-3-tert-butyl-5-methylphenyl) ethane, 2,2-bis (4-cyanatophenyl) propane, 2,2-bis (4-cyanato-3-methylphenyl) propane, 2, 2-bis (4-cyanato-3-tert-butylphenyl) propane, 2,2-bis (4-cyanato-3-iso-propylphenyl) Propane, 2,2-bis (4-cyanato-3,5-dimethylphenyl) propane, 2,2-bis (2-cyanato-3-tert-butyl-5-methylphenyl) propane, 2,2-bis ( 4-cyanato-3-tert-butyl-6-methylphenyl) propane, 2,2-bis (3-allyl-4-cyanatophenyl) propane, 2,2-bis (4-cyanatophenyl) hexafluoropropane 1,1-bis (4-cyanatophenyl) butane, 1,1-bis (4-cyanato-3-methylphenyl) butane, 1,1-bis (4-cyanato-3-tert-butylphenyl) butane 1,1-bis (4-cyanato-3-iso-propylphenyl) butane, 1,1-bis (4-cyanato-3,5-dimethylphenyl) butane, 1,1-bis (2-si Anato-3-tert-butyl-5-methylphenyl) butane, 1,1-bis (4-cyanato-3-tert-butyl-6-methylphenyl) butane, 1,1-bis (3-allyl-4-) Cyanatophenyl) butane, bis (4-cyanatophenyl) ether, bis (4-cyanato-3-methylphenyl) ether, bis (4-cyanato-3-tert-butylphenyl) ether, bis (4-cyanato-) 3-iso-propylphenyl) ether, bis (4-cyanato-3,5-dimethylphenyl) ether, bis (2-cyanato-3-tert-butyl-5-methylphenyl) ether, bis (4-cyanatophenyl) ) Sulfide, bis (4-cyanato-3-methylphenyl) sulfide, bis (4-cyanato-3-tert-butylphenyl) ) Sulfide, bis (4-cyanato-3-iso-propylphenyl) sulfide, bis (4-cyanato-3,5-dimethylphenyl) sulfide, bis (2-cyanato-3-tert-butyl-5-methylphenyl) Sulfide, bis (4-cyanatophenyl) sulfone, bis (4-cyanato-3-methylphenyl) sulfone, bis (4-cyanato-3-tert-butylphenyl) sulfone, bis (4-cyanato-3-iso-) Propylphenyl) sulfone, bis (4-cyanato-3,5-dimethylphenyl) sulfone, bis (2-cyanato-3-tert-butyl-5-methylphenyl) sulfone, bis (4-cyanatophenyl) carbonyl, bis (4-cyanato-3-methylphenyl) carbonyl, bis (4-cyanato-3-te) t-butylphenyl) carbonyl, bis (4-cyanato-3-iso-propylphenyl) carbonyl, bis (4-cyanato-3,5-dimethylphenyl) carbonyl, bis (2-cyanato-3-tert-butyl-5) -Methylphenyl) carbonyl, 1,1-bis (4-cyanatophenyl) cyclohexane, 1,1-bis (4-cyanato-3-methylphenyl) cyclohexane, tris (4-cyanatophenyl) phosphite and tris ( 4-Cyanatophenyl) phosphate.

  As a prepolymer production method as described above, a cyanate ester compound is polymerized using, for example, acids such as mineral acids and Lewis acids, salts such as sodium alcoholates and tertiary amines, and salts such as sodium carbonate as catalysts. The method etc. can be mentioned. At this time, a novolak resin or an oligomer of a hydroxyl group-containing thermoplastic resin (for example, hydroxypolyphenylene ether or hydroxypolystyrene) and cyanogen halide may be added to the polymerization reaction system.

  In addition, what is preferable as cyanate ester resin is obtained by reaction of 2, 2-bis (4-cyanatophenyl) propane, 1, 1-bis (4-cyanatophenyl) butane, a novolak resin, and cyanogen halide. Cyanate ester resins. Two or more cyanate ester resins may be used in combination.

  When a cyanate ester resin is used as the resin component, it is preferable to add a curing catalyst and other resins to the resin composition of the present invention in order to improve thermosetting. The resin composition of the present invention using a cyanate ester resin (hereinafter sometimes referred to as “cyanate ester resin composition”) can exhibit excellent dielectric properties as described later when the degree of curing is high. Therefore, it is necessary to sufficiently cure the cyanate ester resin, but the curing reaction of the cyanate ester resin may require a time of 2 hours or more at a high temperature of 200 ° C. or higher. In order to accelerate the curing reaction, it is preferable to use a curing catalyst.

