JP2013075940A - Flame retardant resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a phosphazene compound capable of effectively improving the flame retardancy of a molded resin article, providing the molded resin article with excellent electrical properties, especially a low dielectric constant (ε) and low dielectric loss tangent (tanδ), and also having a high heat resistance.SOLUTION: There is provided a method for producing a cyclic phosphazene compound containing ethenylphenoxy group expressed by formula (1), comprising a reaction step to form a carbon-carbon bond of a cyclic phosphazene compound containing a phenoxy group having a leaving group and an ethenyl compound. In formula (1), n is an integer of 1-6; at least one A group is ethenylphenoxy expressed by formula (2); and the other A groups are aryloxy.

Description

  The present invention relates to a flame retardant resin composition comprising an ethenylphenoxy group-containing cyclic phosphazene compound.

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

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

  Therefore, phosphazene-based flame retardants have been studied for improving the reliability (heat resistance and thermal stability) of resin molded products at high temperatures. As an example, Patent Documents 6 and 7 include A phosphazene-based flame retardant having a reactive group such as an ethenylphenoxy group is disclosed. Even if this type of phosphazene flame retardant is added in a large amount to the resin composition, it is difficult to impair the heat resistance of the resin molded product. However, it is not sufficient in terms of the essential effect that it is difficult to increase, and it also impairs the mechanical properties (particularly high glass transition temperature) of the resin molded product.

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

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

  Furthermore, electronic information devices such as computers are equipped with a high-speed microprocessor having an operating frequency exceeding 3 GHz, and a delay of a high-speed pulse signal on a printed wiring board is a problem. Since the delay time of the signal becomes longer in proportion to the square root of the relative dielectric constant εr of the insulator around the wiring in the printed wiring board, a high-speed computer or the like requires a wiring board substrate having a low dielectric constant. For this reason, the flame retardant used also needs to make it difficult to impair the dielectric properties of the resin molded product, that is, to achieve a low dielectric constant and a low dielectric loss tangent of the resin molded product.

JP 2000-103939 A JP 2004-83671 A JP 2004-210849 A JP 2005-248134 A JP 2007-45916 A Japanese Patent Laid-Open No. 4-13683 JP 2011-26513 A

  An object of the present invention is to effectively improve the flame retardancy of a resin molded body, and the electrical characteristics of the resin molded body, in particular, low dielectric constant (ε) and dielectric loss tangent (tan δ), and high heat resistance. The realization of phosphazene compounds.

  As a result of repeated studies to solve the above-mentioned problems, the present inventors have found that a molded article comprising a novel flame-retardant resin composition containing a cyclic phosphazene compound having an ethenylphenoxy group has excellent flame retardancy. At the same time, it was found to be excellent in electrical characteristics and heat resistance.

  The production method of the present invention relates to a method for producing an ethenylphenoxy group-containing cyclic phosphazene compound represented by the following formula (1) according to the present invention, and includes a phenoxy group-containing cyclic phosphazene compound having a leaving group, and ethenyl A step of performing a carbon-carbon bond forming reaction with the compound.

In formula (1), n shows the integer of 1-6. A represents a group selected from the group consisting of the following A1 group and A2 group, and at least one is an A2 group.
A1 group: 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 alkyloxy group, and an aryl group may be substituted.
A2 group: an ethenylphenoxy group represented by the following formula (2).

  The production method of the present invention uses a phenoxy group-containing cyclic phosphazene compound having a leaving group represented by the following formula (3).

In formula (3), m shows the integer of 1-6. E represents a group selected from the group consisting of the following E1 group and E2 group, and at least one is E2 group.
E1 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 alkyloxy group, and an aryl group may be substituted.
E2 group: a substituted phenoxy group represented by the following formula (4).

  In formula (4), X is a leaving group, which represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

  The method for producing an ethenylphenoxy group-containing cyclic phosphazene compound of the present invention is a carbon-carbon bond forming reaction using a cross-coupling reaction.

  The flame-retardant resin composition of the present invention includes a resin component and an ethenylphenoxy group-containing cyclic phosphazene compound represented by the formula (1).

  The flame retardant resin composition of the present invention was 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 may contain at least one polymerizable material.

  The flame retardant resin composition of the present invention may contain a polymerization initiator.

  The flame retardant resin composition of the present invention includes an ethenylphenoxy group-containing cyclic phosphazene compound represented by the formula (1), an ethenylphenoxy group-containing cyclic phosphazene compound represented by the formula (1), a thermopolymerizable monomer, A flame retardant polymerization composition obtained by reacting a polymerizable oligomer, a photopolymerizable monomer, a photopolymerizable oligomer, a radiation polymerizable monomer, and at least one polymerizable material selected from the group of polymerizable materials consisting of a radiation polymerizable oligomer. It may be a thing.

  The resin component used here is, for example, from the group consisting of polyphenylene ether resin, epoxy resin, polyimide resin, bismaleimide resin, cyanate ester resin, bismaleimide-cyanate ester resin, polybutadiene resin, polystyrene resin and polyisoprene resin. At least one selected.

  The resin molded product of the present invention comprises the flame retardant resin composition of the present invention.

  The electric / electronic component of the present invention uses the resin molded body of the present invention.

  Since the method for producing an ethenylphenoxy group-containing cyclic phosphazene compound according to the present invention includes the steps as described above, an ethenylphenoxy group-containing cyclic phosphazene compound having a specific structure according to the present invention can be produced. .

  Since the flame-retardant resin composition of the present invention comprises a resin component and an ethenylphenoxy group-containing cyclic phosphazene compound having a specific structure as described above, the flame-retardant resin composition for forming a resin molded body When used, it exhibits excellent flame retardancy and heat resistance and can achieve excellent electrical properties, particularly low dielectric constant and low dielectric loss tangent.

  Since the resin molded body of the present invention is composed of the flame retardant resin composition of the present invention, it exhibits excellent flame resistance and heat resistance, and can achieve excellent electrical characteristics, particularly low dielectric constant and low dielectric loss tangent. it can.

  Since the flame retardant resin composition of the present invention includes a flame retardant polymer composition composed of an ethenylphenoxy group-containing cyclic phosphazene compound having a specific structure as described above, the flame retardant for forming a resin molded body is included. When used in a conductive resin composition, it exhibits excellent flame retardancy and heat resistance, and can achieve excellent electrical properties, particularly low dielectric constant and low dielectric loss tangent.

  Since the electrical / electronic component of the present invention uses the resin molded body of the present invention, it exhibits excellent flame resistance and heat resistance, and can achieve excellent electrical characteristics, particularly low dielectric constant and low dielectric loss tangent. it can.

Ethenylphenoxy group-containing cyclic phosphazene compound The ethenylphenoxy 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 1 to 6, but the ethenylphenoxy group-containing cyclic phosphazene compound of the present invention has a smaller n in the formula (1), which will be described later. When used in products, it is easy to realize a resin molded body having a high glass transition temperature. For this reason, n in the formula (1) is preferably an integer of 1 to 4, particularly preferably 1 or 2. That is, as this cyclic phosphazene compound, a cyclotriphosphazene compound (trimer) in which n in formula (1) is 1, a cyclotetraphosphazene compound (tetramer) in which n in formula (1) is 2, 1) cyclopentaphosphazene compound (pentamer) in which n is 3; cyclohexaphosphazene compound (hexamer) in which n is 4 in formula (1); cyclohepta in which n in formula (1) is 5 Mention may be made of phosphazene compounds (7-mer) and cyclooctaphosphazene compounds (octer) in which n in formula (1) is 6. Among them, a cyclotriphosphazene compound in which n in formula (1) is 1, a cyclotetraphosphazene compound in which n in formula (1) is 2, a cyclopentaphosphazene compound in which n in formula (1) is 3, and a formula ( A cyclohexaphosphazene compound in which n is 4 in 1) is preferred, and cyclotriphosphazene in which n is 1 and cyclotetraphosphazene in which n is 2 are particularly preferred.

