JP5170510B2 - Reactive 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 method for producing the same, and more particularly to a reactive group-containing cyclic phosphazene compound and a method for producing the same.

  In the fields of industrial and consumer equipment and electrical products, synthetic resins have advantages over other materials in terms of processability, chemical resistance, weather resistance, electrical properties and mechanical strength. Since it has many, it is used frequently, and the usage is increasing. However, since synthetic resins have the property of being easily combusted, they are required to be provided with flame retardancy, and in recent years, the required performance is gradually increasing. For this reason, resin compositions 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. Also, phosphoric acid ester-based, phosphoric acid amide-based, phosphoric acid amide ester-based, and ammonium polyphosphate-based materials are easily hydrolyzed, so resin molded products that require mechanical and electrical long-term reliability. It is substantially difficult to use in the manufacturing material. 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 Hoffwazen flame retardant is likely to bleed out (elution) from the resin molded product 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 are being studied for improvement to improve the reliability of resin molded products at high temperatures (no high temperature reliability, no bleed out at high temperatures, or bulges). As examples, Patent Documents 6 to 10 disclose phosphazene compounds having an acryloyloxy group or a methacryloyloxy group, and polymers using the same. In this type of phosphazene compound, since the acryloyloxy group or methacryloyloxy group has polymerization reactivity, it can be used alone as a thermosetting resin. It can also be used as a part. The polymer of the phosphazene compound and the polymer obtained by using the phosphazene compound as part of the monomer have good high temperature reliability of the molded product, and have flame retardancy due to the phosphazene compound. Therefore, it is expected to be used as a resin material for products for electric and electronic parts.
However, a resin molded body made of this type of polymer is insufficient in terms of flame retardancy required as an essential effect, and is not satisfactory in mechanical properties (particularly, high glass transition temperature and adhesion). It is enough.

JP-A 64-14239 JP-A 64-14240 JP 2001-335676 A Japanese Patent Laid-Open No. 6-247989 JP-A-8-193091

  An 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 body and that does not easily impair the high temperature reliability of the resin molded body.

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

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

(In the formula (1), n represents an integer of 3 to 8, A represents a group selected from the group consisting of the following A1, 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.
A3 group: a substituted phenyloxy group having an allyl group and a hydroxyl group represented by the following formula (2), formula (3) or formula (4).

Z in Formula (4) represents O, S, SO ₂ , CH ₂ , CHCH ₃ , C (CH ₃ ) ₂ , C (CH ₃ ) CH ₂ CH ₃ or CO. )

  In the reactive group-containing cyclic phosphazene compound, for example, in formula (1), 2 to 2n-2 of 2n A are A3 groups.

  In the reactive group-containing cyclic phosphazene compound, for example, n in the formula (1) is 3 or 4. Furthermore, the reactive group-containing cyclic phosphazene compound includes, for example, two or more reactive group-containing cyclic phosphazene compounds in which n in formula (1) is different.

The method for producing a reactive group-containing cyclic phosphazene compound according to the present invention includes the following steps.
[Process]
By the group selected from the group consisting of the following E1, E2, and E3 groups so that at least one of the halogen atoms of the cyclic phosphonitrile dihalide represented by the following formula (5) is substituted by the E3 group: A step of producing a substituted allyloxy group-containing cyclic phosphonitrile (step 1);

(In Formula (5), n shows the integer of 3-8, X shows 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 substituted phenyloxy group having an allyloxy group represented by the following formula (6), formula (7) or formula (8).

Z in Formula (8) represents O, S, SO ₂ , CH ₂ , CHCH ₃ , C (CH ₃ ) ₂ , C (CH ₃ ) CH ₂ CH ₃ or CO. )

A step (Step 2) for producing a cyclic phosphonitrile substituted product having an allyl group and a hydroxyl group by rearranging the allyloxy group of the cyclic phosphonitrile-containing cyclic phosphonitrile substituted with Claisen.
A process for producing a reactive group-containing cyclic phosphazene compound comprising:

  The resin composition of the present invention contains a resin component and the reactive group-containing cyclic phosphazene compound of the present invention. This resin composition is, for example, at least one selected from a polymerizable material group consisting of a thermopolymerizable monomer, a thermopolymerizable oligomer, a photopolymerizable monomer, a photopolymerizable oligomer, a radiation polymerizable monomer, and a radiation polymerizable oligomer. It further includes a polymerizable material.

  The resin molded body of the present invention is composed of the resin composition of the present invention.

  The polymerizable composition of the present invention contains the reactive group-containing cyclic phosphazene compound of the present invention. The polymerizable composition further includes, for example, at least one polymerizable material of a monomer and an oligomer that can be polymerized with the reactive group-containing cyclic phosphazene compound.

  Another resin composition of the present invention includes a resin component and a polymer of the polymerizable composition of the present invention. Moreover, the other resin molding of this invention consists of the polymeric composition or resin composition of this invention.

  Since the reactive group-containing cyclic phosphazene compound of the present invention has a specific structure as described above, it is difficult to impair the mechanical properties (particularly, high glass transition temperature and adhesion) of the resin molding. It is possible to effectively increase the flammability, and it is difficult to impair the high temperature reliability of the resin molded body.

  Since the method for producing a reactive group-containing cyclic phosphazene compound according to the present invention includes the steps as described above, the reactive group-containing cyclic phosphazene compound having the specific structure as described above according to the present invention is produced. Can do.

  Since the resin composition of the present invention uses the reactive group-containing cyclic phosphazene compound of the present invention or the resin component and the reactive group-containing cyclic phosphazene compound of the present invention, a practical mechanical It is possible to obtain a resin molding exhibiting properties and flame retardancy and having high temperature reliability.

  Since the polymerizable composition of the present invention includes the reactive group-containing cyclic phosphazene compound of the present invention, the polymer exhibits a practical mechanical property and flame retardancy, and has a high temperature reliability. Can be obtained.

  Since the resin molded article of the present invention is composed of the resin composition of the present invention or the polymerizable composition of the present invention, it has practical mechanical properties (particularly, high glass transition temperature and adhesion) and flame retardancy. And high temperature reliability.

Reactive group-containing cyclic phosphazene compound The reactive 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 8, preferably an integer of 3 to 6, and particularly preferably 3 or 4. That is, particularly preferable as the reactive group-containing cyclic phosphazene compound are a reactive group-containing cyclotriphosphazene (trimer) in which n is 3 and a reactive group-containing cyclotetraphosphazene (tetramer) in which n is 4. is there. The reactive 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 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 1-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, Isopropenylphenoxy group, 1-butenylphenoxy group, sec-butenylphenoxy group, 1-pentenylphenoxy group, 1-hexenylphenoxy group, phenylphenoxy group, naphthyl Alkoxy group, anthryl group and phenanthryloxy groups and the like. Of these, a phenoxy group, a methylphenoxy group, a dimethylphenoxy group, a diethylphenoxy group, a 1-propenylphenoxy group, a phenylphenoxy group, and a naphthyloxy group are preferable, and a phenoxy group, a methylphenoxy group, a dimethylphenoxy group, and a naphthyloxy group are particularly preferable. preferable.

[Group A3]
A substituted phenyloxy group having an allyl group and a hydroxyl group represented by the following formula (2), formula (3) or formula (4).

In the formula (4), Z represents O, S, SO ₂ , CH ₂ , CHCH ₃ , C (CH ₃ ) ₂ , C (CH ₃ ) CH ₂ CH ₃ or CO.

