Phosphorus compound, method for synthesizing same, and use thereof

Abstract

The purpose of the present invention to provide: a novel phosphorus compound; a method for synthesizing the compound; a flame retardant containing the compound; and a resin composition containing the compound and a resin component. The purpose of the present invention is to additionally provide: a prepreg using the resin composition; a resin-equipped metal foil; a thermosetting resin film; a metal-clad laminated board; a printed wiring board; and an adhesive. The present invention relates to a phosphorus compound represented by chemical formula (I), a synthesis method, and a use thereof. (In the formula, the R1's are the same or different and represent a hydrogen atom, a C1 to C10 alkyl group, a C2 to C10 alkenyl group, a C2 to C10 alkynyl group, or an aryl group optionally substituted with a C1 to C10 alkyl group or phenyl group; R2 represents a C1 to C10 alkyl group, a C2 to C10 alkenyl group, a C2 to C10 alkynyl group, or an aryl group optionally substituted with a C1 to C10 alkyl group or phenyl group, and when there are a plurality of R2's, the R2's may be the same or different; Y1 represents a phenylene group optionally substituted with a C1 to C10 alkyl group, a naphthylene group, or a group indicated by formula (A); and the n's are the same or different and represent an integer of 0-3.) (In the formula, the R3's are the same or different and represent a hydrogen atom, a C1 to C10 alkyl group, a C2 to C10 alkenyl group, a C2 to C10 alkynyl group, or an aryl group optionally substituted with a C1 to C10 alkyl group or phenyl group; and Y2 represents a single bond, a C1 to C15 alkylene group optionally substituted with a phenyl group, a C5 to C15 cycloalkylene group, a C5 to C15 cycloalkylidene group optionally substituted with a C1 to c10 alkyl group, a phenylene group, an adamantane-1,3-ylene group, an adamantane-2-ylidene group, an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group, or a fluorene-9-ylidene group.)

Description

Phosphorus compounds, their synthesis methods and uses

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

[0002] In recent years, electronic devices have become smaller and more powerful, and in multilayer printed wiring boards, build-up layers have become more numerous, resulting in a demand for finer and denser wiring. In particular, for high-frequency applications, insulating materials (resin materials) with low dielectric loss tangents are required to reduce transmission loss of electrical signals. Such resin materials are required to have not only good electrical properties but also flame retardancy after curing, and various flame retardants have been investigated.

[0003] A phosphorus compound represented by the chemical formula (V) is known as a conventional flame retardant (see, for example, Patent Document 1). This phosphorus compound has a reactive group (vinyl group) and a phosphorus atom in the molecule.

[0004]

[0005] Patent Document 2 describes a reactive flame retardant characterized by containing an organic cyclic phosphorus compound having an unsaturated group at its terminal, which is represented by formula (I) (for example, a compound represented by formula (I-17)).

[0006] Patent Document 3 describes a reactive flame retardant characterized by containing an organophosphorus compound represented by formula (IVa) (for example, a compound represented by formula (IVa-4)).

[0007] Although cured products of resin compositions containing these phosphorus compounds exhibit excellent properties such as flame retardancy, electrical properties, and heat resistance, there is still room for improvement in thermal expansion and electrical properties. In addition, these phosphorus compounds have problems such as low moisture absorption resistance and low hydrolysis resistance.

[0008] Chinese Patent Application Publication No. 109762115 International Publication No. 2005 / 026251 International Publication No. 2005 / 012415

[0009] The present invention aims to provide a novel phosphorus compound, a method for synthesizing the compound, a flame retardant containing the compound, and a resin composition containing the compound and a resin component. It also aims 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.

[0010] As a result of extensive research aimed at solving the above problems, the present inventors have found that the above object can be achieved by a phosphorus compound having four vinylphenyl groups, and have thus completed the present invention. That is, the first invention is a phosphorus compound represented by chemical formula (I):

[0011] (In the formula, R １ are the same or different and represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an aryl group which may be substituted with an alkyl group having 1 to 10 carbon atoms or a phenyl group. ２ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an aryl group which may be substituted with an alkyl group having 1 to 10 carbon atoms or a phenyl group; R ２ When there are a plurality of Y, they may be the same or different. １ represents a phenylene group, a naphthylene group, or a group represented by formula (A) which may be substituted with an alkyl group having 1 to 10 carbon atoms; and n may be the same or different and represents an integer of 0 to 3.

