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

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

[0001] The present invention relates to a phosphorus compound having a novel isocyanurate ring, a method for synthesizing the phosphorus compound having the isocyanurate ring, and use of the phosphorus compound having the isocyanurate ring.

Background Art

[0002] In recent years, miniaturization and high performance of electronic devices have advanced. In multilayer printed wiring boards, build-up layers are made multilayered, and miniaturization and high density of wirings are required. In particular, in high-frequency applications, an insulating material (resin material) having a low dielectric tangent is required to reduce transmission loss of electrical signals. In addition to electrical properties, such a resin material is also required to have flame retardancy of a cured product, and a flame retardant has been studied.

[0003] Examples of the flame retardant used for the resin material include inorganic flame retardants and organic flame retardants. Inorganic flame retardants are excellent in dielectric properties, but exhibit water absorption and hydrolyzability, so they tend to cause deterioration of the cured product over time, and there are problems in using them for electrical and electronic devices that require long-term reliability. On the other hand, as for a phosphorus compound which is an organic flame retardant, since it has plasticity, there has been a problem that when the addition amount is increased to enhance the flame retardancy, the mechanical strength of the cured product is impaired.

[0004] As a flame retardant for solving such problems, various substances have been studied. Among them, a phosphorus compound having a radically polymerizable group in the molecule is expected to improve low thermal expansion property, heat resistance, and mechanical strength. For example, Patent Document 1 proposes (2,5-dimethacryloxyphenyl)diphenylphosphine oxide and its analogs as flame retardants. However, in resin compositions using these compounds, there is still room for improvement in terms of low thermal expansion property, heat resistance, mechanical strength, and electrical properties.

Prior Art Documents

Patent Documents

[0005] [Patent Document 1] Pamphlet of International Publication No. 2013 / 114866 [Summary of the Invention] [Problems to be Solved by the Invention]

[0006] An object of the present invention is to provide a phosphorus compound having a novel isocyanurate ring, a method for synthesizing the phosphorus compound having the isocyanurate ring, a flame retardant containing the phosphorus compound having the isocyanurate ring, and a resin composition containing the phosphorus compound having the isocyanurate ring and a resin component. Furthermore, an object of the present invention is to provide a prepreg, a metal foil with resin, a thermosetting resin film, a metal-clad laminate, a printed wiring board, and an adhesive using the resin composition. [Means for Solving the Problems]

[0007] As a result of intensive studies to solve the above problems, the present inventors have found that a phosphorus compound having an isocyanurate ring obtained by reacting a certain phosphorus compound with a certain isocyanurate compound can achieve the intended purpose, and have completed the present invention. That is, the first invention is a phosphorus compound having an isocyanurate ring represented by chemical formula (I).

[0008] [Chemical Formula] (In the formula, R 1 represents an alkyl group, an aryl group, or a benzyl group having 1 to 20 carbon atoms, and R 2 represents a group represented by formula (1). Alternatively, R 1 and R 2 may be linked to form a ring. R 3 represents, independently or identically, an alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms. R 4is 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 is the same or different and represents an alkylene group having 1 to 20 carbon atoms.)

[0009]

Chemical formula

[0010] The second invention is a method for synthesizing a phosphorus compound having an isocyanurate ring of the first invention, which comprises reacting a phosphorus compound represented by chemical formula (II) with an isocyanurate compound represented by chemical formula (III).

[0011]

Chemical formula

[0012]

Chemical formula

[0013] The third invention is a flame retardant containing the phosphorus compound having an isocyanurate ring of the first invention. The fourth invention is a resin composition containing the phosphorus compound having an isocyanurate ring of the first invention and a resin component. The fifth invention is a resin composition according to the fourth invention, characterized in that the resin component is a polyphenylene ether resin. The sixth invention is a prepreg comprising the resin composition according to the fourth invention or the fifth invention and a base material. The seventh invention is a metal foil with resin, comprising a resin layer containing the resin composition according to the fourth invention or the fifth invention or a semi-cured product of the resin composition, and a metal foil. The eighth invention is a thermosetting resin film formed from the resin composition according to the fourth invention or the fifth invention. The ninth invention is a metal-clad laminate comprising an insulating layer containing a cured product of the resin composition according to the fourth invention or the fifth invention and a metal foil. The tenth invention is a printed wiring board comprising an insulating layer containing a cured product of the resin composition according to the fourth invention or the fifth invention, or a cured product of the thermosetting resin film according to the eighth invention, and wiring. The eleventh invention is an adhesive comprising the resin composition according to the fourth invention or the fifth invention as a component.

Advantages of the Invention

[0014] The phosphorus compound having an isocyanurate ring of the present invention is a novel phosphorus compound having an isocyanurate ring. Such a phosphorus compound is expected to be used as a flame retardant for resins. And, since the phosphorus compound having an isocyanurate ring of the present invention has an isocyanurate ring and an unsaturated bond group in the molecule, when used as a raw material (resin material) of a resin, compared with the case of using a conventional phosphorus compound, it is expected to give a cured product excellent in low thermal expansion, heat resistance, adhesiveness (adhesion), mechanical properties, electrical properties and flame retardancy. 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, adhesiveness, mechanical properties, and electrical properties.

Brief Description of the Drawings

[0015]

Figure 1

Figure 2

Mode for Carrying Out the Invention

[0016] (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).

[0017]

Chemical formula

[0018]

Chemical formula

[0019] Examples of the phosphorus compound represented by Chemical Formula (I-1) include phosphorus compounds represented by Chemical Formulas (I-1-1) to (I-1-12). Examples of the phosphorus compound represented by Chemical Formula (I-2) include phosphorus compounds represented by Chemical Formulas (I-2-1) to (I-2-3).

[0020]

Chem.

[0021]

Chem.

[0022]

Chem.

[0023] R 1 and R 4 Examples of the alkyl group having 1 to 20 carbon atoms represented by R and R include linear or branched alkyl groups having 1 to 20 carbon atoms. 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 can be mentioned.

[0024] R 1 and R 4Examples of the aryl group represented by include a phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 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.

[0025] R 1 and R 2 are, as described above, R 1 and R 2 may be linked to form a ring. R 1 and R 2 Examples of R

[0026] R 3 and R 4 Examples of the alkenyl group having 2 to 20 carbon atoms represented by include linear or branched alkenyl groups having 2 to 20 carbon atoms, specifically, vinyl group, allyl group, isopropenyl 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.

[0027] R 3 and R 4Examples of the alkynyl group having 2 to 20 carbon atoms represented by include linear or branched alkynyl groups having 2 to 20 carbon atoms. Specifically, examples thereof include ethynyl group, 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, icosynyl group and the like.

[0028] 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, examples thereof include 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.

[0029] In the phosphorus compound represented by chemical formula (I-1), preferred substituents are as follows. R 1 is preferably an alkyl group having 1 to 5 carbon atoms, phenyl group, 2,6-xylyl group, biphenyl group, 1-naphthyl group, 2-naphthyl group, 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.

[0030] In the phosphorus compound represented by chemical formula (I-2), preferred substituents 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.

[0031] (2. Method for synthesizing phosphorus compound of the present invention) The phosphorus compound of the present invention can be synthesized by reacting a phosphorus compound represented by Chemical Formula (II) with an isocyanurate compound represented by Chemical Formula (III).

[0032] The phosphorus compound represented by Chemical Formula (II) includes a phosphorus compound represented by Chemical Formula (II-1) and a phosphorus compound represented by Chemical Formula (II-2).

[0033] [Chemical formula] (In the formula, R 1 and Y are the same as described 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).)

[0034] [Chemical formula] (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), or a trifluoromethanesulfonyloxy group (OTf).)

[0035] In the above Chemical Formula (II), R 1 and R 8 are as described above, and R 1 and R 8 may be linked to form a ring. Examples of the case where R 1 and R 8 are linked to form a ring include a phosphorus compound represented by Chemical Formula (II-2).