  Specific examples of the A3 group described above include the following. For example, 3-allyl-2-hydroxyphenyloxy group, 2-allyl-3-hydroxyphenyloxy group, 4-allyl-3-hydroxyphenyloxy group, 3-allyl-4-hydroxyphenyloxy group, 3′-allyl 4′-hydroxyphenyl-4-phenyloxy group, 3′-allyl-4′-hydroxyphenyloxy-4-phenyloxy group, 3′-allyl-4′-hydroxyphenylthio-4-phenyloxy group, 3 '-Allyl-4'-hydroxyphenylsulfonyl-4-phenyloxy group, 3'-allyl-4'-hydroxyphenylmethylene-4-phenyloxy group, 3'-allyl-4'-hydroxyphenylethylene-4-phenyl Oxy group, 3'-allyl-4'-hydroxyphenylisopropylidene-4-phenyloxy , 3'-allyl-4'-hydroxyphenyl iso butylidene-4-phenyl group, 3'-allyl-4'-hydroxyphenyl-4- phenyl group, etc. Among these, 3-allyl-2-hydroxyphenyloxy group, 2-allyl-3-hydroxyphenyloxy group, 4-allyl-3-hydroxyphenyloxy group, 3-allyl-4-hydroxyphenyloxy group, 3′- Allyl-4′-hydroxyphenyl-4-phenyloxy group, 3′-allyl-4′-hydroxyphenyloxy-4-phenyloxy group, 3′-allyl-4′-hydroxyphenylsulfonyl-4-phenyloxy group, 3'-allyl-4'-hydroxyphenylisopropylidene-4-phenyloxy group, 3'-allyl-4'-hydroxyphenylcarbonyl-4-phenyloxy group is preferred, and 3-allyl-4-hydroxyphenyloxy group 3′-allyl-4′-hydroxyphenyloxy-4-phenyloxy group, 3′- Lil-4'-hydroxyphenyl-4- phenyl group, 3'-allyl-4'-hydroxyphenyl isopropyl kink Den-4-phenyl 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 reactive group-containing cyclic phosphazene compound of the present invention represented by the formula (1) can be represented in the following form.

[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 reactive-containing cyclic phosphazene compound having such a form include a cyanato group-containing cyclotriphosphazene compound in which n is 3 in formula (1), and a reactive-containing cyclotetrazane in which n is 4 in formula (1). A phosphazene compound, a reactive containing cyclopentaphosphazene compound wherein n in formula (1) is 5 and a reactive containing cyclohexaphosphazene compound wherein n in formula (1) is 6, wherein all of A is 3-allyl -4-hydroxyphenyloxy group, 3'-allyl-4'-hydroxyphenyloxy-4-phenyloxy group, 3'-allyl-4'-hydroxyphenylsulfonyl-4-phenyloxy group or 3'-allyl-4 '-Hydroxyphenylisopropylidene-4-phenyloxy group is a kind of A3 group selected from the group of A3 groups and What Te is two or more A3 groups selected from the A3 group group and can be exemplified any mixture 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.

  A preferable example of the reactive group-containing cyclic phosphazene compound of this form is one in which 2 to (2n-2) of 2n A are A3 groups. In particular, a reactive group-containing cyclotriphosphazene compound in which n in formula (1) is 3, a reactive group-containing cyclotetraphosphazene compound in which n in formula (1) is 4, and n in formula (1) is 5. A reactive group-containing cyclopentaphosphazene compound and a reactive group-containing cyclohexaphosphazene compound in which n in formula (1) is 6, wherein 2 to 2n-2 of 2n A are A3 groups As well as any mixtures thereof. This kind of reactive group-containing cyclic phosphazene compound is a resin having higher high-temperature reliability and mechanical properties (particularly, high glass transition temperature and adhesion) than other reactive group-containing cyclic phosphazene compounds of the present invention. This is advantageous in that a molded body can be realized.

  In addition, it can be confirmed by TOF-MS analysis of a reactive group containing cyclic phosphazene compound whether 2 to (2n-2) of 2n A are A3 groups.

  Specific examples of preferable reactive group-containing cyclic phosphazene compounds of this form include reactive group-containing cyclotriphosphazene compounds in which n in formula (1) is 3, and reactions in which n in formula (1) is 4. A reactive group-containing cyclotetraphosphazene compound, a reactive group-containing cyclopentaphosphazene compound in which n in formula (1) is 5, or a reactive group-containing cyclohexaphosphazene compound in which n in formula (1) is 6. Is a combination of 3-aryl-4-hydroxyphenyloxy group which is A3 group and ethoxy group which is A1 group, 3'-allyl-4'-hydroxyphenyloxy-4-phenyloxy group which is A3 group In combination with ethoxy group which is A1 group, 3′-allyl-4′-hydroxyphenylsulfonyl-4-phenyl which is A3 group Combination of xy group and ethoxy group which is A1 group, combination of 3'-allyl-4'-hydroxyphenylisopropylidene-4-phenyloxy group which is A3 group and ethoxy group which is A1 group A combination of 3-allyl-4-hydroxyphenyloxy group which is A3 group and n-propoxy group which is A1 group, 3'-allyl-4'-hydroxyphenyloxy-4-phenyloxy which is A3 group A combination of a group and an n-propoxy group which is an A1 group, a combination of a 3′-allyl-4′-hydroxyphenylsulfonyl-4-phenyloxy group which is an A3 group and an n-propoxy group which is an A1 group 3'-allyl-4'-hydroxyphenylisopropylidene-4-phenyloxy group which is A3 group and n-group which is A1 group A combination with a poxy group, a combination of 3-allyl-4-hydroxyphenyloxy group which is an A3 group and a phenoxy group which is an A2 group, 3'-allyl-4'-hydroxyphenyloxy which is an A3 group Combination of -4-phenyloxy group and phenoxy group which is A2 group, combination of 3′-allyl-4′-hydroxyphenylsulfonyl-4-phenyloxy group which is A3 group and phenoxy group which is A2 group A combination of 3'-allyl-4'-hydroxyphenylisopropylidene-4-phenyloxy group which is A3 group and phenoxy group which is A2 group, 3-allyl-4-hydroxy which is A3 group Combination of phenyloxy group and methylphenoxy group which is A2 group, 3′-allyl-4′-hy group which is A3 group Combination of droxyphenyloxy-4-phenyloxy group and methylphenoxy group which is A2 group, 3′-allyl-4′-hydroxyphenylsulfonyl-4-phenyloxy group which is A3 group and A2 group Combination with methylphenoxy group, combination of 3'-allyl-4'-hydroxyphenylisopropylidene-4-phenyloxy group which is A3 group and methylphenoxy group which is A2 group, A3 group Combination of 3-allyl-4-hydroxyphenyloxy group and dimethylphenoxy group which is A2 group, 3′-allyl-4′-hydroxyphenyloxy-4-phenyloxy group which is A3 group and A2 group Combination with dimethylphenoxy group, 3'-allyl-4'-hydroxyphene which is A3 group A combination of a rusulfonyl-4-phenyloxy group and a dimethylphenoxy group that is an A2 group, and a 3′-allyl-4′-hydroxyphenylisopropylidene-4-phenyloxy group and an A2 group that are A3 groups. Combination with dimethylphenoxy group, combination of A3 group 3-allyl-4-hydroxyphenyloxy group with A2 group naphthyloxy group, A3 group 3'-allyl-4'-hydroxy Combination of phenyloxy-4-phenyloxy group and naphthyloxy group which is A2 group, 3′-allyl-4′-hydroxyphenylsulfonyl-4-phenyloxy group which is A3 group and naphthyloxy which is A2 group In combination with a group, 3′-allyl-4′-hydroxyphenylisopropyl, which is an A3 group Those of the combination of a naphthyloxy group is Den-4-phenyl group and A2 groups and the like, and any mixture thereof.