  Further, the ethenylphenoxy group-containing cyclic phosphazene compound of the present invention may be a mixture of two or more compounds having different n in the formula (1), but this mixture is a phosphazene compound having a small n in the formula (1). When the content of is higher in the resin composition described later, a resin molded product having a higher glass transition temperature can be easily realized. Therefore, this mixture is preferably a mixture containing 95% or more by weight of the ethenylphenoxy group-containing cyclic phosphazene compound in which n of formula (1) is 1 to 4, and n of formula (1) is 1 or 2 of ethenyl A mixture containing 95% or more by weight of the phenoxy group-containing cyclic phosphazene compound is particularly preferable.

  In the formula (1), A represents a group selected from the group consisting of the following A1 group and A2 group.

[A1 group]
An aryloxy group having 6 to 20 carbon atoms; In the aryloxy group, at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkyloxy 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, methoxyphenoxy group, ethoxyphenoxy group, n-propoxy group Phenoxy group, iso-propoxyphenoxy group, n-butoxyphenoxy group, tert-butoxyphenoxy group, 4-methoxy-3-methylphenoxy group, 4-ethoxy-3-methyl Ruphenoxy group, 4-n-propoxyphenoxy group, 4-iso-propoxy-3-methylphenoxy group, 4-n-butoxy-3-methylphenoxy group, 4-tert-butoxy-3-methylphenoxy group, phenylphenoxy Group, naphthyloxy group, anthryloxy group, phenanthryloxy group and the like. Of these, phenoxy group, methylphenoxy group, dimethylphenoxy group, diethylphenoxy group, methoxyphenoxy group, phenylphenoxy group and naphthyloxy group are preferable, and phenoxy group, methylphenoxy group, dimethylphenoxy group and naphthyloxy group are particularly preferable.

[Group A2]
An ethenylphenoxy group represented by the following formula (2).

  In formula (1), 2n + 4 A are included, at least one of which is an A2 group. Therefore, the ethenylphenoxy group-containing cyclic phosphazene compound of the present invention represented by the formula (1) can be roughly classified into the following forms.

[Form 1]
All 2n + 4 A's are A2 groups.

  Specific examples of the ethenylphenoxy group-containing cyclic phosphazene compound in such a form include an ethenylphenoxy group-containing cyclotriphosphazene compound in which n in the formula (1) is 1, and an n in the formula (1) in which n is 2. Tenenylphenoxy group-containing cyclotetraphosphazene compound, ethenylphenoxy group-containing cyclopentaphosphazene compound in which n is 3 in formula (1), ethenylphenoxy group-containing cyclohexaphosphazene compound in which n is 4 in formula (1), formula An ethenylphenoxy group-containing cycloheptaphosphazene compound in which n in (1) is 5 and an ethenylphenoxy group-containing cyclooctaphosphazene compound in which n in formula (1) is 6 can be mentioned. The ethenylphenoxy group-containing cyclic phosphazene compound of this form may be any mixture of these preferred ethenylphenoxy group-containing cyclic phosphazene compounds.

  Among them, an ethenylphenoxy group-containing cyclotriphosphazene compound in which n in formula (1) is 1, an ethenylphenoxy group-containing cyclotetraphosphazene compound in which n in formula (1) is 2, and n in formula (1) is More preferred are an ethenylphenoxy group-containing cyclopentaphosphazene compound which is 3, an ethenylphenoxy group-containing cyclohexaphosphazene compound wherein n in the formula (1) is 4, and any mixture thereof, and n in the formula (1) is 1 Particularly preferred are ethenylphenoxy group-containing cyclotriphosphazene compounds of formula (1), ethenylphenoxy group-containing cyclotetraphosphazene compounds of formula (1) wherein n is 2, and any mixtures thereof.

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

  Examples of the ethenylphenoxy group-containing cyclic phosphazene compound of this form include an ethenylphenoxy group-containing cyclotriphosphazene compound in which n in the formula (1) is 1, and an ethenylphenoxy group-containing cyclohexane in which n in the formula (1) is 2. A tetraphosphazene compound, an ethenylphenoxy group-containing cyclopentaphosphazene compound in which n in formula (1) is 3, an ethenylphenoxy group-containing cyclohexaphosphazene compound in which n in formula (1) is 4, n in formula (1) An ethenylphenoxy group-containing cycloheptaphosphazene compound in which n is 5, and an ethenylphenoxy group-containing cyclooctaphosphazene compound in which n in formula (1) is 6, 1 to 2n + 4 A to (2n + 3) Preference is given to those having A2 groups as well as any mixtures thereof. This type of ethenylphenoxy group-containing cyclic phosphazene compound realizes a resin molded product with better mechanical strength (particularly higher glass transition temperature) than other forms of ethenylphenoxy group-containing cyclic phosphazene compounds of the present invention. It is advantageous where possible.

  Specific examples of such preferable ethenylphenoxy group-containing cyclic phosphazene compounds include ethenylphenoxy group-containing cyclotriphosphazene compounds in which n in formula (1) is 1, and ethenyl in which n in formula (1) is 2. A phenoxy group-containing cyclotetraphosphazene compound, an ethenylphenoxy group-containing cyclopentaphosphazene compound in which n in formula (1) is 3, an ethenylphenoxy group-containing cyclohexaphosphazene compound in which n in formula (1) is 4, 1) an ethenylphenoxy group-containing cycloheptaphosphazene compound in which n is 5 and an ethenylphenoxy group-containing cyclooctaphosphazene compound in which n is 6 in formula (1), wherein A is an A1 group In combination with ethenylphenoxy group which is A2 group, methyl group which is A1 group A combination of a nonoxy group and an ethenylphenoxy group which is an A2 group, a combination of a dimethylphenoxy group which is an A1 group and an ethenylphenoxy group which is an A2 group, a naphthyloxy group and an A2 group which are A1 groups Mention may be made of combinations with certain ethenylphenoxy groups and any mixtures thereof.

  Among them, an ethenylphenoxy group-containing cyclotriphosphazene compound in which n in formula (1) is 1, an ethenylphenoxy group-containing cyclotetraphosphazene compound in which n in formula (1) is 2, and n in formula (1) is 3 is an ethenylphenoxy group-containing cyclopentaphosphazene compound of formula (1) and n is 4 in the formula (1), and A is a phenoxy group that is an A1 group and an A2 group More preferred are a combination with an ethenylphenoxy group, a combination of a methylphenoxy group which is an A1 group with an ethenylphenoxy group which is an A2 group, and an arbitrary mixture thereof, and n in the formula (1) is 1 Certain ethenylphenoxy group-containing cyclotriphosphazene compounds and ethenylphenoxy wherein n in formula (1) is 2 Containing cyclotetraphosphazene compounds, wherein A is a combination of a phenoxy group that is an A1 group and an ethenylphenoxy group that is an A2 group, a methylphenoxy group that is an A1 group, and an ethenylphenoxy group that is an A2 group; Particularly preferred are combinations of these and any mixtures thereof.

Manufacturing method of ethenylphenoxy group-containing cyclic phosphazene compound The manufacturing method of ethenylphenoxy group-containing cyclic phosphazene is described in various documents and patents, for example, Non-Patent Documents 1 to 3 and Patent Document 8.

Lianhui Cong and Christopher W. Allen, Phosphorus, Sulfur, and Silicon, 179, 961, 2004 Lianhui Cong and Christopher W. Allen, PMSE Preprints, 93, 783, 2005 Ho Lim and Ji Young Chang, J. Mater. Chem., 20, 749, 2010 JP-A-10-53596

  However, the method for producing an ethenylphenoxy group-containing cyclic phosphazene described in these non-patent literatures and patent literatures comprises chlorophosphazene compound and p-hydroxystyrene in the presence of an alkali metal salt or base of p-hydroxystyrene. It is reacting. In these production methods, since p-hydroxystyrene is an unstable compound, in the reaction step with the chlorophosphazene compound, the ethenyl group of p-hydroxystyrene reacts to produce a by-product, resulting in a decrease in yield. There is a risk. Moreover, since an excessive amount of expensive alkali metal salt of p-hydroxystyrene is used, it is not economical.

  The method for producing an ethenylphenoxy group-containing cyclic phosphazene compound of the present invention includes a carbon-carbon bond forming reaction step by a cross-coupling reaction between a phenoxy group-containing cyclic phosphazene compound having a leaving group and a vinyl compound.