[0036] Examples of the phosphorus compound represented by Chemical Formula (II-1) include phosphorus compounds represented by Chemical Formulas (II-1-1) to (II-1-10). In addition, examples of the phosphorus compound represented by Chemical Formula (II-2) include phosphorus compounds represented by Chemical Formulas (II-2-1) to (II-2-4).

[0037]

Chem.

[0038]

Chem.

[0039] These phosphorus compounds can be purchased and used as commercially available reagents. Alternatively, they can be synthesized, for example, according to the methods described in 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.

[0040] Examples of the isocyanurate compound represented by Chemical Formula (III) include isocyanurate compounds represented by Chemical Formulas (III-1) to (III-3).

[0041]

Chem.

[0042] These isocyanurate compounds can be purchased and used as commercially available reagents. Alternatively, they can be synthesized, for example, according to the method described in JP-A-2016-216399.

[0043] An example of synthesizing the phosphorus compound represented by Chemical Formula (I-1) by reacting the phosphorus compound represented by Chemical Formula (II-1) with the isocyanurate compound represented by Chemical Formula (III) is shown in Reaction Scheme (A). Also, an example of synthesizing the phosphorus compound represented by Chemical Formula (I-2) by reacting the phosphorus compound represented by Chemical Formula (II-2) with the isocyanurate compound represented by Chemical Formula (III) is shown in Reaction Scheme (B).

[0044]

Chemical formula

[0045]

Chemical formula

[0046] In Reaction Scheme (A), the usage amount (charged amount) of the isocyanurate compound represented by Chemical Formula (III) is preferably an appropriate ratio in the range of 2 to 4 times the molar amount with respect to the usage amount (charged amount) of the phosphorus compound represented by Chemical Formula (II-1). In Reaction Scheme (B), the usage amount (charged amount) of the isocyanurate compound represented by Chemical Formula (III) is preferably an appropriate ratio in the range of 1 to 2 times the molar amount with respect to the usage amount (charged amount) of the phosphorus compound represented by Chemical Formula (II-2).

[0047] In Reaction Schemes (A) and (B), it is preferable to use a base (i) for removing the acid by-produced during the progress of the reaction. Further, if necessary, a reaction catalyst (ii) and a reaction solvent (iii) may be appropriately used.

[0048] Examples of the base (i) 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, tripotassium phosphate, tricesium phosphate, dilithium hydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dicesium hydrogen phosphate, lithium dihydrogen phosphate, sodium dihydrogen phosphate, potassium dihydrogen phosphate, cesium dihydrogen phosphate, lithium acetate, sodium acetate, potassium acetate, cesium acetate, sodium alkoxide, potassium alkoxide, t - butoxypotassium, etc. These may be used alone or in combination of two or more.

[0049] In reaction scheme (A), the amount (charged amount) of the base (i) used is preferably an appropriate ratio in the range of 2 to 5 times the molar amount relative to the amount (charged amount) of the phosphorus compound represented by chemical formula (II - 1). In reaction scheme (B), the amount (charged amount) of the base (i) used is preferably an appropriate ratio in the range of 1 to 2.5 times the molar amount relative to the amount (charged amount) of the phosphorus compound represented by chemical formula (II - 2).

[0050] Examples of the reaction catalyst (ii) include alkali metal iodide salts such as lithium iodide, sodium iodide, potassium iodide, etc. These may be used alone or in combination of two or more.

[0051] In reaction scheme (A), the amount (charged amount) of the reaction catalyst (ii) used is preferably an appropriate ratio in the range of 0.01 to 0.3 times the molar amount relative to the amount (charged amount) of the phosphorus compound represented by chemical formula (II - 1). In reaction scheme (B), the amount (charged amount) of the reaction catalyst (b) is preferably set at an appropriate ratio in the range of 0.01 to 0.3 times the molar amount of the phosphorus compound represented by chemical formula (II-2).

[0052] The reaction solvent (c) is not particularly limited as long as it does not inhibit the reaction. For example, solvents such as tetrahydrofuran, dioxane, ethyl acetate, acetonitrile, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric triamide, and water can be mentioned, and if necessary, these can be combined and used in appropriate amounts.

[0053] In reaction schemes (A) and (B), the reaction temperature is preferably set in the range of 50 to 140°C. Also, the reaction time is appropriately set according to the set reaction temperature, but it is preferably set in the range of 1 to 30 hours.

[0054] After completion of the reaction, the phosphorus compound of the present invention, which is the target product, can be taken out from the obtained reaction solution (reaction mixture) by means such as concentration of the reaction solution by distilling off the reaction solvent or a solvent extraction method. Furthermore, if necessary, it can be purified by means such as washing with water or the like, activated carbon treatment, silica gel chromatography, recrystallization, and the like.

[0055] (3. Flame Retardant and Resin Composition) The flame retardant and resin composition of the present invention contains the phosphorus compound of the present 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 article) 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 may contain other flame retardants, polymerizable components, polymerization initiators, reactive diluents, fluororesins, inorganic fillers, and additives, if necessary. Further, in the present invention, the resin composition means a state of a mixture before curing.

[0056] [Resin component] The resin component (including uncured 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 a molded article of resin. Examples of the resin component 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 (such as polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate, etc.), unsaturated polyester resin, polyester imide resin, polyketone resin, polycarbonate resin, polyamide resin, polyimide resin, polyamideimide resin, polycarbodiimide resin, polyetherimide resin, polyether ketone resin, polyether ether ketone resin (PEEK resin), polyether sulfone resin, polythioether sulfone resin, polysulfone resin, polyphenylene sulfide resin, polyether nitrile resin, polyarylate resin, polybenzimidazole resin, benzoxazine resin, liquid crystal polymer resin, silicone resin, epoxy resin, polyurethane resin, phenol resin, melamine resin, urea resin, diallyl phthalate resin, and the like. These may be used alone or in combination of two or more.

[0057] The blending 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, more preferably 1 to 80 parts by weight, based on 100 parts by weight of the resin component.

[0058] [Other flame retardants] In the resin composition of the present invention, a flame retardant other than the phosphorus compound of the present invention (other flame retardants) may be used in combination as a flame retardant. Examples of other flame retardants include, for example, phosphate ester compounds, phosphazene compounds, phosphite ester compounds, phosphine compounds, melamine phosphate, phosphoric acid amide compounds, phosphoric acid amide ester compounds, phosphinate compounds and their salts, ammonium phosphate, ammonium polyphosphate, melam, melam polyphosphate, melem, melem polyphosphate, red phosphorus, melon, melamine, melamine pyrophosphate, melamine cyanurate, succinoguanamine, phosphonic acid esters, phosphinic acid esters, phosphine oxides, ethylene bispentabromobenzene, ethylene bistetrabromophthalimide and the like. Examples of 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 ester compounds such as aromatic condensed phosphate ester compounds, cyclic phosphate ester compounds and the like. Examples of phosphazene compounds include, for example, cyclic or chain phosphazene compounds. Cyclic phosphazene compounds are also called cyclophosphazenes and are compounds having a cyclic structure with double bonds containing phosphorus and nitrogen as constituent elements in the molecule. Examples of phosphite ester compounds include, for example, trimethyl phosphite, triethyl phosphite and the like. Examples of phosphine compounds include, for example, tris-(4-methoxyphenyl)phosphine, triphenylphosphine and the like. These may be used alone or in combination of two or more thereof.

[0059] The compounding amount of other flame retardants 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 1 to 50 parts by weight with respect to 100 parts by weight of the resin component.