  Among these, the reactive group-containing cyclotriphosphazene compound in which n in the formula (1) is 3, a reactive group-containing cyclotetraphosphazene compound in which n in the formula (1) is 4, and n in the formula (1) is 5. A reactive group-containing cyclopentaphosphazene compound, a reactive group-containing cyclohexaphosphazene compound in which n in formula (1) is 6, wherein A is an A3 group 3-allyl-4-hydroxyphenyloxy group and A1 A combination with a group n-propoxy group, a combination of a 3′-allyl-4′-hydroxyphenylsulfonyl-4-phenyloxy group with an A3 group and an n-propoxy group with an A1 group, A3 A combination of a group 3′-allyl-4′-hydroxyphenylisopropylidene-4-phenyloxy group and an n-propoxy group which is an A1 group, A A combination of the 3-aryl-4-hydroxyphenyloxy group as the group and the phenoxy group as the A2 group, the 3′-allyl-4′-hydroxyphenylsulfonyl-4-phenyloxy group and the A2 group as the A3 group A combination with a phenoxy group that is A3, a combination of 3′-allyl-4′-hydroxyphenylisopropylidene-4-phenyloxy group that is an A3 group and a phenoxy group that is an A2 group, an A3 group Combination of 3-allyl-4-hydroxyphenyloxy group and methylphenoxy group which is A2 group, 3′-allyl-4′-hydroxyphenylsulfonyl-4-phenyloxy group which is A3 group and A2 group Combination with methylphenoxy group, A3 group 3'-allyl-4'-hydroxyphenyl isop A combination of a biliden-4-phenyloxy group and a methylphenoxy group which is an A2 group, a combination of a 3-allyl-4-hydroxyphenyloxy group which is an A3 group and a naphthyloxy group which is an A2 group, A3 3'-allyl-4'-hydroxyphenylsulfonyl-4-phenyloxy group as a group and naphthyloxy group as A2 group, 3'-allyl-4'-hydroxyphenylisopropylene as A3 group A combination of a den-4-phenyloxy group and a naphthyloxy group which is an A2 group and an arbitrary mixture thereof are preferable.

  Particularly, a reactive group-containing cyclotriphosphazene compound in which n in formula (1) is 3 or a reactive group-containing cyclotetraphosphazene compound in which n in formula (1) is 4, wherein A is an A3 group. Combination of 3-allyl-4-hydroxyphenyloxy group and phenoxy group which is A2 group, 3′-allyl-4′-hydroxyphenylsulfonyl-4-phenyloxy group which is A3 group and phenoxy which is A2 group In combination with a group, 3'-allyl-4'-hydroxyphenylisopropylidene-4-phenyloxy group as an A3 group and a phenoxy group as an A2 group, 3-allyl as an A3 group A combination of a 4-hydroxyphenyloxy group and a methylphenoxy group that is A2 group, 3′-allyl-4′-hy group that is A3 group A combination of a loxyphenylsulfonyl-4-phenyloxy group and a methylphenoxy group which is an A2 group, a 3′-allyl-4′-hydroxyphenylisopropylidene-4-phenyloxy group and an A2 group which are A3 groups Combinations with certain methylphenoxy groups and any mixtures thereof are preferred.

Production method of reactive group-containing cyclic phosphazene compound When producing the reactive group-containing cyclic phosphazene compound of the present invention, first, a cyclic phosphonitrile dihalide represented by the following formula (5) is prepared.

  In the formula (5), n represents an integer of 3 to 8. 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 8, hexachlorocyclo Triphosphazene (n is 3), octachlorocyclotetraphosphazene (n is 4), decachlorocyclopentaphosphazene (n is 5), dodecachlorocyclohexaphosphazene (n is 6), hexachrome A mixture of rocyclotriphosphazene and octachlorocyclotetraphosphazene, a mixture of cyclic phosphonitrile dichlorides having n of 3 to 8, and the like. Of these, hexachlorocyclotriphosphazene, octachlorocyclotetraphosphazene, a mixture of hexachlorocyclotriphosphazene and octachlorocyclotetraphosphazene, and a mixture of cyclic phosphonitrile dichloride having n of 3 to 8, more preferably hexachlorocyclotriphosphazene, hexachloro Particular preference is given to mixtures of cyclotriphosphazene and octachlorocyclotetraphosphazene and mixtures of cyclic phosphonitrile dichlorides with n of 3 to 8.

  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-propene Examples include -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]
Phenols having an allyloxy group, which are the following compound B3-1, compound B3-2 or compound B3-3.

Compound B3-1
Phenols having an allyloxy group represented by the following formula (6).

Examples of the phenols having an allyloxy group include 2-allyloxyphenol, 3-allyloxyphenol, and 4-allyloxyphenol. Among these, 2-allyloxyphenol and 4-allyloxyphenol are preferable, and 4-allyloxyphenol is particularly preferable.

Compound B3-2
Phenols having an allyloxy group represented by the following formula (7).

Examples of phenols having an allyloxy group include 4′-allyloxyphenyl-4-phenol.

Compound B3-3
Phenols having an allyloxy group represented by the following formula (8).

Z in Formula (8) represents O, S, SO ₂ , CH ₂ , CHCH ₃ , C (CH ₃ ) ₂ , C (CH ₃ ) CH ₂ CH ₃ or CO. )

  Examples of the phenols having an allyloxy group include 4′-allyloxyphenyloxy-4-phenol, 4′-allyloxyphenylthio-4-phenol, 4′-allyloxyphenylsulfonyl-4-phenol, and 4 ′. -Allyloxyphenylmethylene-4-phenol, 4'-allyloxyphenylethylene-4-phenol, 4'-allyloxyphenylisopropylidene-4-phenol, 4'-allyloxyphenylisobutylidene-4-phenol, 4'-allyloxyphenylcarbonyl-4-phenol and the like. Among these, 4'-allyloxyphenyloxy-4-phenol, 4'-allyloxyphenylsulfonyl-4-phenol, 4'-allyloxyphenyl isopropylidene-4-phenol, 4'-allyloxyphenylcarbonyl-4 -Phenol is preferred, 4'-allyloxyphenyloxy-4-phenol, 4'-allyloxyphenylsulfonyl-4-phenol, 4'-allyloxyphenyl isopropylidene-4-phenol is particularly preferred.

[Step 1]
In the manufacturing method of the reactive group containing cyclic phosphazene compound of this invention, it shows by following Formula (9) using cyclic phosphonitrile dihalide represented by the above-mentioned formula (5), and above-mentioned compound B1-B3. Then, a substituted cyclic phosphonitrile (cyclic phosphazene compound) is produced.

In Formula (9), n shows the integer of 3-8. E represents a group selected from the group consisting of the following E1 group, E2 group and E3 group, provided that at least one of E is E3 group. Such a cyclic phosphonitrile-substituted product (cyclic phosphazene compound) is obtained by reacting the cyclic phosphonitrile dihalide represented by the above formula (5) with the above-mentioned compounds B1 to B3 to obtain the total halogen of the cyclic phosphonitrile dihalide. It can be produced by substituting an atom with a group selected from the group consisting of the above-mentioned E1, E2 and E3 groups such that at least one atom is substituted with the above-mentioned E3 group.
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 substituted phenyloxy group having an allyloxy group represented by the following formula (6), formula (7) or formula (8).

