WO2023007982A1 - Phosphorus compound having isocyanurate ring, synthetic method therefor, and use of said phosphorus compound having isocyanurate ring - Google Patents

Abstract

The present invention provides: a novel phosphorus compound having an isocyanurate ring; a synthetic method for said phosphorus compound; a flame retardant containing said phosphorus compound; and a resin composition containing said phosphorus compound and a resin component. Moreover, provided are: a prepreg using said resin composition; a metal foil with a resin; a thermosetting resin film; a metal-clad laminate; a printed wiring board; and an adhesive. The present invention pertains to: a phosphorus compound having an isocyanurate ring and represented by chemical formula (I); a synthetic method therefor; and a use thereof. (In the formula, R¹ represents a C1-C20 alkyl group, an aryl group, or a benzyl group, and R² represents a group represented by formula (1). Alternatively, R¹ and R² may be linked to form a ring. Each R³ identically or differently represents a C2-C20 alkenyl group or a C2-C20 alkynyl group. Each R⁴ identically or differently represents a hydrogen atom, a C1-C20 alkyl group, an aryl group, a benzyl group, a C2-C20 alkenyl group, or a C2-C20 alkynyl group. Each Y identically or differently represents a C1-C20 alkylene group.) (In the formula, R³, R⁴, and Y are the same as above.)

Description

Phosphorus compound having isocyanurate ring, method for synthesizing same, and use of phosphorus compound having isocyanurate ring

The present invention relates to a novel phosphorus compound having an isocyanurate ring, a method for synthesizing the phosphorus compound having the isocyanurate ring, and utilization of the phosphorus compound having the isocyanurate ring.

2. Description of the Related Art In recent years, as electronic devices have become smaller and have higher performance, multilayer printed wiring boards are required to have multiple build-up layers and finer and higher density wiring.
In particular, for high-frequency applications, an insulating material (resin material) with a low dielectric loss tangent is desired in order to reduce the transmission loss of electrical signals. Such resin materials are required to have flame retardancy in cured products in addition to electrical properties, and flame retardants have been studied.

Flame retardants used in resin materials include inorganic flame retardants and organic flame retardants.
Inorganic flame retardants have excellent dielectric properties, but because they exhibit water absorption and hydrolyzability, they tend to cause deterioration over time of cured products. had a problem.
On the other hand, since phosphorus compounds, which are organic flame retardants, have plasticity, there is a problem that increasing the amount of addition to enhance flame retardancy impairs the mechanical strength of the cured product.

Various substances have been investigated as flame retardants for solving such problems. Among them, phosphorus compounds having radically polymerizable groups in the molecule are expected to improve low thermal expansion properties, heat resistance and mechanical strength.
For example, Patent Document 1 proposes (2,5-dimethacryloxyphenyl)diphenylphosphine oxide and analogues thereof as flame retardants. However, resin compositions using these compounds still have room for improvement in terms of low thermal expansion, heat resistance, mechanical strength and electrical properties.

WO2013/114866

An object of the present invention is to provide a novel phosphorus compound having an isocyanurate ring, a method for synthesizing the phosphorus compound, a flame retardant containing the phosphorus compound, and a resin composition containing the phosphorus compound and a resin component. and
A further object is to provide a prepreg, a resin-coated metal foil, a thermosetting resin film, a metal-clad laminate, a printed wiring board, and an adhesive using the resin composition.

The present inventors have made intensive studies to solve the above problems, and as a result, a phosphorus compound having an isocyanurate ring obtained by reacting a certain phosphorus compound with a certain isocyanurate compound , recognized that the intended purpose could be achieved, and completed the present invention.
That is, the first invention is a phosphorus compound having an isocyanurate ring represented by the chemical formula (I).

（式中、Ｒ^１は、炭素数１～２０のアルキル基、アリール基、またはベンジル基を表し、Ｒ^２は、式（１）で示される基を表す。或いは、Ｒ^１およびＲ^２が連結して環を形成してもよい。Ｒ^３は、同一または異なって、炭素数２～２０のアルケニル基、または炭素数２～２０のアルキニル基を表す。Ｒ^４は、同一または異なって、水素原子、炭素数１～２０のアルキル基、アリール基、ベンジル基、炭素数２～２０のアルケニル基、または炭素数２～２０のアルキニル基を表す。Ｙは、同一または異なって、炭素数１～２０のアルキレン基を表す。）

(In the formula, R ¹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group, or a benzyl group, and R ² represents a group represented by formula (1). Alternatively, R ¹ and R ² are linked may form a ring, R ³ is the same or different and represents an alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms, and R ⁴ is the same or different and is hydrogen represents an atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, a benzyl group, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, and Y is the same or different and each has 1 to 20 carbon atoms. 20 alkylene group).

（式中、Ｒ^３、Ｒ^４およびＹは、前記と同様である。）

(Wherein, R ³ , R ⁴ and Y are the same as defined above.)

The second invention is a phosphorus compound having an isocyanurate ring represented by the chemical formula (I-1).

（式中、Ｒ^１、Ｒ^３、Ｒ^４およびＹは、前記と同様である。）

(Wherein, R ¹ , R ³ , R ⁴ and Y are the same as defined above.)

The third invention is a phosphorus compound having an isocyanurate ring represented by chemical formula (I-2).

（式中、Ｒ^３、Ｒ^４およびＹは、前記と同様である。）

(Wherein, R ³ , R ⁴ and Y are the same as defined above.)

A fourth invention is a method for synthesizing a phosphorus compound having an isocyanurate ring according to the first invention, comprising a step of reacting a phosphorus compound represented by the chemical formula (II) with an isocyanurate compound represented by the chemical formula (III). is.

（式中、Ｒ^１は、前記と同様であり、Ｒ^８は、－Ｙ－Ｘを表す。或いは、Ｒ^１およびＲ^８が連結して環を形成してもよい。Ｙは、前記と同様である。Ｘは、同一または異なって、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メシルオキシ基（ＯＭｓ）、トシルオキシ基（ＯＴｓ）、またはトリフルオロメタンスルホニルオキシ基（ＯＴｆ）を表す。）

(In the formula, R ¹ is the same as defined above, and R ⁸ represents -YX. Alternatively, R ¹ and R ⁸ may be linked to form a ring. Y is the same as defined above. X is the same or different and represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a mesyloxy group (OMs), a tosyloxy group (OTs), or a trifluoromethanesulfonyloxy group (OTf).)

（式中、Ｒ^３およびＲ^４は、前記と同様である。）

(In the formula, R ³ and R ⁴ are the same as above.)