  The method for producing an ethenylphenoxy group-containing cyclic phosphazene compound according to the present invention uses a phenoxy group-containing cyclic phosphazene compound having a stable leaving group, and the leaving group is carbon-carbon using a cross-coupling reaction under mild conditions. Since it converts into an ethenyl group by performing bond formation reaction, the production | generation of the by-product which the ethenyl group reacted can be suppressed. In addition, it is economical because an inexpensive p-halogenated phenol is used.

  The ethenylphenoxy group-containing cyclic phosphazene compound of the present invention can be produced by the following method.

  First, a phenoxy group-containing cyclic phosphazene compound having a leaving group represented by the following formula (3) is prepared.

  In formula (3), m represents an integer of 1 to 6, preferably an integer of 1 to 4, and particularly preferably 1 or 2. Examples of such a cyclic phosphazene compound include a cyclotriphosphazene compound (trimer) in which m is 1 in the formula (3), a cyclotetraphosphazene compound (tetramer) in which m is 2 in the formula (3), and a formula (3). A cyclopentaphosphazene compound (pentamer) in which m is 3; a cyclohexaphosphazene compound in which m is 4 in the formula (3) (hexamer); a cycloheptaphosphazene compound in which m is 5 in the formula (3) (7 quantities) And cyclooctaphosphazene compounds (octamers) in which m is 6 in the formula (3). Of these, the cyclotriphosphazene compound in which m is 1 in formula (3), the cyclotetraphosphazene compound in which m is 2 in formula (3), the cyclopentaphosphazene compound in which m is 3 in formula (3), and the formula (3) A cyclohexaphosphazene compound in which m is 4 is preferred, and a cyclotriphosphazene compound in which m is 1 in formula (3) and a cyclotetraphosphazene compound in which m is 2 in formula (3) are particularly preferred.

  In formula (3), E is a group selected from the group consisting of the following E1 group and E2 group, and at least one of E is E2 group.

[E1 group]
An aryloxy group having 6 to 20 carbon atoms; In the aryloxy group, at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkyloxy 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, methoxyphenoxy group, ethoxyphenoxy group, n-propoxy group Phenoxy group, iso-propoxyphenoxy group, n-butoxyphenoxy group, tert-butoxyphenoxy group, 4-methoxy-3-methylphenoxy group, 4-ethoxy-3-methyl Ruphenoxy group, 4-n-propoxyphenoxy group, 4-iso-propoxy-3-methylphenoxy group, 4-n-butoxy-3-methylphenoxy group, 4-tert-butoxy-3-methylphenoxy group, phenylphenoxy Group, naphthyloxy group, anthryloxy group, phenanthryloxy group and the like. Of these, phenoxy group, methylphenoxy group, dimethylphenoxy group, diethylphenoxy group, methoxyphenoxy group, phenylphenoxy group and naphthyloxy group are preferable, and phenoxy group, methylphenoxy group, dimethylphenoxy group and naphthyloxy group are particularly preferable.

[E2 group]
A substituted phenoxy group represented by the following formula (4).

  In the formula (4), X represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of such a substituted phenoxy group include a 4-fluorophenoxy group, a 4-chlorophenoxy group, a 4-bromophenoxy group, and a 4-iodophenoxy group. Of these, 4-chlorophenoxy group, 4-bromophenoxy group, and 4-iodophenoxy group are preferable, and 4-chlorophenoxy group and 4-bromophenoxy group are particularly preferable.

  In addition to the halogen atom, examples of the leaving group include OTs, OTf, OCOR, OR, and SR, which can be appropriately selected and used.

  In the formula (3), 2m + 4 E are contained, at least one of which is an E2 group. Therefore, the phenoxy group-containing cyclic phosphazene compound having a leaving group represented by the formula (3) can be roughly classified into the following forms.

[Form A]
All 2m + 4 E's are E2 groups.

  Specific examples of the phenoxy group-containing cyclic phosphazene compound having a leaving group in such a form include a phenoxy group-containing cyclotriphosphazene compound having a leaving group in which m is 1 in formula (3), A phenoxy group-containing cyclotetraphosphazene compound having a leaving group in which m is 2, a phenoxy group-containing cyclopentaphosphazene compound having a leaving group in which m is 3 in formula (3), and m in formula (3) is 4. Phenoxy group-containing cyclohexaphosphazene compound having a certain leaving group, phenoxy group-containing cycloheptaphosphazene compound having a leaving group in which m is 5 in formula (3), and leaving group in which m is 6 in formula (3) A phenoxy group-containing cyclooctaphosphazene compound having a 4-fluorophenoxy group, wherein E is an E2 group, and 4-chloro, which is an E2 group Phenoxy group, a 4-bromophenoxy group and E2 groups are E2 group is 4-iodo-phenoxy group. Further, the phenoxy group-containing cyclic phosphazene compound having a leaving group of this form may be any mixture of these preferable phenoxy group-containing cyclic phosphazene compounds.

  Among them, a phenoxy group-containing cyclotriphosphazene compound having a leaving group in which m in formula (3) is 1, a phenoxy group-containing cyclotetraphosphazene compound having a leaving group in which m in formula (3) is 2, (3) a phenoxy group-containing cyclopentaphosphazene compound having a leaving group in which m is 3 and a phenoxy group-containing cyclohexaphosphazene compound having a leaving group in which m is 4 in formula (3), wherein E is A 2-chlorophenoxy group that is an E2 group, a 4-bromophenoxy group that is an E2 group, a 4-iodophenoxy group that is an E2 group, and an arbitrary mixture thereof, wherein m in the formula (3) is Phenoxy group-containing cyclotriphosphazene compound having a leaving group which is 1 and a phenoxy group-containing cycloteto having a leaving group in which m is 2 in formula (3) A phosphazene compound, E is an E2 groups are E2 group 4-chlorophenoxy group, an E2 group 4-bromophenoxy group and any mixtures thereof are particularly preferred.

[Form B]
A part (that is, at least one) of 2m + 4 E is an E2 group, and the other E is a group selected from the group consisting of an E1 group. In this case, the other Es other than the E2 group may all be the same E1 group, or may be a mixture of two or more E1 groups.

  The phenoxy group-containing cyclic phosphazene compound having a leaving group of this form includes a phenoxy group-containing cyclotriphosphazene compound having a leaving group in which m in the formula (3) is 1, and m in the formula (3) is 2. A phenoxy group-containing cyclotetraphosphazene compound having a leaving group, a phenoxy group-containing cyclopentaphosphazene compound having a leaving group in which m is 3 in formula (3), and a leaving group in which m is 4 in formula (3). A phenoxy group-containing cyclohexaphosphazene compound having a phenoxy group-containing cycloheptaphosphazene compound having a leaving group in which m is 5 in formula (3) and a phenoxy group having a leaving group in which m is 6 in formula (3) Cyclooctaphosphazene compound, wherein 1 to (2m + 3) of 2m + 4 E is E2 group, and any mixture thereof It is preferred.

  Specific examples of the phenoxy group-containing cyclic phosphazene compound having such a preferred leaving group include a phenoxy group-containing cyclotriphosphazene compound having a leaving group in which m in the formula (3) is 1, m in the formula (3) A phenoxy group-containing cyclotetraphosphazene compound having a leaving group in which m is 2, a phenoxy group-containing cyclopentaphosphazene compound having a leaving group in which m is 3 in formula (3), and m in formula (3) is 4. A phenoxy group-containing cyclohexaphosphazene compound having a leaving group, a phenoxy group-containing cycloheptaphosphazene compound having a leaving group in which m is 5 in formula (3), and a leaving group in which m is 6 in formula (3). A phenoxy group-containing cyclooctaphosphazene compound having E, wherein E is a phenoxy group that is an E1 group and a 4-fluorophenoxy group that is an E2 group In combination with a group, a combination of a methylphenoxy group that is an E1 group and a 4-fluorophenoxy group that is an E2 group, a combination of a dimethylphenoxy group that is an E1 group and a 4-fluorophenoxy group that is an E2 group A combination of a naphthyloxy group that is an E1 group and a 4-fluorophenoxy group that is an E2 group, a combination of a phenoxy group that is an E1 group and a 4-chlorophenoxy group that is an E2 group, an E1 group A combination of a methylphenoxy group that is E2 and a 4-chlorophenoxy group that is an E2 group, a combination of a dimethylphenoxy group that is an E1 group and a 4-chlorophenoxy group that is an E2 group, and a naphthyloxy that is an E1 group In combination with a 4-chlorophenoxy group which is an E2 group, a phenoxy group which is an E1 group A combination of 4-bromophenoxy group which is E2 group, a combination of methylphenoxy group which is E1 group and 4-bromophenoxy group which is E2 group, dimethylphenoxy group which is E1 group and E2 group Combination of 4-bromophenoxy group, combination of naphthyloxy group which is E1 group and 4-bromophenoxy group which is E2 group, phenoxy group which is E1 group and 4-iodophenoxy group which is E2 group A combination of a methylphenoxy group that is an E1 group and a 4-iodophenoxy group that is an E2 group, a combination of a dimethylphenoxy group that is an E1 group and a 4-iodophenoxy group that is an E2 group A combination of a naphthyloxy group as an E1 group and a 4-iodophenoxy group as an E2 group And any mixtures thereof.

