JP2023020775A - Phosphorus compound having isocyanurate ring, synthetic method therefor, and use of said phosphorus compound having isocyanurate ring - Google Patents

Abstract

To provide: a novel phosphorus compound having an isocyanurate ring; a flame retardant containing the phosphorus compound; a resin composition containing the phosphorus compound and a resin component; and uses thereof.SOLUTION: The present invention pertains to a phosphorus compound having an isocyanurate ring represented by chemical formula (I) (where, R1 is a C1-C20 alkyl group, an aryl group, or a benzyl group, R2 is a group having 1,3,5-triazine-2,4,6-trione skeleton. OR, R1 and R2 may be linked to form a ring. R3 may be the same or different to represent a C2-20 alkenyl group or a C2-20 alkynyl group. R4 may be the same or different to represent a hydrogen atom, a C1-20 alkyl group, an aryl group, a benzyl group, a C2-20 alkenyl group, or a C2-20 alkynyl group. Y may be the same or different to represent a C1-20 alkylene group).SELECTED DRAWING: None

Description

TECHNICAL FIELD 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, making them suitable for use in electrical and electronic equipment that requires long-term reliability. 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, a phosphorus compound having a radically polymerizable group in the molecule is expected to improve low thermal expansion, 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.

International Publication No. 2013/114866 pamphlet

The present invention provides a novel phosphorus compound having an isocyanurate ring, a method for synthesizing a phosphorus compound having the isocyanurate ring, a flame retardant containing the phosphorus compound having the isocyanurate ring, and a phosphorus compound having the isocyanurate ring. An object of the present invention is to provide a resin composition containing a resin component.
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、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、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、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, R ⁴ is the same or different and represents a hydrogen atom, represents 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 are alkylene having 1 to 20 carbon atoms; represents a 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 the synthesis of a phosphorus compound having an isocyanurate ring according to the first invention, characterized by reacting a phosphorus compound represented by the chemical formula (II) with an isocyanurate compound represented by the chemical formula (III). The method.

（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）、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), 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.)

3rd invention is a flame retardant containing the phosphorus compound which has an isocyanurate ring of 1st invention.
A fourth invention is a resin composition containing the phosphorus compound having an isocyanurate ring of the first invention and a resin component.
A fifth invention is the resin composition according to the fourth invention, wherein the resin component is a polyphenylene ether resin.
A sixth invention is a prepreg comprising the resin composition of the fourth invention or the fifth invention and a substrate.
A seventh invention is a resin-coated metal foil comprising a resin layer containing the resin composition of the fourth or fifth invention or a semi-cured material of the resin composition, and a metal foil.
An eighth invention is a thermosetting resin film formed from the resin composition of the fourth invention or the fifth invention.
A ninth invention is a metal-clad laminate comprising an insulating layer containing a cured product of the resin composition of the fourth invention or the fifth invention, and a metal foil.
A tenth invention is a printed wiring board comprising an insulating layer containing a cured product of the resin composition of the fourth or fifth invention, or a cured product of the thermosetting resin film of the eighth invention, and wiring. is.
An eleventh invention is an adhesive containing the resin composition of the fourth invention or the fifth 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、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、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、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; 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. .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、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、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, and 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）、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 described above. X is the same or different, fluorine atom, chlorine atom, bromine atom, iodine atom, mesyloxy group (OMs), tosyloxy group (OTs), trifluoromethane represents a sulfonyloxy group (OTf).)

（式中、Ｙは、前記と同様である。Ｘは、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）、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, Y is the same as described above. X represents a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a mesyloxy group (OMs), a tosyloxy group (OTs), a trifluoromethanesulfonyloxy group (OTf). .)

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, for example, can be synthesized 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 preferred.
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 preferred.