A fifth invention is a flame retardant containing the phosphorus compound having an isocyanurate ring according to any one of the first to third inventions.
A sixth invention is a resin composition containing the phosphorus compound having an isocyanurate ring according to any one of the first to third inventions and a resin component.
A seventh invention is the resin composition of the sixth invention, wherein the resin component is a polyphenylene ether resin.
An eighth invention is a prepreg comprising the resin composition of the sixth invention or the seventh invention and a substrate.
A ninth invention is a resin-coated metal foil comprising a resin layer containing the resin composition of the sixth or seventh invention or a semi-cured product of the resin composition, and a metal foil.
A tenth invention is a thermosetting resin film formed from the resin composition of the sixth invention or the seventh invention.
An eleventh invention is a metal-clad laminate comprising an insulating layer containing a cured product of the resin composition of the sixth invention or the seventh invention, and a metal foil.
A twelfth invention is a printed wiring board comprising an insulating layer containing a cured product of the resin composition of the sixth or seventh invention, or a cured product of the thermosetting resin film of the tenth invention, and wiring. is.
A thirteenth invention is an adhesive containing the resin composition of the sixth invention or the seventh invention as a component.

The phosphorus compound having an isocyanurate ring of the present invention is a novel phosphorus compound having an isocyanurate ring. Such phosphorus compounds are expected to be used as flame retardants for resins.
Then, the phosphorus compound having an isocyanurate ring of the present invention has an isocyanurate ring and an unsaturated bond group in the molecule, so when used as a resin raw material (resin material), a conventional phosphorus compound can be used. It is expected that a cured product having low thermal expansion, heat resistance, adhesiveness (adhesion), mechanical properties, electrical properties and flame retardancy will be obtained. Therefore, the resin composition of the present invention can be suitably used as a material for printed wiring boards and the like.
Furthermore, the adhesive of the present invention is expected to be excellent in flame retardancy, low thermal expansion, heat resistance, adhesion, mechanical properties and electrical properties.

1 is an IR spectrum chart of the white powder obtained in Example 1. FIG. 4 is an IR spectrum chart of the white powder obtained in Example 2. FIG.

(1. Phosphorus compound having an isocyanurate ring)
The present invention relates to a phosphorus compound having an isocyanurate ring represented by the above chemical formula (I) (hereinafter sometimes referred to as "the phosphorus compound of the present invention"). The phosphorus compound of the present invention includes a phosphorus compound represented by the chemical formula (I-1) and a phosphorus compound represented by the chemical formula (I-2).

（式中、Ｒ^１は、炭素数１～２０のアルキル基、アリール基、またはベンジル基を表す。Ｒ^３は、同一または異なって、炭素数２～２０のアルケニル基、または炭素数２～２０のアルキニル基を表す。Ｒ^４は、同一または異なって、水素原子、炭素数１～２０のアルキル基、アリール基、ベンジル基、炭素数２～２０のアルケニル基、または炭素数２～２０のアルキニル基を表す。Ｙは、同一または異なって、炭素数１～２０のアルキレン基を表す。）

(wherein R ¹ represents an alkyl group having 1 to 20 carbon atoms ^, an aryl group or a benzyl group; R ⁴ is the same or different and represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, a benzyl group, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms. and Y are the same or different and represent an alkylene group having 1 to 20 carbon atoms.)

（式中、Ｒ^３は、炭素数２～２０のアルケニル基、または炭素数２～２０のアルキニル基を表す。Ｒ^４は、水素原子、炭素数１～２０のアルキル基、アリール基、ベンジル基、炭素数２～２０のアルケニル基、または炭素数２～２０のアルキニル基を表す。Ｙは、炭素数１～２０のアルキレン基を表す。）

(wherein R ³ represents an alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms; R ⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, a benzyl group; , represents an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms.Y represents an alkylene group having 1 to 20 carbon atoms.)

Examples of the phosphorus compound represented by the chemical formula (I-1) include phosphorus compounds represented by the chemical formulas (I-1-1) to (I-1-12).
Further, examples of the phosphorus compound represented by the chemical formula (I-2) include phosphorus compounds represented by the chemical formulas (I-2-1) to (I-2-3).

Examples of the alkyl group having 1 to 20 carbon atoms represented by R ¹ and R ⁴ include chain or branched alkyl groups having 1 to 20 carbon atoms, and specifically, methyl group, ethyl group, n -propyl group, isopropyl group, n-butyl group, t-butyl group, n-pentyl group, n-hexyl group, heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group , pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, icosyl group and the like.

Aryl groups represented by R ¹ and R ⁴ include phenyl, 2-tolyl, 3-tolyl, 4-tolyl, 2,3-xylyl, 2,4-xylyl, 2,5- xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,4,6-trimethylphenyl group, 2,3,5-trimethylphenyl group, 2,3,6- trimethylphenyl group, 2,4,5-trimethylphenyl group, 2,3,5,6-tetramethylphenyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group and the like.

R ¹ and R ^{2 may} be linked to form ^a ring as described above. Examples of R ¹ and R ² linked to form a ring include phosphorus compounds represented by the chemical formula (I-2).

Examples of the alkenyl group having 2 to 20 carbon atoms represented by R ³ and R ⁴ include chain or branched alkenyl groups having 2 to 20 carbon atoms, specifically vinyl group, allyl group, iso propenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group , hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, icosenyl group and the like.

The alkynyl group having 2 to 20 carbon atoms represented by R ³ and R ⁴ includes a chain or branched alkynyl group having 2 to 20 carbon atoms, and specifically, an ethynyl group and a 1-propynyl group. , 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, pentynyl group, hexynyl group, heptynyl group, octynyl group, nonynyl group, decynyl group, undecynyl group, dodecynyl group, tridecynyl group, tetradecynyl group , pentadecynyl group, hexadecynyl group, heptadecynyl group, octadecynyl group, nonadecynyl group, icosinyl group and the like.

Examples of the alkylene group having 1 to 20 carbon atoms represented by Y include linear or branched alkylene groups having 1 to 20 carbon atoms, specifically, methylene group, methylmethylene group, dimethylene group, trimethylene group, ethylmethylene group, dimethylmethylene group, tetramethylene group, pentamethylene group, hexamethylene group, heptamethylene group, octamethylene group, nonamethylene group, decamethylene group, undecamethylene group, dodecamethylene group and the like.

Preferred substituents in the phosphorus compound represented by the chemical formula (I-1) are as follows.
R ¹ is preferably an alkyl group having 1 to 5 carbon atoms, a phenyl group, a 2,6-xylyl group, a biphenyl group, a 1-naphthyl group, a 2-naphthyl group and a benzyl group.
R ³ and R ⁴ are the same as each other, and are preferably an alkenyl group having 2 to 4 carbon atoms or an alkynyl group having 2 to 4 carbon atoms.
Y is preferably a methylene group.

Preferred substituents in the phosphorus compound represented by the chemical formula (I-2) are as follows.
R ³ and R ⁴ are the same as each other, and are preferably an alkenyl group having 2 to 4 carbon atoms or an alkynyl group having 2 to 4 carbon atoms.
Y is preferably a methylene group.

(2. Method for Synthesizing the Phosphorus Compound of the Present Invention)
The phosphorus compound of the present invention can be synthesized by reacting a phosphorus compound represented by the chemical formula (II) with an isocyanurate compound represented by the chemical formula (III).