  The curing catalyst that can be used here is not particularly limited as long as it is a compound that can accelerate the curing reaction of the cyanate ester resin, and examples thereof include copper (II) acetylacetonate and cobalt (II) acetylacetate. Chelate compounds of acetylacetonate and metal such as nato, cobalt (III) acetylacetonate, zinc (II) acetylacetonate and manganese (II) acetylacetonate, copper octylate, cobalt octylate, zinc octylate, naphthene Carboxylic acid metal salt catalysts such as copper acid, cobalt naphthenate and zinc naphthenate, N- (4-hydroxyphenyl) maleimide, p-tert-butylphenol, p-tert-amylphenol, p-tert-octylphenol, 4-alkyl Alkylphenols such as myrphenol and nonylphenol Examples thereof include compounds having active hydrogen such as diols, phenol resins, and alcohols having low volatility. These curing catalysts can be used alone or in appropriate combination. Preferred as the curing catalyst is a chelate compound of acetylacetonate and metal, particularly copper (II) acetylacetonate or zinc (II) acetylacetonate and metal in that the curing reaction can be further promoted. It is a chelate compound.

  The amount of the curing catalyst used can be set according to the type of the curing catalyst and the degree of promoting the curing reaction. For example, when the curing catalyst is a chelate compound of acetylacetonate and metal, it is preferably used in the range of 0.001 to 0.1 parts by weight with respect to 100 parts by weight of the cyanate ester resin composition. Moreover, when a curing catalyst is another compound, it is preferable to use in 0.1 to 20 weight part with respect to 100 weight part of cyanate ester resin compositions. If the amount of the curing catalyst used is less than the above range, the effect of promoting the curing reaction may be insufficient, and if it exceeds the above range, the storage stability of the resulting cyanate ester resin composition will be impaired. May occur.

  The cyanate ester resin composition reacts with an appropriate amount of a monovalent phenolic compound to the cyanate group-containing cyclic phosphazene compound of the present invention, thereby converting the cyanate group to imide carbonate and reducing the remaining cyanate group after curing. Can do. By reducing the number of highly polar cyanate groups after curing, the dielectric constant and dielectric loss tangent of the entire cured product can be lowered to the value of a cured product consisting only of a cyanate ester resin. Monovalent phenolic compounds used for this purpose are preferably those having high reactivity with cyanato groups, monofunctionality and relatively low molecular weight, and good compatibility with cyanate ester compounds. Examples of such monovalent phenol compounds include p-tert-butylphenol, p-tert-amylphenol, p-tert-octylphenol, 4-cumylphenol and nonylphenol used as curing catalysts. Can do.

  The epoxy resin that can be used in the resin composition of the present invention is not particularly limited as long as it is a compound having two or more epoxy groups in one molecule. Specific examples thereof include phenol novolac type epoxy resins, brominated phenol novolak type epoxy resins, orthocresol novolak type epoxy resins, biphenyl novolac type epoxy resins, bisphenol-A novolak type epoxy resins and naphthol novolak type epoxy resins. Type epoxy resin, bisphenol-A type epoxy resin, brominated bisphenol-A type epoxy resin, bisphenol-F type epoxy resin, bisphenol-AD type epoxy resin, bisphenol-S type epoxy resin obtained by reaction of aldehydes with aldehydes , Biphenol type epoxy resin, naphthalene type epoxy resin, cyclopentagen type epoxy resin, alkyl-substituted biphenol type epoxy resin, polyfunctional phenol type epoxy resin Resin, obtained by reaction of phenols such as tris (hydroxyphenyl) methane and epichlorohydrin, obtained by reaction of phenolic epoxy resin, trimethylolpropane, oligopropylene glycol, hydrogenated bisphenol-A and the like with epichlorohydrin Aliphatic epoxy resin, hexahydrophthalic acid, tetrahydrophthalic acid or phthalic acid obtained by reaction of epichlorohydrin or 2-methylepichlorohydrin, glycidyl ester epoxy resin, obtained by reaction of amine such as diaminodiphenylmethane or aminophenol with epichlorohydrin Heterocyclic epoxies obtained by the reaction of polyamines such as glycidylamine epoxy resins and isocyanuric acid with epichlorohydrin Phosphazene compounds having a glycidyl group, an epoxy-modified phosphazene resins, isocyanate modified epoxy resin, cyclic aliphatic epoxy resins and urethane-modified epoxy resins. Among these, phenol novolac type epoxy resins, orthocresol novolac type epoxy resins, bisphenol-A type epoxy resins, biphenol type epoxy resins, biphenyl novolac type epoxy resins, naphthalene type epoxy resins, polyfunctional phenol type epoxy resins and tris (hydroxy) Phenolic epoxy resins obtained by reaction of phenyl) methane with epichlorohydrin are preferred. These epoxy resins may be used alone or in combination of two or more.