  Among them, a phenoxy group-containing cyclotriphosphazene compound having a leaving group in which m in formula (3) is 1, a phenoxy group-containing cyclotetraphosphazene compound having a leaving group in which m in formula (3) is 2, (3) a phenoxy group-containing cyclopentaphosphazene compound having a leaving group in which m is 3 and a phenoxy group-containing cyclohexaphosphazene compound having a leaving group in which m is 4 in formula (3), wherein E is A combination of a phenoxy group that is an E1 group and a 4-chlorophenoxy group that is an E2 group, a combination of a methylphenoxy group that is an E1 group and a 4-chlorophenoxy group that is an E2 group, and an E1 group Combination of phenoxy group and 4-bromophenoxy group which is E2 group, methylphenoxy group which is E1 group and 4-bromine which is E2 group Combination with phenoxy group, combination of phenoxy group which is E1 group and 4-iodophenoxy group which is E2 group, combination of methylphenoxy group which is E1 group and 4-iodophenoxy group which is E2 group And any mixture thereof, a phenoxy group-containing cyclotriphosphazene compound having a leaving group in which m is 1 in formula (3) and a phenoxy having a leaving group in which m is 2 in formula (3) A group-containing cyclotetraphosphazene compound in which E is a combination of a phenoxy group that is an E1 group and a 4-chlorophenoxy group that is an E2 group, a methylphenoxy group that is an E1 group, and a 4-chloro group that is an E2 group Combination with phenoxy group, combination of phenoxy group which is E1 group and 4-bromophenoxy group which is E2 group Ones were those and any mixtures thereof in combination with 4-bromophenoxy group is methylphenoxy group and E2 groups are E1 groups are particularly preferred.

Methods for producing such a phenoxy group-containing cyclic phosphazene compound having a leaving group are described in various documents, for example, Non-Patent Documents 4 and 5 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 JAGER, 2004, NOVA SCIENCE PUBLISHERS INC. Company

  The method for producing an ethenylphenoxy group-containing cyclic phosphazene compound of the present invention can be obtained by a carbon-carbon bond forming reaction between a phenoxy group-containing cyclic phosphazene compound having a leaving group and an ethenyl compound.

  Such a carbon-carbon bond forming reaction is described in various documents, for example, Non-Patent Document 6 and Non-Patent Document 7.

Metal-Catalyzed Cross-Coupling Reactions, Volume 1, A.M. de. Meijere, F.M. Diederich, 2004, WILEY-VCH Verlag GmbH & Co. KGaA Scott E.M. Denmark, C.I. R. Buller, Org. Synth. 86.274.2009

  The ethenyl compound used in the method for producing the ethenylphenoxy group-containing cyclic phosphazene compound of the present invention is not particularly limited, but vinyl magnesium halides such as vinyl lithium, vinyl magnesium chloride, vinyl magnesium bromide and vinyl magnesium iodide, Vinyl zinc halides such as vinyl zinc chloride, vinyl zinc bromide and vinyl zinc iodide, vinyl silane compounds, vinyl tin compounds, 1,3-divinyltetramethylsiloxane and 1,3,5,7-tetravinyl-1,3 , 5,7-tetramethylcyclotetrasiloxane and other silicic acid vinyl esters, 4,4,5,5-tetramethyl-2-vinyl-1,3,2-dioxaborane and other boric acid vinyl esters, vinyl chloride , Vinyl halides such as vinyl bromide and vinyl iodide Le compounds and unsaturated hydrocarbon compounds such as ethylene and the like. These ethenyl compounds may be commercially available or may be prepared in a reaction system.

  In the method for producing an ethenylphenoxy group-containing cyclic phosphazene compound of the present invention, the amount of the ethenyl compound used is preferably 1 to 20 equivalents relative to the leaving group of the phenoxy group-containing cyclic phosphazene compound having a leaving group. 05 to 5 equivalents are particularly preferred. When the amount of the ethenyl compound used is less than 1.0 equivalent, the conversion of the leaving group to the vinyl group becomes insufficient, and the obtained ethenylphenoxy group-containing cyclic phosphazene compound may not exhibit good characteristics. . Moreover, when there are more usage-amounts of an ethenyl compound than 20.0 equivalent, since the quantity of an unreacted ethenyl compound increases, it is not economical.

  In the method for producing an ethenylphenoxy group-containing cyclic phosphazene compound of the present invention, a catalyst can be used as necessary. The catalyst used here is not particularly limited. For example, palladium-activated carbon, palladium (II) chloride, palladium (II) acetate, dichlorobis (acetonitrile) palladium (II), dichlorobis (benzonitrile) palladium ( II), bis (acetylacetonato) palladium (II), dichlorobis (triphenylphosphine) palladium (II), tetrakis (triphenylphosphine) palladium (0), bis (dibenzylideneacetone) palladium (0), tris (di Benzylideneacetone) dipalladium (0), [1,2-bis (diphenylphosphino) ethane] palladium (II) dichloride, [1,3-bis (diphenylphosphino) propane] palladium (II) dichloride and [1, 1'-bis ( Phenyl compounds such as phenylphosphino) ferrocene] palladium (II) dichloride, nickel chloride, bis (acetylacetonato) nickel (II), [1,2-bis (diphenylphosphino) ethane] nickel (II) dichloride, [1,3-bis (diphenylphosphino) propane] nickel (II) dichloride, [1,1′-bis (diphenylphosphino) ferrocene] nickel (II) dichloride, bis (2,4-pentanedionate) nickel (II) Nickel compounds such as hydrate, bis (tricyclohexylphosphine) nickel (II) dichloride, bis (diphenylphosphine) nickel (II) dichloride, and Raney nickel, dodecacarbonyltriruthenium (0) and dihydridocar Ruthenium compounds such as nyltris (triphenylphosphine) ruthenium (II), rhodium compounds such as rhodium (III) chloride, di-μ-chlorobis (η-1,5-cyclooctadiene) diiridium (I), etc. Iridium compounds, iron (III) chloride-tetramethylethylenediamine complex, iron (III) fluoride-tetramethylethylenediamine complex iron (III) -1,3-bis (2,6-diisopropylphenyl) imidazolium chloride complex, Iron compounds such as iron (III) fluoride-1,3-bis (2,6-diisopropylphenyl) imidazolium chloride complex and iron (III) -1,2-bis (diphenylphosphino) benzene complex; Copper compounds such as copper, copper bromide and copper iodide, which may be used alone or in combination. It may be used in combination or more. Moreover, these catalysts may use a commercially available thing and may prepare in a reaction system.

  The method for producing the ethenylphenoxy group-containing cyclic phosphazene compound of the present invention may use a base as necessary. Although the base used here is not particularly limited, for example, amines such as trimethylamine, triethylamine, diisopropylethylamine, pyridine and imidazole, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and cesium hydroxide , Alkali metal carbonates such as potassium bicarbonate, sodium bicarbonate, potassium carbonate, sodium carbonate and cesium carbonate, methylmagnesium chloride, ethylmagnesium chloride, methylmagnesium bromide, ethylmagnesium bromide, tert-butylmagnesium chloride and odor And alkylmagnesium halides such as tert-butylmagnesium and alkyllithiums such as n-butyllithium, sec-butyllithium and tert-butyllithium. .