The phosphorus compound represented by the chemical formula (II) includes the phosphorus compound represented by the chemical formula (II-1) and the phosphorus compound represented by the chemical formula (II-2).

（式中、Ｒ^１およびＹは、前記と同様である。Ｘは、同一または異なって、フッ素原子、塩素原子、臭素原子、ヨウ素原子、メシルオキシ基（ＯＭｓ）、トシルオキシ基（ＯＴｓ）またはトリフルオロメタンスルホニルオキシ基（ＯＴｆ）を表す。）

(In the formula, R ¹ and Y are the same as defined above. X is the same or different, fluorine atom, chlorine atom, bromine atom, iodine atom, mesyloxy group (OMs), tosyloxy group (OTs) or trifluoromethane represents a sulfonyloxy group (OTf).)

（式中、ＸおよびＹは、前記と同様である。）

(Wherein, X and Y are the same as defined above.)

^In the chemical formula (II), R ¹ and R ⁸ may be linked to form ^a ring as described above. Examples of R ¹ and R ⁸ linked to form a ring include phosphorus compounds represented by the chemical formula (II-2).

Phosphorus compounds represented by chemical formula (II-1) include, for example, phosphorus compounds represented by chemical formulas (II-1-1) to (II-1-10).
Further, examples of the phosphorus compound represented by the chemical formula (II-2) include phosphorus compounds represented by the chemical formulas (II-2-1) to (II-2-4).

These phosphorus compounds can be used by purchasing commercially available reagents, for example, Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry, 44B(6), 1248-1251(2005), RSC Advances, 6( 57), 52485-52394 (2016), Youji Huaxue, 13(5), 527-532(1993), Agricultural and Biological Chemistry, 46(2), 411-418(1982), etc. Can be synthesized.

Examples of isocyanurate compounds represented by chemical formula (III) include isocyanurate compounds represented by chemical formulas (III-1) to (III-3).

These isocyanurate compounds can be used by purchasing commercially available reagents, or can be synthesized, for example, according to the method described in JP-A-2016-216399.

Reaction scheme (A) shows an example of synthesizing a phosphorus compound represented by the chemical formula (I-1) by reacting a phosphorus compound represented by the chemical formula (II-1) with an isocyanurate compound represented by the chemical formula (III). shown in
An example of synthesizing the phosphorus compound represented by the chemical formula (I-2) by reacting the phosphorus compound represented by the chemical formula (II-2) with the isocyanurate compound represented by the chemical formula (III) is shown in the reaction scheme ( B).

（式中、Ｒ^１、Ｒ^３、Ｒ^４、ＹおよびＸは、前記と同様である。）

(Wherein, R ¹ , R ³ , R ⁴ , Y and X are the same as defined above.)

（式中、Ｒ^３、Ｒ^４、ＹおよびＸは、前記と同様である。）

(Wherein, R ³ , R ⁴ , Y and X are the same as defined above.)

In the reaction scheme (A), the amount (charged amount) of the isocyanurate compound represented by the chemical formula (III) is 2 to 2 to the amount (charged amount) of the phosphorus compound represented by the chemical formula (II-1) An appropriate ratio within the range of 4-fold molar is preferable.
In the reaction scheme (B), the amount (charged amount) of the isocyanurate compound represented by the chemical formula (III) is 1 to An appropriate ratio within the range of 2-fold molar is preferable.

In the reaction schemes (A) and (B), it is preferable to use a base (a) for removing the acid by-produced as the reaction progresses. Moreover, if necessary, a reaction catalyst (b) and a reaction solvent (c) may be used as appropriate.

Examples of the base (a) include trimethylamine, triethylamine, N,N-diisopropylethylamine, diazabicyclononene, diazabicycloundecene, pyridine, imidazole, sodium hydride, potassium hydride, lithium hydroxide, sodium hydroxide. , potassium hydroxide, cesium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, lithium hydrogen carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, cesium hydrogen carbonate, trilithium phosphate, trisodium phosphate, triphosphate Potassium, tricesium phosphate, dilithium hydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dicesium hydrogen phosphate, lithium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, phosphorus cesium dihydrogenate, lithium acetate, sodium acetate, potassium acetate, cesium acetate, sodium alkoxide, potassium alkoxide, potassium t-butoxy, and the like. These may be used alone or in combination of two or more.

In the reaction scheme (A), the amount (amount charged) of the base (a) is 2 to 5 times the amount (amount charged) of the phosphorus compound represented by the chemical formula (II-1). An appropriate ratio is preferable.
In the reaction scheme (B), the amount (amount charged) of the base (a) used is 1 to 2.5 times the molar amount (amount charged) of the phosphorus compound represented by the chemical formula (II-2). An appropriate ratio within the range is preferable.

Examples of the reaction catalyst (b) include alkali metal iodide salts such as lithium iodide, sodium iodide and potassium iodide. These may be used alone or in combination of two or more.

In the reaction scheme (A), the amount (charged amount) of the reaction catalyst (b) used is 0.01 to 0.3 with respect to the used amount (charged amount) of the phosphorus compound represented by the chemical formula (II-1). It is preferable to use an appropriate ratio within the range of double moles.
In the reaction scheme (B), the amount (charged amount) of the reaction catalyst (b) used is 0.01 to 0.3 with respect to the used amount (charged amount) of the phosphorus compound represented by the chemical formula (II-2). It is preferable to use an appropriate ratio within the range of double moles.

The reaction solvent (c) is not particularly limited as long as it does not inhibit the reaction.
Solvents such as tetrahydrofuran, dioxane, ethyl acetate, acetonitrile, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, dimethylformamide, dimethylacetamide, dimethylsulfoxide, hexamethylphosphoric acid triamide, water, etc., and if necessary, Suitable amounts thereof can be used in combination.

In reaction schemes (A) and (B), the reaction temperature is preferably set in the range of 50 to 140°C. The reaction time is appropriately set according to the set reaction temperature, but is preferably set within the range of 1 to 30 hours.

After completion of the reaction, the target phosphorus compound of the present invention can be isolated from the obtained reaction solution (reaction mixture) by means of, for example, concentration of the reaction solution by distilling off the reaction solvent, solvent extraction, or the like. .
Furthermore, if necessary, purification can be carried out using means such as washing with water, etc., treatment with activated carbon, silica gel chromatography, recrystallization, and the like.

(3. Flame retardant and resin composition)
The flame retardant and resin composition of the invention contain the phosphorus compound of the invention. Since the phosphorus compound of the present invention has a high flame retardant effect, it can be suitably used as a flame retardant for resins. By containing the phosphorus compound of the present invention in the resin composition, the cured product (molded product) of the resin composition exhibits excellent flame retardancy.
In addition to the phosphorus compound and the resin component of the present invention, the resin composition of the present invention contains other flame retardants, polymerizable components, polymerization initiators, reactive diluents, fluororesins, inorganic fillers, It may contain additives. Moreover, in the present invention, the resin composition means the state of the mixture before curing.

