Cyclic phosphazene compound having oxaphosphorin ring-containing structure and mixture thereof, method for producing cyclic phosphazene compound having oxaphosphorin ring-containing structure, resin composition, resin molded product, and electrical / electronic component

Abstract

The novel cyclic phosphono-nitrogen compound shown in formula (1) of this invention, used as a flame retardant for resin materials, can inhibit the degradation of the physical properties of resin materials and improve their flame retardancy, while achieving good dielectric properties. In formula (1), n ​​is an integer from 3 to 8. R1 and R2 are either (i) or (ii) as follows: (i) each independently is a nitro group, an alkyl or alkoxy group of 1 to 8 carbons that can be substituted with an alkyl or aryl group of 1 to 6 carbons, or an aryl or aryloxy group of 6 to 20 carbons that can be substituted with an alkyl or aryl group of 1 to 6 carbons; (ii) forming a saturated or unsaturated cyclic structure between each other that can be substituted with an alkyl or carbonyl group of 1 to 6 carbons. a and b are each independently an integer from 0 to 4. The type of structure containing an oxyphosphonohexane ring in each repeating unit is independent.

Description

Technical Field

[0001] This invention relates to a cyclic phosphazene compound having a structure containing an oxaphosphorine ring, and more particularly to a specific cyclic phosphazene compound having a structure containing an oxaphosphorine ring. Prior Technology

[0002] Materials used in high-capacity / high-speed communication devices carrying fifth-generation (5G) or next-generation high-speed mobile communication systems require, in terms of dielectric properties, both a low dielectric constant (Dk) to reduce signal propagation delay and a low dielectric tangent (Df) to reduce signal attenuation (i.e., Low Dk / Df). Although various resin materials have been proposed as materials capable of achieving Low Dk / Df, flame retardants are usually added to achieve flame retardancy because resin materials are generally flammable.

[0003] However, while flame retardants can improve the flame retardancy of resin materials, they may also alter the physical properties of the resin materials, leading to a deterioration in their mechanical, electrical, or dielectric properties. For example, patent documents 1 to 3 describe phosphine oxide as a flame retardant immiscible with resins, explaining that phosphine oxide can achieve a low Dk / Df ratio in resin materials. However, regarding phosphine oxide, due to its low phosphorus atom content related to the flame retardancy mechanism of resin materials, the amount added relative to the resin material must be increased to achieve the desired flame retardancy. Furthermore, since trace amounts of chloride ions cannot be avoided during its manufacturing process, increasing the amount added relative to the resin material may deteriorate the electrical properties of the resin material due to these chloride ions.

[0004] Furthermore, patent documents 4 to 7 describe the use of trioxobiphenylcyclotriphosphine as a flame retardant, and state that this phosphine compound has a high melting point and can achieve a low Dk / Df ratio. However, since this phosphine compound is synthesized from chlorocyclotriphosphine as a starting material, unsubstituted chlorine may remain in the phosphine ring. In trioxobiphenylcyclotriphosphine, the chlorine remaining in the phosphine ring will be converted into a P-OH group due to hydrolysis, which will reduce the long-term stability in the resin material and may deteriorate the electrical properties of the resin material. [Previous Technical Documents] [Patent Literature]

[0005] [Patent Document 1] Taiwan Patent Application Publication No. 2015 / 42575 [Patent Document 2] Japanese Patent Application Publication No. 2019-023263 [Patent Document 3] Japanese Patent Application Publication No. 2019-044031 [Patent Document 4] International Publication No. 2019 / 198766 [Patent Document 5] U.S. Patent Application Publication No. 2019 / 0367727 [Patent Document 6] Chinese Patent Application Publication No. 110204862 [Patent Document 7] U.S. Patent Application Publication No. 2020 / 0071477 Summary of the Invention

[0006] [The problem the invention aims to solve] This invention attempts to realize a novel cyclic phosphonium nitride compound, which can be used as a flame retardant for resin materials, especially in suppressing the degradation of the physical properties of resin materials while improving flame retardancy, and can achieve Low Dk / Df. [Methods used to solve problems]

[0007] The cyclic phosphazene compound of the present invention has a structure containing an oxyphosphazene ring, as represented by the following formula (1).

[0008]

[0009] In formula (1), n ​​is an integer from 3 to 8. R1 and R2 are either (i) or (ii) as follows: (i) each is independently a nitro group, an alkyl or alkoxy group of 1 to 8 carbons that can be substituted with at least one alkyl or aryl group of 1 to 6 carbons, or an aryl or aryloxy group of 6 to 20 carbons that can be substituted with at least one alkyl or aryl group of 1 to 6 carbons; (ii) they form saturated or unsaturated cyclic structures that can be substituted with alkyl or carbonyl groups of 1 to 6 carbons. a and b are independently integers from 0 to 4. Furthermore, the type of structure containing the oxyphosphonohexane ring in each repeating unit is independent.

[0010] In the present invention, n in a morphological formula (1) of the cyclic phosphazene compound is 3 or 4.

[0011] Another type of cyclic phosphazene compound of the present invention is one in which n is 3 and a and b are 0 in formula (1). An example of this type of cyclic phosphazene compound of the present invention is a mixture of non-mirror image isomers. Another example of this type of cyclic phosphazene compound of the present invention is a cis-cis-cis configuration of adjacent oxophosphazene rings. Yet another example of this type of cyclic phosphazene compound of the present invention is a trans-cis-trans configuration of adjacent oxophosphazene rings.

[0012] Another aspect of the present invention relates to a mixture of cyclic phosphazene compounds having a structure containing an oxophosphazene ring, the mixture comprising two or more of the cyclic phosphazene compounds of the present invention having a structure containing an oxophosphazene ring.

[0013] The novel cyclic phosphono-nitrogen compound and mixtures thereof of the present invention having a structure containing an oxyphosphono-nitrogen ring are flame retardants for use as resin materials.

[0014] Another aspect of the present invention relates to a method for manufacturing a cyclic phosphazene compound having a structure containing an oxophosphazene ring. This manufacturing method includes the following steps 1 and 2: Step 1 involves using an azide agent to derive the dichlorodibenzoxyphosphazenecyclohexane compound shown in formula (2) into an azide intermediate; Step 2 involves subjecting the azide intermediate obtained in the previous step to a cyclization reaction.

[0015]

[0016] In formula (2), R1 and R2 are either (i) or (ii) as follows: (i) are independently a nitro group, an alkyl or alkoxy group of carbon 1 to 8 that can be substituted with at least one alkyl or aryl group of carbon 1 to 6, or an aryl or aryloxy group of carbon 6 to 20 that can be substituted with at least one alkyl or aryl group of carbon 1 to 6; (ii) form a saturated or unsaturated cyclic structure between each other that can be substituted with an alkyl or carbonyl group of carbon 1 to 6. Also, a and b are independently integers from 0 to 4.

[0017] In one type of this manufacturing method, the azide intermediate used in step 2 is a mixture of two or more of the aforementioned azide intermediates. In this type, the mixture of the aforementioned azide intermediates is obtained by using two or more of the aforementioned dichlorodibenzoxycyclohexane compounds in step 1.

[0018] According to the manufacturing method of the present invention, the novel cyclic phosphonium nitride compound of the present invention having a structure containing an oxyphosphonium heterocyclohexane ring can be manufactured.

[0019] Another perspective of the present invention relates to a resin composition comprising: a resin component, and one or more cyclic phosphonium compounds of the present invention having a structure containing an oxophosphonium-hexane ring.

[0020] In the resin composition of the present invention, the resin component is selected, for example, from at least one of the group consisting of epoxy resin, phenolic resin, unsaturated polyester resin, diallyl phthalate resin, maleimide resin, polyimide resin, benzoxazine resin, benzocyclobutene resin, polyolefin resin, styrene resin, polyester resin, aliphatic polyamide resin, semi-aromatic polyamide resin, polycarbonate resin, polyphenylene ether resin, polyarylate resin, and modified resins thereof.

[0021] The resin composition of the present invention contains one or more novel cyclic phosphono-nitrogen compounds of the present invention, which can improve flame retardancy while inhibiting the deterioration of the physical properties of the resin material, and can achieve Low Dk / Df.

[0022] Another viewpoint of the present invention relates to resin molded articles, the resin molding system being composed of the resin composition of the present invention.

[0023] Because the resin molding system of the present invention is composed of the resin composition of the present invention, it can improve flame retardancy while suppressing the deterioration of the physical properties of the resin material, and can achieve Low Dk / Df.

[0024] Another perspective of the present invention relates to electrical / electronic components, which include the resin molded body of the present invention.

[0025] The electrical / electronic components of this invention contain the resin molded body of this invention, which can suppress the degradation of the physical properties of the resin material while improving flame retardancy and achieving Low Dk / Df. Implementation

[0026] Cyclic phosphazene compounds possessing a structure containing an oxophosphorus heterocyclohexane ring. The cyclic phosphazene compound of the present invention has a structure containing an oxyphosphazene ring, as represented by the following formula (1).

[0027]

[0028] In equation (1), n ​​represents an integer from 3 to 8. Therefore, the cyclic phosphazene compounds with a structure containing an oxophosphazene ring shown in equation (1) are: cyclic phosphazene compounds with a structure containing an oxophosphazene ring of n=3 (trimer), cyclic phosphazene compounds with a structure containing an oxophosphazene ring of n=4 (tetramer), cyclic phosphazene compounds with a structure containing an oxophosphazene ring of n=5 (pentamer), cyclic phosphazene compounds with a structure containing an oxophosphazene ring of n=6 (hexamer), cyclic phosphazene compounds with a structure containing an oxophosphazene ring of n=7 (heptamer), or cyclic phosphazene compounds with a structure containing an oxophosphazene ring of n=8 (octamer).

[0029] When the cyclic phosphonium nitride compound of the present invention is used as a component of a resin composition for manufacturing resin molded bodies for electrical / electronic components, the smaller the value of n, the easier it is to achieve a resin molded body with excellent dielectric properties. Therefore, when the cyclic phosphonium nitride compound of the present invention is used as a material for manufacturing resin molded bodies for electrical / electronic components, it is preferably an integer of 3 to 4 in formula (1), with n of 3 being particularly preferred. Furthermore, when the cyclic phosphonium nitride compound of the present invention is a mixture of two or more substances with different n values, the greater the content of the substance with the smaller n value, the easier it is to achieve a resin molded body with excellent dielectric properties. Therefore, when the cyclic phosphonium nitride compound of the present invention is a mixture of substances with different n values ​​and is used as a material for manufacturing resin molded bodies for electrical / electronic components, it is preferably a mixture containing 95% or more of substances with n of 3 to 4 by mass ratio, and particularly preferably a mixture containing 95% or more of substances with n of 3 by mass ratio.

[0030] In formula (1), R1 and R2 can independently represent nitro, R-1 or R-2 below, or R-3 below. Also, in formula (1), a and b, which represent the number of substituents R1 and R2, can be independent integers from 0 to 4.

[0031] R-1: An alkyl or alkoxy group having 1 to 8 carbon atoms that can be substituted with at least one group selected from alkyl and aryl groups having 1 to 6 carbon atoms.

[0032] Examples of alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, dibutyl, tributyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, 2-ethylhexyl, benzyl, and 2-phenylethyl. Examples of alkoxy groups include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, dibutoxy, tributoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, n-nonoxy, 2-ethylhexoxy, benzyloxy, and 2-phenylethyloxy.

[0033] When using the cyclic phosphazene compound of the present invention as a material for manufacturing resin molded bodies for electrical / electronic parts, R-1 is preferably methyl, ethyl, n-propyl, benzyl or methoxy, with methyl or ethyl being particularly preferred.

[0034] R-2: It can be an aryl or aryloxy group having 6 to 20 carbons that can be substituted by at least one group selected from alkyl and aryl groups having 1 to 6 carbons.