  When the above-described epoxy resin is used as the resin component (hereinafter, such a resin composition may be referred to as “epoxy resin composition”), the cyanate group-containing cyclic phosphazene compound of the present invention is obtained by reaction with an epoxy group, Since it forms an oxazolidone ring, it can function as a curing agent for epoxy resins. Moreover, the epoxy resin composition may contain the other hardening | curing agent together with the cyanato group containing cyclic phosphazene compound of this invention. When the epoxy resin composition uses the cyanate group-containing cyclic phosphazene compound of the present invention in combination with another curing agent as a curing agent, the total amount of the curing agent (that is, the cyanate group-containing cyclic phosphazene compound of the present invention and others) The ratio of the cyanato group-containing cyclic phosphazene compound of the present invention to the total amount of the curing agent is preferably 0.1 to 99% by weight, more preferably 0.5 to 90% by weight. When the ratio of the cyanato group-containing cyclic phosphazene compound is less than 0.1% by weight, the resin molded body made of the resin composition may not exhibit sufficient flame retardancy.

  Other curing agents that can be used in combination with the cyanato group-containing cyclic phosphazene compound in the epoxy resin composition are not particularly limited. For example, polyamine curing agents such as aliphatic polyamines, aromatic polyamines, and polyamide polyamines, Acid anhydride curing agents such as hexahydrophthalic anhydride and methyltetrahydrophthalic anhydride, phenolic curing agents such as phenol novolac and cresol novolac, phosphazene compounds having a hydroxyl group, Lewis acids such as boron trifluoride and their salts And dicyandiamides. These may be used alone or in combination of two or more.

  In the epoxy resin composition, the amount of the curing agent (that is, the cyanate group-containing cyclic phosphazene compound of the present invention or the combined use of the cyanato group-containing cyclic phosphazene compound of the present invention and the above-mentioned other curing agent) It is preferably set to 0.5 to 1.5 equivalents, more preferably 0.6 to 1.2 equivalents, per 1 equivalent of epoxy group.

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

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

  The resin composition of the present invention such as the above-described cyanate ester resin composition and 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 cyanate group-containing cyclic phosphazene compound of the present invention reacts with the resin component of the cyanate group, and is stably held in the cured product. Therefore, the high temperature reliability of the cured product is improved. Hard to lose. In addition, the cyanate group-containing cyclic phosphazene compound of the present invention can enhance the flame retardancy without impairing the mechanical properties (particularly the glass transition temperature) of such a 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 addition, since the dielectric properties of polymer materials are greatly influenced by the orientation polarization of the dipoles of the molecules used, the dielectric constant can be lowered by reducing the number of polar groups in the molecule. The dielectric loss tangent can be lowered by suppressing the mobility of the group. Although the cyanate group-containing cyclic phosphazene compound contained in the resin composition of the present invention has a highly polar cyanate group, it can form a symmetric and rigid triazine structure upon curing. It is difficult to increase the rate and dielectric loss tangent. For this reason, according to the resin composition of the present invention, a cured product having a low dielectric constant and dielectric loss tangent can be obtained. Therefore, the resin composition of the present invention is used for semiconductor encapsulation and circuit boards (in particular, metal-clad laminates, printed wiring board substrates, printed wiring board adhesives, printed wiring board adhesive sheets, and printed wiring board use). Insulating circuit protective film, conductive paste for printed wiring board, sealing agent for multilayer printed wiring board, circuit protective agent, cover lay film, cover ink), etc. are particularly suitable as materials for manufacturing electrical and electronic parts. .

Polymerizable composition The polymerizable composition of the present invention contains the cyanate group-containing cyclic phosphazene compound of the present invention. Two or more kinds of cyanato group-containing cyclic phosphazene compounds may be used. This polymerizable composition can be blended with various additives in a range that does not impair the intended physical properties, depending on the application. Available additives are the same as those mentioned in the description of the resin composition.

  Further, the polymerizable composition may contain a curing catalyst in order to improve thermosetting. The curing catalyst that can be used here is usually the same as that described in the description of the resin composition, that is, a chelate compound of acetylacetonate and a metal, a carboxylic acid metal salt catalyst, an alkylphenol, a phenol resin. And compounds having active hydrogen such as alcohols having low volatility.

  Further, as in the case of the resin composition described above, this polymerizable composition reduces cyanate groups converted to imide carbonate to reduce cyanate groups remaining after curing, and lowers the dielectric constant and dielectric loss tangent of the polymer (cured product). For the purpose of making it, a monovalent phenol compound may be contained. The monovalent phenol compounds used for this purpose are the same as those mentioned in the description of the resin composition.

  The polymerizable composition of the present invention can be obtained by uniformly mixing required components. In general, when this polymerizable composition is heated, polymerization between cyanate group-containing cyclic phosphazene compounds proceeds to become a polymer, thereby forming a cured product (resin molded product). Since this cured product is substantially composed of the cyanate group-containing cyclic phosphazene polymer of the present invention, it has excellent flame retardancy and high temperature reliability, and also has excellent mechanical properties due to its high glass transition temperature. . For this reason, the polymerizable composition of the present invention can be widely used as a material for producing a resin molded body used in various fields.