Z in Formula (8) represents O, S, SO ₂ , CH ₂ , CHCH ₃ , C (CH ₃ ) ₂ , C (CH ₃ ) CH ₂ CH ₃ or CO. )

  In this step, compounds B1 to B3 are appropriately selected and used depending on the type of reactive group-containing cyclic phosphazene compound to be produced. Specifically, it is as follows.

[Method for producing reactive group-containing cyclic phosphazene compound]
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 converted into compound B3. Substitution with the derived E3 group, and all of the remaining other active halogen atoms are replaced with at least one group of the E1 group derived from the compound B1 and the E2 group derived from the compound B2. As a method for this, any of the following methods can be adopted.

<Method A>
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 reactive 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, some of the active halogen atoms remain, and the target reactive 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>
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 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, some of the active halogen atoms remain, and the target reactive 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. Moreover, it is preferable to set the usage-amount of a base to 1.1-2.1 equivalent of the quantity of the active halogen atom of cyclic phosphonitrile dihalide, and to set to 1.1-1.4 equivalent. More preferred. When the amount used is less than 1.1 equivalents, a part of the active halogen atom remains, and the target reactive 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 C>
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 (step A). 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 (step B).

  Step A of this method may be carried out by reacting an alkali metal salt of compound B3 with cyclic phosphonitrile dihalide, or a base that captures hydrogen halide with compound B3 against cyclic phosphonitrile dihalide. You may make it react in presence of. Step B may be carried out by reacting the partially substituted product obtained in Step A with an alkali metal salt of at least one of Compound B1 and Compound B2, or obtained in Step A. The partially substituted product may be reacted with at least one of compound B1 and compound B2 in the presence of a base that captures hydrogen halide.

<Method D>
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 (step A). Next, compound B3 is reacted with the partially substituted product thus obtained, and all of the remaining active halogen atoms are substituted with E3 groups derived from compound B3 (step B).

  Step A 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 with respect to cyclic phosphonitrile dihalide, At least one of compound B1 and compound B2 may be reacted in the presence of a base that captures hydrogen halide. Step B may be carried out by reacting the partially substituted product obtained in Step A with an alkali metal salt of Compound B3. Alternatively, Compound B3 may be used on the partially substituted product obtained in Step A. You may make it react in presence of the base which capture | acquires a 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, lithium salt and sodium 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 sodium hydroxide, potassium hydroxide, lithium 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, 4,4-dimethylaminopyridine, 4 Aliphatic or aromatic amines such as 1,4-diethylaminopyridine and 4-diisopropylaminopyridine, alkali metal carbonates such as sodium carbonate, potassium carbonate, sodium bicarbonate and potassium bicarbonate, sodium hydroxide, potassium hydroxide and water Alkali metal hydroxides such as lithium oxide are preferred. In particular, alkali metal hydroxides such as triethylamine, pyridine and potassium 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, cyclopentyl methyl ether and diphenyl ether, aromatic hydrocarbons such as benzene, toluene, chlorobenzene, nitrobenzene, xylene, ethylbenzene and isopropylbenzene, chloroform and chloride Halogenated hydrocarbons such as methylene, aliphatic hydrocarbons such as pentane, hexane, cyclohexane, heptane, octane, nonane, undecane and dodecane, heterocyclic aromatic hydrocarbons such as pyridine, tertiary amines, etc. Down system and preferable to use an organic solvent of cyanide-based or the like. 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 0 ° 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.

  The reactive group-containing cyclic phosphazene compound according to the present invention is produced according to the above-described production method, particularly those in which 2 to 2n-2 of A in formula (1) are A3 groups. In this case, it is preferable to adopt the above-described method C or method D.

  Here, when adopting Method C, 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 D, 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.

  The allyloxy group-containing cyclic phosphazene compound obtained by the above production process 1 can be isolated and purified from the reaction system by ordinary methods such as filtration, solvent extraction, column chromatography, and recrystallization.

[Step 2]
Next, the allyloxy group of the E3 group of the allyloxy group-containing cyclic phosphonitrile substituted product obtained in the above step 1 is subjected to Claisen rearrangement to convert the allyloxy group portion of the E3 group into an allyl group and a hydroxyl group. Thereby, the cyclic phosphonitrile substituted product obtained in Step 1 is a reactive group-containing cyclic phosphazene compound in which the allyloxy group portion is converted into an allyl group and a hydroxyl group.

  A method for converting the allyloxy group of E3 into a Claisen rearrangement to convert to an allyl group and a hydroxyl group, that is, for the Claisen rearrangement, a method of reacting for about 10 hours usually by heating to 200 ° C. or higher with a heating medium or an electric heater ( Patent Document 11) and a method of dislocation in a short time of about 30 minutes by microwave irradiation (Patent Document 12) have been proposed. Moreover, it describes in various literatures, for example, the following nonpatent literatures 3-5.

JP-A-60-169456 JP 2004-345955 A THE THERMAL, ALIPHATIC CLAISEN REARRANGEMENT, F.R. E. By ZIEGLER, CHEM. REV. magazine. 1988, 88, 1423-1452 MICROWAVES IN ORGANIC SYNTHESIS, A. LOUPY, 2002, WILEY-VCH CONTROLLED MICROWAVE HEATING IN MODERN ORGANIC SYNTHESIS, C.I. O. By KAPPE, ANGEW. CHEM. INT. ED magazine. 2004, 43, 6250-6284

  The method for rearranging the allyloxy group of the E3 group of the substituted cyclic phosphonitrile containing an allyloxy group is described in many known literatures such as Non-Patent Documents 3 to 5 described above, and is selected from various reaction conditions. be able to. For example, the reaction can be carried out by heating in the absence of a catalyst or in the presence of a catalyst, and further in the absence of a solvent or in the presence of a solvent. When performed without a catalyst, the allyloxy group-containing cyclic phosphonitrile substitution product can be allowed to proceed by a method of heating at 150 to 350 ° C., preferably 180 to 300 ° C. for 0.1 to 10 hours. Further, when the reaction is carried out in the presence of a catalyst such as an acid, alkali or transition metal catalyst, the reaction can proceed under milder conditions than in the case of no catalyst. Furthermore, although it can react without a solvent, when reacting in a solvent, an inert and high boiling point solvent is preferable. For example, N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidinone, polar solvents such as dimethyl sulfoxide, chlorobenzenes such as o-dichlorobenzene and trichlorobenzene, paraffin oil, tetralin, Solvents having a high boiling point such as carbitol and ionic liquids composed of onium salts such as aliphatic ammonium, alicyclic ammonium, imidazolium, pyridinium, and other phosphonium-based onium salts can be used. When using a solvent, the cyclic phosphonitrile substitution product obtained in Step 1 is used by dissolving or dispersing in the solvent. The reaction temperature in this case is usually about 190 to 220 ° C. In some cases, a small amount may be used as long as the cyclic phosphonitrile substitution product obtained in Step 1 is moistened. Moreover, a normal electric heater or a heat medium can be used for heating.

  In addition, a rearrangement reaction can be performed by microwave irradiation. In the present invention, it is preferable to carry out the reaction in a molten state by using a microwave because the reaction time can be remarkably shortened while suppressing the generation of by-products. When the rearrangement reaction is performed by irradiation with microwaves, it is preferable that the raw material is previously melted or dissolved in a solvent, and the rearrangement reaction is performed by irradiation with microwaves in that state. In order to bring the raw material into a molten state in advance, the raw material may be irradiated with microwaves to be in a molten state, or may be brought into a molten state by a conventional heating method using an electric heater or a heat medium.