[0035] Examples of aryl groups include: phenyl, methylphenyl, dimethylphenyl, ethylphenyl, ethylmethylphenyl, diethylphenyl, n-propylphenyl, isopropylphenyl, isopropylmethylphenyl, isopropylethylphenyl, diisopropylphenyl, n-butylphenyl, dibutylphenyl, tributylphenyl, n-pentylphenyl, n-hexylphenyl, phenylphenyl, naphthyl, anthraceneyl, and phenanthrene. Examples of aryloxy groups include: phenyloxy, methylphenyloxy, dimethylphenyloxy, ethylphenyloxy, ethylmethylphenyloxy, diethylphenyloxy, n-propylphenyloxy, isopropylphenyloxy, isopropylmethylphenyloxy, isopropylethylphenyloxy, diisopropylphenyloxy, n-butylphenyloxy, dibutylphenyloxy, tributylphenyloxy, n-pentylphenyloxy, n-hexylphenyloxy, phenylphenyloxy, naphthyloxy, anthraceneyloxy, and phenanthreneyloxy.

[0036] When using the cyclic phosphazene compound of the present invention as a material for manufacturing resin molded bodies for electrical / electronic parts, R-2 is preferably phenyl, methylphenyl, dimethylphenyl, diethylphenyl, phenylphenyl, naphthyl or phenyloxy, with phenyl or methylphenyl being particularly preferred.

[0037] R-3: A saturated or unsaturated cyclic structure formed between R1 and R2, wherein the cyclic structure may be substituted by an alkyl or carbonyl group having 1 to 6 carbon atoms.

[0038] Examples of repeating units of formula (1) that have the saturated cyclic structure of an oxygen-containing phosphorus heterocyclohexane ring can be listed as shown in formulas (3) and (4) below.

[0039]

[0040] Furthermore, as an example of a repeating unit possessing the formula (1) of "a structure having an oxygen-containing phosphorus-hexane ring with the unsaturated cyclic structure", the following formula (5) can be cited.

[0041]

[0042] In the cyclic phosphazene compounds of the present invention, the types of structures containing oxyphosphazene rings in each repeating unit are independent. Therefore, the cyclic phosphazene compounds of the present invention may be those in which all the structures containing oxyphosphazene rings are the same, or they may be those having two or more types of structures containing oxyphosphazene rings.

[0043] Specific examples of the cyclic phosphazene compounds of the present invention shown in Formula (1) can be listed as follows: any one of the following: a cyclic triphosphazene compound having a structure containing an oxophosphazene ring when n is 3 in Formula (1); a cyclic tetraphosphazene compound having a structure containing an oxophosphazene ring when n is 4 in Formula (1); a cyclic pentaphosphazene compound having a structure containing an oxophosphazene ring when n is 5 in Formula (1); a cyclic hexaphosphazene compound having a structure containing an oxophosphazene ring when n is 6 in Formula (1); a cyclic heptaphosphazene compound having a structure containing an oxophosphazene ring when n is 7 in Formula (1); or a cyclic octaphosphazene compound having a structure containing an oxophosphazene ring when n is 8 in Formula (1), wherein a, b, R1 and R2 are combinations of those in Table 1 below.

[0044] [Table 1] Table 1 Combination example a b R1 R2 1 0 0 — — 2 1 0 methyl — 3 0 1 — methyl 4 2 0 methyl — 5 0 2 — methyl 6 1 1 methyl methyl 7 1 0 Ethyl — 8 0 1 — Ethyl 9 1 0 Third butyl — 10 2 0 Methyl and third butyl — 11 1 0 benzyl — 12 0 1 — methoxy 13 0 2 — methyl and methoxy 14 1 0 Phenyl — 15 1 0 Nitro — 16 0 0 They form saturated ring structures as shown in equation (3) between each other. 17 0 0 They form saturated ring structures as shown in equation (4) between each other. 18 0 0 They form unsaturated ring structures as shown in equation (5) between each other.

[0045] When the cyclic phosphonium nitride compound of the present invention is used as a material for manufacturing resin molded bodies for electrical / electronic parts, in the above examples, the preferred system is a cyclic triphosphonium nitride compound of formula (1) with n=3 or a cyclic tetraphosphonium nitride compound of formula (1) with n=4, and is a combination of example 1, 2 or 3, and the most preferred system is a cyclic triphosphonium nitride compound of formula (1) with n=3, and is a combination of example 1 or 2.

[0046] In the above examples, the cyclotriphosphine compound with n=3 in formula (1) and which is combination example 1 has the structure shown in formula (6) below.

[0047]

[0048] The cyclic phosphazene compound with a structure containing an oxophosphane ring, as shown in formula (6), can usually be obtained as a mixture of non-mirror image isomers if manufactured by the manufacturing method described later. That is, in the stereoconfiguration of the structure containing the oxophosphane ring described above, it can be obtained as a mixture of the cis-cis-cis type (hereinafter also referred to as "cis type") shown in formula (7) and the trans-cis-trans type (hereinafter also referred to as "trans type") shown in formula (8).

[0049]

[0050]

[0051] Such mixtures of non-mirror image isomers can be used directly as mixtures, but they can also be used as individual substances by isolating the cis and trans forms separately. Isolation methods include, for example, a combination of separation and filtration utilizing solubility in solvents such as toluene; or separation by solvent extraction, recrystallization, or column chromatography.

[0052] The mixture of cyclic phosphazene compounds of the present invention comprises two or more cyclic phosphazene compounds of the present invention having a structure containing an oxophosphane ring. Examples of such mixtures include any mixture of those listed as specific examples of cyclic phosphazene compounds of the present invention having a structure containing an oxophosphane ring. When using the cyclic phosphazene compounds of the present invention as materials for manufacturing resin molded bodies for electrical / electronic components, it is preferable to use a mixture of a cyclic triphosphazene compound of formula (1) with n=3 and a cyclic tetraphosphazene compound of formula (2) with n=4, and any combination selected from the group consisting of combinations 1, 2 and 3.

[0053] Furthermore, the mixture of cyclic phosphazene compounds of the present invention can be a mixture of isomers such as the mixture of non-mirror image isomers of the above-described cyclic triphosphazene compounds. Cyclic phosphazene compounds of the present invention with n of 4 or more in Formula (1) can generally be obtained as a mixture of stereoisomers having various non-mirror image isomers and mirror image isomers if manufactured by the manufacturing method described later.

[0054] <Method for manufacturing cyclic phosphonium compounds with a structure containing an oxyphosphonium heterocyclohexane ring> The cyclic phosphazene compound of the present invention having a structure containing an oxophosphazene ring can be manufactured, for example, by any of the following manufacturing methods 1 to 4, which use a dichlorodibenzooxophosphazene compound as a starting material and cyclize intermediates derived from the starting material intermolecularly.

[0055] Manufacturing Method 1 In this manufacturing method, for example, it is based on the manufacturing method of cyclic phosphazene compounds described in Non-Patent Document 1 or 2 below, that is, the manufacturing method includes the following steps 1 and 2: Step 1 is to azid a chlorodibenzoxyphosphazene compound; Step 2 is to cyclize the azid intermediate obtained in Step 1.

[0056] [Non-patent literature 1] G.Tesi,CPHaber,CMDouglas,Proc.Chem.Soc.,London,1960,p.219. [Non-patent literature 2] RHKratzer,KLPaciorek,Inorg.Chem.,1965,Vol.4,p.1767.

[0057] Chlorodibenzoxoxophosphazenehexane compounds: In this manufacturing method, firstly, a dichlorodibenzoxyphosphonohexane compound of the following formula (2) is prepared as a raw material.

[0058]

[0059] In equation (2), R1 and R2 each independently represent a nitro group, or R-1, R-2 or R-3 as described below. Also, in equation (2), a and b, which represent the number of substituents R1 and R2, are each independent integers from 0 to 4.

[0060] R-1: R-1 is the same as in equation (1).

[0061] R-2: R-2 is the same as in equation (1).

[0062] R-3: The saturated or unsaturated cyclic structure formed between R1 and R2, wherein the cyclic structure may be substituted by alkyl or carbonyl groups having 1 to 6 carbon atoms.

[0063] Examples of dichlorodibenzoxoxycyclohexane compounds that possess the structure of "a saturated cyclic structure containing an oxophosphorus hexane ring" as shown in formula (2) can be listed as shown in formulas (9) and (10) below.

[0064]

[0065] Furthermore, examples of dichlorodibenzoxyphosphine compounds that possess the structure of "an unsaturated cyclic structure containing an oxophosphine ring" as shown in formula (2) can be listed as shown in the following formula (11).

[0066]

[0067] Regarding the cyclic phosphazene compounds of the present invention having a structure containing an oxophosphazene ring, in the manufacture of the specific examples mentioned above, the dichlorodibenzoxophosphazene compounds used as raw materials are selected from the combinations of a, b, R1 and R2 of formula (2) corresponding to those in Table 1 above.

[0068] The dichlorodibenzoxylphosphonic hexane compound shown in formula (2) can be manufactured by reacting the phenol shown in formula (12) with phosphorus trichloride and then adding a catalyst such as zinc chloride to induce a cyclization reaction.

[0069]

[0070] In equation (12), R1 and R2, as well as a and b, are the same as in equation (2).

[0071] The method for manufacturing such dichlorodibenzoxophosphazenecyclohexane compounds is described in the following patent documents 8 and 9 and non-patent documents 3 and 4.

[0072] [Patent Document 8] U.S. Patent No. 3,702,878 [Patent Document 9] US Patent No. 5391798 [Non-patent literature 3] Stephen D.Pastor,John D.Spivack,Leander P.Steinhuebel,Phosphorus and Sulfur,1987,Vol.31,p.71. [Non-patent literature 4] Asfia Qureshi,Allan S.Hay,J.Chem.Res(M),1998,p.1601.

[0073] The phenols represented by formula (12) can be those having R1 and R2 and a and b of "cyclic phosphazene compounds having a structure containing an oxophosphazene ring" corresponding to the purpose. Examples of such phenols include: 2-phenylphenol, 2-methyl-6-phenylphenol, 3-methyl-6-phenylphenol, 3-methyl-2-phenylphenol, 4-methyl-2-phenylphenol, 2-(2-methylphenyl)phenol, 2-(3-methylphenyl)phenol, 2-(4-methylphenyl)phenol, 2,3-dimethyl-6-phenylphenol, 2,5-dimethyl-6-phenylphenol, 3,5-dimethyl-2-phenylphenol, 4,5- Dimethyl-2-phenylphenol, 2-(2,3-dimethylphenyl)phenol, 2-(2,4-dimethylphenyl)phenol, 2-(2,5-dimethylphenyl)phenol, 2-(3,5-dimethylphenyl)phenol, 2'-hydroxy-2,3'-dimethylbiphenyl, 2'-hydroxy-2,5'-dimethylbiphenyl, 2'-hydroxy-3,5'-dimethylbiphenyl, 2'-hydroxy-4,5'-dimethylbiphenyl, 2'-hydroxy 2-Ethyl-6-phenylphenol, 4-Ethyl-2-phenylphenol, 2-(2-ethylphenyl)phenol, 2-(4-ethylphenyl)phenol, 2-tert-butyl-6-phenylphenol, 4-tert-butyl-2-phenylphenol, 2-tert-butyl-4-methyl-6-phenylphenol, 5-benzyl-2-phenylphenol, 2-(2-methoxyphenyl)phenol, 2-(3-methoxyphenyl)phenol, 2-( 4-Methoxyphenyl)phenol, 2-(2-Methoxy-5-methylphenyl)phenol, 2-(4-Methoxy-2-methylphenyl)phenol, 2-(4-Methoxy-3-methylphenyl)phenol, 2-(4-Ethoxy-2-methylphenyl)phenol, 2,3-Diphenylphenol, 2,6-Diphenylphenol, 4-Nitro-2-phenylphenol, 4-Hydroxyfenone, 4-Hydroxyfenone, and 4-Phenanthrol, etc.