[0012] (In the formula, R ３ are the same or different and represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an aryl group which may be substituted with an alkyl group having 1 to 10 carbon atoms or a phenyl group. ２represents a single bond, an alkylene group having 1 to 15 carbon atoms which may be substituted with a phenyl group, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms which may be substituted with an alkyl group having 1 to 10 carbon atoms, a phenylene group, an adamantane-1,3-ylene group, an adamantane-2-ylidene group, an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group, or a fluoren-9-ylidene group.

[0013] The second invention is a method for synthesizing a phosphorus compound according to the first invention, characterized in that a compound represented by chemical formula (II) is reacted with phosphoryl chloride, and then a vinylphenol compound represented by chemical formula (III) is reacted therewith.

[0014] (In the formula, Y １ is the same as above.)

[0015] (In the formula, R １ , R ２ and n is the same as above.

[0016] The third invention is a method for synthesizing a phosphorus compound according to the first invention, characterized in that a vinylphenol compound represented by chemical formula (III) is reacted with phosphoryl chloride, and then a compound represented by chemical formula (II) is reacted therewith.

[0017] (In the formula, R １ , R ２ and n is the same as above.

[0018] (In the formula, Y １ is the same as above.)

[0019] The fourth invention is a flame retardant containing the phosphorus compound of the first invention. The fifth invention is a resin composition containing the phosphorus compound of the first invention and a resin component. The sixth invention is a prepreg comprising the resin composition of the fifth invention and a substrate. The seventh invention is a resin-coated metal foil comprising a resin layer containing the resin composition of 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 of the fifth invention. The ninth invention is a metal-clad laminate comprising an insulating layer containing a cured product of the resin composition of 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 of the fifth invention or a cured product of the thermosetting resin film of the eighth invention, and wiring. The eleventh invention is an adhesive comprising the resin composition of the fifth invention.

[0020] The phosphorus compound of the present invention has four reactive groups (vinyl groups) and two phosphorus atoms in its molecule, and is therefore expected to be useful as a flame retardant for various resins. Furthermore, since the phosphorus compound of the present invention has a high phosphorus content in its molecule and four reactive groups, when used as a resin raw material (resin material), it is expected to provide a cured product with low thermal expansion (low CTE) and excellent flame retardancy, electrical properties (e.g., low dielectric tangent), heat resistance, moisture absorption resistance, and hydrolysis resistance compared to conventional phosphorus compounds. Therefore, the resin composition of the present invention can be suitably used as a material for printed wiring boards, etc. Furthermore, the adhesive of the present invention is expected to have excellent adhesion, flame retardancy, electrical properties (e.g., low dielectric tangent), heat resistance, moisture absorption resistance, and hydrolysis resistance.

[0021] 1 is an IR spectrum chart of a pale yellow liquid obtained in Example 1. FIG. 2 is an IR spectrum chart of a white solid obtained in Example 2. FIG. 3 is an IR spectrum chart of a yellow liquid obtained in Example 3. FIG. 4 is an IR spectrum chart of a yellow liquid obtained in Example 4. FIG. 5 is an IR spectrum chart of a yellow liquid obtained in Example 5.

[0022] 1. Phosphorus Compound The present invention relates to a phosphorus compound represented by chemical formula (I) (hereinafter, sometimes referred to as the "phosphorus compound of the present invention"). Examples of the phosphorus compound of the present invention include compounds represented by chemical formulas (I-1) to (I-72).

[0023]

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043] R １ , R ２ and R ３Examples of the alkyl group having 1 to 10 carbon atoms represented by the formula (I) include linear or branched alkyl groups having 1 to 10 carbon atoms (preferably alkyl groups having 1 to 6 carbon atoms, more preferably alkyl groups having 1 to 4 carbon atoms), and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an s-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group.