[0060] [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 polymerizable components include vinyl chloride, butadiene, isoprene, styrene, impact-resistant polystyrene precursor, acrylonitrile-styrene resin (AS resin) precursor, acrylonitrile-butadiene-styrene resin (ABS resin) precursor, methyl methacrylate-butadiene-styrene resin (MBS resin) precursor, methyl methacrylate-acrylonitrile-butadiene-styrene resin (MABS resin) precursor, acrylonitrile-acrylic rubber-styrene resin (AAS resin) precursor, methyl (meth)acrylate, epoxy acrylate resin precursor, epoxidized oil acrylate resin precursor, urethane acrylate resin precursor, polyester acrylate resin precursor, polyether acrylate resin precursor, acrylic acrylate resin precursor, unsaturated polyester resin precursor, vinyl / acrylic resin precursor, 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, glycidyl ether epoxy resin precursor, and photocurable or thermosetting polyimide resin precursor, silicon-containing resin precursor, epoxy resin precursor, etc. These may be used alone or in combination of two or more thereof.

[0061] The blending amount of the polymerizable component 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 1 to 50 parts by weight with respect to 100 parts by weight of the resin component.

[0062] [Polymerization initiator] The resin composition of the present invention may contain a polymerization initiator. The polymerization initiator can be appropriately selected according to the method of polymerizing the resin composition of the present invention. Examples of the polymerization initiator include thermal polymerization initiators, photopolymerization initiators, radical polymerization initiators, and the like. Examples of the thermal polymerization initiator include azo compounds such as 2,2-azobisisobutyronitrile (AIBN), 2,2-azobis(2-methylbutyronitrile), azobis-2,4-dimethylvaleronitrile, azobiscyclohexylnitrile, and azobiscyanovaleric acid; peroxides such as benzoyl peroxide, dicumyl peroxide, and diisopropyl peroxydicarbonate; and acid generators such as aromatic sulfonate salts. These may be used alone or in combination of two or more.

[0063] Examples of the photopolymerization initiator 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. 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 as necessary.

[0064] Examples of the radical polymerization initiator include peroxides such as di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxide)hexane, 2,5-dimethyl-2,5-di(t-butylperoxide)hexyne-3, α,α′-di(t-butylperoxy)diisopropylbenzene, and t-butylperoxybenzoate. These may be used alone or in combination of two or more.

[0065] The compounding amount of the polymerization initiator 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 0.1 to 3 parts by weight, based on 100 parts by weight of the resin component.

[0066] [Reactive diluent] The resin composition of the present invention may contain a reactive diluent as needed. Examples of the reactive diluent 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 glycidyl esters of tertiary carboxylic acids; and aromatic alkyl glycidyl ethers such as styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, p-s-butylphenyl glycidyl ether, and nonylphenyl glycidyl ether. These may be used alone or in combination of two or more.

[0067] The compounding amount of the reactive diluent 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 20 parts by weight, based on 100 parts by weight of the resin component.

[0068] [Fluororesin] The resin composition of the present invention may contain a fluororesin for the purpose of improving the flame retardancy (particularly the dripping prevention performance) of the cured product (formed body). Examples of the fluororesin include polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-ethylene copolymer (ETFE), poly(chlorotrifluoroethylene) (CTFE), polyvinylidene fluoride (PVdF), and the like. These may be used alone or in combination of two or more.

[0069] The compounding quantity 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, based on 100 parts by weight of the resin component.

[0070] [Inorganic filler] The resin composition of the present invention may contain an inorganic filler for the purpose of improving the flame retardancy (particularly the dripping prevention performance) and mechanical strength of the cured product (formed body). Examples of the inorganic filler 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, glass short fibers, glass fine powder, hollow glass, fibrous alkali metal titanates (such as potassium titanate fibers, sodium titanate fibers, etc.), fibrous borates (such as aluminum borate fibers, magnesium borate fibers, zinc borate fibers, etc.), zinc oxide fibers, titanium oxide fibers, magnesium oxide fibers, gypsum fibers, aluminum silicate fibers, calcium silicate fibers, silicon carbide fibers, titanium carbide fibers, silicon nitride fibers, titanium nitride fibers, carbon fibers, alumina fibers, alumina-silica fibers, zirconia fibers, quartz fibers, flaky titanates, flaky titanium dioxide, etc. These may be used alone or in combination of two or more. Particularly for reducing the dielectric constant of the resin composition, it is preferable to use low-dielectric-constant fillers such as silica and boron nitride as the inorganic filler. Examples of silica include ground silica, fused silica, natural silica, calcined silica, synthetic silica, crystalline silica, amorphous silica, etc. The average particle diameter 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, when the resin composition is used for a metal-clad laminate or the like, the adhesion to the metal foil is improved. Also, for the purpose of suppressing the deterioration of the resin component, the surface of the inorganic filler may be coated with a silane coupling agent.

[0071] The compounding amount of the inorganic filler in the resin composition of the present invention is not particularly limited. From the balance between the improvement of flame retardancy and mechanical properties, the compounding amount of the inorganic filler is 0 to 200 parts by weight, preferably 5 to 100 parts by weight, based on 100 parts by weight of the resin component.

[0072] [Additives] The resin composition of the present invention may contain various additives within a range that does not impair the intended physical properties, depending on its use, the type of resin component, etc. Examples of the additives include white carbon, aluminum nitride, zinc borate, zinc stannate, zinc molybdate, molybdenum oxide, silicon nitride, aerosil, wollastonite, nanocarbons (nanotubes, graphene, fullerenes, etc.), organic fibers (aramid fibers, polyparaphenylene benzobisoxazole fibers, etc.), silane coupling agents, waxes, fatty acids and their metal salts, release agents (acid amides, paraffin, etc.), chlorinated paraffin, silicone-based flame retardants, bromine-based flame retardants, flame retardant aids (antimony trioxide, etc.), ultraviolet absorbers (benzophenone compounds, benzotriazole compounds, cyanoacrylate compounds, triazine compounds, etc.), antioxidants (hindered phenol compounds, styrenated phenol compounds, organic phosphorus-based peroxide decomposers, organic sulfur-based peroxide decomposers, etc.), fluorescent brighteners (stilbene derivatives, etc.), light stabilizers (hindered amine compounds, etc.), photosensitizers, brighteners, metal deactivators (benzotriazole compounds, etc.), light-shielding agents (rutile-type titanium oxide, zinc oxide, chromium oxide, cerium oxide, etc.), matting agents (organic nickel, etc.), curing agents, curing accelerators, crosslinking agents, diluents, fluidity modifiers, polymerization inhibitors, dyes, pigments, colorants, antifogging agents, antifungal agents, antibacterial agents, deodorants, plasticizers, antistatic agents, surfactants, defoaming agents, foaming agents, leveling agents, lubricants, lubricants, thixotropy imparting agents, thickeners, nucleating agents, reinforcing agents, compatibilizers, conductive agents, antiblocking agents, antitracking agents, phosphorescent agents, plasticizers, adhesives, adhesives, tackifiers, various stabilizers, etc. These may be used alone or in combination of two or more.

[0073] The compounding amount of the additive 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, based on 100 parts by weight of the resin component.

[0074] The resin composition of the present invention can be produced by mixing and / or kneading a resin component, the flame retardant of the present invention and, if necessary, other flame retardants, polymerizable components, polymerization initiators, reactive diluents, fluororesins, inorganic fillers, and additives by a known method. For example, a mixture of components in the form of liquid, powder, beads, flakes or pellets can be mixed and / or kneaded using an extruder (single-screw extruder, twin-screw extruder, etc.), a kneader (Banbury mixer, pressure kneader, two-roll mill, three-roll mill, etc.), or the like.

[0075] (4. Thermally radical curable resin composition) The resin composition of the present invention (hereinafter referred to as "the thermally radical curable resin composition of the present invention") contains the phosphorus compound of the present invention and a thermally radical curable resin component. In addition, the thermally radical curable resin composition of the present invention may contain, in addition to the phosphorus compound and the thermally radical curable resin component of the present invention, other resin components, other flame retardants, crosslinking agents, compatibilizers, radical polymerization initiators, inorganic fillers, stress relaxants, organic solvents, and additives, if necessary. In the present invention, the resin composition means the state of the mixture before curing.