[0074] When the desired "cyclic phosphazene compound having a structure containing an oxophosphazene ring" has one such structure, only one substance corresponding to the desired oxophosphazene ring structure needs to be used as the aforementioned phenol. However, when the desired "cyclic phosphazene compound having a structure containing an oxophosphazene ring" has two or more such structures, two or more substances corresponding to the desired oxophosphazene ring structure can be mixed and used as the aforementioned phenol.

[0075] The dibenzoxanoxocyclohexane compounds shown in formula (2) can be manufactured not only by using the above-mentioned phenols, but also by chlorinating dibenzoxanoxocyclohexane oxides with phosphorus trichloride as described in Non-Patent Document 5.

[0076] [Non-patent literature 5] P.Abranyi-Balogha,G.Keglevich,Synthetic Communications,2011,vol.41,p.1421.

[0077] Step 1: In this step, the chlorodibenzoxoxyphosphacyclohexane compound of formula (2) that is the object of azidegation can be a mixture of one or more substances, depending on the type of oxyphosphacyclohexane ring structure possessed by the target cyclic phosphazene compound. The mixture of two or more substances can be a mixture prepared by mixing two or more chlorodibenzoxoxyphosphacyclohexane compounds of formula (2) prepared separately, or a mixture obtained by mixing two or more phenols when preparing the chlorodibenzoxoxyphosphacyclohexane compound of formula (2).

[0078] In the azidation of dichlorodibenzoxycyclohexane compounds, various known azidating agents can be used. Examples of usable azidating agents include: metal azides such as lithium azide, sodium azide, and potassium azide; organoazides such as trimethylsilyl azide, p-toluenesulfonyl azide, and tosyl azide (TsN3); and phosphatidyl azide compounds such as diphenylphosphoryl azide (DPPA). From a generality point of view, sodium azide, trimethylsilyl azide, or DPPA is preferred among these azidating agents, with sodium azide being particularly preferred. Azidating agents can also be used by mixing two or more together.

[0079] From the viewpoint of fully carrying out the azidation reaction, the amount of azidating agent used is preferably set to about 1 to 2 equivalents, and even better to set it to about 1.1 to 1.3 equivalents, relative to the dichlorodibenzoxyphosphonohexane compounds shown in formula (2).

[0080] In this step, the dichlorodibenzoxanoxocyclohexane compound shown in formula (2) and the azidating agent are typically added to a solvent, and an azidation reaction is carried out. The temperature can be raised to approximately 40 to 250°C. The solvent used is not particularly limited in type, but aprotic polar solvents are preferred. Examples of aprotic polar solvents include organic solvents such as acetone, acetonitrile, N,N-dimethylformamide, and dimethyl sulfoxide. Among such aprotic polar solvents, N,N-dimethylformamide or dimethyl sulfoxide, which have high specific dielectric properties and are readily available at low cost, are particularly preferred. Solvents can be used by mixing two or more together.

[0081] Through the azidation reaction in this step, the chlorodibenzoxyphosphazenecyclohexane compound shown in formula (2) is derived into an azidation intermediate.

[0082] In this step, when using the mixture of chlorodibenzoxoxyphosphacyclohexane compounds shown in formula (2), a mixture of azide intermediates corresponding to the mixture of chlorodibenzoxoxyphosphacyclohexane compounds shown in formula (2) can be obtained in this step.

[0083] Step 2: The azide intermediate obtained in step 1 is subjected to a cyclization reaction to derive the desired cyclic phosphonium alkene compound with an oxophosphonium hexane ring. The azide intermediate used in this step for the cyclization reaction is a mixture of one or more substances, depending on the type of oxophosphonium hexane ring structure possessed by the desired cyclic phosphonium alkene compound. The mixture of two or more substances can be a mixture prepared by mixing two or more azide intermediates separately prepared in step 1, or a mixture obtained in step 1 by using a mixture of two or more chlorodibenzoxophosphonium hexane compounds as shown in formula (2).

[0084] In this step, the cyclization reaction can be carried out in the reaction solution obtained in step 1 by stirring or allowing it to stand. At this time, the reaction system can be heated. The heating temperature of the reaction system is usually set between 40 and 100°C. The degree of cyclization reaction, that is, the degree of trimerization, tetramerization, or other n-merization of the azide intermediate, can be controlled within a certain range by selecting the type of solvent available in this step (described later) and adjusting the reaction temperature.

[0085] Cyclization reactions can be carried out in a solvent-free environment or in a solvent. There are no particular limitations on the types of solvents that can be used, as long as they do not adversely affect the cyclization reaction; however, aprotic polar solvents are generally preferred. Examples of preferred aprotic polar solvents include organic solvents such as acetone, acetonitrile, N,N-dimethylformamide, and dimethyl sulfoxide, with N,N-dimethylformamide or dimethyl sulfoxide being particularly preferred due to their high dielectric constant and inexpensive availability. Solvents can be used by mixing two or more solvents. When using a solvent, the heating temperature for the cyclization reaction is controlled within the range that does not exceed the boiling point of the solvent.

[0086] The desired cyclic phosphazene compound with an oxophosphazene ring structure obtained in this step can usually be obtained as a mixture of multiple substances with different numbers of repeating units of formula (1). Furthermore, when one azidation intermediate is used in this step, the oxophosphazene ring structure of each repeating unit of formula (1) in the desired cyclic phosphazene compound is the same. Furthermore, when two or more azidation intermediates are used in this step, the oxophosphazene ring structure of each repeating unit of formula (1) in the desired cyclic phosphazene compound is two or more.

[0087] The cyclic phosphazene compound with a structure containing an oxophosphane ring obtained in this step can usually be purified from the reaction system by conventional methods such as filtration, solvent extraction, column chromatography, or recrystallization.

[0088] Manufacturing Method 2 In this manufacturing method, a cyclic phosphazene compound having a structure containing an oxophosphane ring is manufactured according to the following steps 1 and 2: Step 1 is to chlorinate a dichlorodibenzoxyphosphane compound to derive a trichloro-dibenzoxyphosphorane compound; Step 2 is to cyclize the trichloro-dibenzoxyphosphorane compound obtained in Step 1.

[0089] Step 1: The dichlorodibenzoxoxyphosphacene compounds used in this step are those shown in formula (2) used in manufacturing method 1. Depending on the type of oxyphosphacene ring structure possessed by the desired cyclic phosphazene compound, a mixture of one or more substances may be used. The mixture of two or more substances may be a mixture prepared by mixing two or more separately prepared dichlorodibenzoxoxyphosphacene compounds, or a mixture obtained by mixing two or more phenols when preparing dichlorodibenzoxoxyphosphacene compounds.

[0090] In this step, for example, according to the description in Non-Patent Document 6 below, a chlorodibenzoxyphosphorane compound is reacted with a chlorinating agent to chlorinate, thereby deriving a trichloro-dibenzoxyphosphorane compound.

[0091] [Non-Patent Document 6] J.Gloede,U.Piepera,B.Costisella,RP.Kruger,Z.Anorg.Allg.Chem.2003,Vol.629,p.998.

[0092] In this step, various known chlorinating agents can be used. Chlorine is a preferred example of a chlorinating agent. From the viewpoint of ensuring sufficient chlorination while inhibiting over-chlorination, the amount of chlorinating agent used is preferably set to 1 to 1.1 equivalents, and more preferably 1.01 to 1.05 equivalents, relative to dichlorodibenzoxyphosphazenecyclohexane compounds.

[0093] In this step, the chlorination reaction is typically carried out by adding a chlorinating agent to the dichlorodibenzoxanoxazine compound in the absence of a solvent or in a solvent. The temperature can be heated to approximately 40 to 150°C. While there are no particular limitations on the type of solvent used, aprotic solvents are preferred. Examples of aprotic solvents include organic solvents such as chlorobenzene, dichlorobenzene, toluene, xylene, and mesitylene. Among these aprotic solvents, chlorobenzene or dichlorobenzene are preferred because the solvent itself is not easily chlorinated. Solvents can be used by mixing two or more solvents together.

[0094] In this step, the trichloro-dibenzoxanoxane derivative obtained by chlorinating dichlorodibenzoxanoxane compounds is represented by the following formula (13). R1 ​​and R2, as well as a and b in formula (13), are the same as in formula (2).

[0095]

[0096] When a mixture of chlorodibenzoxoxyphosphane compounds is used in this step, a mixture of trichloro-dibenzoxoxyphosphane compounds corresponding to the mixture of chlorodibenzoxoxyphosphane compounds shown in formula (13) can be obtained in this step.

[0097] Step 2: In this step, the trichloro-dibenzoxylphosphine compound obtained in step 1 undergoes a cyclization reaction to derive the desired cyclic phosphonium nitride compound containing an oxophosphonium hexane ring. The trichloro-dibenzoxylphosphine compound used in this step is a mixture of one or more substances, depending on the type of oxophosphonium hexane ring structure possessed by the desired cyclic phosphonium nitride compound. The mixture of two or more substances can be a mixture prepared by mixing two or more trichloro-dibenzoxylphosphine compounds separately prepared in step 1, or a mixture obtained in step 1 by using a mixture of two or more trichloro-dibenzoxylphosphine compounds.

[0098] The trichloro-dibenzoxanone compound obtained in step 1 is obtained by reacting with ammonia or ammonium chloride and cyclizing, for example, according to the description in Patent Document 10 or Non-Patent Document 7 or 8 below.

[0099] [Patent Document 10] U.S. Patent No. 2,853,517 [Non-patent literature 7] CPHaber,DLHerring,EALawton,J.Am.Chem.Sci.,1958,Vol.80,p.2116. [Non-patent literature 8] M.Taillefer,F.Plenat,C.Chamalet-Combes,V.Vicente,HJCristau,Phosphorus Res.Bull.,1999,Vol.10,p.696.

[0100] The cyclization reaction of trichloro-dibenzoxanthane compounds using ammonia or ammonium chloride can be carried out in a solvent-free environment or in a solvent. When using a solvent, there are no particular limitations on the type of solvent that will not adversely affect the cyclization reaction, but aprotic solvents are generally preferred. Examples of preferred aprotic solvents include organic solvents such as chlorobenzene, dichlorobenzene, toluene, xylene, and mesitylene, but chlorobenzene or toluene, which are readily available at low cost, are preferred. Solvents can be used by mixing two or more solvents.

[0101] Furthermore, in cyclization reactions, the reaction system can be heated. The heating temperature of the reaction system is usually set to 40 to 170°C, but when using solvents, the heating temperature is controlled within the range that does not exceed the boiling point of the solvent.

[0102] The cyclization reaction, that is, the degree of trimerization, tetramerization, and other n-merization of trichloro-dibenzoxophosphine compounds, can be controlled to a certain extent by selecting the type of solvent used in this step and adjusting the reaction temperature.

[0103] The desired cyclic phosphazene compound with a structure containing an oxophosphane ring obtained in this step can usually be obtained as a mixture of multiple substances with different numbers of repeating units of formula (1). Furthermore, when one trichloro-dibenzoxophosphane compound is used in this step, the oxophosphane ring structure of each repeating unit of formula (1) in the desired cyclic phosphazene compound is the same. Furthermore, when two or more trichloro-dibenzoxophosphane compounds are used in this step, the oxophosphane ring structure of each repeating unit of formula (1) in the desired cyclic phosphazene compound is two or more.

[0104] Manufacturing method 3 In this manufacturing method, chloramine is reacted with a chlorodibenzoxycyclohexane compound according to the description in Non-Patent Document 9 below, and the intermediate product is cyclized, thereby producing a cyclic phosphazene compound having a structure containing a phosphazene ring.

[0105] [Non-patent literature 9] ITGilson,HHSisler,Inorg.Chem.,1965,Vol.4,p.273.