  The method for producing the ethenylphenoxy group-containing cyclic phosphazene compound of the present invention can be carried out in a solvent or without a solvent. Although the solvent used here is not specifically limited, For example, ethers, such as aromatic hydrocarbons, such as toluene and xylene, ethyl ether, tetrahydrofuran, and a dioxane, can be mentioned. The reaction temperature is not particularly limited as long as the ethenylphenoxy group-containing phosphazene compound is not polymerized, but is preferably -78 to 150 ° C, particularly preferably -50 to 120 ° C.

  The target ethenylphenoxy group-containing cyclic phosphazene compound obtained by the reaction of a phenoxy group-containing cyclic phosphazene compound having such a leaving group with an ethenyl compound can be used for filtration, solvent extraction, column chromatography, recrystallization, etc. It can be isolated and purified from the reaction system by ordinary methods.

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

  In the resin composition of the present invention, as the ethenylphenoxy group-containing cyclic phosphazene compound of the present invention, one kind may be used, or two or more kinds of ethenylphenoxy group-containing cyclic phosphazene compounds 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, polystyrene, high-impact 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, polymethyl Methacrylate, polycarbonate, polyphenylene ether, modified polyphenylene ether, aliphatic polyamide, aromatic polyamide, polyethylene terephthalate (PET) 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, a reactive functional group such as a carboxyl group, an epoxy group, an amino group, a hydroxyl group, and an anhydrous dicarboxyl group is introduced into a part or all of the polyphenylene ether by some method such as graft reaction or copolymerization. Things are used. When the resin composition of the present invention is used as a material for casings or parts for electronic equipment, particularly OA equipment, AV equipment, communication equipment, and home appliances, polyester resin, ABS resin, It is preferable to use polycarbonate, polyphenylene ether, polybutadiene resin, polyisoprene resin, or the like.

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

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

  In the resin composition of the present invention, the amount of the ethenylphenoxy group-containing cyclic phosphazene compound can be appropriately set according to various conditions such as the type of the resin component and the use of the resin composition. It is preferable to set to 0.1 to 100 parts by weight with respect to 100 parts by weight of the resin component in terms of conversion, more preferably to set to 0.5 to 50 parts by weight, and to set to 1 to 30 parts by weight. Further preferred. When the amount of the ethenylphenoxy group-containing cyclic phosphazene compound used is less than 0.1 parts by weight, the resin molded body made of the resin composition may not exhibit sufficient flame retardancy. On the other hand, if the amount exceeds 100 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.

  The resin composition of the present invention is at least one selected from the group of polymerizable materials consisting of a thermopolymerizable monomer, a thermopolymerizable oligomer, a photopolymerizable monomer, a photopolymerizable oligomer, a radiation polymerizable monomer, and a radiation polymerizable oligomer. It may further contain a polymerizable material.

  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, isoprene, styrene, high 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 Body, epoxidized oil acrylate resin precursor, urethane acrylate resin precursor, polyester acrylate resin precursor, polyether acrylate resin precursor, acrylic acrylate resin precursor, unsaturated polymer Ester 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 Body, 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 And glycidyl ether epoxy resin precursor. Of these, butadiene, isoprene, styrene, epoxy acrylate resin precursor, urethane acrylate resin precursor, polyester acrylate resin precursor, and the like are preferable. These polymerizable materials may be used alone or in combination of two or more as required.

  Moreover, the resin composition of this invention can mix | blend various additives in the range which does not impair the target physical property according to the kind of resin component, the use of a resin composition, etc. Available additives include, for example, natural silica, calcined silica, synthetic silica, amorphous silica, white carbon, alumina, aluminum hydroxide, magnesium hydroxide, calcium silicate, calcium carbonate, zinc borate, zinc stannate, oxidation Titanium, zinc oxide, molybdenum oxide, zinc molybdate, natural mica, synthetic mica, aerosil, kaolin, clay, talc, calcined kaolin, calcined clay, calcined talc, wollastonite, short glass fiber, glass fine powder, hollow glass and Inorganic fillers such as potassium titanate fibers, organic fibers such as aramid fibers or polyparaphenylene benzbisoxazole fibers, surface treatment agents for fillers such as silane coupling agents, waxes, fatty acids and their metal salts, acid amides And mold release agents such as paraffin, chlorine Paraffin, phosphate ester, condensed phosphate ester, phosphate amide, phosphate amide ester, phosphinate, phosphinate salt, phosphorus flame retardants such as ammonium phosphate and red phosphorus, melamine, melamine cyanurate, melam, melem, melon and Nitrogen flame retardants such as succinoguanamine, silicone flame retardants, flame retardants such as bromine flame retardants, flame retardant aids such as antimony trioxide, anti-dripping agents such as polytetrafluoroethylene (PTFE), benzotriazole UV absorbers such as, hindered phenols, antioxidants such as styrenated phenols, photopolymerization initiators such as thioxanthones, fluorescent brighteners such as stilbene derivatives, curing agents, dyes, pigments, colorants, light stabilizers , Photosensitizer, thickener, lubricant, defoamer, leveling agent, brightener, heavy You may be mentioned inhibitor, thixotropic agents, plasticizers and antistatic agents.

  When the resin composition of the present invention is used for a material for electric and electronic fields, specifically, a sealant or a substrate for electronic parts such as LSI, a polyphenylene ether represented by the following formula (5) as a resin component: Can be used.

In the formula (5), r represents an integer of 30 to 1,000. L ^{1 to} L ⁴ are groups selected from a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, and an aryl group having 6 to 20 carbon atoms. In the aryl group having 6 to 20 carbon atoms, at least one group selected from an alkyl group having 1 to 6 carbon atoms, an alkenyl group, and an aryl group may be substituted.

  Specific examples of the polyphenylene ether represented by the formula (5) include poly (methylphenylene) ethers such as poly (2-methyl-1,4-phenylene) ether, poly (2,6) as homopolymers thereof. -Poly (dimethylphenylene) ethers such as dimethyl-1,4-phenylene) ether, poly (methylethylphenylene) ethers such as poly (2-methyl-6-ethyl-1,4-phenylene) ether, poly ( Poly (diethylphenylene) ethers such as 2,6-diethyl-1,4-phenylene) ether, poly (ethylpropylphenylene) such as poly (2-ethyl-6-n-propyl-1,4-phenylene) ether Poly (dipropylphenylene) ethers such as ethers and poly (2,6-n-propyl-1,4-phenylene) ether , Poly (methylpropylphenylene) ethers such as poly (2-methyl-6-n-propyl-1,4-phenylene) ether, poly (2-methyl-6-n-butyl-1,4-phenylene) Poly (methylbutylphenylene) ethers such as ether, poly (methylisopropylphenylene) ethers such as poly (2-methyl-6-isopropyl-1,4-phenylene) ether, poly (2-ethyl-6-isopropyl-) Homogeneous such as poly (ethyl isopropyl phenylene) ethers such as 1,4-phenylene) ether and poly (methyl hydroxyethyl phenylene) ethers such as poly (2-methyl-6-hydroxyethyl-1,4-phenylene) ether Polymers. Further, as a copolymer having a phenylene ether structure as a main monomer unit, a copolymer of 2,6-dimethylphenol and o-cresol, 2,6-dimethylphenol and 2,3,6-trimethylphenol, and and a copolymer with o-cresol.

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

  The above-described polyphenylene ethers may be used alone or in combination of two or more as necessary.