[0076] [Thermally radical curable resin component] The thermally radical curable resin component (including uncured and semi-cured resins) used in the thermally radical curable resin composition of the present invention includes, for example, polyphenylene ether resin, bismaleimide resin, bismaleimide-triazine resin, polyfunctional styrene compound, benzocyclobutene resin, polytetrafluoroethylene resin, acrylic resin, and the like.

[0077] Examples of the polyphenylene ether resin include compounds having a structure represented by formula (2).

[0078] [Chemical formula] (In the formula, R a represents, independently or identically, 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 and usually represents an integer of 1 or more.)

[0079] R a Examples of the alkyl group having 1 to 6 carbon atoms represented by include linear or branched alkyl groups having 1 to 6 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-pentyl group, n-hexyl group, etc., among which the methyl group is preferred. R a Examples of the alkenyl group having 2 to 6 carbon atoms represented by include linear or branched alkenyl groups having 2 to 6 carbon atoms, specifically, vinyl group, allyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, pentenyl group, hexenyl group, etc. R a represents, independently or identically, preferably a hydrogen atom or a methyl group. n is preferably 1 to 400.)

[0080] As one aspect of the compound having the structure represented by formula (2), for example, a compound having the structure represented by formula (2-1), a compound having the structure represented by formula (2-2), a compound having the structure represented by formula (2-3), etc. can be mentioned.)

[0081]

Chemical formula

[0082]

Chemical formula

[0083]

Chemical formula

[0084] 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 (for example, a group having a carbon-carbon double bond such as a (meth)acrylic group, an allyl group, a vinylbenzyl group, etc.). The crosslinkable group is preferably present at the terminal of the molecule of this compound.

[0085] As a preferred embodiment of the compound having the structure represented by formula (2), for example, the compound represented by chemical formula (IV) can be mentioned.

[0086]

Chemical formula

[0087]

Chemical formula

[0088]

Chemical formula

[0089] R b , R c and R d Examples of the alkyl group having 1 to 3 carbon atoms represented by are methyl group, ethyl group, n-propyl group, isopropyl group, etc. R b and R c are preferably a hydrogen atom, and R d is preferably a hydrogen atom or a methyl group.

[0090] Examples of the alkylene group having 1 to 10 carbon atoms represented by Z include 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, etc. Z is preferably -C(=O)-, -Ph-, -Ph-CH2- or -Ph-CH2CH2-.

[0091] R e Examples of the alkyl group having 1 to 6 carbon atoms represented by include linear or branched alkyl groups having 1 to 6 carbon atoms, specifically, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, t-butyl group, n-pentyl group, n-hexyl group, etc. R e Examples of the alkenyl group having 2 to 6 carbon atoms represented by include linear or branched alkenyl groups having 2 to 6 carbon atoms, specifically, vinyl group, allyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, pentenyl group, hexenyl group, etc. R e Examples of the aryl group represented by include, for example, phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, etc. R e is preferably a hydrogen atom or a methyl group.

[0092] Examples of the alkylene group having 1 to 6 carbon atoms which may be substituted with a phenyl group represented by W include a methylene group, a methylmethylene group, a dimethylmethylene group, a phenylmethylene group, a phenylmethylmethylene group, a diphenylmethylene group, and the like. Examples of the cycloalkylene group represented by W include a 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, 2,2-dichloroethylene-1,1-diyl, and the like. Examples of -(alkylene)-(phenylene)-(alkylene)- represented by W include -(alkylene having 1 to 3 carbon atoms)-(phenylene)-(alkylene having 1 to 3 carbon atoms)- and the like. Examples of the alkylene having 1 to 3 carbon atoms include a methylene group, a methylmethylene group, a dimethylene group, a trimethylene group, an ethylmethylene group, a dimethylmethylene group, and the like, and preferably a dimethylmethylene group. Examples of the phenylene group include a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, and preferably a 1,4-phenylene group. W is preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 1 to 3 carbon atoms (particularly a dimethylmethylene group).

[0093] Y a is preferably a group represented by the 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.).

[0094] Preferred examples of the compounds represented by Chemical Formula (IV) include a compound represented by Chemical Formula (IV-1), a compound represented by Chemical Formula (IV-2), a compound represented by Chemical Formula (IV-3), and the like.

[0095]

Chemical Structure

[0096] [Chemical formula] (In the formula, R a , R b , R c , R d , W, and n are the same as described above.)

[0097] [Chemical formula] (In the formula, n is the same as described above.)

[0098] These polyphenylene ether resins can be synthesized according to or in accordance with known methods, for example, as described in U.S. Patent No. 4,059,568, The Journal of Organic Chemistry, 34, 297-303 (1969), etc.

[0099] The weight average molecular weight (Mw) of the polyphenylene ether resin is usually from 1,000 to 120,000, preferably from 1,000 to 50,000, and more preferably from 1,000 to 20,000. The weight average molecular weight can be measured using gel permeation chromatography (GPC) in terms of styrene conversion.

[0100] The bismaleimide resin is a compound having two maleimide groups in the molecule, and means the bismaleimide compound before curing. Examples of the bismaleimide resin include aliphatic bismaleimide compounds, aromatic bismaleimide compounds, and the like.

[0101] Examples of the aliphatic bismaleimide compound 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.

[0102] Examples of the aromatic bismaleimide compound 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′-benzophenone bismaleimide, 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-phenylene bis(4-maleimidophenoxy), bis[3-(4-maleimidophenoxy)phenyl]sulfone, bis[4-(3-maleimidophenoxy)phenyl]ketone, 1,3-phenylene bis(4-maleimidophenoxy), bis[4-(4-maleimidophenylthio)phenyl]ether, etc. These may be used alone or in combination of two or more kinds.

[0103] The bismaleimide-triazine resin is not particularly limited as long as it is a prepolymerized product mainly composed of a maleimide compound and a cyanate ester compound. For example, a product obtained by heating and melting 2,2-bis(4-cyanatophenyl)propane and bis(3-ethyl-5-methyl-4-maleimidophenyl)methane and subjecting them to a polymerization reaction, a product obtained by heating and melting a novolac-type cyanate ester resin and bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, subjecting them to a polymerization reaction, and then dissolving the product in methyl ethyl ketone can be mentioned.

[0104] Examples of the polyfunctional styrene compound include 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 a divinylbenzene polymer (oligomer) having a vinyl group in the side chain.

[0105] The benzocyclobutene resin is not particularly limited as long as two or more benzocyclobutene groups are bonded directly or via an organic group.

[0106] In the thermoradical curable resin composition of the present invention, the above-described thermoradical curable resin component may be used alone or in combination of two or more.

[0107] [Other resin components] In the thermoradical curable resin composition of the present invention, in addition to the thermoradical curable resin, resin components other than the thermoradical curable resin component (other resin components) may be used in combination as necessary. Examples of the other resin components include the resin components described above (the resin components described in paragraph

[0056] ), styrene block copolymers, and the like. Examples of the styrene block copolymer include styrene-butadiene block copolymer, styrene-isoprene block copolymer, styrene-ethylene / butylene-styrene block copolymer (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.

[0108] There is no particular limitation on the blending amount of the other resin components in the thermoradical curable resin composition of the present invention, and it is 0 to 1000 parts by weight, preferably 50 to 800 parts by weight, more preferably 100 to 700 parts by weight with respect to 100 parts by weight of the thermoradical curable resin component.

[0109] [Flame retardant] In the thermoradical curable resin composition of the present invention, in addition to the phosphorus compound of the present invention as a flame retardant, flame retardants other than the phosphorus compound of the present invention (other flame retardants described in paragraph

[0058] ) may be used in combination as necessary.