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, and 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 polyethylene resin, chlorinated polyethylene resin, polyvinyl chloride resin, polypropylene resin, polyisoprene resin, polybutadiene resin, polystyrene resin, impact-resistant polystyrene resin, acrylonitrile-styrene resin (AS resin), acrylonitrile- Butadiene-styrene resin (ABS resin), methyl methacrylate-butadiene-styrene resin (MBS resin), methyl methacrylate-acrylonitrile-butadiene-styrene resin (MABS resin), acrylonitrile-acrylic rubber-styrene resin (AAS resin), polymethyl (meth ) Acrylate resin, polyester resin (polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate, etc.), unsaturated polyester resin, polyesterimide resin, polyketone resin, polycarbonate resin, polyamide resin, polyimide resin, polyamideimide resin, polycarbodiimide resin , polyetherimide resin, polyetherketone resin, polyetheretherketone resin (PEEK resin), polyethersulfone resin, polythioethersulfone resin, polysulfone resin, polyphenylene sulfide resin, polyethernitrile resin, polyarylate resin, polybenzimidazole resins, benzoxazine resins, liquid crystal polymer resins, silicone resins, epoxy resins, polyurethane resins, phenol resins, melamine resins, urea resins, diallyl phthalate resins, and the like. 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).
Examples of other flame retardants include phosphate ester compounds, phosphazene compounds, phosphite ester compounds, phosphine compounds, melamine phosphate, phosphate amide compounds, phosphate amide ester compounds, phosphinate compounds and their salts, and ammonium phosphate. , ammonium polyphosphate, melam, melam polyphosphate, melem, melem polyphosphate, red phosphorus, melon, melamine, melamine pyrophosphate, melamine cyanurate, succinoguanamine, phosphonate, phosphinate, phosphine oxide, ethylene bispenta Bromobenzene, ethylenebistetrabromophthalimide and the like can be mentioned.
Phosphate ester compounds include, for example, triphenyl phosphate, tricresyl phosphate, xylenyl diphenyl phosphate, cresyl diphenyl phosphate, 1,3-phenylene bis(di-2,6-xylenyl phosphate), 9,10 -dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO), condensed phosphate compounds such as aromatic condensed phosphate compounds, cyclic phosphate compounds, and the like.
Phosphazene compounds include, for example, cyclic or chain phosphazene compounds. A cyclic phosphazene compound, also called cyclophosphazene, is a compound with a cyclic structure having a double bond in the molecule, the constituent elements of which are phosphorus and nitrogen.
Examples of phosphite compounds include trimethyl phosphite, triethyl phosphite and the like.
Examples of phosphine compounds include tris-(4-methoxyphenyl)phosphine and triphenylphosphine.
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.).
Examples of these polymerization components include vinyl chloride, butadiene, isoprene, styrene, high-impact polystyrene precursors, acrylonitrile-styrene resin (AS resin) precursors, acrylonitrile-butadiene-styrene resin (ABS resin) precursors, methyl Methacrylate-butadiene-styrene resin (MBS resin) precursor, methyl methacrylate-acrylonitrile-butadiene-styrene resin (MABS resin) precursor, acrylonitrile-acrylic rubber-styrene resin (AAS resin) precursor, methyl (meth)acrylate, epoxy Acrylate resin precursors, epoxidized oil acrylate resin precursors, urethane acrylate resin precursors, polyester acrylate resin precursors, polyether acrylate resin precursors, acrylic acrylate resin precursors, unsaturated polyester resin precursors, vinyl/acrylate resin precursors body, vinyl ether-based resin precursor, polyene/thiol resin precursor, silicon acrylate resin precursor, polybutadiene acrylate resin precursor, polystyryl (ethyl) methacrylate resin precursor, polycarbonate acrylate resin precursor, alicyclic epoxy resin precursor, Examples include glycidyl ether epoxy resin precursors, photocurable or thermosetting polyimide resin precursors, silicon-containing resin precursors, and epoxy resin precursors. 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 thermal polymerization initiators include 2,2-azobisisobutyronitrile (AIBN), 2,2-azobis(2-methylbutyronitrile), azobis-2,4-dimethylvaleronitrile, and azobiscyclohexyl. azo compounds such as nitrile and azobiscyanovaleric acid; peroxides such as benzoyl peroxide, dicumyl peroxide and diisopropylperoxydicarbonate; acid generators such as aromatic sulfonates; These may be used alone or in combination of two or more.

Examples of photopolymerization initiators include acetophenone-based photopolymerization initiators, benzophenone-based photopolymerization initiators, benzoin-based photopolymerization initiators, thioxanthone-based photopolymerization initiators, sulfonium-based photopolymerization initiators, and iodonium-based photopolymerization initiators. etc. These may be used alone or in combination of two or more.
When using a photopolymerization initiator, a sensitizer such as a tertiary amine may be used in combination, if necessary.

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.
Examples of reactive diluents 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 tertiary carboxylic acid glycidyl ester; styrene oxide and phenyl glycidyl. aromatic alkyl glycidyl ether such as ether, cresyl glycidyl ether, p-s-butylphenyl glycidyl ether, nonylphenyl glycidyl ether; These may be used alone or in combination of two or more.