  The resin composition of this invention can mix | blend a polymerization initiator in the range which does not impair the physical property. The polymerization initiator is not particularly limited as long as it is capable of heating or absorbing active energy rays such as ultraviolet rays or electron beams and polymerizing an unsaturated group such as an ethenylphenoxy group. Benzoin such as benzoin, benzoin methyl ether or benzoin ethyl ether and alkyl ethers thereof, acetophenone, 2,2-dimethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, etc. Acetophenones, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinoamino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1-butanone and A, such as N, N-dimethylaminoacetophenone Noacetophenones, 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone and anthraquinones such as 1-chloroanthraquinone, 2,4-dimethylthioxanthone, 2-chlorothioxanthone and 2,4-diisopropylxanthone Thioxanthones, ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal, organic peroxides such as benzoyl peroxide and cumene peroxide, 2,4,5-triarylimidazole dimer, riboflavin tetrabutyrate, 2-mercapto Thiols such as benzimidazole, 2-mercaptobenzoxazole and 2-mercaptobenzothiazole, 2,4,6-tris-sec-triazine, 2,2,2-trib Moethanol, organic halides such as tribromomethylphenylsulfone, benzophenones such as benzophenone and 4,4′-bisdiethylaminobenzophenone, acid generators such as aromatic sulfonates, and 2,4,6-trimethylbenzoyldiphenyl Examples include phosphine oxide, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinoamino-1-propanone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -1 -Butanone and aromatic sulfonates are particularly preferred.

  According to the resin composition of the present invention, a resin composition having a low dielectric constant and dielectric loss tangent can be obtained. Therefore, the resin composition of the present invention is used for semiconductor encapsulation and circuit boards (in particular, metal-clad laminates, printed wiring board substrates, printed wiring board adhesives, printed wiring board adhesive sheets, and printed wiring board use). Insulating circuit protective film, conductive paste for printed wiring board, sealing agent for multilayer printed wiring board, circuit protective agent, cover lay film, cover ink), etc. are particularly suitable as materials for manufacturing electrical and electronic parts. .

Flame Retardant Polymerization Composition The resin composition of the present invention is an ethenylphenoxy group-containing cyclic phosphazene compound of the present invention, or an ethenylphenoxy group-containing cyclic phosphazene compound and a thermally polymerizable monomer, a thermally polymerizable oligomer, a photopolymerizable monomer. And a flame retardant polymerization composition obtained by reacting at least one polymerizable material selected from the group of polymerizable materials consisting of a photopolymerizable oligomer, a radiation polymerizable monomer and a radiation polymerizable oligomer. The ethenylphenoxy group-containing cyclic phosphazene compound used here may be used alone or in combination of two or more as required.

  The polymerizable material used here may contain other polymerizable material capable of reacting (copolymerizing) with the ethenylphenoxy 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 preferable. Two or more of these polymerizable materials may be used in combination. Examples of the aromatic vinyl monomer include styrene, methylstyrene, dimethylstyrene, ethylstyrene, isopropylstyrene, chlorostyrene, dichlorostyrene, acetoxystyrene, hydroxystyrene, 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 acrylate, butyl acrylate, butyl methacrylate, octyl acrylate, octyl methacrylate, nonyl acrylate, nonyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, glycidyl acrylate, glycidyl methacrylate, Examples include acrylic esters or methacrylic esters such as vinyl acrylate and vinyl methacrylate, and vinyl esters such as vinyl acetate, vinyl butyrate, vinyl caproate, and vinyl stearate. It is. Of these, acrylonitrile, methyl acrylate and methyl methacrylate are particularly preferred. As the vinyl ether monomer, it is usually preferable to use divinyl ethers.

  When these polymerizable materials are reacted 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 (AIBN), azobis-2, Examples include azo compounds such as 4-dimethylvaleronitrile, azobiscyclohexylnitrile, azobiscyanovaleric acid, 2,2-azobis (2-methylbutyronitrile), and acid generators such as aromatic sulfonates. .

On the other hand, when reacting these polymerizable materials 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. can be mentioned, for example.
When the polymerizable material is reacted by irradiation with energy rays, usually, a photopolymerization initiator and a sensitizer are added as necessary to the polymerizable material, and when various energy rays are irradiated to this, The objective flame-retardant polymerization composition can be obtained.

  Furthermore, the flame retardant polymerization composition of the present invention may contain a known reactive diluent or additive 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, 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 as required. On the other hand, the thing similar to what is used in the resin composition of this invention can be used.

The flame-retardant polymerization composition of the present invention is excellent in heat resistance, electrical properties, mechanical properties and heat resistance, and has excellent flame retardancy and low smoke generation based on an ethenylphenoxy group-containing cyclic phosphazene compound. Show. For this reason, this flame-retardant polymerization composition can be widely used as a material for production of various resin moldings, for coatings, for adhesives, and for other uses. In particular, this flame-retardant polymerization composition is used 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 boards). Insulating circuit protective film, conductive paste for printed wiring board, sealing agent for multilayer printed wiring board, circuit protective agent, coverlay film, cover ink), etc. .

EXAMPLES The present invention will be specifically described below with reference to examples and comparative examples, but the present invention is not limited by these. In the following, “unit” in “unit mol” means the smallest structural unit of the cyclic phosphazene compound, for example, (PNA ₂ ) for formula (1), and when A is chlorine, 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 produced in Synthesis Examples, Reference Examples and Examples were identified based on the results of ¹ H-NMR spectrum and ³¹ P-NMR spectrum, and TOF-MS and IR spectrum measurements.

Synthesis Example 1 (Production of phenoxy group-containing cyclic phosphazene compound having a leaving group according to Form B)
A 5-liter 4-neck flask equipped with a thermometer, stirrer, condenser and dropping funnel was charged with hexachlorocyclotriphosphazene (243.4 g, 2.10 unit mol) under a nitrogen stream, and tetrahydrofuran (800 mL) was added. And dissolved. To this was added dropwise a tetrahydrofuran solution (1,000 mL) of sodium phenoxide (325.1 g, 2.80 mol) prepared previously at 10 to 20 ° C. over 1.5 hours, and then stirred at 20 to 30 ° C. for 5 hours. The reaction solution was poured into a toluene (2,000 mL) suspension of potassium 4-chlorophenoxide (280.0 g, 1.68 unit mol) prepared in advance, and aged at 110 ° C. for 3 hours. The reaction mixture was cooled to room temperature, diluted with toluene, washed twice with 5% aqueous sodium hydroxide solution, neutralized, and further washed with water. The organic layer was concentrated under reduced pressure to obtain 517.7 g (yield 97%) of the product. The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
6.7 to 6.8 (4H), 6.8 to 7.0 (8H), 7.0 to 7.4 (16H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.5 to 10.5
◎ ¹³ C-NMR spectrum (in deuterated chloroform, δ, ppm):
118.0, 120.8, 122.7, 125.1, 129.5, 132.4, 149.5, 150.3
◎ TOF-MS:
728, 761, 797

From the above analysis results, this product is [N ₃ P ₃ (OC ₆ H ₄ Cl) ₁ (OC ₆ H ₅ ) ₅ ], [N ₃ P ₃ (OC ₆ H ₄ Cl) ₂ (OC ₆ H ₅ ) ₄ ], [N ₃ P ₃ (OC ₆ H ₄ Cl) ₃ (OC ₆ H ₅ ) ₃ ], and the average composition thereof is [N ₃ P ₃ (OC ₆ H ₄ Cl) _2.0 ( OC ₆ H ₅ ) _4.0 ] was confirmed to be a 4-chlorophenoxy group-containing cyclic phosphazene compound.

Synthesis Example 2 (Production of phenoxy group-containing cyclic phosphazene compound having a leaving group according to Form B)
A 5-liter 4-neck flask equipped with a thermometer, stirrer, condenser and dropping funnel was charged with hexachlorocyclotriphosphazene (243.4 g, 2.10 unit mol) under a nitrogen stream, and tetrahydrofuran (800 mL) was added. And dissolved. To this was added dropwise a tetrahydrofuran solution (1,000 mL) of sodium phenoxide (243.8 g, 2.10 mol) prepared previously at 10 to 20 ° C. over 1.5 hours, and then stirred at 20 to 30 ° C. for 5 hours. The reaction solution was poured into a toluene (2,000 mL) suspension of potassium 4-bromophenoxide (576.3 g, 2.73 mol) prepared in advance, and aged at 110 ° C. for 3 hours. The reaction mixture was cooled to room temperature, diluted with toluene, washed twice with 5% aqueous sodium hydroxide solution, neutralized, and further washed with water. The organic layer was concentrated under reduced pressure to obtain 631.6 g (yield 97%) of the product. The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
6.7 to 6.8 (2H), 6.8 to 7.0 (2H), 7.0 to 7.4 (5H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.5 to 10.5
◎ ¹³ C-NMR spectrum (in deuterated chloroform, δ, ppm):
118.0, 120.8, 122.7, 125.1, 129.5, 132.4, 149.5, 150.3
◎ TOF-MS:
851,930,1009

From the above analysis results, this product is [N ₃ P ₃ (OC ₆ H ₄ Br) ₄ (OC ₆ H ₅ ) ₂ ], [N ₃ P ₃ (OC ₆ H ₄ Br) ₃ (OC ₆ H _5]. ) ₃ ], [N ₃ P ₃ (OC ₆ H ₄ Br) ₂ (OC ₆ H ₅ ) ₄ ], the average composition of which is [N ₃ P ₃ (OC ₆ H ₄ Br) _3.0 ( it was confirmed that OC ₆ H _{5) 3.0]} is a 4-bromophenoxy group-containing cyclic phosphazene compound.