[0110] There is no particular limitation on the blending amount of the phosphorus compound of the present invention in the thermoradical curable resin composition of the present invention, and it is 1 to 200 parts by weight, preferably 1 to 160 parts by weight, more preferably 2 to 100 parts by weight with respect to 100 parts by weight of the resin component (the total of the thermoradical curable resin component and other resin components). Further, there is no particular limitation on the blending amount of the other flame retardants in the thermoradical curable resin composition of the present invention, and it is 0 to 100 parts by weight, preferably 1 to 80 parts by weight, more preferably 1 to 40 parts by weight with respect to 100 parts by weight of the resin component (the total of the thermoradical curable resin component and other resin components).

[0111] [Crosslinking agent] The thermally radical-curable resin composition of the present invention may contain a crosslinking agent within a range where the effects of the resin composition can be exhibited. Examples of the crosslinking agent include monobenzyl diallyl isocyanurates such as mono(alkyl having 6 to 20 carbon atoms) diallyl isocyanurate, 1-benzyl-3,5-diallyl isocyanurate, 1-(4-vinylbenzyl)-3,5-diallyl isocyanurate, triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, triallyl trimellitate, polyfunctional styrene compounds (the polyfunctional styrene compounds described in paragraph

[0104] ), and the like. These may be used alone or in combination of two or more kinds.

[0112] There is no particular limitation on the blending amount of the crosslinking agent in the thermally radical-curable resin composition of the present invention, and it is 0 to 200 parts by weight, preferably 5 to 150 parts by weight, more preferably 10 to 100 parts by weight with respect to 100 parts by weight of the resin component (the total of the thermally radical-curable resin component and other resin components).

[0113] The thermally radical-curable resin composition of the present invention may further contain other components, for example, compatibilizers, radical polymerization initiators (the radical polymerization initiators described in paragraph

[0064] ), inorganic fillers (the inorganic fillers described in paragraph

[0070] ), stress relaxants, organic solvents, additives (the additives described in paragraph

[0072] ), etc., if necessary.

[0114] [Compatibilizer] Examples of the compatibilizer include 1,2-polybutadiene, 1,4-polybutadiene, maleic-modified polybutadiene, acrylic-modified polybutadiene, epoxy-modified polybutadiene, and the like. These may be used alone or in combination of two or more kinds.

[0115] There is no particular limitation on the blending amount of the compatibilizer in the thermally radical-curable resin composition of the present invention, and it is 0 to 100 parts by weight, preferably 20 to 50 parts by weight with respect to 100 parts by weight of the resin component (the total of the thermally radical-curable resin component and other resin components).

[0116] [Radical polymerization initiator] The compounding amount of the radical polymerization initiator in the thermoradical curable resin composition of the present invention is not particularly limited, and is 0.001 to 10 parts by weight, preferably 0.005 to 5 parts by weight, more preferably 0.01 to 3 parts by weight with respect to 100 parts by weight of the resin component (total of the thermoradical curable resin component and other resin components).

[0117] [Inorganic filler] The compounding amount of the inorganic filler in the thermoradical curable resin composition of the present invention is not particularly limited, and is 0 to 500 parts by weight, preferably 1 to 200 parts by weight, more preferably 5 to 100 parts by weight with respect to 100 parts by weight of the resin component (total of the thermoradical curable resin component and other resin components).

[0118] [Stress reliever] The stress reliever is not particularly limited, and examples thereof include silicone resin particles. The average particle diameter of the stress reliever is preferably 10 μm or less. By using such a stress reliever having such an average particle diameter, when the thermoradical curable resin composition of the present invention is used for a metal-clad laminate or the like, the adhesion to the metal foil is improved.

[0119] The compounding amount of the stress reliever in the thermoradical curable resin composition of the present invention is not particularly limited, and is 0 to 100 parts by weight, preferably 0 to 50 parts by weight with respect to 100 parts by mass of the resin component (total of the thermoradical curable resin component and other resin components).

[0120] [Organic solvent] The organic solvent is not particularly limited as long as it can dissolve or disperse the thermoradical curable resin component, and examples thereof include ketone solvents such as methyl ethyl ketone (MEK); ether solvents such as dibutyl ether; ester solvents such as ethyl acetate; amide solvents such as dimethylformamide; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; chlorinated hydrocarbon solvents such as trichloroethylene. These may be used alone or in combination of two or more. The thermoradical curable resin composition of the present invention containing an organic solvent can be used to impregnate a substrate as a resin varnish to produce a prepreg, as described later.

[0121] The blending 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 and applying the resin varnish to the substrate, and is 30 to 1000 parts by weight, preferably 100 to 500 parts by weight, based on 100 parts by mass of the resin component (total of the thermoradical curable resin component and other resin components).

[0122] [Additive] The blending amount of the additive in the thermoradical curable 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, based on 100 parts by weight of the resin component (total of the thermoradical curable resin component and other resin components).

[0123] The thermoradical curable resin composition of the present invention can be produced by mixing and / or kneading a thermoradical curable resin component, the flame retardant of the present invention, and, if necessary, other resin components, other flame retardants, crosslinking agents, compatibilizers, radical polymerization initiators, inorganic fillers, stress relaxants, organic solvents, and additives by a known method. For example, it can be produced by mixing and / or kneading a mixture of each component in the form of liquid, powder, beads, flakes or pellets using an extruder (single-screw extruder, twin-screw extruder, etc.), a kneader (Banbury mixer, pressure kneader, two-roll, three-roll, etc.), etc.

[0124] (5. Use of the resin composition of the present invention) The resin composition described in 3. above and the thermoradical curable resin composition described in 4. above (hereinafter, both are collectively referred to as "the resin composition of the present invention") can be suitably used for applications such as prepregs, metal foils with resin, thermosetting resin films, metal-clad laminates, printed wiring boards, resin boards, semiconductor devices, adhesives, etc.

[0125] [Prepreg] The prepreg of the present invention will be described. When manufacturing a prepreg for use in RCC or the like using the resin composition of the present invention, the resin composition of the present invention can be prepared in a varnish form and used as a resin varnish. Such a resin varnish can be prepared, for example, as follows. First, each component (each component included in the resin composition of the present invention) that can be dissolved in an organic solvent is put into an organic solvent and dissolved. At this time, heating may be performed as necessary. Then, components that are not soluble in the organic solvent (each component included in the resin composition of the present invention) that are used as necessary, such as an inorganic filler, etc., are added and dispersed using a ball mill, bead mill, planetary mixer, roll mill, etc. until a predetermined dispersed state is achieved, whereby a varnish-like resin composition of the present invention can be prepared.

[0126] The prepreg of the present invention includes the resin composition of the present invention or a semi-cured product of the resin composition of the present invention and a base material. This semi-cured product is one in which the resin composition of the present invention is in a state of being cured halfway (B-staged state).

[0127] As the prepreg of the present invention, a prepreg including a semi-cured product (a resin composition in a B-staged state) of the resin composition of the present invention and a base material may be used, or a prepreg including the resin composition of the present invention before curing (a resin composition in the A-stage) and a base material may also be used.

[0128] Examples of the base material used for the prepreg include glass cloth, aramid cloth, polyester cloth, LCP (liquid crystal polymer) non-woven fabric, glass non-woven fabric, aramid non-woven fabric, polyester non-woven fabric, pulp paper, lint paper, etc. The material of the glass cloth includes, in addition to ordinary E-glass, D-glass, S-glass, NE-glass, quartz glass, L-glass, etc. When using glass cloth, a laminate with excellent mechanical strength can be obtained. As the glass cloth, a flattened glass cloth is preferable. The flattening process can be performed, for example, by continuously pressing the glass cloth with a press roll at an appropriate pressure to compress the yarn flat. Examples of the thickness of the base material include those of 0.02 to 0.3 mm.

[0129] The proportion of the base material in the prepreg is 20 to 80% by weight, preferably 25 to 70% by weight, in the whole prepreg.