[Resin component]
The resin component (including pre-cured and semi-cured resins) used in the resin composition of the present invention is not particularly limited as long as it is commonly used as a material for resin moldings.
Examples of resin components include polybutadiene resins, polystyrene resins, impact-resistant polystyrene resins, polyimide resins, benzoxazine resins, and liquid crystal polymer resins. These may be used alone or in combination of two or more.

The amount of the phosphorus compound of the present invention in the resin composition of the present invention is not particularly limited, and is 0.1 to 200 parts by weight, preferably 0.5 to 100 parts by weight, and more than 100 parts by weight of the resin component. Preferably, it is 1 to 80 parts by weight.

[Other flame retardants]
The resin composition of the present invention may be used in combination with a flame retardant other than the phosphorus compound of the present invention (another flame retardant).
Other flame retardants include, for example, phosphate ester compounds, phosphazene compounds, phosphite ester compounds, phosphine compounds, phosphoramide compounds, phosphoramide ester compounds, melam, melam polyphosphate, melem, melem polyphosphate, melamine , melamine cyanurate, phosphonate, phosphinate, phosphine oxide and the like.
These may be used alone or in combination of two or more.

The amount of the other flame retardant compounded in the resin composition of the present invention is not particularly limited, and is 0 to 200 parts by weight, preferably 0.5 to 100 parts by weight, more preferably 0.5 to 100 parts by weight, with respect to 100 parts by weight of the resin component. 1 to 50 parts by weight.

[Polymerizable component]
The resin composition of the present invention may contain a polymerizable component (polymerizable monomer and/or oligomer). Examples of the polymerizable component include vinyl compounds, vinylidene compounds, diene compounds, acrylic compounds, cyclic compounds (epoxy compounds, lactone compounds, lactam compounds, cyclic ether compounds, etc.).
These polymerizable components include, for example, butadiene, isoprene, and styrene. These may be used alone or in combination of two or more.

The amount of the polymerizable component in the resin composition of the present invention is not particularly limited. ~50 parts by weight.

[Polymerization initiator]
The resin composition of the present invention may contain a polymerization initiator. The polymerization initiator can be appropriately selected depending on the method of polymerizing the resin composition of the present invention. Examples of polymerization initiators include thermal polymerization initiators, photopolymerization initiators, radical polymerization initiators, and the like.

Examples of radical polymerization initiators include di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butyl peroxide)hexane, 2,5-dimethyl-2,5-di(t -butylperoxide)hexyne-3, α,α'-di(t-butylperoxy)diisopropylbenzene, t-butylperoxybenzoate and other peroxides. These may be used alone or in combination of two or more.

The amount of the polymerization initiator compounded in the resin composition of the present invention is not particularly limited, and is 0 to 10 parts by weight, preferably 0.05 to 5 parts by weight, more preferably 0 parts by weight with respect to 100 parts by weight of the resin component. .1 to 3 parts by weight.

[Reactive diluent]
The resin composition of the present invention may optionally contain a reactive diluent.

The amount of the reactive diluent compounded in the resin composition of the present invention is not particularly limited, and is 0 to 100 parts by weight, preferably 0.1 to 50 parts by weight, more preferably 0.1 to 50 parts by weight, with respect to 100 parts by weight of the resin component. 0.1 to 20 parts by weight.

[Fluororesin]
The resin composition of the present invention may contain a fluororesin for the purpose of improving the flame retardancy (especially anti-dripping performance) of the cured product (formed body).

The blending amount of the fluororesin in the resin composition of the present invention is not particularly limited, and is 0 to 20 parts by weight, preferably 0.1 to 10 parts by weight, per 100 parts by weight of the resin component.

[Inorganic filler]
The resin composition of the present invention may contain an inorganic filler for the purpose of improving flame retardancy (especially anti-dripping performance) and mechanical strength of the cured product (formed product).
Examples of inorganic fillers include silica, alumina, and boron nitride. These may be used alone or in combination of two or more.
For the purpose of suppressing deterioration of the resin component, a silane coupling agent may be used to coat the surface of the inorganic filler.

The blending amount of the inorganic filler in the resin composition of the present invention is not particularly limited. The amount of the inorganic filler to be blended is 0 to 200 parts by weight, preferably 5 to 100 parts by weight, based on 100 parts by weight of the resin component from the viewpoint of the balance between improvement in flame retardancy and improvement in mechanical properties.

[Additive]
The resin composition of the present invention may contain various additives in accordance with its use, the type of resin component, etc., as long as the desired physical properties are not impaired.
Examples of additives include silane coupling agents, antioxidants (hindered phenol compounds, styrenated phenol compounds, organic phosphorus peroxide decomposers, organic sulfur peroxide decomposers, etc.), light stabilizers ( hindered amine compounds, etc.), curing agents, curing accelerators, cross-linking agents, diluents, fluidity modifiers, polymerization inhibitors, plasticizers, thixotropic agents, thickeners, compatibilizers, adhesives, adhesives, adhesives A property-imparting agent, various stabilizers, and the like can be mentioned. These may be used alone or in combination of two or more.

The amount of the additive compounded in the resin composition of the present invention is not particularly limited, and is 0 to 50 parts by weight, preferably 1 to 20 parts by weight, per 100 parts by weight of the resin component.

The resin composition of the present invention contains the flame retardant of the present invention and optionally other flame retardants, polymerizable components, polymerization initiators, reactive diluents, fluororesins, inorganic fillers and additives in the resin component. It can be produced by mixing and/or kneading by known methods.

(4. Thermal radical curable resin composition)
The resin composition of the present invention (hereinafter referred to as "the heat radically curable resin composition of the present invention") contains the phosphorus compound of the present invention and a heat radically curable resin component. Further, the thermoradical-curable resin composition of the present invention contains, in addition to the phosphorus compound and the thermoradical-curable resin component of the present invention, other resin components, other flame retardants, cross-linking agents, compatibilizers, It may contain radical polymerization initiators, inorganic fillers, stress relaxation agents, organic solvents, and additives. Moreover, in the present invention, the resin composition means the state of the mixture before curing.

[Thermal radical curable resin component]
The thermoradical-curable resin component (including uncured and semi-cured resins) used in the thermoradical-curable resin composition of the present invention includes, for example, polyphenylene ether resins, bismaleimide resins, bismaleimide-triazine resins, poly Functional styrene compounds, benzocyclobutene resins, polytetrafluoroethylene resins, acrylic resins and the like are included.

Examples of polyphenylene ether resins include compounds having a structure represented by formula (2).