[0044] R １ , R ２ and R ３ Examples of the alkenyl group having 2 to 10 carbon atoms represented by the formula (I) include linear or branched alkenyl groups having 2 to 10 carbon atoms (preferably alkenyl groups having 2 to 6 carbon atoms, more preferably alkenyl groups having 2 to 4 carbon atoms), and specific examples thereof include vinyl groups, allyl groups, isopropenyl groups, 1-butenyl groups, 2-butenyl groups, 3-butenyl groups, pentenyl groups, hexenyl groups, heptenyl groups, octenyl groups, nonenyl groups, and decenyl groups.

[0045] R １ , R ２ and R ３ Examples of the alkynyl group having 2 to 10 carbon atoms represented by the formula (I) include linear or branched alkynyl groups having 2 to 10 carbon atoms (preferably, an alkynyl group having 2 to 6 carbon atoms, and more preferably, an alkynyl group having 2 to 4 carbon atoms), and specific examples thereof include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a pentynyl group, a hexynyl group, a heptynyl group, an octynyl group, a nonynyl group, and a decynyl group.

[0046] R １ , R ２ and R ３Examples of the aryl group which may be substituted with an alkyl group or a phenyl group having 1 to 10 carbon atoms and which is represented by the formula (I) include an aryl group which may be substituted with an alkyl group or a phenyl group having 1 to 6 carbon atoms (further, 1 to 4 carbon atoms), such as a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, a 2,3-xylyl group, a 2,4-xylyl group, a 2,5-xylyl group, a 2,6-xylyl group, a 3,4-xylyl group, a 3,5-xylyl group, a 2,4,6-trimethylphenyl group, a 2,3,5-trimethylphenyl group, a 2,3,6-trimethylphenyl group, a 2,4,5-trimethylphenyl group, a 2,3,5,6-tetramethylphenyl group, a biphenylyl group, a 1-naphthyl group, and a 2-naphthyl group.

[0047] Y １ and Y ２ Examples of the phenylene group which may be substituted with an alkyl group having 1 to 10 carbon atoms, represented by the formula (I), include a phenylene group which may be substituted with an alkyl group having 1 to 6 carbon atoms (further, 1 to 4 carbon atoms), and examples thereof include a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, a 2-methyl-1,4-phenylene group, a 2,6-dimethyl-1,4-phenylene group, a 2,3-dimethyl-1,4-phenylene group, a 2,3,5-trimethyl-1,4-phenylene group, a 2-t-butyl-1, Examples thereof include a 4-phenylene group, a 2,5-di-t-butyl-1,4-phenylene group, and a 2,5-di-t-pentyl-1,4-phenylene group, and preferred are a 2-methyl-1,4-phenylene group, a 2,6-dimethyl-1,4-phenylene group, a 2,3-dimethyl-1,4-phenylene group, a 2,3,5-trimethyl-1,4-phenylene group, a 2-t-butyl-1,4-phenylene group, a 2,5-di-t-butyl-1,4-phenylene group, and a 2,5-di-t-pentyl-1,4-phenylene group.

[0048] Y １ Examples of the naphthylene group represented by the formula (I) include a 1,2-naphthylene group, a 1,3-naphthylene group, a 1,4-naphthylene group, a 1,5-naphthylene group, a 1,6-naphthylene group, a 1,7-naphthylene group, a 1,8-naphthylene group, a 2,3-naphthylene group, a 2,6-naphthylene group, and a 2,7-naphthylene group.