Synthesis Example 3 (Production of phenoxy group-containing cyclic phosphazene compound having a leaving group according to Form A)
A 5-liter 4-neck flask equipped with a thermometer, stirrer, condenser and dropping funnel was charged with hexachlorocyclotriphosphazene (243.4 g, 2.10 unit mol) under a nitrogen stream, and tetrahydrofuran (800 mL) was added. And dissolved. To this was added dropwise a solution of potassium 4-bromophenoxide (1,0097.7 g, 5.2 mol) previously prepared at 10 to 20 ° C. over 3.5 hours. The reaction mixture was heated to reflux for 15 hours, and the solvent was distilled off under reduced pressure. The residue was diluted with toluene, washed twice with 5% aqueous sodium hydroxide solution, neutralized with dilute nitric acid, and further washed with water. The organic layer was concentrated under reduced pressure to obtain 800.5 g (yield 98%) of the product. The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
6.7 to 6.8 (2H), 7.0 to 7.4 (2H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.5 to 10.5
◎ ¹³ C-NMR spectrum (in deuterated chloroform, δ, ppm):
118.0, 122.7, 132.4, 149.5
◎ TOF-MS:
1167

From the above analysis results, this product was confirmed to be a 4-bromophenoxy group-containing phosphazene compound of [N ₃ P ₃ (OC ₆ H ₄ Br) ₆ ].

Reference Example 1 (Production of phenoxy group fully substituted cyclic phosphazene compound)
PHOSPHORUS-NITROGEN COMPOUNDS, H.P. R. [N = P (OC ₆ H ₅ ) ₂ ] ₃ (white solid / melting point: 110 ° C.) using hexachlorocyclotriphosphazene according to the method described in ALLCOCK, 1972, page 151, ACADEMIC PRESS. Obtained.

Example 1 (Production of Ethenylphenoxy Group-Containing Cyclic Phosphazene Compound According to Form 2)
A 10-liter four-necked flask equipped with a thermometer, stirrer, condenser and dropping funnel was charged with tetrakis (triphenylphosphine) palladium (23.1 g, 0.02 mol) and lithium chloride (127.127) under an argon gas atmosphere. 2 g, 3.00 mol). (Are there any solvent?) After stirring at room temperature for 1 hour, the 4-chlorophenoxy group-containing phosphazene compound (254.2 g, 1.00 unit mol) and trimethylvinyltin (190.8 g, produced in Synthesis Example 1) were prepared. A solution of 1.00 mol) in tetrahydrofuran (1,500 mL) was added and stirred under reflux conditions for 24 hours. The reaction mixture was cooled to room temperature and concentrated. The residue was diluted with diethyl ether and purified by silica gel column chromatography. The obtained fraction was concentrated to obtain 223.7 g (yield 90%) of the product. The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
5.1 (1H), 5.6 (1H), 6.6 (1H), 6.7 to 7.3 (14H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.5 to 10.5
◎ IR spectrum (KBr Pellet, cm ⁻¹ )
3100, 1629, 1264, 1200-1160, 950
◎ TOF-MS:
720, 746, 772

From the above analysis results, this product is [N ₃ P ₃ (OC ₆ H ₄ CH═CH ₂ ) (OC ₆ H ₅ ) ₅ ], [N ₃ P ₃ (OC ₆ H ₄ CH═CH ₂ ) _2. (OC ₆ H ₅ ) ₄ ], [N ₃ P ₃ (OC ₆ H ₄ CH═CH ₂ ) ₃ (OC ₆ H ₅ ) 3 ₂ ], the average composition of which is [N ₃ P ₃ (OC _{6 H 4 CH = CH 2)} 2.0 (OC 6 H 5) 4.0] was confirmed to be ethenyl phenoxy group-containing phosphazene compound of the.

Example 2 (Production of ethenylphenoxy group-containing cyclic phosphazene compound according to Form 2)
To a 10 liter four-necked flask equipped with a thermometer, stirrer, condenser and dropping funnel was added palladium dibromide (13.3 g, 0.05 mol) and 2- (di-tert-butyl) under an argon gas atmosphere. Phosphino) biphenyl (29.8 g, 0.10 mol), 2,4,6,8-tetramethyl-2,4,6,8-tetraethenylcyclooctanetetrasiloxane (206.8 g, 0.60 mol), A 1 mol / L tetrabutylammonium fluoride tetrahydrofuran solution (2,000 mL) was added. After stirring at room temperature for 1.0 hour, a solution of 4-bromophenoxy group-containing phosphazene compound (310.1 g, 1.00 unit mol) prepared in Synthesis Example 2 in tetrahydrofuran (1,500 mL) was added at 50 ° C. Aged for 7 hours. The reaction mixture was cooled to room temperature and concentrated. The residue was diluted with diethyl ether and purified by silica gel column chromatography. The obtained fraction was concentrated to obtain 231.5 g (yield 90%) of the product. The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
5.1 (1H), 5.6 (1H), 6.6 (1H), 6.7 to 7.3 (9H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.5 to 10.5
◎ IR spectrum (KBr Pellet, cm ⁻¹ )
3100, 1629, 1264, 1200-1160, 950
◎ TOF-MS:
746, 772, 798

From the above analysis results, the product _{[N 3 P 3 (OC 6} H 4 CH = CH 2) 4 (OC 6 H 5) 2], [N 3 P 3 (OC 6 H 4 CH = CH 2) ₃ (OC ₆ H ₅ ) ₃ ], [N ₃ P ₃ (OC ₆ H ₄ CH═CH ₂ ) ₂ (OC ₆ H ₅ ) ₄ ], and the average composition thereof is [N ₃ P ₃ (OC it was confirmed that ₆ is _{H 4 CH = CH 2) 3.0} (OC 6 H 5) 3.0 ethenyl phenoxy group-containing phosphazene compound of the.

Example 3 (Production of ethenylphenoxy group-containing cyclic phosphazene compound according to Form 1)
Instead of the phenoxy group-containing cyclic phosphazene compound having a leaving group produced in Synthesis Example 1, the phenoxy group-containing cyclic phosphazene compound having a leaving group produced in Synthesis Example 2 (194.5 g, 0.5 unit mol) was used. Was the same as in Example 1 except that 128.9 g (yield 91%) of the product was obtained. The analysis result of this product was as follows.

◎ ¹ H-NMR spectrum (in deuterated chloroform, δ, ppm):
5.1 (1H), 5.6 (1H), 6.6 (1H), 6.7 to 7.3 (4H)
◎ ³¹ P-NMR spectrum (in deuterated chloroform, δ, ppm):
Trimer (P = N) ₃ 9.5 to 10.5
◎ IR spectrum (KBr Pellet, cm ⁻¹ )
3100, 1629, 1264, 1200-1160, 950
◎ TOF-MS:
958

From the above analysis results, this product was confirmed to be an ethenylphenoxy group-containing phosphazene compound of [N ₃ P ₃ (OC ₆ H ₄ CH═CH ₂ ) ₆ ].