（式中、Ｒ^ａは、同一または異なって、水素原子、炭素数１～６のアルキル基または炭素数２～６のアルケニル基を表す。ｎは、繰り返し単位の数を表し、通常、１以上の整数を表す。）

(In the formula, R ^a is the same or different and represents a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 6 carbon atoms. n represents the number of repeating units, usually 1 or more. represents an integer of

The alkyl group having 1 to 6 carbon atoms represented by R ^a includes a chain or branched alkyl group having 1 to 6 carbon atoms, and specifically, a methyl group, an ethyl group, and an n-propyl group. , isopropyl group, n-butyl group, t-butyl group, n-pentyl group, n-hexyl group and the like, of which methyl group is preferred.
Examples of the alkenyl group having 2 to 6 carbon atoms represented by R ^a include chain or branched alkenyl groups having 2 to 6 carbon atoms, and specific examples include vinyl group, allyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, pentenyl group, hexenyl group and the like.
R ^a is the same or different and is preferably a hydrogen atom or a methyl group.
n is preferably 1-400.

As one aspect of the compound having the structure represented by formula (2), for example, a compound having a structure represented by formula (2-1), a compound having a structure represented by formula (2-2), a compound having a structure represented by formula (2- A compound having a structure represented by 3) and the like can be mentioned.

（式中、ｎは、前記と同様である。）

(In the formula, n is the same as described above.)

（式中、ｎは、前記と同様である。）

(In the formula, n is the same as described above.)

（式中、ｎは、前記と同様である。）

(In the formula, n is the same as described above.)

The compound having the structure represented by formula (2) preferably has two or more structures represented by formula (2) in the molecule. Further, this compound preferably has a crosslinkable group (eg, a group having a carbon-carbon double bond such as (meth)acrylic group, allyl group, vinylbenzyl group, etc.). The crosslinkable groups are preferably present at the ends of the molecule of this compound.

A preferred embodiment of the compound having the structure represented by formula (2) is, for example, the compound represented by chemical formula (IV).

（式中、Ｘ^ａは、同一または異なって、水素原子または式（３）で示される基を表す。Ｙ^ａは、－Ｏ－または式（４）で示される基を表す。Ｒ^ａは、前記と同様である。ｎは、同一または異なって、前記と同様である。）

(Wherein, X ^a is the same or different and represents a hydrogen atom or a group represented by formula (3). Y ^a represents —O— or a group represented by formula (4). R ^a is It is the same as above, and n is the same or different and is the same as above.)

（式中、Ｒ^ｂ、Ｒ^ｃおよびＲ^ｄは、同一または異なって、水素原子または炭素数１～３のアルキル基を表す。Ｚは、同一または異なって、炭素数１～１０のアルキレン基、－Ｃ（＝Ｏ）－、－Ｐｈ－、－Ｐｈ－ＣＨ_２－または－Ｐｈ－ＣＨ_２ＣＨ_２－を表す。）

(wherein R ^b , R ^c and R ^d are the same or different and represent a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; Z is the same or different and an alkylene group having 1 to 10 carbon atoms; represents -C(=O)-, -Ph-, -Ph-CH ₂ - or -Ph-CH ₂ CH ₂ -.)

（式中、Ｒ^ｅは、同一または異なって、水素原子、炭素数１～６のアルキル基、炭素数２～６のアルケニル基、またはアリール基を表す。Ｗは、フェニル基で置換されていてもよい炭素数１～６のアルキレン基、シクロアルキレン基、ハロゲン原子で置換されていてもよい炭素数２～６のアルケンジイル基、－Ｃ（＝Ｏ）－、－Ｓ（Ｏ）_ｍ－（ｍは、０、１または２を表す。）、または－（アルキレン）－（フェニレン）－（アルキレン）－を表す。）

(wherein R ^e are the same or different and represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, or an aryl group; W is substituted with a phenyl group; an alkylene group having 1 to 6 carbon atoms, a cycloalkylene group, an alkenediyl group having 2 to 6 carbon atoms which may be substituted with a halogen atom, -C(=O)-, -S(O) _m -(m represents 0, 1 or 2.), or represents -(alkylene)-(phenylene)-(alkylene)-.)

Examples of alkyl groups having 1 to 3 carbon atoms represented by R ^b , R ^c and R ^d include methyl group, ethyl group, n-propyl group and isopropyl group. R ^b and R ^c are preferably hydrogen atoms, and R ^d is preferably a hydrogen atom or a methyl group.

The alkylene group having 1 to 10 carbon atoms represented by Z includes methylene group, methylmethylene group, dimethylene group, trimethylene group, ethylmethylene group, dimethylmethylene group, tetramethylene group, pentamethylene group, hexamethylene group, hepta methylene group, octamethylene group, nonamethylene group, decamethylene group and the like.
Z is preferably -C(=O)-, -Ph-, -Ph-CH ₂ - or -Ph-CH ₂ CH ₂ -.

Examples of the alkyl group having 1 to 6 carbon atoms represented by R ^e include chain or branched alkyl groups having 1 to 6 carbon atoms, and specifically, methyl group, ethyl group and n-propyl group. , isopropyl group, n-butyl group, t-butyl group, n-pentyl group, n-hexyl group and the like.
Examples of the alkenyl group having 2 to 6 carbon atoms represented by R ^e include linear or branched alkenyl groups having 2 to 6 carbon atoms, and specifically, vinyl group, allyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, pentenyl group, hexenyl group and the like.
Examples of the aryl group represented by R ^e include phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group and the like.
R ^e is preferably a hydrogen atom or a methyl group.

The alkylene group having 1 to 6 carbon atoms which may be substituted with a phenyl group represented by W includes, for example, a methylene group, a methylmethylene group, a dimethylmethylene group, a phenylmethylene group, a phenylmethylmethylene group and a diphenylmethylene group. etc.
Examples of the cycloalkylene group represented by W include cyclohexane-1,1-diyl group and the like.
Examples of the alkenediyl group having 2 to 6 carbon atoms which may be substituted with a halogen atom represented by W include ethylene-1,1-diyl and 2,2-dichloroethylene-1,1-diyl. .
-(Alkylene)-(phenylene)-(alkylene)- represented by W includes, for example, -(alkylene having 1 to 3 carbon atoms)-(phenylene)-(alkylene having 1 to 3 carbon atoms)- and the like. mentioned. The alkylene having 1 to 3 carbon atoms includes methylene group, methylmethylene group, dimethylene group, trimethylene group, ethylmethylene group, dimethylmethylene group and the like, preferably dimethylmethylene group. The phenylene group includes 1,2-phenylene group, 1,3-phenylene group and 1,4-phenylene group, preferably 1,4-phenylene group.
W is preferably an alkylene group having 1 to 6 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms (especially a dimethylmethylene group).

Y ^a is preferably a group represented by formula (4) (wherein R ^e represents a hydrogen atom or a methyl group, and W represents an alkylene group having 1 to 3 carbon atoms).

Among the compounds represented by the chemical formula (IV), preferred examples include the compound represented by the chemical formula (IV-1), the compound represented by the chemical formula (IV-2), the compound represented by the chemical formula (IV-3), and the like. mentioned.