[0106] The dichlorodibenzoxoxyphosphacene compounds used in this manufacturing method are those shown in formula (2) used in manufacturing method 1. Depending on the type of oxyphosphacene ring structure possessed by the desired cyclic phosphazene compound, a mixture of one or more substances is used. The mixture of two or more substances can be a mixture prepared by mixing two or more separately prepared dichlorodibenzoxoxyphosphacene compounds, or a mixture obtained by mixing two or more phenols when preparing dichlorodibenzoxoxyphosphacene compounds.

[0107] From the perspective of fully carrying out the chlorination reaction of dichlorodibenzoxoxyphoscyclohexane compounds while inhibiting the over-progression of the chlorination reaction, the amount of chloramine used is preferably set to about 1 to 1.1 equivalents, and even better to set it to about 1.01 to 1.05 equivalents, compared to dichlorodibenzoxoxyphoscyclohexane compounds.

[0108] The reaction of dichlorodibenzoxyphosphazenecyclohexane compounds with chloramines can be carried out in a solvent-free environment or in a solvent. When using a solvent, there are no particular limitations on the type of solvent that will not adversely affect the cyclization reaction, but aprotic solvents are preferred. Examples of preferred aprotic solvents include organic solvents such as chlorobenzene, dichlorobenzene, toluene, xylene, and mesitylene, but chlorobenzene or toluene, which are readily available at low cost, are preferred. Solvents can be used by mixing two or more solvents together.

[0109] In the reaction of dichlorodibenzoxoxocyclohexane compounds with chloramines, the reaction system can be heated. The heating temperature of the reaction system is usually set between 40 and 170°C, but when using a solvent, the heating temperature is controlled within the range that does not exceed the boiling point of the solvent.

[0110] In the reaction of dichlorodibenzoxoxyphosphacyclohexane compounds with chloramines, the dichlorodibenzoxoxyphosphacyclohexane compounds undergo chloramine addition. Moreover, the addition product (i.e., the intermediate product) is condensed through a dehydrochlorination process to carry out a cyclization reaction, thereby obtaining the desired cyclic phosphazene compound with a structure containing an oxyphosphacyclohexane ring.

[0111] The cyclization reaction, that is, the degree of trimerization, tetramerization, and n-merization of dichlorodibenzoxyphosphazenecyclohexane compounds, can be controlled within a certain range by selecting the type of solvent used and adjusting the reaction temperature.

[0112] The desired cyclic phosphazene compound with a structure containing an oxophosphane ring obtained by this manufacturing method can usually be obtained as a mixture of multiple substances with different numbers of repeating units of formula (1). Furthermore, when using one chlorodibenzo-oxophosphane hexane compound, it is such that the oxophosphane ring structure of each repeating unit of formula (1) in the desired cyclic phosphazene compound is the same; when using two or more chlorodibenzo-oxophosphane hexane compounds, it is such that the oxophosphane ring structure of each repeating unit of formula (1) in the desired cyclic phosphazene compound is two or more.

[0113] Manufacturing method 4 In this manufacturing method, a cyclic phosphonamidate compound having a structure containing an oxophosphonacyclohexane ring is manufactured according to the following steps 1 and 2: Step 1 is to prepare a phosphonamidate compound as shown in the following formula (14) from a dichlorobenzoxophosphonacyclohexane compound; Step 2 is to derive the phosphonamidate compound obtained in Step 1 into a cyclic phosphonamidate compound.

[0114]

[0115] In equation (14), R1 and R2, as well as a and b, are the same as in equation (2).

[0116] Step 1: This process includes the following steps 1A, 1B and 1C: Step 1A is to derive the dibenzo-oxaphosphane-oxide compound into the dibenzo-oxaphosphane-oxide compound shown in formula (15) below; Step 1B is to derive the dibenzo-oxaphosphane-oxide compound obtained in Step 1A into the dibenzo-oxaphosphane-oxide compound shown in formula (16) below; Step 1C is to derive the dibenzo-oxaphosphane-oxide compound obtained in Step 1B into the desired phosphatamine ester compound.

[0117] Step 1A The dichlorodibenzoxoxyphosphacene compounds used in this step are those shown in formula (2) used in manufacturing method 1. Depending on the type of oxyphosphacene ring structure possessed by the desired cyclic phosphazene compound, a mixture of one or more substances can be used. The mixture of two or more substances can be a mixture prepared by mixing two or more separately prepared dichlorodibenzoxoxyphosphacene compounds, or a mixture obtained by mixing two or more phenols when preparing dichlorodibenzoxoxyphosphacene compounds.

[0118] In this step, for example, according to the description in Patent Document 11 or Patent Document 12 below, the dibenzoxazine cyclohexane compound is hydrolyzed to derive the dibenzoxazine cyclohexane oxide compound shown in the following formula (15).

[0119] [Patent Document 11] U.S. Patent No. 5481017 [Patent Document 12] US Patent No. 5,821,376

[0120]

[0121] R1 and R2, as well as a and b in equation (15), are the same as those in equation (2).

[0122] In the hydrolysis of dichlorodibenzoxyphosphazenecyclohexane compounds, various known hydrolytic agents can be used. Examples of usable hydrolytic agents include water, ice, and water vapor.

[0123] From the perspective of allowing the hydrolysis reaction to proceed fully while inhibiting excessive hydrolysis, the amount of hydrolysing agent used is preferably set between 1 and 100 equivalents, and even better, between 10 and 50 equivalents, compared to dichlorodibenzoxyphosphonohexane compounds.

[0124] In this step, the hydrolysis reaction of dichlorodibenzoxyphosphazenecyclohexane compounds is typically carried out by adding a hydrolyzing agent in the absence of a solvent or in a solvent. The reaction system can be heated to approximately 40 to 150°C. When using a solvent, there are no particular limitations as long as it does not significantly hinder the hydrolysis reaction, but aprotic solvents are preferred. Examples of aprotic solvents include organic solvents such as chlorobenzene, dichlorobenzene, toluene, xylene, mesitylene, acetone, tetrahydrofuran, and acetonitrile. Among such aprotic solvents, chlorobenzene or toluene is preferred because it is easily separated from the hydrolyzing agent. Solvents can be used by mixing two or more solvents together.

[0125] When a mixture of dibenzoxophosphazenecyclohexane compounds is used in this step, a mixture of dibenzoxophosphazenecyclohexane-oxide compounds corresponding to the mixture of dibenzoxophosphazenecyclohexane compounds shown in formula (15) can be obtained in this step.

[0126] Step 1B In this step, for example, the dibenzoxazine cyclohexane oxide compound obtained in step 1A is chlorinated according to the description in Non-Patent Document 10 below, to derive the chloro-dibenzoxazine cyclohexane oxide compound shown in the following formula (16).

[0127] [Non-patent literature 10] A.Salmeia,G.Baumgartner,M.Jovic,A.Gossi,W.Riedl,T.Zich,S.Gann,Org. Process Res.Dev., 2018, Vol.22, p.1570-1577.

[0128]

[0129] R1 and R2, as well as a and b in equation (16), are the same as those in equation (2).

[0130] In this step, depending on the type of dibenzoxazine cyclohexane oxide compound desired, one or a mixture of two or more dibenzoxazine cyclohexane oxide compounds obtained in step 1A are used. The mixture of two or more substances can be a mixture prepared by mixing two or more dibenzoxazine cyclohexane oxide compounds separately prepared in step 1A, or it can be a mixture obtained in step 1A by using a mixture of two or more dibenzoxazine cyclohexane oxide compounds.

[0131] In this step, the dibenzoxazine cyclohexane oxide compound obtained in step 1A is essentially reacted with a chlorinating agent to carry out chlorination. Various known chlorinating agents can be used. For example, carbon tetrachloride, chlorine, sulfonyl chloride, trichloroisocyanuric acid (TCCA), or N-chlorosuccinimide (NCS) as described in Non-Patent Document 10 can be used.

[0132] Chlorination reactions can be carried out in a solvent-free environment or in a solvent. When using a solvent, there are no particular limitations as long as it does not significantly hinder the chlorination reaction, but aprotic solvents are preferred. Examples of aprotic solvents include organic solvents such as chlorobenzene, dichlorobenzene, toluene, xylene, and mesitylene. Among these aprotic solvents, chlorobenzene or toluene, which are readily available at low cost, are preferred. Solvents can be used by mixing two or more solvents together.

[0133] In chlorination reactions, the reaction system can be heated. The heating temperature is typically set between 40 and 100°C, but when using a solvent, the heating temperature is controlled to not exceed the solvent's boiling point. The degree of chlorination of the dibenzoxazine cyclohexane oxide compound can be controlled within a certain range by choosing the type of solvent and adjusting the reaction temperature.

[0134] In this step, when a mixture of dibenzoxazine cyclohexane-oxide compounds is used, a mixture of chloro-dibenzoxazine cyclohexane-oxide compounds corresponding to the mixture of dibenzoxazine cyclohexane-oxide compounds shown in formula (16) can be obtained in this step.

[0135] Step 1C In this step, for example, according to the description in Non-Patent Document 11 below, the chloro-dibenzoxanoxophosphine cyclohexane-oxide compound obtained in step 1B is reacted with an amination agent to derive the desired phosphatidylamine ester compound.

[0136] [Non-patent literature 11] N.Kreutzkamp,H.Schindler,Arch.Pharm.(Weiheim),1960,Vol.293,p.296-305.

[0137] In this step, depending on the type of phosphatidyl ester compound of interest, one or more of the chloro-dibenzoxazine cyclohexane-oxide compounds obtained in step 1B are used. The mixture of two or more substances can be a mixture prepared by mixing two or more chloro-dibenzoxazine cyclohexane-oxide compounds separately prepared in step 1B, or it can be a mixture obtained in step 1B by using a mixture of two or more dibenzoxazine cyclohexane-oxide compounds.

[0138] In this step, the chloro-dibenzoxanoxophosphine cyclohexane-oxide compound obtained in step 1B is essentially amination by reacting it with an amination agent. Various known amination agents can be used. For example, ammonia water or ammonia gas as described in Non-Patent Document 11 can be used.

[0139] Amination reactions can be carried out in a solvent-free environment or in a solvent. When using a solvent, there are no particular limitations as long as it does not significantly hinder the amination reaction, but aprotic solvents are preferred. Examples of aprotic solvents include organic solvents such as chlorobenzene, dichlorobenzene, toluene, xylene, and mesitylene. Among these aprotic solvents, chlorobenzene or toluene, which are readily available at low cost, are preferred. Solvents can be used by mixing two or more solvents together.

[0140] In amination reactions, the reaction system can be heated. The optimal heating temperature is typically set between 40 and 100°C, but when using a solvent, the heating temperature should be controlled within the solvent's boiling point. The degree of amination of the chloro-dibenzoxanthoxyphosphine-cyclohexane oxide compound can be controlled within a certain range by selecting the type of solvent and adjusting the reaction temperature.

[0141] In this step, when a mixture of chloro-dibenzoxazine cyclohexane-oxide compounds is used, a mixture of phosphatidylamine ester compounds corresponding to the mixture of chloro-dibenzoxazine cyclohexane-oxide compounds as shown in formula (14) can be obtained in this step.

[0142] Step 2: In this step, for example, according to Non-Patent Document 12, the phosphatidyl ester compound obtained in step 1 is cyclized by the Appel reaction to generate the desired cyclic phosphazene compound having a structure containing an oxophosphazene ring.

[0143] [Non-patent literature 12] Rolf Appel,Heinz Einig,Chem.Ber.1975,Vol.108,p.914.

[0144] In this step, depending on the type of oxyphosphazene compound containing an oxocyclohexane ring, one or more of the phosphatidylamine ester compounds obtained in step 1 are used. The mixture of two or more substances can be a mixture prepared by mixing two or more phosphatidylamine ester compounds separately prepared in step 1, or it can be a mixture obtained in step 1C of step 1 by using a mixture of two or more chloro-dibenzoxazine cyclohexane oxide compounds.