[0130] Examples of the method for producing the prepreg include, for example, a method of preparing the resin composition of the present invention in a varnish form and impregnating or coating the base material. Examples of the impregnating / coating method include a method of dipping the base material (dipping), a method of coating using a roll, die coat, bar coat, etc., and a method of spraying using a spray or the like. This impregnating / coating can be repeated a plurality of times as necessary. Also, it is possible to repeat the impregnating / coating using a plurality of resin compositions having different resin component concentrations. After impregnating / coating, drying or heating may be performed.

[0131] The base material impregnated / coated with the resin composition of the present invention can obtain a prepreg in a semi-cured state (B-stage state) by heating at 80 to 180°C for 1 to 10 minutes.

[0132] Table 1 shows a preferred formulation example (excluding organic solvents) when the resin composition of the present invention is used for the prepreg.

[0133]

Table 1

[0134] By using such a prepreg, it is possible to manufacture a metal-clad laminate or a printed wiring board excellent in electrical properties (for example, dielectric properties, etc.), heat resistance, flame retardancy, adhesive strength, and chemical resistance.

[0135] [Metal foil with resin] The metal foil with resin of the present invention will be described. The metal foil with resin of the present invention includes 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 metal foil with resin of the present invention has 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. Further, the metal foil with resin of the present invention may have another layer between the resin layer and the metal foil.

[0136] As described above, the resin layer may be a semi-cured product (resin composition in a B-stage state) of the resin composition of the present invention, or may be 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 substrate, the same ones as those of the substrate of the prepreg can be used.

[0137] Examples of the metal foil include copper foil, aluminum foil, etc. The thickness of the copper foil is, for example, about 12 to 70 μm.

[0138] Examples of the method for manufacturing the metal foil with resin of the present invention include a method of applying the resin composition of the present invention prepared in a varnish form as described above onto a metal foil. The method of application is not particularly limited as long as it can apply the resin composition of the present invention to the metal foil. For example, methods of applying using a roll, die coating, bar coating, etc., or methods of spraying by spraying, etc. are included. Further, after application, drying or heating may be performed.

[0139] The metal foil coated with the resin composition of the present invention can be heated at 80 to 180°C for 1 to 10 minutes to obtain a metal foil with resin in a semi-cured state (B-stage state).

[0140] The preferred compounding examples (excluding organic solvents) when using the resin composition of the present invention for a metal foil with resin containing a substrate are the same as those in the case of the prepreg described above (see Table 1 in paragraph

[0133] ). Further, Table 2 shows the preferred compounding examples (excluding organic solvents) when using the resin composition of the present invention for a metal foil with resin not containing a substrate.

[0141]

Table 2

[0142] By using such a metal foil with resin, it is possible to manufacture metal-clad laminates and printed wiring boards that are excellent in electrical properties (e.g., dielectric properties, etc.), heat resistance, flame retardancy, adhesive strength, and chemical resistance.

[0143] [Thermosetting resin film] The thermosetting resin film of the present invention will be described. The thermosetting resin film of the present invention can be manufactured by forming it into a desired shape using the resin composition of the present invention. For example, the thermosetting resin film of the present invention can be manufactured by applying the resin composition of the present invention onto a support and then drying it. The support is not particularly limited, and examples thereof include metal foils such as copper and aluminum, and organic films such as polyester resin, polyethylene resin, and polyethylene terephthalate resin (PET). The support may be subjected to a release treatment with a silicone-based compound or the like. Note that the resin composition of the present invention can be used in various shapes, and the shape is not particularly limited.

[0144] The method for applying the resin composition of the present invention to the support is not particularly limited, but from the viewpoints of thinning and film thickness control, a gravure method, a slot die method, a doctor blade method, etc. are preferable. In the slot die method, an uncured film (the thermosetting resin film of the present invention) of the resin composition having a thickness of 5 to 300 μm after thermosetting can be obtained.

[0145] 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 coating thickness, etc. For example, the conditions can be 50 to 120 °C for 1 to 60 minutes. The thermosetting resin film of the present invention obtained in this way has good storage stability. Note that the thermosetting resin film can be peeled off from the support at a desired timing.

[0146] The curing of the thermosetting resin film of the present invention can be carried out, for example, at 150 to 230 °C for 30 to 180 minutes. The curing of the thermosetting resin film of the present invention may be carried out after sandwiching the thermosetting resin film between substrates on which wiring is formed by a copper foil or the like, or may be carried out after appropriately laminating the thermosetting resin film on which wiring is formed by a copper foil or the like. Further, the thermosetting resin film can also be used as a coverlay film for protecting the wiring on the substrate, and the curing conditions at that time are the same. In addition, the thermosetting resin film of the present invention can be suitably used for a flexible copper-clad laminate (FCCL) for a flexible printed wiring board (FPC), a copper-clad laminate (CCL) for a multilayer substrate, or a build-up material.

[0147] Table 3 shows a preferred formulation example (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 preferably added appropriately so that the viscosity is in the range of 200 to 3000 mPa·s.

[0148]

Table 3

[0149] [Metal-clad laminate] The metal-clad laminate of the present invention will be described. The metal-clad laminate of the present invention includes an insulating layer containing a cured product of the resin composition of the present invention and a metal foil. The metal-clad laminate has a metal foil on the surface of the insulating layer. Further, the metal-clad laminate may include another layer between the insulating layer and the metal foil. Further, the insulating layer may or may not contain a base material. As the base material, the same materials as those of the base material of the prepreg can be used. As the metal foil, the same materials as those of the metal foil of the resin-coated metal foil can be used.

[0150] Examples of the method for manufacturing a metal-clad laminate include, for example, the method using the above-described prepreg. Examples of the method for producing a metal-clad laminate using a prepreg include a method in which one or more prepregs are stacked, and further, metal foils such as copper foil are stacked on both or one side of the upper and lower surfaces thereof, and this is heated and press-molded to be laminated and integrated. By this method, a laminate with metal foil on both or one side can be manufactured. The heating and pressing conditions can be appropriately set according to the thickness of the metal-clad laminate to be manufactured, the composition of the resin composition used in the prepreg, etc. For example, the conditions can be a temperature of 170 to 220 °C, a pressure of 1.5 to 5.0 MPa, and a time of 60 to 150 minutes. In addition, the metal-clad laminate can also be manufactured without using a prepreg. For example, there are a method in which a varnish-like resin composition of the present invention is applied on 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 method in which a thermosetting resin film using a metal foil as a support is cured, etc.

[0151] A preferred compounding example (excluding organic solvents) when using the resin composition of the present invention in a metal-clad laminate containing a substrate is the same as that in the case of the above-described prepreg (see Table 1 in paragraph

[0133] ). Also, a preferred compounding example (excluding organic solvents) when using the resin composition of the present invention in a metal-clad laminate not containing a substrate is the same as that in the case of the resin-coated metal foil not containing a substrate described above (see Table 2 in paragraph

[0141] ).

[0152] By using such a metal-clad laminate, a printed wiring board excellent in electrical characteristics (for example, dielectric characteristics, etc.), heat resistance, flame retardancy, adhesive strength, and chemical resistance can be manufactured.

[0153] [Printed Wiring Board] The printed wiring board of the present invention will be described. The printed wiring board of the present invention includes 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. Further, the printed wiring board of the present invention may be provided with other layers between the insulating layer and the wiring. Further, the insulating layer may or may not contain a base material. As the base material, the same material as the base material of the prepreg can be used. The printed wiring board of the present invention includes 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, and thus has excellent electrical properties (e.g., dielectric properties, etc.) and high flame retardancy.

[0154] The wiring is not particularly limited as long as it is the wiring provided on the printed wiring board. For example, there is wiring formed by partially removing a metal foil laminated on the insulating layer. Further, as the wiring, for example, wiring formed by a method using subtractive, additive, semi-additive, chemical mechanical polishing (CMP), trench, inkjet, squeegee, transfer, etc. can be mentioned.