（式中、Ｒ^ａ、Ｒ^ｄ、Ｗおよびｎは、前記と同様である。）

(Wherein, R ^a , R ^d , W and n are the same as defined above.)

（式中、Ｒ^ａ、Ｒ^ｂ、Ｒ^ｃ、Ｒ^ｄ、Ｗおよびｎは、前記と同様である。）

(Wherein, R ^a , R ^b , R ^c , R ^d , W and n are the same as defined above.)

（式中、ｎは、前記と同様である。）

(In the formula, n is the same as described above.)

These polyphenylene ether resins can be synthesized according to or according to known methods, for example, US Pat. No. 4,059,568, The Journal of Organic Chemistry, 34, 297-303 (1969).

The weight average molecular weight (Mw) of the polyphenylene ether resin is usually 1,000 to 120,000, preferably 1,000 to 50,000, and more preferably 1,000 to 20,000. A weight average molecular weight can be measured using a gel permeation chromatography (GPC) by styrene conversion.

A bismaleimide resin is a compound having two maleimide groups in the molecule, and means a bismaleimide compound before curing. Examples of bismaleimide resins include aliphatic bismaleimide compounds and aromatic bismaleimide compounds. These may be used alone or in combination of two or more.

Polyfunctional styrene compounds include, for example, bisvinylphenylmethane, 1,2-bis(m-vinylphenyl)ethane, 1,2-bis(p-vinylphenyl)ethane, 1-(p-vinylphenyl)-2 -(m-vinylphenyl)ethane, 1,3-bis(m-vinylphenylethyl)benzene, 1,3-bis(p-vinylphenylethyl)benzene, 1-(p-vinylphenylethyl)-3-( m-vinylphenylethyl)benzene, 1,4-bis(m-vinylphenylethyl)benzene, 1,4-bis(p-vinylphenylethyl)benzene, 1,6-bis(vinylphenyl)hexane and side chains Examples include divinylbenzene polymers (oligomers) having vinyl groups.

The benzocyclobutene resin is not particularly limited as long as two or more benzocyclobutene groups are bonded directly or via an organic group.

In the thermoradical-curable resin composition of the present invention, the above-mentioned thermoradical-curable resin components may be used alone, or two or more of them may be used in combination.

[Other resin components]
In the thermoradical-curable resin composition of the present invention, in addition to the thermoradical-curable resin component, if necessary, resin components other than the thermoradical-curable resin component (other resin components) may be used in combination. Other resin components include, for example, the resin components described above (the resin components described in the section 3. Flame retardant and resin composition), styrene block copolymers, and the like.
Examples of styrene block copolymers include styrene-butadiene block copolymers, styrene-isoprene block copolymers, styrene-ethylene/butylene-styrene block copolymers (SEBS), styrene-(ethylene-ethylene/propylene )-styrene block copolymer (SEEPS), styrene-ethylene/propylene-styrene block copolymer (SEPS), and the like. These may be used alone or in combination of two or more.

The amount of the other resin components in the thermoradical-curable resin composition of the present invention is not particularly limited, and is 0 to 1000 parts by weight, preferably 50 to 800 parts by weight, based on 100 parts by weight of the thermoradical-curable resin component. parts, more preferably 100 to 700 parts by weight.

[Flame retardants]
In addition to the phosphorus compound of the present invention as a flame retardant, the heat radical curable resin composition of the present invention may optionally contain a flame retardant other than the phosphorus compound of the present invention (e.g., the above (3. Flame retardant and resin composition). ) may be used in combination with the flame retardants described in the section [Other flame retardants].

The amount of the phosphorus compound of the present invention to be incorporated in the thermoradical-curable resin composition of the present invention is not particularly limited. 1 to 200 parts by weight, preferably 1 to 160 parts by weight, more preferably 2 to 100 parts by weight.
In addition, the amount of other flame retardants in the thermoradical-curable resin composition of the present invention is not particularly limited, and is , 0 to 100 parts by weight, preferably 1 to 80 parts by weight, more preferably 1 to 40 parts by weight.

[Crosslinking agent]
The thermoradical-curable resin composition of the present invention may contain a cross-linking agent as long as the effects of the resin composition can be exhibited.
Examples of cross-linking agents include mono(alkyl having 6 to 20 carbon atoms) diallyl isocyanurate, 1-benzyl-3,5-diallyl isocyanurate, 1-(4-vinylbenzyl)-3,5-diallyl isocyanurate, and the like. Monobenzyl diallyl isocyanurate, triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, triallyl trimellitate, polyfunctional styrene compounds (e.g., the above (4. Thermal radical curable resin polyfunctional styrene compounds described in the section [Thermoradially curable resin component] of Composition)) and the like. These may be used alone or in combination of two or more.

The amount of the cross-linking agent in the thermoradical-curable resin composition of the present invention is not particularly limited, and is 0 to 200 parts per 100 parts by mass of the resin component (total of the thermoradical-curable resin component and other resin components). parts by weight, preferably 5 to 150 parts by weight, more preferably 10 to 100 parts by weight.

The thermoradical curable resin composition of the present invention may optionally contain other components such as a compatibilizer, a radical polymerization initiator (e.g., the [radical polymerization Initiator] section), inorganic filler (e.g., the inorganic filler described in the section [Inorganic filler] of (3. Flame retardant and resin composition) above), stress relaxation agents, organic solvents, additives (for example, the additives described in the section [Additives] in (3. Flame retardant and resin composition) described above) and the like.

[Compatibilizer]
Examples of compatibilizers include 1,2-polybutadiene, 1,4-polybutadiene, malein-modified polybutadiene, acrylic-modified polybutadiene, and epoxy-modified polybutadiene. These may be used alone or in combination of two or more.

The content of the compatibilizer in the thermoradical-curable resin composition of the present invention is not particularly limited, and is 0 to 0 per 100 parts by mass of the resin component (total of the thermoradical-curable resin component and other resin components). 100 parts by weight, preferably 20 to 50 parts by weight.

[Radical polymerization initiator]
The amount of the radical polymerization initiator to be blended in the thermoradical-curable resin composition of the present invention is not particularly limited. 0.001 to 10 parts by weight, preferably 0.005 to 5 parts by weight, more preferably 0.01 to 3 parts by weight.

[Inorganic filler]
The amount of the inorganic filler compounded in the thermoradical-curable resin composition of the present invention is not particularly limited, and is 0 to 0 per 100 parts by weight of the resin component (total of the thermoradical-curable resin component and other resin components). 500 parts by weight, preferably 1 to 200 parts by weight, more preferably 5 to 100 parts by weight.

[Organic solvent]
The organic solvent is not particularly limited as long as it can dissolve or disperse the thermoradical curable resin component. Examples include ketone solvents such as methyl ethyl ketone (MEK); aromatic hydrocarbon solvents such as benzene, toluene and xylene. mentioned. These may be used alone or in combination of two or more.