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).
Examples of fluororesins include polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-ethylene copolymer polymer (ETFE), poly(trifluorochloroethylene) (CTFE), polyfluorovinylidene (PVdF), and the like. These may be used alone or in combination of two or more.

The amount of the fluororesin compounded 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 body).
Examples of inorganic fillers include mica, natural mica, synthetic mica, kaolin, calcined kaolin, talc, calcined talc, wollastonite, silica, alumina, boron nitride, clay, calcined clay, titania, barium sulfate, barium carbonate, Calcium carbonate, calcium sulfate, aluminum hydroxide, magnesium hydroxide, calcium silicate, titanium oxide, zinc oxide, zinc borate, glass beads, glass balloons, glass flakes, short glass fibers, fine glass powder, hollow glass, fibrous titanate Alkali metal salt (potassium titanate fiber, sodium titanate fiber, etc.), fibrous borate (aluminum borate fiber, magnesium borate fiber, zinc borate fiber, etc.), zinc oxide fiber, titanium oxide fiber, magnesium oxide fiber, gypsum fiber, aluminum silicate fiber, calcium silicate fiber, silicon carbide fiber, titanium carbide fiber, silicon nitride fiber, titanium nitride fiber, carbon fiber, alumina fiber, alumina-silica fiber, zirconia fiber, quartz fiber, flaky titanate, Examples include flaky titanium dioxide. These may be used alone or in combination of two or more.
In particular, in order to lower the dielectric constant of the resin composition, it is preferable to use a low dielectric constant filler such as silica or boron nitride as the inorganic filler. Examples of silica include pulverized silica, fused silica, natural silica, fired silica, synthetic silica, crystalline silica, amorphous silica, and the like.
The average particle size of the inorganic filler is preferably 5 μm or less. For example, by using an inorganic filler such as silica particles having an average particle diameter of 5 μm or less, adhesion to metal foil is improved when the resin composition is used for a metal-clad laminate or the like.
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 amount of the inorganic filler compounded 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 white carbon, aluminum nitride, zinc borate, zinc stannate, zinc molybdate, molybdenum oxide, silicon nitride, aerosil, wollastonite, nanocarbons (nanocarbon tubes, graphene, fullerene, etc.). , organic fibers (aramid fiber, polyparaphenylenebenzbisoxazole fiber, etc.), silane coupling agents, waxes, fatty acids and their metal salts, release agents (acid amides, paraffin, etc.), chlorinated paraffin, silicone-based hard Retardants, brominated flame retardants, flame retardant aids (antimony trioxide, etc.), UV absorbers (benzophenone compounds, benzotriazole compounds, cyanoacrylate compounds, triazine compounds, etc.), antioxidants (hindered phenol compounds, styrenated phenol compounds, organic phosphorus peroxide decomposers, organic sulfur peroxide decomposers, etc.), fluorescent brighteners (stilbene derivatives, etc.), light stabilizers (hindered amine compounds, etc.), photosensitizers, brighteners, metals Deactivator (benzotriazole compound, etc.), light shielding agent (rutile-type titanium oxide, zinc oxide, chromium oxide, cerium oxide, etc.), quenching agent (organic nickel, etc.), curing agent, curing accelerator, cross-linking agent, diluent, Fluidity regulators, polymerization inhibitors, dyes, pigments, coloring agents, antifogging agents, antifungal agents, antibacterial agents, deodorants, plasticizers, antistatic agents, surfactants, antifoaming agents, blowing agents, leveling agents , lubricants, lubricants, thixotropic agents, thickeners, nucleating agents, reinforcing agents, compatibilizers, conductive agents, anti-blocking agents, anti-tracking agents, phosphorescent agents, plasticizers, adhesives, adhesives, tackiness Examples include imparting agents and various stabilizers. 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 in a known manner. For example, a mixture of liquid, powder, beads, flakes or pellets is mixed with an extruder (single-screw extruder, twin-screw extruder, etc.), a kneader (Banbury mixer, pressure kneader, two rolls, three It can be manufactured by mixing and/or kneading using rolls, etc.).

(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.

Preferred embodiments of the compound having the structure represented by formula (2) include, 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 based on known methods such as those described in 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.

Examples of aliphatic bismaleimide compounds include N,N'-(2,2,4-trimethylhexamethylene)bismaleimide, N,N'-decamethylenebismaleimide, N,N'-octamethylenebismaleimide, N,N'-heptamethylenebismaleimide, N,N'-hexamethylenebismaleimide, N,N'-pentamethylenebismaleimide, N,N'-tetramethylenebismaleimide, N,N'-trimethylenebismaleimide, N,N'-ethylenebismaleimide, N,N'-(oxydimethylene)bismaleimide, 1,13-bismaleimide-4,7,10-trioxatridecane, 1,11-bismaleimide-3,6 , 9-trioxaundecane and the like.