Examples 4 to 6 (Flame-retardant resin composition → (Flame-retardant polymer composition) → Resin molding)
Ethenyl phenoxy group-containing cyclic phosphazene compound produced in Examples 1 to 3, styrene (Tokyo Chemicals reagent), bisphenol A type epoxy resin (Mitsubishi Chemical's trade name “jER828”), acid generator (manufactured by Sanshin Chemical Industry Co., Ltd.) Trade name “Sun-Aid SI-100L”) and methyl ethyl ketone (MEK) were added at a ratio shown in Table 1 and stirred to prepare a varnish. The prepared varnish was applied to a PET film and dried at room temperature for 1 hour and at 90 ° C. for 30 minutes. This was peeled off, a predetermined amount was put in a PTFE spacer, and heated and pressurized under vacuum at 120 ° C. for 30 minutes, 150 ° C. for 30 minutes, and 180 ° C. for 100 minutes to obtain a cured product. This cured product was evaluated for flame retardancy, dielectric properties and heat resistance.

Comparative Example 1 (Flame-retardant resin composition → resin molding)
Test pieces were prepared in the same manner as in Examples 4 to 6, except that the cyclic phosphazene compound produced in Reference Example 1 was used instead of the ethenylphenoxy group-containing cyclic phosphazene compound produced in Examples 1 to 3. did. These test pieces were evaluated for dielectric properties, flame retardancy and heat resistance.

(Flame retardance)
Based on UL-94 standard vertical combustion test of Underwriters' Laboratories Inc., using test pieces with a length of 125 mm, a width of 12.5 mm and a thickness of 1.2 mm It was classified into V-0, V-1, V-2, and non-standard four-stage flame retardant classes according to the combustion time and the presence or absence of cotton ignition by droppings during combustion. V-0 is the highest evaluation, and the evaluation decreases in the order of V-1, V-2, and non-standard.

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

(Heat-resistant)
Using a DTG-60 (trade name) manufactured by Shimadzu Corporation, the temperature range of 30 to 600 ° C. was raised at 10 ° C./min in a nitrogen atmosphere, and a 5% weight loss temperature {Td (5%)} was set. evaluated. The higher the 5% weight loss temperature, the better the heat resistance.

  As is apparent from Table 1, the cured products of Examples 4 to 6 exhibit excellent dielectric properties, flame retardancy, and heat resistance.

Synthesis Example 4 (Production of flame retardant polymerization composition of ethenylphenoxy group-containing cyclic phosphazene compound)
A 1-liter separable flask was charged with the ethenylphenoxy group-containing cyclic phosphazene compound (150 g), AIBN (4.5 g) and toluene (300 mL) prepared in Example 1, heated under nitrogen conditions at 70 ° C. for 3 hours. Stir. Further AIBN (3.0 g) was added and stirred at 70 ° C. for 3 hours, and then heated at 100 ° C. for 1 hour to complete the reaction. The reaction solution was concentrated and toluene was distilled off to obtain 157.5 g of a flame retardant polymerization composition.

Synthesis Example 5 (Production of flame retardant polymerization composition of ethenylphenoxy group-containing cyclic phosphazene compound)
The same operation as in Synthesis Example 3 was carried out except that the ethenylphenoxy group-containing cyclic phosphazene compound (150 g) produced in Example 2 was used instead of the ethenylphenoxy group-containing cyclic phosphazene compound produced in Example 1. 157.5 g of a flame retardant polymerization composition was obtained.

Synthesis Example 6 (Production of flame retardant polymerization composition of ethenylphenoxy group-containing cyclic phosphazene compound and styrene (molar ratio = 50/50))
A 1 liter separable flask was charged with the ethenylphenoxy group-containing cyclic phosphazene compound (134 g) prepared in Example 1, styrene (Tokyo Kasei reagent, 16 g), AIBN (4.5 g) and toluene (300 mL), and nitrogen was added. The mixture was heated under conditions and stirred at 70 ° C. for 3 hours. Further AIBN (3.0 g) was added and stirred at 70 ° C. for 3 hours, and then heated at 100 ° C. for 1 hour to complete the reaction. The reaction solution was concentrated and toluene was distilled off to obtain 157.5 g of a flame retardant polymerization composition.

Examples 7 to 9 (Flame-retardant polymer composition of flame-retardant resin composition → resin molded body)
Flame retardant polymerization composition of ethenylphenoxy group-containing cyclic phosphazene compound produced in Synthesis Examples 4 to 6, polystyrene (trade name “HF77” of PS Japan) and polyphenylene ether (trade name “Zylon S202A” of Asahi Kasei Chemicals) Were weighed at the ratio shown in Table 1 and mixed uniformly with a blender. This mixture was put into a hopper of a twin screw extruder (screw diameter 30 mm, L / D = 42), and melt kneaded and pelletized under the conditions of a cylinder temperature of 250 to 280 ° C. and a screw rotation speed of 200 rpm. After the pellets were dried at 90 ° C. for 6 hours, injection molding was performed with an injection molding machine under the conditions of a cylinder temperature of 260 to 280 ° C. and a mold temperature of 80 ° C. to prepare test pieces. The produced test piece was evaluated for dielectric properties, flame retardancy and heat resistance.

Comparative Example 2 (Flame-retardant resin composition → resin molding)
Except having used the cyclic phosphazene compound produced in Reference Example 1 in place of the flame-retardant polymerization composition of the ethenylphenoxy group-containing cyclic phosphazene compound produced in Synthesis Examples 4 to 6, as in Examples 7 to 9 A test piece was prepared by operating. The produced test piece was evaluated for dielectric properties, flame retardancy and heat resistance.

As is apparent from Table 2, the resin compositions produced in Examples 7 to 9 have excellent dielectric properties, flame retardancy and heat resistance.

Claims (10)

An ethenylphenoxy group-containing cyclic compound represented by the following formula (1) including a step of producing a compound having an ethenyl group by a carbon-carbon bond forming reaction between a phenoxy group-containing cyclic phosphazene compound having a leaving group and an ethenyl compound. A method for producing a phosphazene compound.

(In Formula (1), n shows the integer of 1-6, A shows group selected from the group which consists of following A1 group and A2 group, and at least one is A2 group.
A1 group: 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 alkyloxy group, and an aryl group may be substituted.
A2 group: an ethenylphenoxy group represented by the following formula (2). )

The method for producing an ethenylphenoxy group-containing cyclic phosphazene compound according to claim 1, wherein the phenoxy group-containing cyclic phosphazene compound having a leaving group is represented by the following formula (3).

(In the formula (3), m represents an integer of 1 to 6, E represents a group selected from the group consisting of the following E1 group and E2 group, and at least one is an E2 group.
E1 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 alkyloxy group, and an aryl group may be substituted.
E2 group: a substituted phenoxy group represented by the following formula (4). )

(In formula (4), X is a leaving group, and represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.)   The method for producing an ethenylphenoxy group-containing cyclic phosphazene compound according to claim 1 or 2, wherein the carbon-carbon bond forming reaction is a cross-coupling reaction.   A flame retardant resin composition comprising a resin component and an ethenylphenoxy group-containing cyclic phosphazene compound represented by formula (1).   5. At least one polymerizable material selected from a polymerizable material group 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. The flame-retardant resin composition as described in 2.   The flame retardant resin composition according to claim 4, which may contain a polymerization initiator.   An ethenylphenoxy group-containing cyclic phosphazene compound represented by the formula (1), or an ethenylphenoxy group-containing cyclic phosphazene compound represented by the formula (1), a thermopolymerizable monomer, a thermopolymerizable oligomer, a photopolymerizable monomer, and a photopolymerization. 7. A flame retardant polymerization composition obtained by reacting at least one polymerizable material selected from a polymerizable material group consisting of a polymerizable oligomer, a radiation polymerizable monomer and a radiation polymerizable oligomer. The flame-retardant resin composition as described in 2.   The resin component is at least one selected from the group consisting of polyphenylene ether resins, epoxy resins, polyimide resins, bismaleimide resins, cyanate ester resins, bismaleimide-cyanate ester resins, polybutadiene resins, polystyrene resins, and polyisoprene resins. The flame-retardant resin composition according to any one of claims 4 to 7,   The resin molding which consists of a flame-retardant resin composition in any one of Claim 4 to 8. An electric / electronic component using the resin molded body according to claim 9.