[0155] Examples of the method for manufacturing a printed wiring board include a method using the above-described metal-clad laminate. Examples of the method for manufacturing a printed wiring board using a metal-clad laminate include a method of forming a circuit by etching the metal foil on the surface of the metal-clad laminate. By this method, a printed wiring board having a conductor pattern as a circuit provided on the surface of the metal-clad laminate can be obtained.

[0156] The preferred compounding example (excluding organic solvents) when the resin composition of the present invention is used for a printed wiring board having a base material in the insulating layer is the same as that in the case of the above-described prepreg (see Table 1 in paragraph

[0133] ). Further, the preferred compounding example (excluding organic solvents) when the resin composition of the present invention is used for a printed wiring board having no base material in the insulating layer is the same as that in the case of the copper foil with resin having no base material described above (see Table 2 in paragraph

[0141] ).

[0157] The printed wiring board thus obtained is excellent in electrical properties (e.g., dielectric properties, etc.), heat resistance, flame retardancy, and chemical resistance, and sufficiently suppresses peeling of the circuit. Further, even in the form of a package with a semiconductor chip bonded thereto, it is easy to mount, has no variation in quality, and is also excellent in signal speed and impedance.

[0158] [Resin plate] The resin composition of the present invention can also be used as a resin plate cured in a plate shape. For example, there can be mentioned a resin plate obtained by applying the varnish-like resin composition of the present invention in a plate shape, drying it, and then curing it. Further, as the resin plate, for example, an unclad plate obtained by removing the metal foil of the metal-clad laminate plate can also be mentioned.

[0159] [Semiconductor device] The case where the resin composition of the present invention is used in a semiconductor device will be described. A semiconductor device can be manufactured by using the resin composition of the present invention or the thermosetting resin film of the present invention and curing it. This semiconductor device is excellent in electrical characteristics (for example, dielectric characteristics, etc.) and has high flame retardancy due to the cured product of the resin composition of the present invention or the cured product of the thermosetting resin film of the present invention, and is suitable for high-frequency applications. A semiconductor device refers to all devices that can function by utilizing semiconductor characteristics, and includes electronic components, semiconductor circuits, modules incorporating these, electronic devices, and the like.

[0160] [Adhesive] The adhesive of the present invention will be described. 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 metal, inorganic materials, and resin materials. In particular, it is preferable as an adhesive between metal and a material selected from metal, inorganic materials, and resin materials.

[0161] Examples of the above-mentioned metal include copper, aluminum, titanium, nickel, tin, iron, silver, gold, and alloys thereof. Among these metals, copper is preferable. Further, as the form of the metal, there can be mentioned plates, foils, plated films, etc. made of these metals.

[0162] Examples of the inorganic materials include silicon, ceramics, carbon used as a filler, inorganic salts, glass, etc. Specifically, silicon compounds such as silicon, silicon carbide, silica, glass, diatomaceous earth, calcium silicate, talc, glass beads, sericite activated clay, bentonite, aluminosilicate, mica, etc.; oxides such as alumina, zinc oxide, iron oxide, magnesium oxide, tin oxide, titanium oxide, etc.; hydroxides such as magnesium hydroxide, aluminum hydroxide, basic magnesium carbonate, etc.; carbonates such as calcium carbonate, zinc carbonate, hydrotalcite, magnesium carbonate, etc.; sulfates such as barium sulfate, gypsum, etc.; titanates such as barium titanate, etc.; nitrides such as aluminum nitride, silicon nitride, etc.; graphites such as flaky graphite (natural graphite), expanded graphite, expanded graphite (synthetic graphite), etc.; activated carbons; carbon fibers; carbon black, etc. Among these inorganic materials, silicon, ceramics (such as alumina, silicon carbide, aluminum nitride, silicon nitride, barium titanate, etc.), glass and inorganic salts are preferred.

[0163] Examples of the resin materials 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 resin, fluorine-containing resin, polyether resin, polyetherimide resin, polyetheretherketone resin, polyester resin, silicone resin, liquid crystal resin, etc. These may be mixed, modified with each other, or combined. 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 are preferred.

[0164] As a method of bonding materials using an adhesive, it can be carried out by known methods. Specifically, (1) applying an adhesive to the surface of a material selected from a metal, an inorganic material, and a resin material, and pressing and bonding (curing) another material to part or all of the applied adhesive, or (2) sticking a semi-cured adhesive formed in a sheet shape to the surface of a material selected from a metal, an inorganic material, and a resin material, and pressing and bonding (curing) another material to part or all of the other surface of the adhesive.

[0165] As a method of curing the adhesive, it can be carried out by known methods. For example, a method of heating and pressurizing using a hot press machine, a method of heat-treating after drying the initially applied adhesive, etc. can be mentioned. As the conditions for heating and pressurizing, for example, the temperature can be 50 to 300 °C (particularly, 80 to 250 °C), the pressure can be 0.1 to 50 MPa (particularly, 0.5 to 10 MPa), and the time can be about 1 minute to 10 hours (particularly, about 30 minutes to 5 hours).

[0166] By using the adhesive of the present invention, two materials, particularly two materials with different materials, can be bonded, so it can be suitably used for various electrical or electronic components, semiconductor wafers, printed wiring boards, flexible metal-clad laminates and other electronic devices.

[0167] A preferred formulation example (excluding organic solvents) when using the resin composition of the present invention as an adhesive is the same as that in the case of the aforementioned thermosetting resin film (see Table 3 in paragraph

[0148] ).

[0168] In this specification, the terms "comprising" or "having" shall include the concepts of "consisting essentially of" and "consisting of".

Examples

[0169] Hereinafter, the present invention will be described in more detail by examples (synthesis tests, evaluation tests) and comparative examples (evaluation tests), but the present invention is not limited thereto. The "parts" used here represent "parts by weight" unless otherwise specified. The main raw materials used in the reference examples and the synthesis tests are as follows.

[0170] [Main raw materials] · 2-Phenoxy-5,5-bis(bromomethyl)-1,3,2-dioxaphospholane 2-oxide (Synthesized according to the method described in 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 Chemicals Corporation, see Chemical Formula (III-1).) · N,N-Dimethylformamide (manufactured by Fujifilm Wako Pure Chemical Corporation) · Potassium carbonate (manufactured by Fujifilm Wako Pure Chemical Corporation) · Potassium iodide (manufactured by Fujifilm Wako Pure Chemical Corporation) · Isopropyl alcohol (manufactured by Fujifilm Wako Pure Chemical Corporation) · 4-(Methanesulfonyloxy)methyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane 1-oxide (Synthesized according to the method described in RSC Advances, 6(57), 52485-52494(2016). See Chemical Formula (II-2-1).) · Sodium carbonate (manufactured by Fujifilm Wako Pure Chemical Corporation) · Sodium iodide (manufactured by Fujifilm Wako Pure Chemical Corporation)

[0171] The main raw materials (excluding the phosphorus compounds of the present invention) used in the evaluation tests are as follows. [Main raw materials] (A) Flame retardant · 1,3-Phenylenebis(di-2,6-xylyl phosphate) (manufactured by Daihachi Chemical Industry Co., Ltd., trade name "PX-200", see Chemical Formula (V).)

[0172] [Chemical formula]

[0173] (B) Thermally radical curable 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, styrene-based block copolymer, trade name "Tufprene A", styrene / butadiene weight ratio = 40 / 60) (D) Crosslinking agent · 1-Dodecyl-3,5-diallyl isocyanurate (manufactured by Shikoku Chemicals Corporation) (E) Radical polymerization initiator · α,α′-Di(t-butylperoxy) diisopropylbenzene (manufactured by NOF Corporation, trade name "Perbutyl P") (F) Inorganic filler · Silica (manufactured by Admatechs Co., Ltd., trade name "Admafine SC2300-SVJ") (G) Organic solvent · Toluene (manufactured by Fujifilm Wako Pure Chemical Corporation)

[0174] The methods of the evaluation tests (evaluation of flame retardancy, measurement of Tg and CTE, evaluation of adhesion) adopted in the examples and comparative examples are as follows.