Examples of aromatic bismaleimide compounds include N,N'-(4-methyl-1,3-phenylene)bismaleimide, N,N'-(1,3-phenylene)bismaleimide, N,N'- (1,4-phenylene)bismaleimide, N,N'-(1,2-phenylene)bismaleimide, N,N'-(1,5-naphthylene)bismaleimide, N,N'-(4-chloro- 1,3-phenylene)bismaleimide, N,N'-(methylenedi-p-phenylene)bismaleimide, N,N'-(4,4'-biphenylene)bismaleimide, N,N'-(sulfonyldi-p -phenylene)bismaleimide, N,N'-(oxydi-p-phenylene)bismaleimide, N,N'-(3,3'-dimethyl-4,4'-biphenylene)bismaleimide, N,N'-( benzylidenedi-p-phenylene)bismaleimide, N,N'-[methylenebis(3-chloro-4-phenylene)]bismaleimide, N,N'-[methylenebis(3-methyl-4-phenylene)]bismaleimide, N,N'-[methylenebis(3-methoxy-4-phenylene)]bismaleimide, N,N'-(thiodi-p-phenylene)bismaleimide, N,N'-3,3'-benzophenonebismaleimide, N , N′-[methylenebis(3-methyl-5-ethyl-4-phenylene)]bismaleimide, N,N′-[tetramethylenebis(oxy-p-phenylene)]bismaleimide, 2,2-bis[4 -(4-maleimidophenoxy)phenyl]propane, bis[4-(4-maleimidophenoxy)phenyl)]sulfone, 1,4-phenylenebis(4-maleimidophenoxy), bis[3-(4-maleimidophenoxy)phenyl ] sulfone, bis[4-(3-maleimidophenoxy)phenyl]ketone, 1,3-phenylenebis(4-maleimidophenoxy), bis[4-(4-maleimidophenylthio)phenyl]ether and the like. These may be used alone or in combination of two or more.

The bismaleimide-triazine resin is not particularly limited as long as it contains a maleimide compound and a cyanate ester compound as main components and is prepolymerized. For example, 2,2-bis(4-cyanatophenyl)propane and bis(3-ethyl-5-methyl-4-maleimidophenyl)methane are melted by heating and polymerized, and novolac-type cyanate esters A resin and bis(3-ethyl-5-methyl-4-maleimidophenyl)methane are heated and melted, polymerized, and then dissolved in methyl ethyl ketone.

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-described thermoradical-curable resin components may be used alone or in combination of two or more.

[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 paragraph [0056]), styrene-based 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 thermal radical curable resin composition of the present invention may optionally contain a flame retardant other than the phosphorus compound of the present invention (another flame retardant described in paragraph [0058]). may be used together.

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 compound (multifunctional styrene compound according to paragraph [0104]) etc. 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 (the radical polymerization initiator described in paragraph [0064]), an inorganic filler (paragraph Inorganic fillers described in [0070]), stress relaxation agents, organic solvents, additives (additives described in paragraph [0072]), and the like may be contained.

[Compatibilizer] Examples of the compatibilizer 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 content of the radical polymerization initiator in the thermally radically curable resin composition of the present invention is not particularly limited, and the resin component (total of the thermally radically curable resin component and other resin components) is 100% by weight. 0.001 to 10 parts by weight, preferably 0.005 to 5 parts by weight, and more preferably 0.01 to 3 parts by weight.

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

[Stress Relaxation Agent] The stress relaxation agent is not particularly limited, and examples thereof include silicone resin particles. The average particle size of the stress relaxation agent is preferably 10 μm or less. By using the stress relaxation agent having such an average particle size, the adhesiveness to the metal foil is improved when the thermoradical-curable resin composition of the present invention is used for a metal-clad laminate or the like.

The amount of the stress relaxation agent 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 0 to 50 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); ether solvents such as dibutyl ether; ethyl acetate and the like. amide solvents such as dimethylformamide; aromatic hydrocarbon solvents such as benzene, toluene and xylene; chlorinated hydrocarbon solvents such as trichlorethylene. These may be used alone or in combination of two or more. As will be described later, the thermoradical-curable resin composition of the present invention containing an organic solvent can be used as a resin varnish for impregnating a base material to produce a prepreg.