  Further, the cyanate group-containing cyclic phosphazene compound contained in the polymerizable composition of the present invention has a highly polar cyanate group, but can produce a symmetric and rigid triazine structure upon curing. Therefore, it is difficult to increase the dielectric constant and dielectric loss tangent of the cured product. For this reason, according to the polymerizable composition of the present invention, a cured product having a low dielectric constant and dielectric loss tangent can be obtained. Accordingly, the polymerizable composition of the present invention is suitable for semiconductor encapsulation and circuit boards (in particular, metal-clad laminates, printed wiring board substrates, printed wiring board adhesives, printed wiring board adhesive sheets, printed wiring boards. Insulating circuit protective film for printed circuit board, conductive paste for printed wiring board, sealing agent for multilayer printed wiring board, circuit protective agent, coverlay film, cover ink), etc. is there.

EXAMPLES The present invention will be specifically described below with reference to examples and the like, but the present invention is not limited by these.
In the following, “unit” in “unit mol” means the smallest structural unit of the cyclic phosphazene compound, for example, (PNA ₂ ) for general formula (1) and (PNX ₂ ) for general formula (3). ). 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 examples and the like were prepared by measuring ¹ H-NMR spectrum and ³¹ P-NMR spectrum, CHN elemental analysis, IR spectrum, chlorine element (residual element) by potentiometric titration method using silver nitrate after alkali melting. Chlorine) analysis, analysis of phosphorus element by ICP-AES after microwave wet decomposition, and TOF-MS analysis. The hydroxyl equivalent is determined by neutralization titration according to the method for measuring hydroxyl value defined in JIS K 0070-1992 “Testing methods for acid value, saponification value, ester value, iodine value, hydroxyl value and unsaponified product of chemical products”. The hydroxyl value mgKOH / g was measured according to the method, and the hydroxyl equivalent weight g / eq. Converted to.

Example 1 (Production of cyanato group-containing cyclic phosphazene compound according to Form B)
[Step 1: Production of a substituted cyclic phosphonitrile by the above-mentioned method Bd]
Under a nitrogen stream, hexachlorocyclotriphosphazene (86.9 g, 0.75 unit mol) was charged into a 1 liter four-necked flask equipped with a thermometer, stirrer, condenser and dropping funnel, and chlorobenzene (MCB, 581 g). To dissolve. A solution of sodium phenoxide (87 g, 0.75 mol) in tetrahydrofuran (THF, 160 g) was slowly added dropwise over 5 hours, and the mixture was stirred at 25 ° C. for 24 hours. The obtained reaction solution was added to a MCB (813 g) suspension of 4-hydroxybenzaldehyde potassium salt (140.5 g, 0.975 mol) prepared in advance, and then tetrabutylammonium bromide (1.5 g, 0.0047 mol). Was added and refluxed at 110 ° C. for 3 hours. After cooling the reaction mixture to room temperature, 5% aqueous sodium hydroxide solution (700 g), water (100 g), and MCB (111 g) were added, and the mixture was transferred to a separatory funnel. After separating the aqueous layer, the MCB layer was washed twice with a 2% aqueous sodium hydroxide solution (500 g), neutralized with dilute nitric acid, and washed with water. The MCB layer was concentrated under reduced pressure to obtain 187.7 g (yield: 96.5%) of the product. The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
-C ₆ H ₄ - and _{OC 6 H 5 6.9~7.8 (30H)} , -CHO 9.95 (3H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.9
IR spectrum (KBr):
Confirmed 1704 cm ⁻¹ (CHO).
◎ CHNP elemental analysis:
Theoretical value C: 60.2%, H: 3.9%, N: 5.0%, P: 12.0%
Measured value C: 60.4%, H: 3.9%, N: 5.5%, P: 12.1%
◎ 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 CHO) (OC ₆ H ₅ ) ₅ ], [N ₃ = P ₃ (OC ₆ H ₄ CHO)]. ₂ (OC ₆ H ₅ ) ₄ ], [N ₃ = P ₃ (OC ₆ H ₄ CHO) ₃ (OC ₆ H ₅ ) ₃ ], [N ₃ = P ₃ (OC ₆ H ₄ CHO) ₄ (OC ₆ H ₅ ) ₂ ], and the average composition was confirmed to be [N ₃ = P ₃ (OC ₆ H ₄ CHO) _2.7 (OC ₆ H ₅ ) _3.3 ].