[0049] Y ２ Examples of the alkylene group having 1 to 15 carbon atoms and which may be substituted with a phenyl group represented by the formula (I) include linear or branched alkylene groups having 1 to 15 carbon atoms (preferably alkylene groups having 1 to 10 carbon atoms, more preferably alkylene groups having 1 to 6 carbon atoms), such as a methylene group, an ethylene group, a propylene group, a butylene group, a methylmethylene group, a dimethylmethylene group, a propan-1-ylidene group, a butan-1-ylidene group, a butan-2-ylidene group, a 2-methylpropan-1-ylidene group, a pentan-2-ylidene group, a 3-methylbutan-1-ylidene group, a hexane-2-ylidene group, a heptan-4-ylidene group, a 2-ethylhexan-1-ylidene group, a nonan-2-ylidene group, a phenylmethylene group, a phenylmethylmethylene group, and a diphenylmethylene group.

[0050] Y ２ Examples of the cycloalkylene group having 5 to 15 carbon atoms represented by the formula (I) include a cycloalkylene group having 5 to 8 carbon atoms, such as a 1,3-cyclopentylene group, a 1,2-cyclopentylene group, a 1,4-cyclohexylene group, a 1,3-cyclohexylene group, and a 1,2-cyclohexylene group.

[0051] Y ２ Examples of the cycloalkylidene group having 5 to 15 carbon atoms which may be substituted with an alkyl group having 1 to 10 carbon atoms, represented by the formula (I), include a cyclopentylidene group, a cyclohexylidene group, a cycloheptylidene group, a cyclododecylidene group, a 3-methylcyclohexan-1-ylidene group, and a 3,3,5-trimethylcyclohexan-1-ylidene group.

[0052] In the phosphorus compound of the present invention, preferred substituents are as follows: １ are preferably the same and are a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms, or an aryl group which may be substituted with an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and even more preferably a hydrogen atom, a methyl group, or a t-butyl group. ２are preferably the same and are an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms, or an aryl group which may be substituted with an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 4 carbon atoms, and even more preferably a methyl group or a t-butyl group. ３ are the same or different and are preferably a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, an alkenyl group having 2 to 5 carbon atoms, an alkynyl group having 2 to 5 carbon atoms, or an aryl group which may be substituted with an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and even more preferably a hydrogen atom or a methyl group. １ is preferably a phenylene group, a naphthylene group, or a group represented by formula (A), which may be substituted with an alkyl group having 1 to 10 carbon atoms (more preferably 1 to 6 carbon atoms, particularly preferably 1 to 4 carbon atoms). ２ is preferably a single bond, an alkylene group having 1 to 4 carbon atoms which may be substituted with a phenyl group, a cycloalkylidene group having 5 to 15 carbon atoms which may be substituted with an alkyl group having 1 to 10 carbon atoms (further having 1 to 6 carbon atoms, particularly having 1 to 4 carbon atoms), or a fluoren-9-ylidene group, and is preferably a single bond, a methylene group, an ethylene group, a methylmethylene group, a dimethylmethylene group, a propan-1-ylidene group, a butan-1-ylidene group, a butan-2-ylidene group, a 2-methylpropan-ylidene group, or More preferably, n is a 4-methylcyclohexane-1-ylidene group, a phenylmethylene group, a phenylmethylmethylene group, a diphenylmethylene group, a cyclopentylidene group, a cyclohexylidene group, a cycloheptylidene group, a cyclododecylidene group, a 4-methylcyclohexane-1-ylidene group, a 3,3,5-trimethylcyclohexane-1-ylidene group, or a fluoren-9-ylidene group, and even more preferably a single bond, a methylene group, a methylmethylene group, or a dimethylmethylene group. Preferably, n is the same and an integer of 0 to 2, and more preferably an integer of 0 to 1.

[0053] When used as a flame retardant for a cured resin material, the phosphorus compound represented by chemical formula (I) preferably has at least one of the structures shown below, from the viewpoint of improving the electrical properties of the cured resin material. (i) In chemical formula (I), one or two ortho-positions (o-positions) of each of the four phenyl groups have substituents other than hydrogen atoms. The substituents are within the range defined above. (ii) In chemical formula (I), Y １ is a group represented by formula (A), R ３ wherein one or more (even two or more) of the above may be the same or different and have a substituent other than a hydrogen atom. The substituent is within the range defined above. The mechanism by which the electrical properties of the cured resin material are improved is not entirely clear, but is presumed to be as follows: A phosphorus compound having the above structure inhibits rotation between the oxygen atom of the phosphate ester and the aromatic ring, and therefore it is believed that the electrical properties, such as dielectric properties, of a cured resin material containing the phosphorus compound are improved.