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.

[Additives] The amount of additives in the thermoradical-curable resin composition of the present invention is not particularly limited. , 0 to 50 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. For example, a mixture of liquid, powder, beads, flakes or pellets is mixed with an extruder (single-screw extruder, twin-screw extruder, etc.), a kneader (Banbury mixer, pressure kneader, two rolls, three It can be manufactured by mixing and/or kneading using rolls, etc.).

(5. Applications of the resin composition of the present invention)
3 above. and the resin composition described in 4 above. The thermoradical curable resin composition described in (hereinafter both are collectively referred to as "the resin composition of the present invention") is a prepreg, a resin-coated metal foil, a thermosetting resin film, a metal-clad laminate, a printed wiring It can be suitably used for applications such as plates, resin plates, semiconductor devices, and adhesives.

[Prepreg]
The prepreg of the present invention will be explained.
When the resin composition of the present invention is used to produce a prepreg to be used for RCC or the like, the resin composition of the present invention can be prepared in the form of a varnish and used as a resin varnish. Such a resin varnish can be prepared, for example, as follows.
First, each component that can be dissolved in an organic solvent (each component contained in the resin composition of the present invention) is put into an organic solvent and dissolved. At this time, it may be heated, if necessary. Thereafter, components that are not soluble in the organic solvent used as necessary (each component contained in the resin composition of the present invention), such as inorganic fillers, are added, and ball mills, bead mills, planetary mixers, roll mills, etc. are added. The varnish-like resin composition of the present invention can be prepared by using and dispersing until a predetermined dispersed state is obtained.

The prepreg of the present invention comprises the resin composition of the present invention or a semi-cured product of the resin composition of the present invention, and a substrate. This semi-cured product is a state in which the resin composition of the present invention is partially cured (B-staged state).

The prepreg of the present invention may be a prepreg comprising a semi-cured product of the resin composition of the present invention (resin composition in a B-stage state) and a substrate, and the resin composition of the present invention before curing may be used. It may be a prepreg comprising a material (A-stage resin composition) and a substrate.

Base materials used for prepreg include, for example, glass cloth, aramid cloth, polyester cloth, LCP (liquid crystal polymer) nonwoven fabric, glass nonwoven fabric, aramid nonwoven fabric, polyester nonwoven fabric, pulp paper, and linter paper. Materials for the glass cloth include ordinary E glass, D glass, S glass, NE glass, quartz glass, L-glass, and the like. A laminate having excellent mechanical strength can be obtained by using glass cloth. As the glass cloth, flattened glass cloth is preferable. The flattening process can be carried out, for example, by continuously pressurizing the glass cloth with press rolls at an appropriate pressure to flatten the yarn. The thickness of the substrate is, for example, 0.02 to 0.3 mm.

The ratio of the base material in the prepreg is 20 to 80% by weight, preferably 25 to 70% by weight, of the entire prepreg.

Examples of the method for producing a prepreg include a method of preparing the resin composition of the present invention in the form of a varnish, and impregnating or applying the varnish onto a base material. Examples of the impregnation/coating method include a method of immersing the base material (dipping), a method of coating using a roll, die coat, bar coat, etc., and a method of spraying with a spray. This impregnation and application can be repeated multiple times as needed. It is also possible to repeat impregnation and application using a plurality of resin compositions having different resin component concentrations. After impregnation and application, drying or heating may be performed.

A substrate impregnated and coated with the resin composition of the present invention is heated at 80 to 180° C. for 1 to 10 minutes to obtain a prepreg in a semi-cured state (B stage state).

Table 1 shows preferred formulation examples (excluding organic solvents) when the resin composition of the present invention is used in prepregs.

By using such a prepreg, it is possible to produce metal-clad laminates and printed wiring boards with excellent electrical properties (for example, dielectric properties), heat resistance, flame retardancy, adhesive strength, and chemical resistance. .

[Metal foil with resin]
The resin-coated metal foil of the present invention will be described.
The resin-coated metal foil of the present invention comprises a resin layer containing the resin composition of the present invention or a semi-cured product of the resin composition of the present invention, and a metal foil.
The resin-coated metal foil of the present invention comprises a metal foil on the surface of a resin layer containing the resin composition of the present invention or a semi-cured product of the resin composition of the present invention. Moreover, the metal foil with resin of the present invention may have another layer between the resin layer and the metal foil.