The amount of the organic solvent in the thermoradical-curable resin composition of the present invention may be adjusted according to the operation of applying or impregnating/coating the resin varnish onto the base material. 30 to 1,000 parts by weight, preferably 100 to 500 parts by weight, per 100 parts by weight of the total resin components.

[Additive]
The amount of the additive compounded in the thermoradical-curable resin composition of the present invention is not particularly limited, and is 0 to 50 parts per 100 parts by weight of the resin component (total of the thermoradical-curable resin component and other resin components). parts by weight, preferably 1 to 20 parts by weight.

The thermoradical-curable resin composition of the present invention comprises a thermoradical-curable resin component, the flame retardant of the present invention, and optionally other resin components, other flame retardants, cross-linking agents, compatibilizers, and radical polymerization. It can be produced by mixing and/or kneading an initiator, an inorganic filler, a stress relaxation agent, an organic solvent and additives by a known method.

(5. Applications of the resin composition of the present invention)
The resin composition described above in (3. Flame retardant and resin composition) and the thermally radically curable resin composition described in (4. Thermally radically curable resin composition) (hereinafter, both are collectively referred to as " The resin composition of the present invention") can be suitably used for applications such as prepregs, resin-coated metal foils, thermosetting resin films, metal-clad laminates, printed wiring boards, resin boards, semiconductor devices, and adhesives. .

EXAMPLES The present invention will be described in more detail below with reference to examples (synthesis test, evaluation test) and comparative examples (evaluation tests), but the present invention is not limited thereto. "Parts" used herein means "parts by weight" unless otherwise specified.
The main raw materials used in the reference examples and synthesis tests are as follows.

[Main raw material]
2-phenoxy-5,5-bis(bromomethyl)-1,3,2-dioxaphosphorinane 2-oxide (Indian Journal of Chemistry, Section B: Organic Chemistry Including Medicinal Chemistry, 44B(6), 1248-1251 (2005), see chemical formula (II-1-1).)
・ Diallyl isocyanurate (manufactured by Shikoku Chemical Industry, see chemical formula (III-1).)
・N,N-dimethylformamide (manufactured by Fuji Film Wako Pure Chemical Industries)
・ Potassium carbonate (manufactured by Fujifilm Wako Pure Chemical Industries)
・Potassium iodide (manufactured by Fuji Film Wako Pure Chemical Industries)
・Isopropyl alcohol (manufactured by Fujifilm Wako Pure Chemical Industries)
・4-(methanesulfonyloxy)methyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane 1-oxide (RSC Advances, 6(57), 52485-52494(2016) Synthesized according to the described method.See chemical formula (II-2-1).)
・Sodium carbonate (manufactured by Fujifilm Wako Pure Chemical Industries)
・Sodium iodide (manufactured by Fujifilm Wako Pure Chemical Industries)

The main raw materials (excluding the phosphorus compound of the present invention) used in the evaluation test are as follows.
[Main raw material]
(A) Flame retardant 1,3-phenylene bis(di-2,6-xylenyl phosphate) (manufactured by Daihachi Chemical Industry, trade name "PX-200", see chemical formula (V).)

(B) Radical thermosetting resin component Methacryl-modified polyphenylene ether (manufactured by SABIC, polyphenylene ether resin, trade name “SA9000-111”, molecular weight: 2300)
(C) Other resin components Styrene-butadiene block copolymer (manufactured by Asahi Kasei Co., Ltd., styrene-based block copolymer, trade name “Tufprene A”, styrene/butadiene weight ratio = 40/60)
(D) Cross-linking agent 1-dodecyl-3,5-diallyl isocyanurate (manufactured by Shikoku Kasei Kogyo Co., Ltd.)
(E) Radical polymerization initiator α,α′-di(t-butylperoxy)diisopropylbenzene (manufactured by NOF, trade name “PERBUTYL P”)
(F) Inorganic filler/silica (manufactured by Admatechs, trade name “Admafine SC2300-SVJ”)
(G) Organic solvent, toluene (manufactured by Fuji Film Wako Pure Chemical Industries)

The methods of evaluation tests (evaluation of flame retardancy, measurement of Tg and CTE, evaluation of adhesion) employed in Examples and Comparative Examples are as follows.

[Evaluation of flame retardancy]
The resin composition was applied onto a polyimide film having a thickness of 25 μm using a bar coater so that the coating film after drying had a thickness of 50±5 μm, and toluene was distilled off until the weight became constant. Then, a film for evaluation was produced by performing heat treatment under the conditions of 150° C. for 30 minutes and 200° C. for 1 hour. The flame retardancy of this film for evaluation was evaluated according to the UL94 VTM test method of the vertical burning test of the US UL standard.

[Measurement of Tg and CTE]
The resin composition was poured into an aluminum cup having a radius of 3.5 cm to which a release agent was applied so that the thickness after curing was 1.5 mm, and toluene was distilled off until the weight became constant. Then, a cured product for evaluation was produced by performing heat treatment under the conditions of 150° C. for 30 minutes and 200° C. for 1 hour. The cured product for evaluation was measured for glass transition temperature (Tg) and linear expansion coefficient (CTE) using a thermomechanical analyzer (TMA, manufactured by Hitachi High-Tech Science, "TMA7100") (flow gas: nitrogen, rising Temperature condition: 5°C/min.).

[Evaluation of adhesion]
The resin composition was applied onto a 10×10 cm polyimide film (thickness: 40 μm, manufactured by Toray DuPont, “Kapton LK”) so that the thickness after drying would be 15 μm, and toluene was distilled off until the weight became constant. . Next, a glass epoxy base material (FR-4 grade) is layered on the coated surface of the resin composition, and the test is performed by pressing at 150° C. for 30 minutes, 200° C. for 1 hour, and a heating and pressure condition of 0.5 MPa. A piece was made. The normal peel strength of this test piece was measured according to "JIS C6481".

[Example 1]
<2-phenoxy-5,5-bis[(tetrahydro-2,4,6-trioxo-3,5-di-2-propen-1-yl-1,3,5-triazin-1(2H)-yl ) Synthesis of methyl]-1,3,2-dioxaphosphorinane 2-oxide>
40.00 g (100.00 mmol) of 2-phenoxy-5,5-bis(bromomethyl)-1,3,2-dioxaphosphorinane 2-oxide, 46.02 g of diallyl isocyanurate (220 .00 mmol), 34.55 g (250.00 mmol) of potassium carbonate, 1.66 g (10.00 mmol) of potassium iodide, and 200.00 g of dimethylformamide were charged, heated to 100° C. with stirring, and stirred for 36 hours. .
Subsequently, toluene was added to this reaction solution, the solution was washed with water, and the organic layer was concentrated. The obtained concentrate was recrystallized with isopropyl alcohol to obtain 41.50 g of white powder (yield 63.2%).