  The rearrangement reaction is preferably carried out in an inert gas atmosphere such as nitrogen or argon in order to suppress side reactions and polymerization reactions. Further, in order to suppress side reactions, oxidation of BHT (dibutylhydroxytoluene) or the like is prevented. It can also be carried out by adding an agent or an organic base compound such as dimethylaminopyridine or quinoline.

  The microwave used here is an electromagnetic wave having a frequency of 300 MHz to 30 GHz, and since an industrial microwave irradiator uses 2,450 MHz, it may be normally used. Although irradiation time changes with preparation amount, the wattage of a microwave irradiation apparatus, etc., it is 1 to 60 minutes normally at 100 to 10 kW. The reaction temperature is controlled in the range of 150 to 350 ° C., preferably 230 to 300 ° C., more preferably 240 to 280 ° C. by electromagnetic wave on-off or the like. The microwave irradiation experimental apparatus used in the present invention is manufactured and sold by, for example, Shikoku Keiki Kogyo Co., Ltd., Micro Electronics Co., Ltd., Milestone, CEM, and the like.

  Thus, in step 2, the allyloxy group of the E3 group of the substituted allyloxy group-containing cyclic phosphonitrile obtained in step 1 is subjected to Claisen rearrangement to convert the allyloxy group portion into an allyl group and a hydroxyl group. Thereby, the cyclic phosphonitrile substituted product obtained in Step 1 becomes a reactive group-containing cyclic phosphazene compound in which the allyloxy group portion is converted into an allyl group and a hydroxyl group.

  The reactive group-containing cyclic phosphazene compound having an allyl group and a hydroxyl group obtained by the above step 2 may be isolated and purified from the reaction system as necessary. Isolation and purification can be carried out according to ordinary methods such as filtration, solvent extraction, column chromatography and recrystallization.

Resin Composition The resin composition of the present invention contains the reactive group-containing cyclic phosphazene compound of the present invention and a resin component. One type of reactive group-containing cyclic phosphazene compound of the present invention may be used, or two or more types may be used in combination. As the resin component, various thermoplastic resins or thermosetting resins can be used. These resin components may be natural or synthetic.

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

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

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

  In the resin composition of the present invention, the amount of the reactive group-containing cyclic phosphazene compound used can be appropriately set according to various conditions such as the type of the resin component, the use of the resin composition, etc. Is preferably set to 0.1 to 50 parts by weight, more preferably 0.5 to 40 parts by weight, and further preferably 1 to 30 parts by weight. preferable. When the usage-amount of a reactive group containing cyclic phosphazene compound is less than 0.1 weight part, there exists a possibility that the resin molding which consists of the said resin composition may not show sufficient flame retardance. On the other hand, if it exceeds 50 parts by weight, the original properties of the resin component may be impaired, and a resin molded product having such properties may not be obtained.

  Moreover, the resin composition of this invention can mix | blend various additives in the range which does not impair the target physical property according to the kind of resin component, the use of a resin composition, etc. Examples of usable additives include silica, alumina, aluminum hydroxide, magnesium hydroxide, calcium silicate, calcium carbonate, titanium oxide, zinc oxide, zinc molybdate, mica, talc, glass fiber, and potassium titanate fiber. Inorganic fillers, organic fibers such as aramid fibers or polyparaphenylenebenzbisoxazole fibers, surface treatment agents for fillers such as silane coupling agents, waxes, fatty acids and their metal salts, acid amides and paraffins Nitrogen such as mold, phosphate ester, condensed phosphate ester, phosphate amide, phosphate amide ester, ammonium phosphate, red phosphorus, chlorinated paraffin, melamine, melamine cyanurate, melam, melem, melon and succinoguanamine Flame retardant, silicone flame retardant and Flame retardants such as elementary flame retardants, flame retardant aids such as antimony trioxide, anti-dripping agents such as polytetrafluoroethylene (PTFE), epoxy resins, phenol resins, curing agents, pigments, colorants, antioxidants , Ultraviolet absorbers, light stabilizers, lubricants, plasticizers and antistatic agents.

  Furthermore, the resin composition of the present invention is at least selected from a polymerizable material group consisting of a thermopolymerizable monomer, a thermopolymerizable oligomer, a photopolymerizable monomer, a photopolymerizable oligomer, a radiation polymerizable monomer, and a radiation polymerizable oligomer. One polymerizable material may be further included. In this case, the resin composition of the present invention has a polymerization action of these polymerizable materials and the reactive group-containing cyclic phosphazene compound of the present invention, so that an electromagnetic beam such as heat, ultraviolet rays and visible light, an electron beam such as an electron beam, etc. It can be cured by irradiation with energy rays.

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

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

  When the above-mentioned epoxy resin is used as the resin component (hereinafter sometimes referred to as “epoxy resin composition”), the proportion of the reactive group-containing cyclic phosphazene compound of the present invention in the epoxy resin composition is 0.1 to 0.1%. 80 weight% is preferable and 0.5 to 70 weight% is more preferable. When the ratio of the reactive group-containing cyclic phosphazene compound is less than 0.1% by weight, the resin molded body made of the epoxy resin composition may not exhibit sufficient flame retardancy. On the other hand, if it exceeds 80% by weight, the original properties of the epoxy resin component may be impaired, and a resin molded product having such properties may not be obtained.

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

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

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

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

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

Polymerizable composition The polymerizable composition of the present invention contains the reactive group-containing cyclic phosphazene compound of the present invention. The reactive group-containing cyclic phosphazene compound used here may be two or more kinds.

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

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

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

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

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

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

EXAMPLES The present invention will be specifically described below with reference to examples and 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 measured for ¹ H-NMR spectrum and ³¹ P-NMR spectrum, CHN elemental analysis, analysis of elemental chlorine (residual chlorine) by potentiometric titration using silver nitrate after alkali melting, Identification was performed based on the analysis of phosphorus element by ICP-AES after microwave wet decomposition and the results of TOF-MS analysis.

Example 1 (Production of reactive group-containing cyclic phosphazene compound according to Form B)
[Step 1: Production of substituted cyclic phosphonitriles by method 2-D above]
In a 1 liter flask equipped with a stirrer, thermometer, reflux condenser, water separation receiver and nitrogen inlet tube, 58.4 g (0.50 mol) of 48% KOH aqueous solution, 450 ml of chlorobenzene and 47.1 g of phenol ( 0.50 mol) was charged. This was stirred and heated under a nitrogen atmosphere, and water in the flask was removed by azeotropic dehydration (recovered water: about 39 ml) to prepare a potassium potassium salt. The slurry solution was cooled to 20 ° C., and 200 ml of THF was added to prepare a uniform solution.

  On the other hand, in a 2 liter flask equipped with a stirrer, a thermometer, a reflux condenser, a water separation receiver and a nitrogen introduction tube, 76.0 g (0.65 mol) of a 48% KOH aqueous solution, 800 ml of chlorobenzene and 4′- 188.8 g (0.65 mol) of allyloxyphenylsulfonyl-4-phenol was charged. This was stirred and heated in a nitrogen atmosphere, and water in the flask was removed by azeotropic dehydration (recovered water: about 51 ml) to prepare a potassium salt of 4'-allyloxyphenylsulfonyl-4-phenol. The slurry solution was cooled to 20 ° C., and 300 ml of THF was added to prepare a uniform solution.