[0145] In this step, the phosphatidyl ester compound obtained in step 1 is essentially cyclized by reacting it with phosphine such as triarylphosphine or trialkylphosphine, carbon tetrachloride, and a tertiary amine such as triethylamine or diisopropylethylamine via an Appel reaction.

[0146] The cyclization reaction in this step can be carried out in a solvent-free environment or in a solvent. When using a solvent, there are no particular limitations as long as the solvent does not significantly hinder the cyclization reaction, but aprotic solvents are preferred. Examples of aprotic solvents include organic solvents such as chlorobenzene, dichlorobenzene, toluene, xylene, and mesitylene. Among these aprotic solvents, chlorobenzene or toluene, which are readily available at low cost, are preferred. Solvents can be used by mixing two or more solvents together.

[0147] In cyclization reactions, the reaction system can be heated. The optimal heating temperature is typically between 40 and 170°C, but when using a solvent, the temperature should be controlled within the solvent's boiling point. The degree of cyclization, i.e., the trimerization, tetramerization, or other n-merization of phosphatidyl ester compounds, can be controlled within a certain range by selecting the type of solvent and adjusting the reaction temperature.

[0148] The desired cyclic phosphazene compound with a structure containing an oxophosphazene ring obtained in this step can usually be obtained as a mixture of multiple substances with different numbers of repeating units of formula (1). Furthermore, when a phosphatidyl ester compound is used in this step, the oxophosphazene ring structure of each repeating unit of formula (1) in the desired cyclic phosphazene compound is the same. Furthermore, when two or more phosphatidyl ester compounds are used in this step, the oxophosphazene ring structure of each repeating unit of formula (1) in the desired cyclic phosphazene compound is two or more.

[0149] The cyclic phosphazene compound with a structure containing an oxophosphane ring obtained in this step can usually be purified from the reaction system by conventional methods such as filtration, solvent extraction, column chromatography, or recrystallization.

[0150] <Resin Composition> The resin composition of this invention comprises: a cyclic phosphazene compound having a structure containing an oxophosphazene ring, and a resin component. Two or more cyclic phosphazene compounds having a structure containing an oxophosphazene ring may be used in combination.

[0151] There are no particular limitations on the resin composition; various thermoplastic or thermosetting resins can be used. Thermosetting and thermoplastic resins can also be used in combination. Furthermore, the resin composition can be natural or synthetic. Also, the scope of resin composition is intended to include rubber and elastomers.

[0152] Examples of usable thermosetting resins include: epoxy resins, phenolic resins, melamine resins, urea resins, polysiloxane resins, polyurethane resins, unsaturated polyester resins, diallyl phthalate resins, thermosetting acrylic resins, polyimide resins, polycarboxylated imide resins, maleimide resins, maleimide-cyanate ester resins, cyanate ester resins, benzoxazine resins, polybenzimidazole resins, benzocyclobutene resins, natural rubber, isoprene rubber, styrene-butadiene rubber, butadiene rubber, butyl rubber, ethylene-propylene-diene rubber, acrylonitrile-butadiene rubber, styrene-isoprene-butadiene rubber, and chloroprene rubber. Two or more thermosetting resins may be used in combination. Furthermore, in the examples above, polyimide resins such as polyimide resin, polycarbonyldiimide resin, maleimide resin, or maleimide-cyanate ester resin can be used in combination with various resins that are thermoplastic or solvent-soluble, from the viewpoint of improving their processability and adhesion.

[0153] In the example of thermosetting resins, epoxy resins, if they are compounds having two or more epoxy groups in one molecule, can be made from various substances. Specific examples include: phenol novolac type epoxy resins, brominated phenol novolac type epoxy resins, o-cresol phenol novolac type epoxy resins, biphenyl phenol novolac type epoxy resins, bisphenol A-phenol novolac type epoxy resins, and naphthol phenol novolac type epoxy resins, which are obtained through the reaction of phenols and aldehydes; bisphenol A type epoxy resins, brominated bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD ​​type epoxy resins, bisphenol S type epoxy resins, biphenol type epoxy resins, naphthyl type epoxy resins, cyclopentadiene type epoxy resins, alkyl-substituted biphenol type epoxy resins, polyfunctional phenol type epoxy resins, and trihydroxyphenylmethane, which are obtained through the reaction of phenols and epichlorohydrin. Phenolic epoxy resins; aliphatic epoxy resins obtained by reacting alcohols such as trimethylolpropane, oligopropylene glycol, and hydrogenated bisphenol A with epichlorohydrin; glycidyl ester epoxy resins obtained by reacting hexahydrophthalic acid, tetrahydrophthalic acid, or phthalic acid with epichlorohydrin or 2-methylepimerol; glycidyl amine epoxy resins obtained by reacting amines such as diaminodiphenylmethane or aminophenol with epichlorohydrin; heterocyclic epoxy resins obtained by reacting polyamines such as triisocyanate with epichlorohydrin; phosphonium-nitrogen compounds with glycidyl groups, epoxy-modified phosphonium-nitrogen resins, isocyanate-modified epoxy resins, cyclic aliphatic epoxy resins, and amine ester-modified epoxy resins, etc. When the resin composition of the present invention is used as a manufacturing material for electrical / electronic components, among the aforementioned epoxy resins, phenolic varnish-type epoxy resins, o-cresol phenolic varnish-type epoxy resins, bisphenol A type epoxy resins, biphenol type epoxy resins, biphenyl phenolic varnish-type epoxy resins, naphthyl type epoxy resins, polyfunctional phenol type epoxy resins, or phenolic type epoxy resins obtained by reacting tris(hydroxyphenyl)methane with epichlorohydrin are preferred. Two or more epoxy resins may be used in combination.

[0154] Examples of usable thermoplastic resins include: polyolefin resins (e.g., polyethylene resin, polypropylene resin, polyisoprene resin, polybutene resin, cyclic polyolefin (COP) resin, and cyclic olefin / copolymer (COC) resin, etc.), chlorinated polyolefin resins (e.g., polyvinyl chloride resin and polyvinylidene chloride resin, etc.), styrene-based resins [e.g., polystyrene resin, impact-resistant polystyrene (HIPS) resin, syndiotactic polystyrene (SPS) resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene copolymer (AS resin), methyl methacrylate-butadiene-styrene copolymer (MBS resin), methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS resin), and acrylonitrile-acrylic rubber-styrene copolymer (AAS resin, etc.], polymethyl methacrylate (PMA), and polymethyl methacrylate (PMMA). Polyvinyl alcohol, polyester resins (such as polyethylene terephthalate resin, polyethylene terephthalate resin, polytrimethylene terephthalate resin, polybutylene terephthalate resin, polymethylene terephthalate resin, polyethylene naphthalate resin, polycyclohexene / dimethylene / paraphthalate resin and polylactic acid resin, etc.), aliphatic polyamine resins [such as polyamine 6 resin, polyamine 66 resin, polyamine 11 resin, polyamine 12 resin, polyamine 46 resin, polyamine...] Copolymers of 6 resin and polyamide 66 resin (polyamide 6 / 66 resin) and copolymers of polyamide 6 resin and polyamide 12 resin (polyamide 6 / 12 resin), etc.; semi-aromatic polyamide resins (such as polyamide MXD6 resin, polyamide 6T resin, polyamide 9T resin, and polyamide 10T resin, etc., which are resins composed of structural units with aromatic rings and structural units without aromatic rings), polyacetal (POM) resin, polycarbonate resin, phenoxy resin, polyphenylene ether system Resins, including polyurethane resins, polyether urethane resins, polyphenylene sulfide resins, polyether nitrile resins, polysulfide urethane resins, polyarylate resins, polyamide-imide resins, polyether-imide resins, polyether aromatic ketone resins (e.g., polyetherketone resins, polyetherketoneketone resins, polyetheretherketoneketone resins, and polyetheretherketone resins), thermoplastic polyimide (TPI) resins, liquid crystal polymer (LCP) resins (liquid crystal polyester resins, etc.), polyamide thermoplastic elastomers, polyester thermoplastic elastomers, and polybenzimidazole resins, etc. Two or more thermoplastic resins may be used in combination.

[0155] Modified polyphenylene ether resins can also be used in the examples of thermoplastic resins, such as polyphenylene ether resins. Modified polyphenylene ether resins are obtained by introducing one or more reactive functional groups, such as acryloxy, methacryloxy, styrene, vinyl, carboxyl, epoxy, amino, hydroacid, and dicarboxylic anhydride groups, into part or all of the polyphenylene ether resin through grafting, copolymerization, or other methods. They can also be obtained by terminal modification using substituents having carbon-carbon unsaturated double bonds. Examples of substituents with carbon-carbon unsaturated double bonds used for terminal modification include at least one substituent selected from vinylphenyl, vinylbenzyl, acryloxy, and methacryloxy. Modified polyphenylene ether resins terminally modified using substituents having carbon-carbon unsaturated double bonds can also be used by adding other compounds with carbon-carbon unsaturated double bonds to the molecule.

[0156] When the resin composition of the present invention is used as a manufacturing material for electrical / electronic components, particularly as insulating materials such as packaging materials for various IC components, substrate materials for wiring boards, interlayer insulating materials, and insulating adhesives; insulating materials, conductive materials, or surface protection materials for Si substrates and SiC substrates; or as housings or parts for OA machines, AV machines, communication machines, or household appliances, the preferred thermosetting or thermoplastic resins used are epoxy resins, phenolic resins, unsaturated polyester resins, diallyl phthalate resins, maleimide resins, polyimide resins, benzoxazine resins, benzocyclobutene resins, polyolefin resins, styrene resins, polyester resins, aliphatic polyamide resins, semi-aromatic polyamide resins, polycarbonate resins, polyphenylene ether resins, polyarylate resins, or modified resins thereof. Two or more of these resin components may be used in combination as needed.

[0157] In the resin composition of the present invention, the amount of the cyclic phosphazene compound having a structure containing an oxophosphazene ring can be appropriately set according to various conditions such as the type of resin component and the application of the resin composition. However, it is generally preferred to set it to 0.1 to 200 parts by mass relative to 100 parts by mass of resin component converted in solids, more preferably to set it to 0.5 to 100 parts by mass, and particularly preferably to set it to 1 to 50 parts by mass. When the amount of the cyclic phosphazene compound having a structure containing an oxophosphazene ring is less than 0.1 parts by mass, the resin molded article made from the resin composition may not exhibit sufficient flame retardancy. Conversely, if it exceeds 200 parts by mass, the original characteristics of the resin component may be impaired, and the resin molded article with the expected characteristics cannot be obtained.

[0158] Furthermore, the resin composition of this invention can be formulated with various additives within a range that does not impair its intended physical properties, depending on the type of resin component or the intended use of the resin composition. Examples of usable additives include: natural silica, calcined silica, synthetic silica, amorphous silica, white carbon, alumina, aluminum hydroxide, magnesium hydroxide, calcium silicate, calcium carbonate, zinc borate, zinc stannate, titanium dioxide, zinc oxide, molybdenum oxide, zinc molybdate, natural mica, synthetic mica, aerosil, kaolin, clay, talc, calcined kaolin, calcined clay, calcined talc, wollastonite, glass short fibers, glass micropowder, insulated glass, and potassium titanate fibers, etc.; surface treatment agents for fillers such as silane coupling agents; waxes, fatty acids and their metal salts, acetylamides, and paraffin wax. Release agents; phosphorus-based flame retardants such as phosphate esters, condensed phosphate esters, amide phosphate, amide phosphate esters, phosphine oxide, bis(diphenylphosphine) oxide, phosphonium nitride, phosphinate, phosphinate salts, ammonium phosphate, and red phosphorus; nitrogen-based flame retardants such as melamine, melamine isocyanate, melam, melem, mellon, and succinoguanamine; flame retardants such as chlorinated paraffin, polysiloxane-based flame retardants, and brominated flame retardants; flame retardant additives such as antimony trioxide; anti-dripping agents such as polytetrafluoroethylene (PTFE). Agents: UV absorbers such as benzotriazole; antioxidants such as hindered phenols and styryl phenols; photopolymerization initiators such as thioxanthones; fluorescent whitening agents such as stilbene derivatives; epoxy resins, phenolic resins, hardeners, dyes, pigments, colorants, light stabilizers, photosensitizers, tackifiers, smoothers, defoamers, leveling agents, gloss agents, polymerization inhibitors, vibration modifiers, plasticizers, and antistatic agents. Two or more additives may be used in combination as needed.