As described above, the resin layer may be a semi-cured product of the resin composition of the present invention (resin composition in a B-stage state), or the resin composition of the present invention before curing ( A-stage resin composition). Further, the resin layer may or may not contain a substrate. As the base material, the same material as the prepreg base material can be used.

Examples of metal foil include copper foil and aluminum foil. The thickness of the copper foil is about 12 to 70 μm.

Examples of the method for producing the resin-coated metal foil of the present invention include a method of coating a metal foil with the resin composition of the present invention prepared in the form of a varnish as described above. The coating method is not particularly limited as long as it is a method capable of coating the resin composition of the present invention on a metal foil. Examples thereof include a coating method using a roll, a die coat, a bar coat, and the like, and a spray method. Moreover, after coating, it may be dried or heated.

The metal foil coated with the resin composition of the present invention is heated at 80 to 180° C. for 1 to 10 minutes to obtain a resin-coated metal foil in a semi-cured state (B-stage state).

Preferred formulation examples (excluding the organic solvent) when the resin composition of the present invention is used for a resin-coated metal foil containing a substrate are the same as those for the prepreg described above (see Table 1 in paragraph [0133]). ). In addition, Table 2 shows preferred formulation examples (excluding organic solvents) when the resin composition of the present invention is used for a resin-coated metal foil that does not contain a substrate.

Metal-clad laminates and printed wiring boards with excellent electrical properties (e.g., dielectric properties), heat resistance, flame retardancy, adhesive strength, and chemical resistance can be produced by using such resin-coated metal foils. be able to.

[Thermosetting resin film]
The thermosetting resin film of the present invention will be explained.
The thermosetting resin film of the present invention can be produced by forming a desired shape using the resin composition of the present invention. For example, the thermosetting resin film of the present invention can be produced by coating the resin composition of the present invention on a support and then drying.
The support is not particularly limited, and examples thereof include metal foils such as copper and aluminum, organic films such as polyester resins, polyethylene resins, and polyethylene terephthalate resins (PET). The support may be subjected to release treatment with a silicone compound or the like. The resin composition of the present invention can be used in various shapes, and the shape is not particularly limited.

The method of applying the resin composition of the present invention to a support is not particularly limited, but from the viewpoint of thinning and controlling film thickness, gravure, slot die, doctor blade, and the like are preferable. In the slot die method, an uncured film (thermosetting resin film of the present invention) of the resin composition having a thickness of 5 to 300 μm after thermosetting can be obtained.

The drying conditions can be appropriately set according to the type and amount of the organic solvent used in the resin composition of the present invention, the thickness of the coating, and the like. For example, the conditions can be 50 to 120° C. for 1 to 60 minutes. The thermosetting resin film of the present invention thus obtained has good storage stability. The thermosetting resin film can be peeled off from the support at desired timing.

The thermosetting resin film of the present invention can be cured, for example, at 150 to 230° C. for 30 to 180 minutes. Curing of the thermosetting resin film of the present invention may be performed after sandwiching the thermosetting resin film between substrates on which wiring of copper foil or the like is formed. The film may be applied after lamination as appropriate. The thermosetting resin film can also be used as a coverlay film for protecting the wiring on the substrate, and the curing conditions are the same.
In addition, the thermosetting resin film of the present invention is suitable for flexible copper clad laminates (FCCL) for flexible printed wiring boards (FPC), copper clad laminates (CCL) for multilayer boards, or build-up materials. Available.

Table 3 shows preferred formulation examples (excluding organic solvents) when the resin composition of the present invention is used for a thermosetting resin film. When an organic solvent is added, it is preferable to add it appropriately so that the viscosity is in the range of 200 to 3000 mPa·s.

[Metal clad laminate]
The metal-clad laminate of the present invention will be described.
A metal-clad laminate of the present invention comprises an insulating layer containing a cured product of the resin composition of the present invention, and a metal foil. A metal-clad laminate comprises a metal foil on the surface of an insulating layer. Moreover, the metal-clad laminate may have another layer between the insulating layer and the metal foil.
Moreover, the insulating layer may or may not contain a substrate. As the base material, the same material as the prepreg base material can be used. As the metal foil, the same metal foil as the resin-coated metal foil can be used.