[0054] Preferred embodiments of the phosphorus compound represented by the chemical formula (I) include the following phosphorus compounds: １ are the same or different and represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an aryl group. ２ are the same or different and represent an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an aryl group; R ２ When there are a plurality of Y, they may be the same or different. １ represents a phenylene group, a naphthylene group, or a group represented by formula (A). n may be the same or different and represents an integer of 0 to 3. In formula (A), R ３ are the same or different and represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an aryl group. Y ２represents a single bond, an alkylene group having 1 to 15 carbon atoms which may be substituted with a phenyl group, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a phenylene group, an adamantane-1,3-ylene group, an adamantane-2-ylidene group, an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group, or a fluoren-9-ylidene group.

[0055] Other preferred embodiments of the phosphorus compound represented by the chemical formula (I) include the following phosphorus compounds: １ are the same and represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. ２ are the same and represent an alkyl group having 1 to 6 carbon atoms or an alkenyl group having 2 to 10 carbon atoms. １ represents a phenylene group, a naphthylene group, or a group represented by formula (A). n may be the same or different and represents an integer of 0 to 2. In formula (A), R ３ are the same or different and represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. ２ represents a single bond, an alkylene group having 1 to 10 carbon atoms which may be substituted with a phenyl group, a cycloalkylene group having 5 to 10 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms, a phenylene group, or a fluoren-9-ylidene group.

[0056] Another preferred embodiment of the phosphorus compound represented by the chemical formula (I) is a phosphorus compound represented by the following chemical formula (Ia): (In the formula, the symbols are the same as above.)

[0057] Another preferred embodiment of the phosphorus compound represented by the chemical formula (I) is a phosphorus compound represented by the following chemical formula (Ib). (In the formula, R １０ are the same or different and represent an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an aryl group which may be substituted with an alkyl group having 1 to 10 carbon atoms. Other symbols are as defined above.)

[0058] Another preferred embodiment of the phosphorus compound represented by the chemical formula (I) is a phosphorus compound represented by the following chemical formula (Ic). (In the formula, Y １０ represents a group represented by formula (A1) or formula (A2). n1 may be the same or different and represents an integer of 0 to 2. Other symbols are as defined above.

[0059] A preferred embodiment of the group represented by formula (A) is a group represented by the following formula (A1). (In the formula, Y ２０ represents a single bond, an alkylene group having 1 to 10 carbon atoms which may be substituted with a phenyl group, a cycloalkylene group having 5 to 8 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms which may be substituted with an alkyl group having 1 to 10 carbon atoms, a phenylene group, an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group, or a fluoren-9-ylidene group. ３０ are the same or different and represent an aryl group which may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. ３１ 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, an alkynyl group having 2 to 6 carbon atoms, or an aryl group which may be substituted with an alkyl group having 1 to 10 carbon atoms. (In the formula, R ３０ are the same or different and represent an aryl group which may be substituted with an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 2 to 6 carbon atoms, or an alkyl group having 1 to 10 carbon atoms. ３１ 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, an alkynyl group having 2 to 6 carbon atoms, or an aryl group which may be substituted with an alkyl group having 1 to 10 carbon atoms. n2 are the same or different and represent an integer of 0 to 3.

[0060] 2. Method for Synthesizing Phosphorus Compounds Examples of methods for synthesizing the phosphorus compounds of the present invention include synthesis methods (1) and (2).

[0061] <Synthesis Method (1)> The phosphorus compound of the present invention can be synthesized by reacting a compound represented by chemical formula (II) with phosphoryl chloride (Step 1), and then reacting the resulting compound with a vinylphenol compound represented by chemical formula (III) (see Reaction Scheme (A)).

[0062] (In the formula, R １ , R ２ , Y １ and n is the same as above.