[0159] In the resin composition of this invention, when a thermosetting resin is used as the resin component, a curing agent or curing accelerator is generally used in conjunction. The type of curing agent or curing accelerator that can be used is not particularly limited, as long as it is generally used with thermosetting resins. Representative examples include: polyamine compounds such as aromatic polyamines, polyamide polyamines, and aliphatic polyamines; phenolic compounds such as phenolic varnishes and cresol varnishes; acid anhydrides such as hexahydrophthalic anhydride and methyltetrahydrophthalic anhydride; phosphonium-nitrogen compounds with hydroxyl groups; Lewis acids such as boron trifluoride and their salts; imidazoles; dicyandiamides; and organometallic salts. Two or more of these can also be appropriately mixed and used.

[0160] When using the resin composition of the present invention as a manufacturing material for electrical / electronic components, epoxy resin can be used as a typical resin component. The amount of curing agent contained in the resin composition containing epoxy resin as a resin component (hereinafter referred to as "epoxy resin composition") is generally preferably set to 0.5 to 1.5 equivalents relative to the epoxy groups of the epoxy resin, and more preferably to 0.6 to 1.2 equivalents.

[0161] In epoxy resin compositions, it is generally preferable to include a curing accelerator in addition to the curing agents or additives already described. Various known curing accelerators can be used, and there are no particular limitations. For example, imidazole compounds such as 2-methylimidazole or 2-ethylimidazole, tertiary amine compounds such as 2-(dimethylaminomethyl)phenol, or triphenylphosphine compounds can be used. The amount of curing accelerator used is generally preferably set at 0.01 to 15 parts by weight relative to 100 parts by weight of epoxy resin, and more preferably at 0.1 to 10 parts by weight.

[0162] The epoxy resin composition can be formulated with known reactive diluents as needed. Various known substances can be used as reactive diluents, without particular limitation. Examples include: aliphatic alkyl glycidyl ethers such as butyl glycidyl ether, 2-ethylhexyl glycidyl ether, and allyl glycidyl ether; alkyl glycidyl esters such as glycidyl methacrylate and tricarboxylic acid glycidyl ester; aromatic alkyl glycidyl ethers such as styrene oxide and phenyl glycidyl ether, cresol glycidyl ether, p-butylphenyl glycidyl ether, and nonylphenyl glycidyl ether. Two or more of these reactive diluents can be used in combination.

[0163] The resin compositions of this invention, such as epoxy resin compositions, are formulated by uniformly mixing the various components. Resin compositions containing thermosetting resins, when placed at a temperature range of approximately 100 to 250°C for 1 to 36 hours according to the resin composition, will undergo a sufficient curing reaction and form a cured product. For example, epoxy resin compositions typically undergo a sufficient curing reaction and form a cured product after being placed at a temperature of 150 to 250°C for 2 to 15 hours. The cyclic phosphazene compounds of this invention, possessing a structure containing an oxyphosphazene ring, have high melting points and low solubility. Therefore, they can improve flame retardancy without compromising the mechanical properties (especially glass transition temperature) of the cured product caused by the resin composition, and can achieve good dielectric properties, especially Low Dk / Df. Therefore, the resin compositions of this invention can be widely used as materials for the manufacture of various resin molded articles, coatings, adhesives, and other applications. In particular, the resin composition of the present invention is suitable as a material for manufacturing electrical / electronic components, such as for semiconductor packaging or for forming circuit substrates (especially metal-coated multilayer boards, printed circuit board substrates, adhesives for printed wiring boards, adhesive sheets for printed wiring boards, insulating circuit protective films for printed wiring boards, conductive pastes for printed wiring boards, sealants for multilayer printed wiring boards, circuit protectants, cover films, and coated inks). [Example]

[0164] The present invention is illustrated below with examples and comparative examples, but the present invention is not limited by these examples. Furthermore, unless otherwise specified, "%" and "parts" refer to "mass %" and "parts by mass," respectively.

[0165] The phosphazene compounds obtained in the examples and synthesis examples were identified based on the following analytical results: determination of 1H-NMR and 31P-NMR spectra, CHN elemental analysis, analysis of chlorine (residual chlorine) by potentiometric titration with silver nitrate after alkali fusion, analysis of phosphorus by ICP-AES after microwave wet decomposition, and analysis by high-resolution mass spectrometer (HRMS) using electrospray ionization (ESI).

[0166] Furthermore, the phosphorus-based flame retardants used in the examples and comparative examples are as follows. Phosphorus-based flame retardant Y: Phosphate ester (trade name "CR-741" of DaBa Chemical Industry Co., Ltd.) Phosphorus-based flame retardant Z: Phosphorus oxide (trade name "PQ-60" manufactured by Taiwan Chin I Chemical Co., Ltd.)

[0167] [Synthetic Example 1 (Synthesis of 6-chloro-6H-dibenzo[c,e][1,2]oxophosphazenecyclohexane)] Following the method described in Stephen D. Pastor, John D. Spivack, Leander P. Steinhuebel, Phosphorus and Sulfur, 1987, Vol. 31, p. 71 (Non-Patent Literature 3 mentioned above), an attempt was made to synthesize 6-chloro-6H-dibenzo[c,e][1,2]oxophosphacyclohexane. The obtained compound was confirmed as the target 6-chloro-6H-dibenzo[c,e][1,2]oxophosphacyclohexane (yield: 85%) based on melting point measurements of 81-83 °C and 1H-NMR and 31P-NMR spectra.

[0168] [Synthetic Example 2 (Synthesis of 6-chloro-4-phenyl-6H-dibenzo[c,e][1,2]oxophosphazenecyclohexane)] Following the method described in Asfia Qureshi, Allan S. Hay, J. Chem. Res (M), 1998, p. 1601 (Non-Patent Literature 4 mentioned above), an attempt was made to synthesize 6-chloro-4-phenyl-6H-dibenzo[c,e][1,2]oxophosphacyclohexane. Based on the melting point of 101-103 °C and the 1H-NMR and 31P-NMR spectra, the obtained compound was confirmed to be the target 6-chloro-4-phenyl-6H-dibenzo[c,e][1,2]oxophosphacyclohexane (yield: 81%).

[0169] [Example 1 (Preparation of a cyclic phosphazene compound having a structure containing an oxyphosphonohexane ring using manufacturing method 1)] In a 5,000 mL four-necked flask equipped with a thermometer, stirrer, and cooling pipe, 234.6 g (1.0 mol) of 6-chloro-6H-dibenzo[c,e][1,2]oxophosphazenecyclohexane synthesized in Synthesis Example 1, 115.2 g (1.0 mol) of trimethylsilyl azide, and 2,000 mL of toluene were loaded under a nitrogen stream and stirred at 50 °C for 24 hours. After cooling the reaction mixture to room temperature, 1,000 mL of deionized water was added, and the mixture was stirred at room temperature for 1 hour. The slurry obtained by the above operation was filtered to obtain a filtrate, which was washed with toluene and deionized water. The resulting wet crystals were dried to obtain 177.8 g of a white powder (yield: 83.4%). The analytical results of this white powder are as follows.

[0170] 1H-NMR spectrum (in deuterated chloroform, δ, ppm): 6.0 to 8.3 (m) 31P-NMR spectrum (in deuterated chloroform, δ, ppm): -10 to 0 (m), 1.8 to 3.5 (m), 15.8 (d), 17.5 (s), 17.9 (dd) CHNP elemental analysis: Theoretical values: C: 67.61%, H: 3.78%, N: 6.57%, P: 14.53% Measured values: C: 67.49%, H: 3.79%, N: 6.55%, P: 14.49% Residual chlorine analysis: <0.01% HRMS(ESI,m / z): Theoretical values: Trimer: [C36H24N3O3P3+H]+: 640.1109, Tetramer: [C48H32N4O4P4+H]+: 853.1452, Pentame: [C60H40N5O5P5+H]+: 1066.1796 Measured values: 640.1097, 853.1444, 1066.1797

[0171] Based on the above analysis, it was confirmed that the obtained white powder is a mixture of N3P3(OC6H4-C6H4)3, N4P4(OC6H4-C6H4)4 and N5P5(OC6H4-C6H4)5 with an average composition of [NP(OC6H4-C6H4)]3.6, which is a cyclic phosphazene compound with a structure containing an oxophosphane ring.

[0172] [Example 2 (isolation of trimer-cis isomer from the cyclic phosphazene compound obtained in Example 1)] In a 2,000 mL four-necked flask equipped with a thermometer, stirrer, and cooling tube, 150.0 g of the white powder obtained in Example 1 and 1,500 mL of toluene were added. The mixture was refluxed and stirred for 3 hours, then cooled to room temperature and stirred for another 2 hours. The slurry obtained by the above operation was filtered to obtain a filtrate. This filtrate was washed with toluene, and the resulting crystals were dried to obtain 36.6 g of colorless crystals. The analytical results of these colorless crystals are as follows.

[0173] 1H-NMR spectrum (in deuterated chloroform, δ, ppm): 7.17(3H,td),7.35(3H,td),7.40(3H,dd),7.47(3H,t),7.61(3H,td),7.85(3H,dd),7.89(3H,m) 31P-NMR spectrum (in deuterated chloroform, δ, ppm): 17.5(s) CHNP elemental analysis: Theoretical values: C: 67.61%, H: 3.78%, N: 6.57%, P: 14.53% Measured values: C: 67.59%, H: 3.80%, N: 6.61%, P: 14.55% Residual chlorine analysis: <0.01% HRMS(ESI,m / z): Theoretical value for trimer: [C36H24N3O3P3+H]+: 640.1109 Measured value: 640.1097

[0174] Based on the above analysis, it was confirmed that the obtained colorless crystalline cis-type N3P3(OC6H4-C6H4)3 is a cyclic phosphazene compound with a structure containing an oxophosphane ring.

[0175] [Example 3 (isolation of trimer-trans isomer and tetramer from the cyclic phosphazene compound obtained in Example 1)] In Example 2, a mother liquor was obtained by filtering the slurry. This mother liquor was concentrated using an evaporator, and the resulting solid was purified by silica gel column chromatography (developing solvent: toluene / ethyl acetate = 9 / 1) to obtain separate chromatographic fractions of the trimer-trans isomer and tetramer contained in the cyclic phosphonium compound obtained in Example 1. After concentrating each fraction under reduced pressure, methanol was added and the mixture was filtered to obtain a filtrate. The filtrate was washed with methanol, and the resulting crystals were dried. This yielded 86.7 g of colorless crystals of the trimer-trans isomer and 15.9 g of a white powder of the tetramer. These analytical results are described below.

[0176] Colorless crystals of the trimeric-trans isomer: 1H-NMR spectrum (in deuterated chloroform, δ, ppm): 7.18(3H,m),7.33(3H,m),7.52(2H,m),7.63(4H,m),7.88(6H,m),8.03(2H,m),8.25(1H,ddd) 31P-NMR spectrum (in deuterated chloroform, δ, ppm): 15.8 (day), 17.9 (dd) CHNP elemental analysis: Theoretical values: C: 67.61%, H: 3.78%, N: 6.57%, P: 14.53% Measured values: C: 67.51%, H: 3.81%, N: 6.54%, P: 14.48% Residual chlorine analysis: <0.01% HRMS(ESI,m / z): Theoretical value for trimer: [C36H24N3O3P3+H]+: 640.1109 Measured value: 640.1097

[0177] Based on the above analysis, it was confirmed that the obtained colorless crystalline trans-type N3P3(OC6H4-C6H4)3 is a cyclic phosphazene compound with a structure containing an oxophosphane ring.