Examples of the method for producing the metal-clad laminate include the method using the prepreg described above. As a method of producing a metal-clad laminate using prepreg, one or more prepregs are laminated, and metal foil such as copper foil is laminated on both sides or one side of the prepreg, and this is laminated by heating and pressing. A method of integration and the like can be mentioned. Double-sided or single-sided foil-clad laminates can be produced by this method.
The heating and pressurizing conditions can be appropriately set according to the thickness of the metal-clad laminate to be produced, the blending of the resin composition used for the prepreg, and the like. For example, temperature: 170 to 220° C., pressure: 1.5 to 5.0 MPa, time: 60 to 150 minutes.
Also, the metal-clad laminate can be produced without using the prepreg. For example, a method in which the varnish-like resin composition of the present invention is applied onto a metal foil, a layer containing the resin composition of the present invention is formed on the metal foil, and then heated and pressed, and a metal foil is used as a support. A method of curing a thermosetting resin film and the like can be mentioned.

Preferred formulation examples (excluding the organic solvent) when the resin composition of the present invention is used for a metal-clad laminate containing a substrate are the same as those for the prepreg described above (see Table 1 in paragraph [0133]). ). In addition, preferred formulation examples (excluding organic solvents) when the resin composition of the present invention is used in a metal-clad laminate containing no substrate are the same as in the metal foil with resin containing no substrate described above. (see Table 2 in paragraph [0141]).

By using such a metal-clad laminate, a printed wiring board having excellent electrical properties (eg, dielectric properties), heat resistance, flame retardancy, adhesive strength, and chemical resistance can be produced.

[Printed wiring board]
The printed wiring board of the present invention will be described.
The printed wiring board of the present invention comprises an insulating layer containing a cured product of the resin composition of the present invention or a cured product of the thermosetting film of the present invention, and wiring. The printed wiring board of the present invention has wiring on the surface of the insulating layer. Moreover, the printed wiring board of the present invention may have another layer between the insulating layer and the wiring.
Moreover, the insulating layer may or may not contain a substrate. Also, as the base material, the same material as the prepreg base material can be used.
The printed wiring board of the present invention is provided with an insulating layer containing a cured product of the resin composition of the present invention or a cured product of the thermosetting resin film of the present invention, thereby having excellent electrical properties (eg, dielectric properties). In addition, it has high flame retardancy.

The wiring is not particularly limited as long as it is wiring provided on a printed wiring board. For example, a wiring formed by partially removing a metal foil laminated on an insulating layer may be used. Examples of wiring include wiring formed by methods using subtractive, additive, semi-additive, chemical mechanical polishing (CMP), trench, inkjet, squeegee, transfer, and the like.

Examples of a method for manufacturing a printed wiring board include a method using the aforementioned metal-clad laminate. Examples of the method of manufacturing a printed wiring board using a metal-clad laminate include a method of etching the metal foil on the surface of the metal-clad laminate to form a circuit. By this method, a printed wiring board can be obtained in which a conductor pattern is provided as a circuit on the surface of the metal-clad laminate.

Preferred formulation examples (excluding the organic solvent) when the resin composition of the present invention is used for a printed wiring board containing a base material in the insulating layer are the same as in the case of the prepreg described above (table in paragraph [0133] 1). In addition, a preferable formulation example (excluding organic solvent) when the resin composition of the present invention is used for a printed wiring board that does not contain a base material in the insulating layer is the above-mentioned resin-coated copper foil that does not contain a base material. (see Table 2 in paragraph [0141]).

The printed wiring board thus obtained has excellent electrical properties (for example, dielectric properties), heat resistance, flame retardancy, and chemical resistance, and the peeling of the circuit is sufficiently suppressed. Furthermore, even in the form of a package in which a semiconductor chip is bonded, it is easy to mount, has no variation in quality, and is excellent in signal speed and impedance.

[Resin plate]
The resin composition of the present invention can also be used as a cured resin plate. For example, a resin plate or the like obtained by applying the resin composition of the present invention in the form of a varnish to form a plate, drying it, and then curing it may be used. Moreover, as a resin board, the unclad board etc. which removed the metal foil of the said metal-clad laminated board are mentioned, for example.

[Semiconductor device]
A case where the resin composition of the present invention is used in a semiconductor device will be described.
A semiconductor device can be produced by using the resin composition of the present invention or the thermosetting resin film of the present invention and curing it. The cured product of the resin composition of the present invention or the cured product of the thermosetting resin film of the present invention provides this semiconductor device with excellent electrical properties (for example, dielectric properties) and high flame retardancy. Suitable for
A semiconductor device refers to a general device that can function by utilizing semiconductor characteristics, and includes electronic components, semiconductor circuits, modules incorporating these, electronic equipment, and the like.

[glue]
The adhesive of the present invention will be explained.
The adhesive of the present invention contains the resin composition of the present invention as a component. The adhesive of the present invention can be used as an adhesive between two materials selected from metals, inorganic materials and resin materials. In particular, it is preferable as an adhesive between metals and materials selected from metals, inorganic materials and resin materials.