[0063] Examples of the compound represented by chemical formula (II) include compounds represented by chemical formulas (II-1) to (II-14).

[0064]

[0065] These compounds can be purchased as commercially available reagents or can be synthesized according to the methods described in, for example, Toxicology and Industrial Health (2022), 38(10), 665-674, Journal of Polymer Research (2017), 24(10), 1-10, etc.

[0066] Examples of the vinylphenol compound represented by the chemical formula (III) include the vinylphenol compounds represented by the chemical formulas (III-1) to (III-33).

[0067]

[0068] These vinylphenol compounds can be purchased and used as commercially available reagents, or can be synthesized in accordance with the methods described in, for example, Royal Society Open Science (2022), 9(4), 220014, Tetrahedron Letters (2005), 46(40), 6893-6896, Current Organic Synthesis (2019), 16(1), 130-135, Organic Letters (2012), 14(18), 4722-4725, Synthesis (2017), 49(23), 5217-5223, etc.

[0069] Phosphoryl chloride can be purchased as a commercially available reagent.

[0070] In the reaction of the first step, the amount of phosphoryl chloride used (charged amount) is preferably an appropriate ratio in the range of 1.5 to 5 times the amount of the compound represented by chemical formula (II) used (charged amount).

[0071] In the reaction of the first step, a base (a) may be used to promote the reaction, and a reaction solvent (b) may be used as needed.

[0072] Examples of the base (a) include trimethylamine, triethylamine, N,N-diisopropylethylamine, diazabicyclononene, diazabicycloundecene, pyridine, 4-dimethylaminopyridine, 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, disodium 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 alkoxides, potassium alkoxides (e.g., potassium t-butoxide), etc. These may be used alone or in combination of two or more. The amount of base (a) used (charged amount) is preferably an appropriate ratio in the range of 0 to 40 times the amount of the compound represented by the chemical formula (II) used (charged amount).

[0073] The reaction solvent (b) is not particularly limited as long as it does not inhibit the reaction, and examples thereof include solvents such as tetrahydrofuran, dioxane, ethyl acetate, acetonitrile, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, N,N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, hexamethylphosphoric triamide, and water, and these can be used in combination in appropriate amounts as necessary.

[0074] In the reaction of the first step, the reaction temperature is preferably set in the range of −100 to 150° C. The reaction time is appropriately set depending on the set reaction temperature, but is preferably set in the range of 0.5 to 100 hours.

[0075] After the reaction of the first step is completed, the target precursor of the phosphorus compound of the present invention (hereinafter, sometimes referred to as "precursor 1 of the present invention") can be isolated from the resulting reaction solution (reaction mixture) by, for example, concentrating the reaction solution by distilling off the reaction solvent or by solvent extraction. Furthermore, if necessary, the precursor can be purified by washing with water or the like, activated carbon treatment, silica gel chromatography, recrystallization, or the like. The precursor 1 of the present invention may be subjected to the aforementioned concentration, extraction, purification, or the like before being subjected to the second step, or the reaction solution obtained after the reaction of the first step may be subjected to the second step as is.

[0076] In the reaction of the second step, the amount (charge amount) of the vinylphenol compound represented by the chemical formula (III) used is preferably an appropriate ratio in the range of 3 to 30 times by mole relative to the amount (charge amount) of the precursor 1 of the present invention.

[0077] In the reaction of the second step, a base (a) may be used to promote the reaction. If necessary, a reaction solvent (b) may be used appropriately. As the base (a) and the reaction solvent (b), those exemplified in the first step can be used. The amount of base (a) used (charged amount) is preferably set to an appropriate ratio in the range of 0 to 40 times the amount of precursor 1 of the present invention used (charged amount).

[0078] In the reaction of the second step, the reaction temperature is preferably set in the range of −100 to 150° C. The reaction time is appropriately set depending on the set reaction temperature, but is preferably set in the range of 0.5 to 100 hours.