[Step 2: Condensation step with phenols]
The compound obtained in Step 1 (187.1 g, 0.241 mol), phenol (274.5 g, 2.89 mol), MCB (in a 2 liter four-necked flask equipped with a thermometer, a stirrer, and a condenser tube, 1,327 g) and p-toluenesulfonic acid (5.92 g, 0.028 mol) were added and stirred at 60 ° C. for 2 hours. Thereafter, a dehydrator (Dean Stark) was attached, and the mixture was further heated to 130 ° C., and the generated water was removed from the system. After completion of the reaction, the mixture was cooled to room temperature, 4-methyl-2-pentanone (MIBK, 801 g) was added, and the mixture was washed with water three times. After the MIBK layer was concentrated under reduced pressure, the concentrated residue was crystallized with a methanol-water mixed solvent to obtain 232 g (yield 75%) of a red product. The analysis result of this product was as follows.

¹ H-NMR spectrum (in heavy acetone, δ, ppm):
_{-CH- 5.4~6.3 (3H), - C} 6 H 4 - and _{OC 6 H 5 6.9~7.8 (49H)} , - OH 8.04 (6H)
◎ ³¹ P-NMR spectrum (in heavy acetone, δ, ppm):
Trimer (P = N) ₃ 9.9
IR spectrum (KBr):
3500 cm ⁻¹ (OH) was confirmed, and disappearance of 1704 cm ⁻¹ was confirmed.
◎ CHNP elemental analysis:
Theoretical value C: 70.1%, H: 4.5%, N: 3.3%, P: 7.2%
Measured value C: 69.7%, H: 4.5%, N: 4.4%, P: 7.6%
◎ Hydroxyl equivalent:
222 g / eq. (Theoretical value 215 g / eq.)

From the above analysis results, the products obtained in this step are {N ₃ = P ₃ [OC ₆ H ₄ CH (C ₆ H ₄ OH) ₂ ] (OC ₆ H ₅ ) ₅ }, {N ₃ = P _{3 [OC 6 H 4 CH (} C 6 H 4 OH) 2] 2 (OC 6 H 5) 4}, {N 3 = P 3 [OC 6 H 4 CH (C 6 H 4 OH) 2] 3 (OC ₆ H ₅ ) ₃ }, {N ₃ = P ₃ [OC ₆ H ₄ CH (C ₆ H ₄ OH) ₂ ] ₄ (OC ₆ H ₅ ) ₂ }, the average composition of which is {N ₃ = it was confirmed that P ₃ is _{[OC 6 H 4 CH (C} 6 H 4 OH) 2] 2.7 (OC 6 H 5) 3.3}. Incidentally, _{(C 6} H 4 OH) substitution ratio of the group of the ^{compounds, 13} the results of C-NMR measurement, ortho: para = 2.5: 1.

[Step 3: Cyanating step]
Into a 3 liter four-necked flask equipped with a thermometer, a stirrer, and a dropping funnel, the compound obtained in Step 2 (200 g, hydroxyl group equivalent 222 g / eq., Hydroxyl group 0.901 eq.), Cyanogen bromide (124 g, 1.18 mol) and MIBK (400 g) were charged, and the internal temperature was cooled to 0 ° C. or lower while stirring. Next, a solution of triethylamine (118.4 g, 1.18 mol) in acetonitrile (550 g) was added dropwise at an internal temperature of 0 ° C. or lower, and then aged at the same temperature for 15 minutes. Toluene (1,200 g) and water (700 g) were added to the reaction mixture, and then transferred to a separatory funnel to separate the lower layer. The upper layer was washed with water (700 g) and then concentrated under reduced pressure at an internal temperature of 35 ° C. or lower to obtain a brown oil. The obtained crude product was dissolved in a mixed solvent of toluene (700 g) and MIBK (320 g), and then slowly dropped into heptane (3,460 g). The precipitated solid was collected by filtration and dried under reduced pressure at 35 ° C. or lower to obtain 206 g (yield 92.4%) of the product. The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
_{-CH- 5.4~6.3 (3H), - C} 6 H 4 - and _OC 6 _H 5 _6.9~7.8 (49H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.9
IR spectrum (KBr):
2260 cm < ^-1 > (OCN) was confirmed.
◎ CHNP elemental analysis:
Theoretical value C: 66.8%, H: 3.9%, N: 9.0%, P: 6.6%
Measured value C: 66.6%, H: 3.9%, N: 8.8%, P: 7.0%

From the above analysis results, the products obtained in this step are {N ₃ = P ₃ [OC ₆ H ₄ CH (C ₆ H ₄ OCN) ₂ ] (OC ₆ H ₅ ) ₅ }, {N ₃ = P ₃ [OC ₆ H ₄ CH (C ₆ H ₄ OCN) ₂ ] ₂ (OC ₆ H ₅ ) ₄ }, {N ₃ = P ₃ [OC ₆ H ₄ CH (C ₆ H ₄ OCN) ₂ ] ₃ (OC ₆ H ₅ ) ₃ }, {N ₃ = P ₃ [OC ₆ H ₄ CH (C ₆ H ₄ OCN) ₂ ] ₄ (OC ₆ H ₅ ) ₂ }, the average composition of which is {N ₃ = it was confirmed that P ₃ is _{[OC 6 H 4 CH (C} 6 H 4 OCN) 2] 2.7 (OC 6 H 5) 3.3}.