[0178] white powder of tetramer 1H-NMR spectrum (in deuterated chloroform, δ, ppm): 6.5 to 7.8 (m) 31P-NMR spectrum (in deuterated chloroform, δ, ppm): 1.8 to 3.5 (m) CHNP elemental analysis: Theoretical values: C: 67.61%, H: 3.78%, N: 6.57%, P: 14.53% Measured values: C: 67.52%, H: 3.83%, N: 6.52%, P: 14.51% Residual chlorine analysis: <0.01% HRMS(ESI,m / z): Theoretical value for tetramer: [C48H32N4O4P4+H]+: 853.1452 Measured value: 853.1444

[0179] Based on the above analysis, it was confirmed that the obtained white powder is a mixture of five isomers of N4P4(OC6H4-C6H4)4, which is a cyclic phosphazene compound with a structure containing an oxophosphazene ring: cis, α-trans, β-trans, γ-trans, and mirror-image isomers. Furthermore, the names of the tetramer stereoisomers are based on the nomenclature described in Non-Patent Document 13 below.

[0180] [Non-patent literature 13] Bernard Grushkin,Alvin J. Berlin,James L.McClanaham, Rip G.Rice,Inorg.Chem.,1966,Vol.5,p.172.

[0181] [Example 4 (Preparation of a cyclic phosphazene compound having a structure containing an oxyphosphonohexane ring using manufacturing method 1)] Except for replacing the 6-chloro-6H-dibenzo[c,e][1,2]oxophosphacyclohexane synthesized in Synthetic Example 1 with 310.7 g (1.0 mol) of 6-chloro-4-phenyl-6H-dibenzo[c,e][1,2]oxophosphacyclohexane synthesized in Synthetic Example 2, the procedure was the same as in Example 1, yielding 274.2 g of white powder (yield: 94.8%). The analytical results of this white powder are as follows.

[0182] 1H-NMR spectrum (in deuterated chloroform, δ, ppm): 6.0 to 8.3 (m) 31P-NMR spectrum (in deuterated chloroform, δ, ppm): -10 to 0 (m), 1.5 to 3.2 (m), 15.5 (d), 17.1 (s), 17.8 (dd) CHNP elemental analysis: Theoretical values: C: 74.74%, H: 4.18%, N: 4.84%, P: 10.71% Measured values: C: 74.70%, H: 4.19%, N: 4.72%, P: 10.66% Residual chlorine analysis: <0.01% HRMS(ESI,m / z): Theoretical values: Trimer: [C54H36N3O3P3+H]+: 868.2048, Tetramer: [C72H48N4O4P4+H]+: 1157.2704, Pentame: [C90H60N5O5P5+H]+: 1446.3361 Measured values: 868.2039, 1157.2712, 1146.3372

[0183] Based on the above analysis, it was confirmed that the obtained white powder is a mixture of N3P3[OC6H3(C6H5)-C6H4]3, N4P4[OC6H3(C6H5)-C6H4]4 and N5P5[OC6H3(C6H5)-C6H4]5, and its average composition is {NP[OC6H3(C6H5)-C6H4]}3.5, which is a cyclic phosphazene compound with a structure containing an oxophosphane ring.

[0184] [Examples 5 to 10 and Comparative Examples 1 to 2 (Manufacturing of Resin Molded Articles)] A varnish was prepared by mixing and stirring a vinyl-terminated polyphenylene ether oligomer (SABIC's trade name "SA-9000"), a styrene-butadiene copolymer (CRAY VALLEY's trade name "RICON184"), the phosphonium nitride compound prepared in Examples 1 to 4, phosphorus-based flame retardant Y or Z, a polymerization initiator (Tokyo Chemical Co., Ltd.'s reagent "t-Butyl Peroxide"), and methyl ethyl ketone (MEK) in the proportions shown in Table 2. This varnish was coated onto a polyethylene terephthalate resin film and left at room temperature for 1 hour, followed by further drying at 90°C for 30 minutes. The dried coating was peeled off and placed in a polytetrafluoroethylene resin spacer. Under vacuum, it was sequentially heated and pressurized at 120°C for 30 minutes, 150°C for 30 minutes, and 180°C for 100 minutes to harden it, thereby obtaining a molded body of the size suitable for evaluation described later.

[0185] [Examples 11 to 15 and Comparative Examples 3 to 4 (Manufacturing of Resin Molded Articles)] A mixture of 651 parts of bisphenol A type epoxy resin (JAPAN / EPOXY / RESIN Co., Ltd.'s trade name "EPIKOTE 1001" / epoxy equivalent 456 g / eq., resin solids content 70%), 300 parts of cresol phenolic varnish epoxy resin (Toto Chemical Co., Ltd.'s trade name "YDCN-704P" / epoxy equivalent 210 g / eq., resin solids content 70%), 303 parts of phenolic varnish type phenolic resin (Showa Polymer Co., Ltd.'s trade name "BRG-558" / hydroxyl equivalent 106 g / eq., resin solids content 70%), 361 parts of aluminum hydroxide, and 0.9 parts of 2-ethyl-4-methylimidazole was prepared by adding the phosphono-nitrogen compounds and phosphorus flame retardants Y or Z manufactured in Examples 1 to 4 in the proportions shown in Table 3, and then adding propylene glycol monomethyl ether (PGM) as a solvent to prepare an epoxy resin varnish with a resin solids content of 65%.

[0186] Then, the prepared epoxy resin varnish was coated and impregnated in 180μm glass cloth, and dried at 160°C to produce a prepreg. Eight sheets of the prepreg were laminated to obtain a laminate, and the laminate was heated and pressurized at 170°C and 4MPa for 100 minutes to obtain a resin molded body of a size suitable for evaluation later.

[0187] [Examples 16 to 21 and Comparative Examples 5 to 6 (Manufacturing of Resin Molded Articles)] Thermoplastic resin (polyphthalamide: SOLVAY's trade name "AMODEL AE-1133"), which had been pre-dried at 100°C for 8 hours, was fed into a biaxial mixing extrusion apparatus (manufactured by Toyo Seiki Co., Ltd.) along with the phosphazene compound and phosphorus-based flame retardant Y or Z produced in Examples 1 to 4 at the proportions shown in Table 4. The mixture was then mixed at 310°C to obtain resin granules. The obtained resin granules were then molded using an injection molding machine (manufactured by Digital Factory Co., Ltd.) at a resin temperature of 300°C and a mold temperature of 120°C to obtain resin molded bodies of a size suitable for evaluation described later.

[0188] [Evaluate] Flame retardancy, dielectric properties, and heat resistance were evaluated for the resin molded articles obtained in Examples 5 to 21 and Comparative Examples 1 to 6. The evaluation methods are described below. The results are presented in Tables 2 to 4.

[0189] <Flammability> A resin molded body measuring 125 mm in length, 12.5 mm in width, and 1.5 mm in thickness was used as a test piece to evaluate its flammability. Here, the flammability was determined according to the UL-94 vertical burning test specification of Underwriter's Laboratories Inc., using the total burning time during 10 exposures to flame and the presence or absence of cotton ignition due to dripping during combustion, categorized into four stages: V-0, V-1, V-2, and out-of-specification. The evaluation of each stage is as follows. The flame retardancy rating is V-0, the highest, decreasing in the order of V-1, V-2, and out-of-specification.

[0190] V-0: Satisfies all of the following conditions. (A) For 5 test pieces, each piece was exposed to the flame twice, for a total of 10 exposures. The total extinguishing time from the exposure to the flame was less than 50 seconds. (B) For the 5 test pieces, each piece was exposed to the flame twice, and the extinguishing time of each piece from the time of exposure to the flame was within 5 seconds. (C) In all test pieces, there was no ignition of the absorbent cotton below 300 mm caused by dripping material. (D) In ​​all the test pieces, the glow after the second contact with the flame was within 30 seconds. (E) None of the test pieces burned the clamps.

[0191] V-1: Satisfies all of the following conditions. (A) For 5 test pieces, each piece was exposed to the flame twice, for a total of 10 exposures. The total extinguishing time from the exposure to the flame was less than 250 seconds. (B) For the 5 test pieces, each piece was exposed to the flame twice, and the extinguishing time of each piece from the time of exposure to the flame was within 30 seconds. (C) In all test pieces, there was no ignition of the absorbent cotton below 300 mm caused by dripping material. (D) In ​​all test pieces, the burning sensation after the second contact with the flame was within 60 seconds. (E) None of the test pieces burned the clamps.

[0192] V-2: Satisfies all of the following conditions. (A) For 5 test pieces, each piece was exposed to the flame twice, for a total of 10 exposures. The total extinguishing time from the exposure to the flame was less than 250 seconds. (B) For the 5 test pieces, each piece was exposed to the flame twice, and the extinguishing time of each piece from the time of exposure to the flame was within 30 seconds. (C) Of the 5 test pieces, at least one piece showed ignition of the absorbent cotton at a depth of 300 mm due to dripping material. (D) In ​​all the test pieces, the burning sensation after the second contact with the flame was within 60 seconds. (E) None of the test pieces burned the clamps.

[0193] <Dielectric Properties: Specific Dielectric Power and Dielectric Tangent> A resin molded body with a length of 80 mm, a width of 3 mm, and a thickness of 1.0 mm was used as a test piece. The specific dielectric constant (Dk) and dielectric tangent (Df) of the test piece were measured according to JIS R1641 "Method for determination of microwave dielectric properties of fine ceramic substrates" at a temperature of 25 °C and a frequency of 10 GHz.

[0194] <Glass transition temperature (Tg)> The dynamic viscoelasticity (DMA) of the resin molded body was measured, with the maximum value of tanδ (loss modulus of elasticity / storage modulus of elasticity) set as the glass transition temperature (Tg). Here, a dynamic viscoelasticity measuring device (PERKIN ELYMER JAPNA's trade name "DMA8000") was used, and the measurement was performed using a stretching module at a heating rate of 5°C / minute.

[0195] <Heat resistance> Test condition 1: The resin molded body was heated at 160°C for 100 hours, and the exudation state on the surface of the resin molded body (exudation state originating from the interior of the resin molded body) was visually observed and evaluated. The evaluation criteria are as follows. The less exudation is visible, the higher the heat resistance of the resin molded body. AA: No seepage is visible at all. A: Almost no seepage is visible. B: Some seepage can be seen. C: Obvious exudation can be seen.

[0196] Test condition 2: After treating the resin molded body at 290°C for 20 minutes, observe for any changes in appearance caused by exudation. If no changes in appearance are observed, the body is assessed as having heat resistance; if changes in appearance are observed, the body is assessed as lacking heat resistance.

[0197] [Table 2]

[0198] As shown in Table 2, compared with the resin molded articles of Comparative Examples 1 and 2, the resin molding systems of Examples 5 to 10 have higher flame retardancy, lower specific dielectric constant Dk and dielectric tangent Df, thus being Low Dk / Df and having excellent dielectric properties. Furthermore, since no leaching of the cyclic phosphonium compounds evaluated for heat resistance was observed, their reliability at high temperatures is high.

[0199] [Table 3]

[0200] As shown in Table 3, compared with the resin molded articles of Comparative Examples 3 and 4, the resin molding systems of Examples 11 to 15 have higher flame retardancy and higher glass transition temperature, and therefore better mechanical properties. Furthermore, since no leaching of the cyclic phosphonium nitride compounds evaluated for heat resistance was observed, the reliability at high temperatures is high.

[0201] [Table 4]

[0202] As shown in Table 4, compared with the resin molded articles of Comparative Examples 5 and 6, the resin molded systems of Examples 16 to 21 have higher flame retardancy, lower specific dielectric constant Dk and dielectric tangent Df, thus being Low Dk / Df and having excellent dielectric properties. Moreover, since no leaching of the cyclic phosphonium compounds evaluated for heat resistance was observed, the reliability at high temperatures is high.