  Next, a THF solution of hexachlorocyclotriphosphazene [58.0 g (0.50 unit mol), THF 200 ml] of hexachlorocyclotriphosphazene was placed in a 3 liter flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube. Prepared. On the other hand, the potassium salt solution of phenol was added dropwise at 5 ° C. over 10 hours with stirring, and the stirring reaction was performed at 25 ° C. for 5 hours. Next, the 4′-allyloxyphenylsulfonyl-4-phenol potassium salt solution was added dropwise to the reaction solution over 1 hour at 25 ° C. with stirring, and the stirring reaction was carried out for 10 hours under reflux (86 ° C.). . After completion of the reaction, the reaction solution was concentrated to about 1,000 ml, and after adding 600 ml of chlorobenzene and 600 ml of water to dissolve the contents, the organic layer was separated using a separatory funnel. This organic layer was washed twice with 5% NaOH aqueous solution, then neutralized with 2% sulfuric acid, further washed with water three times, and chlorobenzene was distilled off to obtain a pale yellow solid product. 207.1 g (yield: 96%) was obtained. This product did not show a clear melting point due to the glassy solid. The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
_{-CH 2 - 4.6 (2H),} = CH 2 5.3~5.4 (2H), - CH = 6.0 (1H), phenyl CH 6.8~7.2 (9H), 7.8-8.0 (4H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.5
◎ CHNP elemental analysis:
Theoretical value C: 58.9%, H: 4.2%, N: 3.2%, P: 7.2%
Measured value C: 58.7%, H: 4.4%, N: 3.1%, P: 7.0%
◎ Residual chlorine analysis:
<0.01%
◎ TOF-MS (m / z):
1087,1283,1480

From the above analysis results, the _{product, [N 3 = P 3 (} OC 6 H 4 -SO 2 -C 6 H 4 OCH 2 CH = CH 2) 2 (OC 6 H 5) 4], [N 3 = _{P 3 (OC 6 H 4 -SO} 2 -C 6 H 4 OCH 2 CH = CH 2) 3 (OC 6 H 5) 3] and _{[N 3 = P 3 (OC} 6 H 4 -SO 2 -C 6 H ₄ OCH ₂ CH═CH ₂ ) ₄ (OC ₆ H ₅ ) ₂ ], the average composition of which is [N═P (OC ₆ H ₄ —SO ₂ —C ₆ H ₄ OCH ₂ CH═CH ₂ ). _1.02 (OC ₆ H ₅ ) _0.98 ] ₃ .

[Step 2: Production of reactive group-containing cyclic phosphazene compound by Claisen rearrangement]
In the autoclave, 86.3 g (0.20 unit mol) of the compound synthesized in the above step and 300 ml of chlorobenzene were charged, heated to 200 ° C., and reacted at the same temperature for 10 hours. When chlorobenzene in the reaction solution was distilled off, 80.2 g (yield: 93%) of a pale yellow solid product was obtained. This product did not show a clear melting point due to the glassy solid. The analysis result of this product was as follows.

¹ H-NMR spectrum (in heavy acetone, δ, ppm):
_{-CH 2 - 3.4 (2H),} = CH 2 5.0~5.1 (2H), - CH = 6.0 (1H), phenyl CH 6.8~7.2 (8H), 7.7 to 7.9 (4H), -OH 9.5 (1H)
◎ ³¹ P-NMR spectrum (in heavy acetone, δ, ppm):
Trimer (P = N) ₃ 9.6
◎ CHNP elemental analysis:
Theoretical value C: 58.9%, H: 4.2%, N: 3.2%, P: 7.2%
Measured value C: 58.8%, H: 4.1%, N: 3.1%, P: 7.3%
◎ Residual chlorine analysis:
<0.01%
◎ TOF-MS (m / z):
1087,1283,1480

From the above analysis results, the product is {N ₃ = P ₃ [OC ₆ H ₄ —SO ₂ —C ₆ H ₃ (OH) (CH ₂ CH═CH ₂ )] ₂ (OC ₆ H ₅ ) ₄ } , {N ₃ = P ₃ [OC ₆ H ₄ —SO ₂ —C ₆ H ₃ (OH) (CH ₂ CH═CH ₂ )] ₃ (OC ₆ H ₅ ) ₃ } and {N ₃ = P ₃ [OC ₆ H ₄ —SO ₂ —C ₆ H ₃ (OH) (CH ₂ CH═CH ₂ )] ₄ (OC ₆ H ₅ ) ₂ }, the average composition of which is {N ₃ = P ₃ [OC ₆ H ₄ was confirmed that _{-SO 2 -C 6 H 3 (OH} ) (CH 2 CH = CH 2)] 1.02 (OC 6 H 5) 0.98} _3.

Example 2 (Production of a reactive group-containing cyclic phosphazene compound according to Form B)
[Step: Production of substituted cyclic phosphonitrile by the above-mentioned method 2-D]
The product obtained in Example 1 was used in Step 2.

[Step 2: Production of reactive group-containing cyclic phosphazene compound by Claisen rearrangement]
Into a heat-resistant glass container equipped with a temperature sensor, an electromagnetic stirrer and a condenser, 21.6 g (0.05 unit mol) of the compound synthesized in Step 1 above and 10 ml of dichlorobenzene were charged. Was installed in a microwave reactor SMW-042 and purged with nitrogen. Subsequently, a 2.45 GHz microwave was irradiated at about 200 W in a nitrogen atmosphere and heated to 160 ° C., and then maintained at 160 ° C. for 24 minutes by intermittent irradiation with the same microwave. Then, it heated up to 260 degreeC and maintained for 24 minutes by about 400W intermittent irradiation. When dichlorobenzene in the reaction product was distilled off, 20.5 g (yield: 95%) of a pale yellow solid product was obtained. This product did not show a clear melting point due to the glassy solid. The analysis result of this product was as follows.

¹ H-NMR spectrum (in heavy acetone, δ, ppm):
_{-CH 2 - 3.4 (2H),} = CH 2 5.0~5.1 (2H), - CH = 6.0 (1H), phenyl CH 6.8~7.2 (8H), 7.7 to 7.9 (4H), -OH 9.5 (1H)
◎ ³¹ P-NMR spectrum (in heavy acetone, δ, ppm):
Trimer (P = N) ₃ 9.6
◎ CHNP elemental analysis:
Theoretical value C: 58.9%, H: 4.2%, N: 3.2%, P: 7.2%
Measured value C: 59.0%, H: 4.2%, N: 3.1%, P: 7.1%
◎ Residual chlorine analysis:
<0.01%
◎ TOF-MS (m / z):
1087,1283,1480

From the above analysis results, the product is {N ₃ = P ₃ [OC ₆ H ₄ —SO ₂ —C ₆ H ₃ (OH) (CH ₂ CH═CH ₂ )] ₂ (OC ₆ H ₅ ) ₄ } , {N ₃ = P ₃ [OC ₆ H ₄ —SO ₂ —C ₆ H ₃ (OH) (CH ₂ CH═CH ₂ )] ₃ (OC ₆ H ₅ ) ₃ } and {N ₃ = P ₃ [OC ₆ H ₄ —SO ₂ —C ₆ H ₃ (OH) (CH ₂ CH═CH ₂ )] ₄ (OC ₆ H ₅ ) ₂ }, the average composition of which is {N ₃ = P ₃ [OC ₆ H ₄ was confirmed that _{-SO 2 -C 6 H 3 (OH} ) (CH 2 CH = CH 2)] 1.02 (OC 6 H 5) 0.98} _3.