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

Example 2 (Production of resin molded body)
The prepolymer was prepared by heating the polymerizable composition composed of the cyanato group-containing cyclic phosphazene compound synthesized in Example 1 at 170 ° C. for 1 hour and triming a part thereof. Next, this was poured into a PTFE mold and cured by heating at 200 ° C. for 2 hours and at 230 ° C. for 3 hours to produce two types of sheet-like cured products (resin moldings) having a thickness of 1/16 inch and 5 mm. . It was confirmed by the IR spectrum that the cured product had completely lost cyanate group (OCN) absorption.

  The obtained sheet-like cured product was examined for combustibility, heat resistance, dielectric properties in the gigahertz band and glass transition temperature. Flammability and heat resistance were evaluated using a 1/16 inch thick sheet-like cured product. The dielectric properties and glass transition temperature were evaluated using a 5 mm thick sheet-like cured product. The evaluation method for each item is as follows. The results are shown in Table 1.

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

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

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

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

(Heat-resistant)
The test piece was treated at 288 ° C. for 20 minutes and the change in appearance was observed. In Table 1, “Yes” indicates that there is no change in appearance due to bleeding out of the cyclic phosphazene compound. “None” indicates that there is a change in appearance due to bleeding out of the cyclic phosphazene compound.

(Dielectric properties)
Using a cavity resonator perturbation method complex dielectric constant evaluation device (trade name of Kanto Electronics Application Development Co., Ltd.), the dielectric constant and dielectric loss tangent of a sheet-like cured product left for 24 hours under the following conditions are measured under the following conditions: did.
Measurement temperature: 22-24 ° C
Measurement humidity: 45-55%
Measurement frequency: 5 GHz

(Glass transition temperature: Tg)
Using a DMS-200 (trade name) manufactured by Seiko Denshi Kogyo Co., Ltd., and measuring length (measurement jig interval) of 20 mm, the storage elastic modulus (ε ′) of the sheet-like cured product is measured under the following conditions. The inflection point of the storage elastic modulus (ε ′) was defined as the glass transition temperature (° C.).

Measurement atmosphere: Dry air atmosphere Measurement temperature: Measurement sample within a range of 20 to 400 ° C .: Cured resin sheet slit to 9 mm width and 40 mm length

  As is clear from Table 1, the sheet-like cured product of Example 2 exhibits a low dielectric constant and an excellent dielectric loss tangent at a frequency in the gigahertz band, and also exhibits a high glass transition temperature.

  For comparison, an attempt was made to produce a sheet-like cured product using the cyclic phosphazene compound synthesized in Comparative Example 1. Here, the cyclic phosphazene compound synthesized in Comparative Example 1 was heated at 170 ° C. for 1 hour, then poured into a PTFE mold and heated at 200 ° C. for 2 hours and at 230 ° C. for 3 hours. The appearance changed from a white solid to a brown solid. When the heated solid was added to toluene, the solid was completely dissolved and no curing had occurred. That is, no sheet-like cured product was obtained, and the same evaluation as in Example 2 could not be performed.

Synthesis Example 1 (Synthesis of soluble polyimide resin)
In a 3 liter glass flask equipped with a stirrer, thermometer, reflux condenser and nitrogen inlet tube, 277.7 g (0.95 mol) of 1,3-bis (3-aminophenoxy) benzene and 3,3 ′ -Dihydroxy-4,4'-diaminobiphenyl (10.7 g, 0.05 mol) and N, N-dimethylformamide (DMF) (700 ml) were charged and dissolved under stirring in a nitrogen atmosphere. Next, the solution in the flask was stirred under a nitrogen atmosphere, and a DMF solution of 4,4 ′-(4,4′-isopropylidenediphenoxy) bisphthalic anhydride (IPBP) [IPBP 520.5 g (1.00 mol) , DMF1,100 ml] was added dropwise at 5 to 10 ° C. over 2 hours, and further stirred at room temperature for 3 hours to obtain a polyamic acid solution. 2,500 g of the resulting polyamic acid solution was transferred to a tray coated with a fluororesin (PTFE), and heated under reduced pressure in a vacuum oven (conditions: 200 ° C., 5.7 hPa or less, 6 hours) to obtain 750 g of a soluble polyimide resin. Obtained.