Examples of the metal include copper, aluminum, titanium, nickel, tin, iron, silver, gold and alloys thereof. Among these metals, copper is preferred. Moreover, as a form of metal, the plate, foil, plated film, etc. which consist of these metals are mentioned.

Examples of the inorganic material include silicon, ceramic, carbon used as a filler, inorganic salt, and glass. Specifically, silicon compounds such as silicon, silicon carbide, silica, glass, diatomaceous earth, calcium silicate, talc, glass beads, sericite activated clay, bentonite, aluminosilicate, mica; alumina, zinc oxide, iron oxide, oxide oxides such as magnesium, tin oxide and titanium oxide; hydroxides such as magnesium hydroxide, aluminum hydroxide and basic magnesium carbonate; carbonates such as calcium carbonate, zinc carbonate, hydrotalcite and magnesium carbonate; Sulfates such as gypsum; Titanates such as barium titanate; Nitrides such as aluminum nitride and silicon nitride; Graphites such as flake graphite (natural graphite), expanded graphite, expanded graphite (synthetic graphite); carbon fibers; carbon black and the like.
Among these inorganic materials, silicon, ceramics (alumina, silicon carbide, aluminum nitride, silicon nitride, barium titanate, etc.), glass and inorganic salts are preferred.

Examples of the resin material include nylon, acrylate resin, epoxy resin, olefin resin, benzoxazine resin, polybenzoxazole resin, silicone resin, polyamide resin, polyimide resin, bismaleimide resin, maleimide resin, cyanate resin, polyphenylene ether resin, Polyphenylene oxide resins, fluorine-containing resins, polyether resins, polyetherimide resins, polyetheretherketone resins, polyester resins, silicone resins, liquid crystal resins, etc., may be mentioned, and these may be mixed, modified with each other, or combined. It can be anything.
Among these resin materials, acrylate resin, epoxy resin, olefin resin, benzoxazine resin, polybenzoxazole resin, bismaleimide resin, polyphenylene ether resin, fluorine-containing resin, polyether resin, liquid crystal resin, silicone resin and polyimide resin. preferable.

A known method can be used as a method of adhering materials using an adhesive. Specifically, (1) an adhesive is applied to the surface of a material selected from metals, inorganic materials, and resin materials, and another material is pressure-bonded (cured) to part or the entirety of the applied adhesive. (2) a semi-cured adhesive formed into a sheet is attached to the surface of a material selected from metals, inorganic materials, and resin materials, and the other surface of the adhesive is partly or entirely covered with another A method of bonding (hardening) by pressing the material of .

As a method for curing the adhesive, a known method can be used. For example, a method of heating and pressurizing using a heat press, and a method of heat-treating after drying the first applied adhesive can be used. Heating/pressurizing conditions are, for example, temperature: 50 to 300° C. (especially 80 to 250° C.), pressure: 0.1 to 50 MPa (especially 0.5 to 10 MPa), time: 1 minute to 10 hours. about 30 minutes to 5 hours.

By using the adhesive of the present invention, it is possible to bond two materials, particularly two materials of different materials. It can be suitably used for devices.

Preferred formulation examples (excluding the organic solvent) when using the resin composition of the present invention as an adhesive are the same as those for the thermosetting resin film described above (see Table 3 in paragraph [0148]).

In this specification, the terms "including" and "having" include the concepts of "consisting essentially of" and "consisting of".

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)

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-penten-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-penten-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 4.

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

From the results of Table 4, 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 (11)

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, R ⁴ is the same or different and represents a hydrogen atom, represents 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 are alkylene having 1 to 20 carbon atoms; represents a group.)

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

(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), 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 comprising the phosphorus compound having an isocyanurate ring according to claim 1 and a resin component. 5. The resin composition according to claim 4, wherein the resin component is a polyphenylene ether resin. A prepreg comprising the resin composition according to claim 4 or 5 and a substrate. A resin-coated metal foil comprising a resin layer containing the resin composition according to claim 4 or 5 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 4 or 5. A metal-clad laminate comprising an insulating layer containing a cured product of the resin composition according to claim 4 or 5, and a metal foil. A printed wiring board comprising an insulating layer containing the cured product of the resin composition according to claim 4 or 5 or the cured product of the thermosetting resin film according to claim 8, and wiring. An adhesive comprising the resin composition according to claim 4 or 5 as a component.

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