Example 3 (Production of reactive group-containing cyclic phosphazene compound according to Form B)
[Step 1: Production of substituted cyclic phosphonitriles by method 2-D above]
Example except that 174.5 g (0.65 mol) of 4′-allyloxyphenyl isopropylidene-4-phenol was used instead of 188.8 g (0.65 mol) of 4′-allyloxyphenylsulfonyl-4-phenol In the same manner as in Example 1, 193.4 g (yield 93%) of a pale yellow solid product was obtained. This product did not show a clear melting point due to the glassy solid. The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
_{-CH 3 1.6 (6H), -} CH 2 -4.6 (2H), = CH 2 5.3~5.4 (2H), - CH = 6.0 (1H), phenyl CH 6 .8 to 7.2 (13H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.8
◎ CHNP elemental analysis:
Theoretical value C: 71.4%, H: 6.0%, N: 3.4%, P: 7.4%
Measured value C: 71.3%, H: 6.2%, N: 3.4%, P: 7.3%
◎ Residual chlorine analysis:
<0.01%
◎ TOF-MS (m / z):
1043, 1217, 1392

From the above analysis results, the _{product, [N 3 = P 3 (} OC 6 H 4 -C (CH 3) 2 -C 6 H 4 OCH 2 CH = CH 2) 2 (OC 6 H 5) 4] , [N ₃ = P ₃ (OC ₆ H ₄ —C (CH ₃ ) ₂ —C ₆ H ₄ OCH ₂ CH═CH ₂ ) ₃ (OC ₆ H ₅ ) ₃ ] and [N ₃ = P ₃ (OC ₆₎ H ₄ —C (CH ₃ ) ₂ —C ₆ H ₄ OCH ₂ CH═CH ₂ ) ₄ (OC ₆ H ₅ ) ₂ ], the average composition of which is [N═P (OC ₆ H ₄ —C). (CH ₃ ) ₂ —C ₆ H ₄ OCH ₂ CH═CH ₂ ) _1.06 (OC ₆ H ₅ ) _0.94 ] ₃ was confirmed.

[Step 2: Production of reactive group-containing cyclic phosphazene compound by Claisen rearrangement]
In an autoclave, 83.2 g (0.20 unit mol) of the compound synthesized in the above step and 300 ml of trichlorobenzene were charged, heated to 220 ° C., and reacted at the same temperature for 12 hours. When trichlorobenzene in the reaction solution was distilled off, 79.0 g (yield: 95%) of a pale yellow solid product was obtained. This product did not show a clear melting point due to the glassy solid. The analysis result of this product was as follows.

¹ H-NMR spectrum (in heavy acetone, δ, ppm):
_{-CH 3 1.6 (6H), -} CH 2 - 3.4 (2H), = CH 2 5.0~5.1 (2H), - CH = 6.0 (1H), phenyl CH 6 .6 to 7.2 (12H), -OH 9.5 (1H)
◎ ³¹ P-NMR spectrum (in heavy acetone, δ, ppm):
Trimer (P = N) ₃ 9.9
◎ CHNP elemental analysis:
Theoretical value C: 71.4%, H: 6.0%, N: 3.4%, P: 7.4%
Measured value C: 71.6%, H: 6.0%, N: 3.3%, P: 7.5%
◎ Residual chlorine analysis:
<0.01%
◎ TOF-MS (m / z):
1043, 1217, 1392

From the above analysis results, this product was obtained as {N ₃ = P ₃ [OC ₆ H ₄ —C (CH ₃ ) ₂ —C ₆ H ₃ (OH) (CH ₂ CH═CH ₂ )] ₂ (OC _{6 H 5) 4}, {N} 3 = P 3 [OC 6 H 4 -C (CH 3) 2 -C 6 H 3 (OH) (CH 2 CH = CH 2)] 3 (OC 6 H 5) 3} and mixtures _{{N 3 = P 3 [OC} 6 H 4 -C (CH 3) 2 -C 6 H 3 (OH) (CH 2 CH = CH 2)] 4 (OC 6 H 5) 2}, Its average composition is {N ₃ = P ₃ [OC ₆ H ₄ —C (CH ₃ ) ₂ —C ₆ H ₃ (OH) (CH ₂ CH═CH ₂ )] _1.06 (OC ₆ H ₅ ) _{0. 94} } ₃ .

Example 4 (Production of a reactive group-containing cyclic phosphazene compound according to Form B)
[Step: Production of substituted cyclic phosphonitrile by the above-mentioned method 2-D]
The product obtained in Example 1 was used in Step 2.

[Step 2: Production of reactive group-containing cyclic phosphazene compound by Claisen rearrangement]
A compound of 20.8 g (0.05 unit mol) synthesized in the above process and 10 ml of dichlorobenzene were charged in a heat-resistant glass container equipped with a temperature sensor, an electromagnetic stirrer and a condenser, and a simple type manufactured by Shikoku Keiki Kogyo Co., Ltd. Installed in microwave reactor SMW-042 and purged with nitrogen. Then, the microwave of nitrogen atmosphere 2.45GHz was irradiated at about 200W, and it heated to 160 degreeC. After maintaining the temperature at 160 ° C. for 25 minutes by intermittent irradiation with the same microwave, the temperature was raised to 260 ° C. and maintained for 30 minutes with about 400 W of intermittent irradiation.
When dichlorobenzene in the reaction product was distilled off, 20.0 g (yield: 96%) of a pale yellow solid product was obtained. This product did not show a clear melting point due to the glassy solid. The analysis result of this product was as follows.

¹ H-NMR spectrum (in heavy acetone, δ, ppm):
_{-CH 3 1.6 (6H), -} CH 2 - 3.4 (2H), = CH 2 5.0~5.1 (2H), - CH = 6.0 (1H), phenyl CH 6 .6 to 7.2 (12H), -OH 9.5 (1H)
◎ ³¹ P-NMR spectrum (in heavy acetone, δ, ppm):
Trimer (P = N) ₃ 9.9
◎ CHNP elemental analysis:
Theoretical value C: 71.4%, H: 6.0%, N: 3.4%, P: 7.4%
Measured value C: 71.5%, H: 5.9%, N: 3.3%, P: 7.3%
◎ Residual chlorine analysis:
<0.01%
◎ TOF-MS (m / z):
1043, 1217, 1392

From the above analysis results, this product was obtained as {N ₃ = P ₃ [OC ₆ H ₄ —C (CH ₃ ) ₂ —C ₆ H ₃ (OH) (CH ₂ CH═CH ₂ )] ₂ (OC _{6 H 5) 4}, {N} 3 = P 3 [OC 6 H 4 -C (CH 3) 2 -C 6 H 3 (OH) (CH 2 CH = CH 2)] 3 (OC 6 H 5) 3} and mixtures _{{N 3 = P 3 [OC} 6 H 4 -C (CH 3) 2 -C 6 H 3 (OH) (CH 2 CH = CH 2)] 4 (OC 6 H 5) 2}, Its average composition is {N ₃ = P ₃ [OC ₆ H ₄ —C (CH ₃ ) ₂ —C ₆ H ₃ (OH) (CH ₂ CH═CH ₂ )] _1.06 (OC ₆ H ₅ ) _{0. 94} } ₃ .

Comparative Example 1 ( Synthesis of {N = P (OC ₆ H ₅ ) ₂ } ₃ )
PHOSPHORUS-NITROGEN COMPOUNDS, H.P. R. [N = P (OC ₆ H ₅ ) ₂ ] ₃ (white solid / melting point: 111 ° C.) using hexachlorocyclotriphosphazene according to the method described in ALLCOCK, 1972, page 151, ACADEMIC PRESS. Obtained.