[0203] [Example 22 (Preparation of a cyclic phosphazene compound having a structure containing an oxyphosphonohexane ring using manufacturing method 2)] A toluene solution of 6-chloro-6H-dibenzo[c,e][1,2]oxaphosphane obtained in Synthesis Example 1 was prepared, and chlorine gas was introduced into the solution to allow it to react, thereby synthesizing 6,6,6-trichloro-6H-dibenzo[c,e][1,2]oxaphosphane. Here, the following determinations of the 31P-NMR spectrum of the reaction solution used in the synthesis confirmed that 6-chloro-6H-dibenzo[c,e][1,2]oxaphosphane was the derivative of the desired 6,6,6-trichloro-6H-dibenzo[c,e][1,2]oxaphosphane. This reaction solution was then directly used in a subsequent reaction. Based on the chloride ion content determined by silver nitrate titration, the content of 6,6,6-trichloro-6H-dibenzo[c,e][1,2]oxophosphine in the reaction solution was confirmed to be 38.2% when the chloride ion content determined by silver nitrate titration was used as the benchmark.

[0204] 31P-NMR spectrum (in deuterated chloroform, δ, ppm): -25.3(s)

[0205] In a 3,000 mL four-necked flask equipped with a thermometer, stirrer, and cooling pipe, 58.8 g (1.1 mol) of ammonium chloride and 1,500 mL of toluene were added under a nitrogen stream to prepare a slurry solution, which was then heated. Next, while the slurry solution was refluxed, 799.8 g (1.0 mol) of a toluene solution of 6,6,6-trichloro-6H-dibenzo[c,e][1,2]oxophosphine was added dropwise over 18 hours. The toluene was then distilled off, and the solution was concentrated until the temperature of the reaction solution reached 160°C, and stirred at the same temperature for 15 hours. Subsequently, 500 mL of deionized water was added to the reaction solution, and the mixture was stirred at room temperature for 1 hour. The resulting slurry solution was filtered to separate the crystals, which were then washed with deionized water and dried to obtain 184.0 g of a white powder (yield: 86.3%). Because the white powder exhibits the following analytical results, it is confirmed that the white powder is a cyclic phosphonium alkene compound containing a dibenzoxoxophosphazene ring as shown in formula (1) (but it is a mixture of substances in which a and b are 0 and n is an integer from 3 to 8).

[0206] 1H-NMR spectrum (in deuterated chloroform, δ, ppm): 6.0 to 8.3 (m) 31P-NMR spectrum (in deuterated chloroform, δ, ppm): -10 to 0 (m), 1.8 to 3.5 (m), 15.8 (d), 17.5 (s), 17.9 (dd) CHNP elemental analysis: Theoretical values: C: 67.61%, H: 3.78%, N: 6.57%, P: 14.53% Measured values: C: 67.55%, H: 3.81%, N: 6.53%, P: 14.48% Residual chlorine analysis: <0.01% HRMS spectrum (ESI, m / z): Theoretical values: Trimer: [C36H24N3O3P3+H]+: 640.1109, Tetramer: [C48H32N4O4P4+H]+: 853.1452, Pentame: [C60H40N5O5P5+H]+: 1066.1796 Measured values: 640.1097, 853.1444, 1066.1797

[0207] [Example 23 (Preparation of a cyclic phosphazene compound having a structure containing an oxyphosphine ring using manufacturing method 3)] In a 3,000 mL four-necked flask equipped with a thermometer, stirrer, and cooling pipe, 234.6 g (1.0 mol) of 6-chloro-6H-dibenzo[c,e][1,2]oxophosphacyclohexane obtained in Synthesis Example 1 and 1,500 mL of diethyl ether were loaded under a nitrogen stream. To maintain the reaction solution temperature below 0°C, 183 mL of a pre-prepared 6M diethyl ether solution of chloramine (chloramine content: 1.1 mol) was added dropwise while cooling. The diethyl ether was then removed by heating the reaction solution, and the mixture was concentrated until the final temperature reached 160°C, and stirred at the same temperature for 19 hours. 500 mL of deionized water was added to the reaction solution and the mixture was stirred at room temperature for 1 hour. The resulting slurry was then filtered to separate the crystals. The separated crystals were then washed with ion-exchanged water and dried to obtain 158.8 g of light brown powder (yield: 74.5%). Since the analytical results of the light brown powder in 1H-NMR, 31P-NMR and HRMS were consistent with the analytical results of the white powder obtained in Example 22, it was confirmed that the light brown powder was a cyclic phosphazene compound containing a dibenzoxoxophosphazene hexane ring as shown in formula (1) (but a mixture of substances in which a and b are 0 and n is an integer from 3 to 8).

[0208] [Example 24 (Preparation of a cyclic phosphazene compound having a structure containing an oxyphosphine ring using manufacturing method 4)] Referring to Patent Documents 11 and 12, the 6-chloro-6H-dibenzo[c,e][1,2]oxophosphane hexane obtained in Synthesis Example 1 was hydrolyzed to prepare 6H-dibenzo[c,e][1,2]oxophosphane-6-oxide. Then, according to Non-Patent Document 10, the obtained 6H-dibenzo[c,e][1,2]oxophosphane-6-oxide was chlorinated. From the 1H-NMR and 31P-NMR spectra, it was confirmed that the product obtained was 6-chloro-6H-dibenzo[c,e][1,2]oxophosphane-2-oxide (yield 94%).

[0209] Subsequently, following the method described in Non-Patent Document 11, the obtained 6-chloro-6H-dibenzo[c,e][1,2]oxophosphine-2-oxide was amination using ammonia. Measurements using 1H-NMR and 31P-NMR spectra confirmed that the product obtained was 6-amino-6H-dibenzo[c,e][1,2]oxophosphine-2-oxide (yield 89%), belonging to the phosphatamine ester family of compounds.

[0210] A 10,000 mL four-necked flask equipped with a thermometer, stirrer, and cooling pipe was prepared. In this flask, 231.2 g (1.0 mol) of the obtained 6-amino-6H-dibenzo[c,e][1,2]oxophosphine-2-oxide, 629.5 g (2.4 mol) of triphenylphosphine, 129.2 g (1.0 mol) of N,N-diisopropylethylamine, and 4,500 mL of xylene were added under a nitrogen stream and the mixture was heated. While refluxing the solution in the flask, 153.8 g (1.0 mol) of carbon tetrachloride was added dropwise over 2 hours, and stirring was continued for 4 hours. The solvent was removed from the reaction solution under reduced pressure. 9,000 mL of methanol was added to the residue and the mixture was stirred to obtain a slurry. The slurry was then filtered to separate the crystals. Next, the separated crystals were washed with methanol and dried to obtain 115.1 g of white powder (yield: 54.0%). The analysis results of each spectrum of 1H-NMR and 31P-NMR confirmed that the white powder was a cyclic phosphazene compound containing a dibenzoxoxophosphazene ring as shown in formula (1) (but it is a mixture of substances in which a and b are 0 and n is an integer from 3 to 8).

[0211] [Example 25 (Preparation of a cyclic phosphazene compound having a structure containing an oxyphosphine ring using manufacturing method 4)] Except for the addition of 73.9 g (0.2 mol) of tetrabutylammonium iodide to the four-necked flask prepared in Example 24 and the use of 99.0 g (1.0 mol) of 1,2-dichloroethane to replace carbon tetrachloride, the operation was the same as in Example 24, yielding 128.3 g of white powder (yield: 60.2%). Analysis of the spectra of 1H-NMR and 31P-NMR confirmed that the white powder was a cyclic phosphazene compound containing a dibenzoxoxophosphazene hexane ring as shown in formula (1) (a mixture of substances where a and b are 0 and n is an integer from 3 to 8).

Claims

1. A cyclic phosphazene compound having a structure containing an oxophosphazene ring, represented by the following formula (1); in formula (1), n ​​is an integer from 3 to 8, and R1 and R2 are either (i) or (ii) below: (i) each independently being a nitro group, an alkyl or alkoxy group of carbon 1 to 8 that can be substituted with at least one of an alkyl or aryl group of carbon 1 to 6, and an aryl or aryloxy group of carbon 6 to 20 that can be substituted with at least one of an alkyl or aryl group of carbon 1 to 6; (ii) forming a saturated or unsaturated cyclic structure between each other that can be substituted with an alkyl or carbonyl group of carbon 1 to 6; a and b are each independently an integer from 0 to 4, and the type of structure containing the oxophosphazene ring of each repeating unit is independent.

2. A cyclic phosphazene compound having a structure containing an oxyphosphazene ring, as described in claim 1, wherein, In equation (1), n ​​is 3 or 4.

3. A cyclic phosphazene compound having a structure containing an oxyphosphazene ring, as described in claim 1, wherein, In equation (1), n ​​is 3, and a and b are 0.

4. The cyclic phosphazene compound having a structure containing an oxophosphane ring as described in claim 3 is a mixture of non-mirror image isomers.

5. A cyclic phosphazene compound having a structure containing an oxyphosphazene ring, as described in claim 3, wherein, The stereoconfiguration of the structure adjacent to the aforementioned oxygen-phosphorus heterocyclohexane ring is cis-cis-cis type.

6. A cyclic phosphazene compound having a structure containing an oxyphosphazene ring, as described in claim 3, wherein, The stereoconfiguration of the structure adjacent to the aforementioned oxophosphorus heterocyclohexane ring is trans-cis-trans.

7. A mixture of cyclic phosphazene compounds having a structure containing an oxophosphane ring, comprising two or more cyclic phosphazene compounds having a structure containing an oxophosphane ring as described in any one of claims 1 to 6.

8. A method for manufacturing a cyclic phosphazene compound having a structure containing an oxophosphazene ring, comprising the following steps 1 and 2: Step 1, using an azidizing agent to degenerate the dichlorodibenzooxophosphazene hexane compound of the following formula (2) into an azidization intermediate; Step 2, subjecting the aforementioned azidization intermediate to a cyclization reaction; In formula (2), R1 and R2 are either (i) or (ii) as follows: (i) are independently nitro, alkyl or alkoxy groups of carbon 1 to 8 that can be substituted with at least one group selected from alkyl or aryl groups of carbon 1 to 6, and aryl or aryloxy groups of carbon 6 to 20 that can be substituted with at least one group selected from alkyl or aryl groups of carbon 1 to 6; (ii) forming a saturated or unsaturated cyclic structure between each other that can be substituted with alkyl or carbonyl groups of carbon 1 to 6; a and b are independently integers from 0 to 4.

9. A method for manufacturing a cyclic phosphazene compound having a structure containing an oxyphosphazene ring as described in claim 8, wherein, The aforementioned azide intermediate used in step 2 is a mixture of two or more of the aforementioned azide intermediates.

10. A method for manufacturing a cyclic phosphazene compound having a structure containing an oxophosphane ring as described in claim 9, wherein, The aforementioned mixture of azide intermediates was obtained by using two or more of the aforementioned dichlorodibenzoxyphoshexane compounds in step 1.

11. A resin composition comprising: a resin component, and one or more cyclic phosphazene compounds having a structure containing an oxophosphane ring as described in any one of claims 1 to 6.

12. The resin composition as described in claim 11, wherein, The aforementioned resin component is selected from at least one of the group consisting of epoxy resin, phenolic resin, unsaturated polyester resin, diallyl phthalate resin, maleimide resin, polyimide resin, benzoxazine resin, benzocyclobutene resin, polyolefin resin, styrene resin, polyester resin, aliphatic polyamide resin, semi-aromatic polyamide resin, polycarbonate resin, polyphenylene ether resin, polyarylate resin, and modified resins thereof.

13. A resin molded article comprising the resin composition described in claim 11.

14. An electrical / electronic component comprising the resin molded body described in claim 13.

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