¹ H-NMR spectrum data of this white powder was as follows.
・¹ H-NMR (d ₆ -DMSO) δ: 7.42(t, 2H), 7.24(t, 1H), 7.21(d, 2H), 5.76-5.85(m, 4H), 5.11-5.27(m, 8H ), 4.86(s, 2H), 4.35-4.48(m, 12H), 4.26(s, 2H).
Moreover, the IR spectrum data of this white powder was as shown in the chart shown in FIG.
From these spectral data, the obtained white powder was identified as the title phosphorus compound represented by the chemical formula (I-1-1).

[Example 2]
<4-(tetrahydro-2,4,6-trioxo-3,5-di-2-propen-1-yl-1,3,5-triazin-1(2H)-yl)methyl-2,6,7 -Synthesis of trioxa-1-phosphabicyclo[2.2.2]octane 1-oxide>
4-(methanesulfonyloxy)methyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane 1-oxide 41.31 g (160.00 mmol), diallyl 35.15 g (168.00 mmol) of isocyanurate, 25.43 g (240.00 mmol) of sodium carbonate, 2.40 g (16.00 mmol) of sodium iodide, and 188.80 g of N,N-dimethylformamide were charged and stirred. The temperature was raised to 100° C. and stirred for 14 hours. After cooling to 30°C, 400 g of water was added, the precipitated solid was filtered off, the solid was washed with a saturated aqueous solution of sodium bicarbonate, water and methanol in that order, and dried under reduced pressure to obtain 45.00 g of white powder. obtained (yield 75.80%).

¹ H-NMR spectrum data of this white powder was as follows.
・¹ H-NMR (d ₆ -DMSO) δ: 5.77-5.86(m, 2H), 5.13-5.29(m, 4H), 4.67(d, 6H), 4.33-4.35(m, 4H), 3.73(s , 2H).
Also, the IR spectrum data of this white powder was as shown in the chart shown in FIG.
From these spectral data, the obtained white powder was identified as the title phosphorus compound represented by the chemical formula (I-2-1).

[Example 3]
107.5 parts by weight of the phosphorus compound synthesized in Example 1 as a flame retardant, 22.4 parts by weight of methacrylic-modified polyphenylene ether as a thermoradical-curable resin component, and a styrene/butadiene block copolymer as other resin components. 138.8 parts by weight, 20.0 parts by weight of 1-dodecyl-3,5-diallyl isocyanurate as a cross-linking agent, and α,α'-di(t-butylperoxy)diisopropylbenzene as a radical polymerization initiator. 1.2 parts by weight, 134.4 parts by weight of silica as an inorganic filler, and 314.8 parts by weight of toluene as an organic solvent were mixed to prepare a thermal radical curable resin composition.
An evaluation test was conducted on this resin composition, and the obtained test results were as shown in Table 1.

[Example 4, Comparative Examples 1 and 2]
Radical thermosetting resin compositions having the compositions shown in Table 1 were prepared in the same manner as in Example 3, and evaluation tests were performed on these resin compositions. The test results obtained were as follows. It was as shown in Table 1.

From the results of Table 1, both Examples 3 and 4 using the phosphorus compound of the present invention having an isocyanurate ring and an unsaturated bond group (allyl group) as a flame retardant in the molecule do not use a flame retardant. Compared with Comparative Example 1, the flame retardance was improved, and the same flame retardancy as Comparative Example 2 using a conventional flame retardant was exhibited.
In addition, both Examples 3 and 4 showed higher Tg and lower CTE than Comparative Examples 1 and 2. This indicates that the crosslink density of the cured products of the resin compositions of Examples 3 and 4 is increased, the heat resistance is high, and the volume change due to temperature can be suppressed.
In addition, in both Examples 3 and 4, compared with Comparative Example 1, the adhesion is improved.
Therefore, by using the phosphorus compound of the present invention (compounds of Examples 1 and 2) as a flame retardant, it is possible to give a cured product excellent in low thermal expansion, heat resistance, adhesiveness (adhesion) and flame retardancy. I understand.

The phosphorus compound of the present invention is expected to be used as a flame retardant for resins.
In addition, the resin composition containing the phosphorus compound of the present invention is expected to give a cured product excellent in low thermal expansion, heat resistance, adhesiveness (adhesion), mechanical properties, electrical properties and flame retardancy. Therefore, it is suitable for materials such as printed wiring boards and materials for adhesives.

Claims (14)

A phosphorus compound having an isocyanurate ring represented by the chemical formula (I).

(In the formula, R ¹ represents an alkyl group having 1 to 20 carbon atoms, an aryl group, or a benzyl group, and R ² represents a group represented by formula (1). Alternatively, R ¹ and R ² are linked may form a ring, R ³ is the same or different and represents an alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms, and R ⁴ is the same or different and is hydrogen represents an atom, an alkyl group having 1 to 20 carbon atoms, an aryl group, a benzyl group, an alkenyl group having 2 to 20 carbon atoms, or an alkynyl group having 2 to 20 carbon atoms, and Y is the same or different and each has 1 to 20 carbon atoms. represents an alkylene group of 20.)

(Wherein, R ³ , R ⁴ and Y are the same as defined above.) 2. The compound according to claim 1, which is a phosphorus compound having an isocyanurate ring represented by the chemical formula (I-1).

(Wherein, R ¹ , R ³ , R ⁴ and Y are the same as defined above.) 2. The compound according to claim 1, which is a phosphorus compound having an isocyanurate ring represented by the chemical formula (I-2).

(Wherein, R ³ , R ⁴ and Y are the same as defined above.) 2. A method for synthesizing a phosphorus compound having an isocyanurate ring according to claim 1, comprising reacting the phosphorus compound represented by the chemical formula (II) with the isocyanurate compound represented by the chemical formula (III).

(In the formula, R ¹ is the same as defined above, and R ⁸ represents -YX. Alternatively, R ¹ and R ⁸ may be linked to form a ring. Y is the same as defined above. X is the same or different and represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a mesyloxy group (OMs), a tosyloxy group (OTs), or a trifluoromethanesulfonyloxy group (OTf).)

(In the formula, R ³ and R ⁴ are the same as above.) A flame retardant containing the phosphorus compound having an isocyanurate ring according to claim 1. A resin composition containing the phosphorus compound having an isocyanurate ring according to claim 1 and a resin component. The resin composition according to claim 6, wherein the resin component is a polyphenylene ether resin. A prepreg comprising the resin composition according to claim 6 or claim 7 and a base material. A resin-coated metal foil comprising a resin layer containing the resin composition according to claim 6 or claim 7 or a semi-cured product of the resin composition, and a metal foil. A thermosetting resin film formed from the resin composition according to claim 6 or claim 7. A metal-clad laminate comprising an insulating layer containing the cured product of the resin composition according to claim 6 or claim 7, and a metal foil. A printed wiring board comprising an insulating layer containing the cured product of the resin composition according to claim 6 or claim 7, and wiring. A printed wiring board comprising an insulating layer containing the cured thermosetting resin film according to claim 10 and wiring. An adhesive containing the resin composition according to claim 6 or 7 as a component.

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