Examples 5 to 9 and Comparative Example 2 (Preparation of resin composition)
Table 1 shows the reactive group-containing cyclic phosphazene compound produced in Examples 1 to 4 or the cyclic phosphazene compound produced in Comparative Example 1 with respect to 100 parts of PC resin (polycarbonate resin: “Iupilon S3000” manufactured by Mitsubishi Gas Chemical Co., Ltd.). And melt kneaded at 220 ° C. for 5 minutes.

  The resin composition thus obtained was heated and pressed at 200 ° C. for 10 minutes using a press molding machine to obtain a sheet having a thickness of 1/24 inch. At this stage, the reactive group of the reactive group-containing cyclic phosphazene compound contained in the resin composition was not reacted. Both surfaces of this sheet were irradiated with an electron beam at room temperature under the conditions of an acceleration voltage of 200 KV, an irradiation dose of 2 MRad, and an absorbed dose of 10 KGy. A specimen having a length of 5 inches, a width of 0.5 inches, and a thickness of 1/24 inches was cut out from the cured sheet thus obtained, and a flammability test (UL-94 flame retardant test) was performed on the specimen. In addition, the heat distortion temperature and blooming property were examined. The evaluation method for each item is as follows. The results are shown in Table 1.

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

V-0: All the following conditions are satisfied.
(A) The total extinguishing time after 10 times of flame contact is within 50 seconds, 5 test pieces twice each.
(B) 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 deformation temperature)
According to ASTM D-648, the load was tested at 1.82 MPa.

(High temperature reliability: blooming)
The test piece was heated at 150 ° C. for 4 hours, and the state of seepage on the surface of the test piece (leaching state from the inside of the test piece: blooming property) was visually observed. The criteria for evaluation are as follows.
A: No oozing is observed.
◯: Almost no seepage is seen.
Δ: Some exudation is observed.
X: Significant exudation is observed.

  As is apparent from Table 1, the sheets (resin molded bodies) made of the resin compositions of Examples 5 to 9 are superior in flame retardancy and have a high heat distortion temperature compared to those of Comparative Example 2. The mechanical properties are excellent, and bleed out of the phosphazene compound evaluated by blooming property is not substantially observed.

Examples 10 to 14 and Comparative Example 3 (Preparation of resin composition)
Epicote 1001 which is a bisphenol A type epoxy resin (trade name of Japan Epoxy Resin Co., Ltd .: epoxy equivalent 456 g / eq., Resin solid content 70%) 651 parts, YDCN-704P which is a cresol novolac epoxy resin (Toto Kasei Co., Ltd.) Obtained in Examples 1 to 4 with respect to a mixture of 300 parts of epoxy equivalent 210 g / eq., Resin solid content 70%), 361 parts of aluminum hydroxide and 0.9 part of 2-ethyl-4-methylimidazole. The obtained reactive group-containing cyclic phosphazene compound or the cyclic phosphazene compound obtained in Comparative Example 1 was added at the ratio shown in Table 2, and propylene glycol monomethyl ether (PGM) was added as a solvent to give an epoxy resin having a resin solid content of 65%. A varnish was prepared.

  Next, the prepared epoxy resin varnish was applied and impregnated on a 180 μm glass woven fabric, and dried at a temperature of 160 ° C. to produce a prepreg. Eight 180 μm glass woven prepregs thus obtained were laminated and heated and pressurized at a temperature of 170 ° C. and a pressure of 4 MPa for 90 minutes. Next, both surfaces of the sheet were irradiated with an electron beam at room temperature under the conditions of an acceleration voltage of 200 KV, an irradiation dose of 2 MRad, and an absorption dose of 10 KGy to obtain a glass epoxy laminate having a thickness of 1.2 mm.

  A test piece having a length of 5 inches, a width of 0.5 inches and a thickness of 1.2 mm was cut out from the glass epoxy laminate, and its combustibility, glass transition temperature (Tg) and heat resistance were examined. Here, the flammability was evaluated by a method based on the UL-94 standard vertical combustion test, as in Examples 5 to 9 and Comparative Example 2. The glass transition temperature was measured by DSC according to JIS K 7121-1987 “Method for measuring plastic transition temperature”. Furthermore, for heat resistance as an evaluation of high temperature reliability, the test piece was treated at 290 ° C. for 20 minutes, and changes in appearance were observed. The results are shown in Table 2. In the results of heat resistance in Table 2, “Yes” means that there is no bleed out of the reactive group-containing cyclic phosphazene compound or the like added to the above-mentioned mixture, and “No” means that bleed out. It means that.

  As is clear from Table 2, the glass epoxy laminate (resin molded body) made of the resin compositions of Examples 10 to 14 is superior in flame retardancy and has a glass transition temperature as compared with that of Comparative Example 3. Since it is high, the mechanical properties are excellent, and further, bleedout of the phosphazene compound evaluated by heat resistance is not substantially observed.

Claims (12)

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

(In the formula (1), n represents an integer of 3 to 8, A represents a group selected from the group consisting of the following A1, 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.
A3 group: a substituted phenyloxy group having an allyl group and a hydroxyl group represented by the following formula (2), formula (3) or formula (4).



Z in Formula (4) represents O, S, SO ₂ , CH ₂ , CHCH ₃ , C (CH ₃ ) ₂ , C (CH ₃ ) CH ₂ CH ₃ or CO. )   The reactive group-containing cyclic phosphazene compound according to claim 1, wherein 2 (2n-2) of 2n A's are A3 groups in the formula (1).   The reactive group containing cyclic phosphazene compound of Claim 1 or 2 whose n of Formula (1) is 3 or 4.   The reactive group containing cyclic phosphazene compound in any one of Claim 1 to 3 containing the 2 or more types of reactive group containing cyclic phosphazene compound from which n of Formula (1) differs. By the group selected from the group consisting of the following E1, E2, and E3 groups so that at least one of the halogen atoms of the cyclic phosphonitrile dihalide represented by the following formula (5) is substituted by the E3 group: A step of producing a substituted allyloxy group-containing cyclic phosphonitrile,

(In Formula (5), n shows the integer of 3-8, X shows 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 substituted phenyloxy group having an allyloxy group represented by the following formula (6), formula (7) or formula (8).



Z in Formula (8) represents O, S, SO ₂ , CH ₂ , CHCH ₃ , C (CH ₃ ) ₂ , C (CH ₃ ) CH ₂ CH ₃ or CO. )
The above-mentioned step of producing a cyclic phosphonitrile substituted product having an allyl group and a hydroxyl group by rearranging the allyloxy group of the cyclic phosphonitrile substituted product containing an allyloxy group, and Claisen rearrangement,
A process for producing a reactive group-containing cyclic phosphazene compound comprising:   A resin composition comprising a resin component and the reactive group-containing cyclic phosphazene compound according to claim 1.   It further comprises at least one polymerizable material selected from the group of polymerizable materials consisting of a thermally polymerizable monomer, a thermally polymerizable oligomer, a photopolymerizable monomer, a photopolymerizable oligomer, a radiation polymerizable monomer, and a radiation polymerizable oligomer. Item 7. The resin composition according to Item 6.   The resin molding which consists of a resin composition of Claim 6 or 7.   A polymerizable composition comprising the reactive group-containing cyclic phosphazene compound according to claim 1.   The polymerizable composition according to claim 9, further comprising at least one polymerizable material selected from monomers and oligomers polymerizable with the reactive group-containing cyclic phosphazene compound.   A resin composition comprising a resin component and the polymerizable composition according to claim 9 or 10.   The resin molding which consists of a polymeric composition or resin composition in any one of Claims 9-11.