Synthesis Example 2 (Synthesis of bifunctional PPE oligomer)
In a 2 liter glass flask equipped with a stirrer, thermometer, reflux condenser and air inlet tube, 1.3 g (0.012 mol) of CuCl, 70.7 g (0.55 mol) of di-n-butylamine and 500 ml of methyl ethyl ketone were added. And 45.4 g (0.16 mol) of 4,4 ′-(1-methylethylidene) bis (2,6-dimethylphenol) previously dissolved in 1,000 ml of methyl ethyl ketone, with stirring at a reaction temperature of 40 ° C. 2,8.6 g (0.48 mol) of 2,6-dimethylphenol was added dropwise over 2 hours while bubbling air at 2 liters / minute, and then bubbling air at 2 liters / minute for 1 hour. Stirring was performed. And the ethylenediaminetetraacetic acid disodium dihydrogen aqueous solution was added to this, and reaction was stopped. Thereafter, washing was performed 3 times with a 3% hydrochloric acid aqueous solution, followed by further washing with ion-exchanged water. The resulting solution was concentrated and further dried under reduced pressure to obtain 101.3 g of a bifunctional PPE oligomer having hydroxyl groups at both ends. This oligomer has a number average molecular weight of 860, a weight average molecular weight of 1,150, and a hydroxyl group equivalent of 455 g / eq. Met.

Examples 3 to 4 (Preparation of resin composition)
50 g of the soluble polyimide resin obtained in Synthesis Example 1, 25.0 g of 2,2′-bis (4-cyanatophenyl) propane (trade name “BADCy” from Lonza), which is a bisphenol A-based cyanate compound, and a table The cyanate group-containing cyclic phosphazene compound shown in 2 was dissolved in dioxolane to obtain a resin solution (resin composition).

  This resin solution was cast on the surface of a 125 μm-thick PET film (trade name “Therapy HP” from Toyo Metallizing Co., Ltd.). Thereafter, it was heated and dried for 3 minutes at 60 ° C., 80 ° C., 100 ° C., 120 ° C. and 140 ° C. in a hot air oven to obtain a two-layer resin sheet using a PET film as a support. From this two-layer resin sheet, the PET film was peeled and removed to obtain a single-layer resin sheet (thickness before heat curing 50 μm). The obtained resin sheet is sandwiched between 18 μm rolled copper foil (trade name “BHY-22B-T” of Japan Energy Co., Ltd.) so that the resin surface is in contact with the roughened copper foil, and the temperature is 230 ° C. and the pressure is 3 MPa. A copper foil laminate (single layer resin sheet sandwiched between rolled copper foils) was obtained by heating and pressurizing for 1 hour under the above conditions.

  The thus obtained copper foil laminate having copper foil layers on both sides was evaluated for solder heat resistance. Moreover, the copper foil of the obtained copper foil laminated body was removed by etching, and the cured sheet was obtained. The cured sheet was measured for dielectric properties, flammability, and glass transition temperature (Tg). The evaluation method of solder heat resistance is as follows. The dielectric properties, flammability and glass transition temperature were measured by the same method and conditions as in Example 2. The results are shown in Table 2.

(Solder heat resistance)
A test piece having a length of 30 mm and a width of 15 mm was cut out from the copper foil laminate, and the test piece was left in an environment of a temperature of 22.5 to 23.5 ° C. and a humidity of 39.5 to 40.5% for 24 hours. Then, the test piece was dipped in molten solder at 288 ° C. for 1 minute, and only the copper foil on one side was etched. Thereafter, the resin portion was visually observed, and if there was no abnormality such as foaming or swelling, it was determined to be acceptable, and the number of failures in 20 samples was examined.

Comparative Example 2 (Preparation of resin composition)
A resin composition was obtained in the same manner as in Examples 3 to 4, except that 25.0 g of the cyclic phosphazene compound produced in Comparative Example 1 was used instead of the cyanato group-containing cyclic phosphazene compound produced in Example 2. . Using this resin composition, a copper foil laminate and a cured sheet were obtained by the same method and conditions as in Examples 3 to 4, and solder heat resistance, dielectric properties, combustibility, and glass transition temperature were evaluated. The results are shown in Table 2.

  As is clear from Table 2, the cured product comprising the resin compositions of Examples 3 to 4 showed a low dielectric constant and an excellent dielectric loss tangent at a gigahertz band frequency as compared with Comparative Example 2, and had a high glass transition. Shows temperature and excellent solder heat resistance.

Examples 5 to 6 (Preparation of resin composition)
20.0 g of the bifunctional PPE oligomer obtained in Synthesis Example 2 (hydroxyl equivalent: 455 g / eq), a cyanato group-containing cyclic phosphazene compound shown in Table 3, and 2,2′-bis (4-cyanatophenyl) propane (Lonza) 50.0 g of a trade name “BADCy” of the company was dissolved in dioxolane to obtain a resin solution (resin composition).