[0079] After completion of the reaction in the second step, the target compound of the present invention can be isolated from the resulting reaction solution (reaction mixture) by, for example, concentrating the reaction solution by distilling off the reaction solvent, solvent extraction, etc. If necessary, the compound can be further purified by washing with water or the like, treatment with activated carbon, silica gel chromatography, recrystallization, etc.

[0080] <Synthesis Method (2)> The phosphorus compound of the present invention can be synthesized by reacting a vinylphenol compound represented by chemical formula (III) with phosphoryl chloride (Step 1), and then reacting the resulting compound with a compound represented by chemical formula (II) (see Reaction Scheme (B)).

[0081] (In the formula, R １ , R ２ , Y １ and n is the same as above.

[0082] In the reaction of the first step, the amount of the vinylphenol compound represented by the chemical formula (III) used (charged amount) is preferably set at an appropriate ratio in the range of 1.5 to 3 times the molar amount of phosphoryl chloride used (charged amount).

[0083] In the reaction of the first step, a base (a) may be used to promote the reaction. If necessary, a reaction solvent (b) may be used appropriately. As the base (a) and the reaction solvent (b), those exemplified in the synthesis method (1) can be used. The amount of base (a) used (charge amount) is preferably set at an appropriate ratio in the range of 0 to 40 times the molar amount of phosphoryl chloride used (charge amount).

[0084] In the reaction of the first step, the reaction temperature is preferably set in the range of −100 to 150° C. The reaction time is appropriately set depending on the set reaction temperature, but is preferably set in the range of 0.5 to 100 hours.

[0085] After the reaction of the first step is completed, the target precursor of the phosphorus compound of the present invention (hereinafter, sometimes referred to as "precursor 2 of the present invention") can be isolated from the resulting reaction solution (reaction mixture) by, for example, concentrating the reaction solution by distilling off the reaction solvent or by solvent extraction. Furthermore, if necessary, the precursor can be purified by washing with water or the like, activated carbon treatment, silica gel chromatography, recrystallization, or the like. The precursor 2 of the present invention may be subjected to the aforementioned concentration, extraction, purification, or the like before being subjected to the second step, or the reaction solution obtained after the reaction of the first step may be subjected to the second step as is.

[0086] In the reaction of the second step, the amount of precursor 2 of the present invention used (charged amount) is preferably an appropriate ratio in the range of 1.5 to 10 times the molar amount of the compound represented by chemical formula (II).

[0087] In the reaction of the second step, a base (a) may be used to promote the reaction. If necessary, a reaction solvent (b) may be used appropriately. As the base (a) and the reaction solvent (b), those exemplified in the synthesis method (1) can be used. The amount of base (a) used (charge amount) is preferably an appropriate ratio in the range of 0 to 40 times the amount of the compound represented by chemical formula (II) used (charge amount).

[0088] In the reaction of the second step, the reaction temperature is preferably set in the range of −100 to 150° C. The reaction time is appropriately set depending on the set reaction temperature, but is preferably set in the range of 0.5 to 100 hours.

[0089] After completion of the reaction in the second step, the target compound of the present invention can be isolated from the resulting reaction solution (reaction mixture) by, for example, concentrating the reaction solution by distilling off the reaction solvent, solvent extraction, etc. If necessary, the compound can be further purified by washing with water or the like, treatment with activated carbon, silica gel chromatography, recrystallization, etc.

[0090] 3. Flame Retardant and Resin Composition The flame retardant and resin composition of the present invention contain the phosphorus compound of the present invention. The phosphorus compound of the present invention has a high flame retardant effect and can therefore be suitably used as a flame retardant for resins. By including the phosphorus compound of the present invention in a resin composition, a cured product (molded product) of the resin composition exhibits excellent flame retardancy. Note that the resin composition of the present invention may contain, in addition to the phosphorus compound of the present invention and a resin component, other flame retardants, polymerizable components, polymerization initiators, reactive diluents, fluororesins, inorganic fillers, and additives as necessary. In addition, in the present invention, the resin composition refers to the state of the mixture before curing.