[0175] [Evaluation of flame retardancy] The resin composition was applied onto a 25-μm-thick polyimide film using a bar coater so that the dried coating film had a thickness of 50 ± 5 μm, and toluene was distilled off until a constant weight was obtained. Subsequently, an evaluation film was prepared by performing heat treatment under the conditions of 150 °C for 30 minutes and 200 °C for 1 hour. The flame retardancy of this evaluation film was evaluated according to the UL94 VTM test method of the vertical burning test of the US UL standard.

[0176] [Measurement of Tg and CTE] The resin composition was poured into an aluminum cup with a radius of 3.5 cm coated with a release agent so that the thickness after curing would be 1.5 mm, and toluene was distilled off until a constant weight was reached. Subsequently, a cured product for evaluation was prepared by performing heat treatment under the conditions of 150 °C for 30 minutes and 200 °C for 1 hour. For this cured product for evaluation, the glass transition temperature (Tg) and the coefficient of linear expansion (CTE) were measured using a thermomechanical analyzer (TMA, manufactured by Hitachi High-Technologies Corporation, "TMA7100") (flow gas: nitrogen, temperature increase condition: 5 °C / min.).

[0177] [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 a constant weight was reached. Subsequently, a glass epoxy substrate (FR-4 grade) was overlaid on the coated surface of the resin composition, and a test piece was prepared by pressing under the heating and pressurizing conditions of 150 °C for 30 minutes, 200 °C for 1 hour, and 0.5 MPa. For this test piece, the normal peel strength was measured in accordance with "JIS C6481".

[0178] [Example 1] [Synthesis of 2-Phenoxy-5,5-bis[(tetrahydro-2,4,6-trioxo-3,5-di-2-penten-1-yl-1,3,5-triazine-1(2H)-yl)methyl]-1,3,2-dioxaphospholane 2-oxide] Into a 1 L eggplant flask, 40.00 g (100.00 mmol) of 2-phenoxy-5,5-bis(bromomethyl)-1,3,2-dioxaphospholane 2-oxide, 46.02 g (220.00 mmol) of diallyl isocyanurate, 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, and while stirring, the temperature was raised to 100 °C and stirred for 36 hours. Subsequently, toluene was added to this reaction solution, washed with water, and the organic layer was concentrated. The obtained concentrate was recrystallized with isopropyl alcohol to obtain 41.50 g of a white powder (yield 63.2%).

[0179] The 1 1H-NMR spectrum data of this white powder was as follows. · 1 1H-NMR (d6-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). Also, the IR spectrum data of this white powder was as shown in the chart of FIG. 1. From these spectrum data, the obtained white powder was identified as the title phosphorus compound represented by chemical formula (I-1-1).

[0180] [Example 2] <Synthesis of 4-(tetrahydro-2,4,6-trioxo-3,5-di-2-penten-1-yl-1,3,5-triazin-1(2H)-yl)methyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane 1-oxide> To a 1 L eggplant flask, 41.31 g (160.00 mmol) of 4-(methanesulfonyloxy)methyl-2,6,7-trioxa-1-phosphabicyclo[2.2.2]octane 1-oxide, 35.15 g (168.00 mmol) of diallyl 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. While stirring, the temperature was raised to 100 °C and stirred for 14 hours. After cooling to 30 °C, 400 g of water was added, and the precipitated solid was filtered off. The solid was washed with saturated aqueous sodium hydrogen carbonate solution, water, and methanol in that order, and dried under reduced pressure to obtain 45.00 g of a white powder (yield 75.80%).

[0181] The 1 1H-NMR spectrum data of this white powder was as follows. · 11H-NMR (d6-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 spectral data of this white powder was as shown in the chart of FIG. 2. From these spectral data, the obtained white powder was identified as the title phosphorus compound represented by the chemical formula (I-2-1).

[0182] [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 methacryl-modified polyphenylene ether as a thermally radical curable resin component, 138.8 parts by weight of styrene-butadiene block copolymer as other resin components, 20.0 parts by weight of 1-dodecyl-3,5-diallylisocyanurate as a crosslinking agent, 1.2 parts by weight of α,α'-di(t-butylperoxy) diisopropylbenzene as a radical polymerization initiator, 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 thermally radical curable resin composition. When an evaluation test was conducted on this resin composition, the obtained test results were as shown in Table 4.

[0183] [Example 4, Comparative Examples 1 - 2] In the same manner as in the case of Example 3, thermally radical curable resin compositions having the compositions shown in Table 4 were prepared, and when evaluation tests were conducted on these resin compositions, the obtained test results were as shown in Table 4.

[0184] [Table 4]

[0185] From the results in Table 4, in both Examples 3 and 4 where the phosphorus compound of the present invention having an isocyanurate ring and an unsaturated bonding group (allyl group) in the molecule was used as a flame retardant, the flame retardancy was improved compared to Comparative Example 1 where no flame retardant was used, and the flame retardancy equivalent to that of Comparative Example 2 using a conventional flame retardant was shown. Also, both Examples 3 and 4 showed higher Tg and lower CTE values compared to Comparative Examples 1 and 2. This indicates that the crosslink density of the cured products of the resin compositions in Examples 3 and 4 increased, the heat resistance was high, and the volume change due to temperature was suppressed. In addition, both Examples 3 and 4 had improved adhesion compared to Comparative Example 1. Therefore, it can be understood that by using the phosphorus compound of the present invention (the compounds in Examples 1 and 2) as a flame retardant, a cured product excellent in low thermal expansibility, heat resistance, adhesiveness (adhesion), and flame retardancy can be obtained.

Industrial Applicability

[0186] The phosphorus compound of the present invention is expected to be used as a flame retardant for resins. In addition, since the resin composition containing the phosphorus compound of the present invention is expected to provide a cured product excellent in low thermal expansibility, heat resistance, adhesiveness (adhesion), mechanical properties, electrical properties, and flame retardancy, it is suitable for materials such as printed wiring boards and materials for adhesives.

Claims

1. A phosphorus compound having an isocyanurate ring represented by chemical formula (I). 【Chemical Formula 1】 (wherein, 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 may be linked to form a ring. R ３ are the same or different and each represents an alkenyl group having 2 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms. R ４ are the same or different and each represents 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 each represents an alkylene group having 1 to 20 carbon atoms.) [Chemical Formula 2] (wherein R ３ , R ４ and Y are the same as described above.)

2. A method for synthesizing a phosphorus compound having an isocyanurate ring according to Claim 1, characterized by reacting a phosphorus compound represented by chemical formula (II) with an isocyanurate compound represented by chemical formula (III). [Chemical Formula 3] (In the formula, R １ is the same as described above, and R ８ represents -Y-X. Alternatively, R １ and R ８ may be linked to form a ring. Y is the same as described 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).) 【Chemical Formula 4】 (wherein R ３ and R ４ are the same as described above.)

3. A flame retardant containing the phosphorus compound having an isocyanurate ring according to Claim 1.

4. A resin composition containing the phosphorus compound having an isocyanurate ring according to Claim 1 and a resin component.

5. The resin composition according to Claim 4, characterized in that the resin component is a polyphenylene ether resin.

6. A prepreg comprising the resin composition according to Claim 4 or Claim 5 and a base material.

7. A metal-clad laminate comprising a resin layer containing the resin composition according to Claim 4 or Claim 5 or a semi-cured product of the resin composition and a metal foil.

8. A thermosetting resin film formed from the resin composition according to Claim 4 or Claim 5.

9. A metal-clad laminate comprising an insulating layer containing a cured product of the resin composition according to Claim 4 or Claim 5 and a metal foil.

10. A printed wiring board comprising an insulating layer containing a cured product of the resin composition according to Claim 4 or Claim 5 or a cured product of the thermosetting resin film according to Claim 8 and a wiring.

11. An adhesive comprising the resin composition according to Claim 4 or Claim 5 as a component.

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