  This resin solution was cast on the surface of a 125 μm-thick PET film (trade name “Therapy HP” from Toyo Metallizing Co., Ltd.). Thereafter, it was heated and dried for 3 minutes at 60 ° C., 80 ° C., 100 ° C., 120 ° C. and 140 ° C. in a hot air oven to obtain a two-layer resin sheet using a PET film as a support. The PET film was peeled and removed from the two-layer resin sheet to obtain a single-layer resin sheet (thickness before heat curing was 50 μm). The obtained resin sheet is sandwiched between 18 μm rolled copper foil (trade name “BHY-22B-T” of Japan Energy Co., Ltd.) so that the resin surface is in contact with the roughened copper foil, and the temperature is 230 ° C. and the pressure is 3 MPa. A copper foil laminate (single layer resin sheet sandwiched between rolled copper foils) was obtained by heating and pressing for 1 hour under the above conditions. And about this copper foil laminated body, the solder heat resistance was evaluated by the method similar to Examples 3-4. Moreover, about the hardening sheet obtained by removing the copper foil of a copper foil laminated body by an etching, the dielectric property, the combustibility, and the glass transition temperature were measured by the method similar to Examples 3-4. The results are shown in Table 3.

Comparative Example 3 (Preparation of resin composition)
A resin composition was obtained in the same manner as in Example 5 except that 30.0 g of the cyclic phosphazene compound produced in Comparative Example 1 was used instead of the cyanato group-containing cyclic phosphazene compound produced in Example 2. Using this resin composition, a copper foil laminate and a cured sheet were obtained by the same method and conditions as in Examples 5 to 6, and solder heat resistance, dielectric properties, flammability, and glass transition temperature were evaluated. The results are shown in Table 3.

  As is clear from Table 3, the cured product comprising the resin compositions of Examples 5 to 6 showed a low dielectric constant and an excellent dielectric loss tangent at a gigahertz band frequency as compared with Comparative Example 3, and a high glass transition. Shows temperature and excellent solder heat resistance.

Claims (10)

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

(In the formula (1), n represents an integer of 3 to 15, A represents a group selected from the group consisting of the following A1, A2, and A3 groups, and at least one is an A3 group.
A1 group: an alkoxy group having 1 to 8 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: 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.
Group A3: a group selected from the group consisting of a cyanatophenyl-substituted phenyloxy group represented by the following formula (2).

In formula (2), X ¹ to X ⁸ each independently represents a hydrogen atom, an alkyl group or an aryl group. )   The cyanate group-containing cyclic phosphazene compound according to claim 1, wherein in formula (1), 1 to (2n-2) of 2n A are A3 groups.   The cyanate group-containing cyclic phosphazene compound according to claim 1 or 2, wherein n in formula (1) is 3 or 4.   The cyanato group-containing cyclic phosphazene compound according to any one of claims 1 to 3, comprising two or more cyanato group-containing cyclic phosphazene compounds having different n in the formula (1). Selected from the group consisting of the following E1, E2, and E3 groups such that at least one of the halogen atoms of the cyclic phosphonitrile dihalide represented by the following formula (3) is substituted by the following E3 group: Substituting with a group to produce a formyl group-containing cyclic phosphonitrile substitution product,

(In formula (3), n represents an integer of 3 to 15, and X represents a halogen atom.
E1 group: An alkoxy group having 1 to 8 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.
E2 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.
E3 group: a group selected from the group consisting of a formyl group-substituted phenyloxy group represented by the following formula (4). )

The above-mentioned formyl group (E3 group: formyl group-substituted phenyloxy group) -containing cyclic phosphonitrile substituted product is reacted with a phenol represented by the following formula (5) to contain a hydroxyl group represented by the following E4 group Producing a cyclic phosphonitrile substitution product;

(In formula (5), X ⁹ to X ¹³ each independently represents a hydrogen atom, an alkyl group or an aryl group.
E4 group: a group selected from the group consisting of a hydroxyl group-substituted phenyloxy group represented by the following formula (6).

In formula (6), X ¹ to X ⁸ each independently represent a hydrogen atom, an alkyl group or an aryl group. )
And a step of reacting the hydroxyl group-containing cyclic phosphonitrile substituted product with cyanogen halide. A method for producing a cyanato group-containing cyclic phosphazene compound.   A resin composition comprising a resin component and the cyanato group-containing cyclic phosphazene compound according to any one of claims 1 to 4.   The resin according to claim 6, wherein the resin component is selected from the group consisting of a cyanate ester resin, an epoxy resin, a polyimide resin, a bismaleimide resin, a bismaleimide-cyanate ester resin, and a modified polyphenylene ether resin. Composition.   The resin molding which consists of a resin composition of Claim 6 or 7.   A polymerizable composition comprising the cyanato group-containing cyclic phosphazene compound according to claim 1.   The resin molding which consists of a polymer of the polymeric composition of Claim 9.