[0091] [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 a material commonly used as a resin molded body. Examples of the resin component include polyethylene resin, chlorinated polyethylene resin, polyvinyl chloride resin, polypropylene resin, polyisoprene 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, and 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 resin, benzoxazine resin, liquid crystal polymer resin, silicone resin, epoxy resin, polyurethane resin, phenolic resin, melamine resin, urea resin, diallyl phthalate resin, etc. These may be used alone or in combination of two or more.

[0092] The amount of the phosphorus compound of the present invention blended in the resin composition of the present invention is not particularly limited, and is 1 to 200 parts by weight, preferably 1 to 160 parts by weight, and more preferably 2 to 150 parts by weight, per 100 parts by weight of the resin component.

[0093] [Other Flame Retardants] The resin composition of the present invention may contain flame retardants (other flame retardants) other than the phosphorus compound of the present invention. Examples of other flame retardants include phosphate ester compounds, phosphazene compounds, phosphite ester compounds, phosphine compounds, melamine phosphate, phosphoric acid amide compounds, phosphoric acid amide ester compounds, phosphinate compounds and salts thereof, 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, ethylenebispentabromobenzene, and ethylenebistetrabromophthalimide. Examples of phosphate ester compounds include triphenyl phosphate, tricresyl phosphate, xylenyl diphenyl phosphate, cresyl diphenyl phosphate, 1,3-phenylenebis(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, and cyclic phosphate ester compounds. Examples of phosphazene compounds include cyclic or chain phosphazene compounds. Cyclic phosphazene compounds, also known as cyclophosphazenes, are compounds with a cyclic structure containing phosphorus and nitrogen as constituent elements and a double bond in the molecule. Examples of phosphite ester compounds include trimethyl phosphite and triethyl phosphite. Examples of phosphine compounds include tris-(4-methoxyphenyl)phosphine and triphenylphosphine. These compounds may be used alone or in combination of two or more.

[0094] The amount of the other flame retardant in the resin composition of the present invention is not particularly limited as long as it does not adversely affect the effects of the present invention, and is 0 to 100 parts by weight, preferably 1 to 80 parts by weight, and more preferably 10 to 40 parts by weight, per 100 parts by weight of the resin component.

[0095] [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, and cyclic compounds (epoxy compounds, lactone compounds, lactam compounds, cyclic ether compounds, etc.). Examples of these polymerizable 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) precursors, methyl methacrylate-acrylonitrile-butadiene-styrene resin (MABS resin) precursors, acrylonitrile-acrylic rubber-styrene resin (AAS resin) precursors, methyl (meth)acrylate, epoxy acrylate resin precursors, epoxidized oil acrylate resin precursors, and urethane acrylate resins. precursor, polyester acrylate resin precursor, polyether acrylate resin precursor, acrylic acrylate resin precursor, unsaturated polyester resin precursor, vinyl / acrylate resin precursor, vinyl ether resin precursor, polyene / thiol resin precursor, silicon acrylate resin precursor, polybutadiene acrylate resin precursor, polystyryl(ethyl)methacrylate resin precursor, polycarbonate acrylate resin precursor, 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.

[0096] The 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, and more preferably 1 to 50 parts by weight, per 100 parts by weight of the resin component.

[0097] [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 for polymerizing the resin composition of the present invention. Examples of the polymerization initiator include a thermal polymerization initiator, a photopolymerization initiator, and a radical polymerization initiator. 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 sulfonates. These may be used alone or in combination of two or more.

[0098] 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. These may be used alone or in combination of two or more. When a photopolymerization initiator is used, a sensitizer such as a tertiary amine may be used in combination, if necessary.

[0099] 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-butyl peroxybenzoate. These may be used alone or in combination of two or more.

[0100] The amount of the polymerization initiator in the resin composition of the present invention is not particularly limited, and is 0.001 to 10 parts by weight, preferably 0.01 to 8 parts by weight, and more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the resin component.

[0101] [Reactive Diluent] The resin composition of the present invention may contain a reactive diluent as needed. 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 esters; 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.

[0102] The 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, and more preferably 0.1 to 20 parts by weight, per 100 parts by weight of the resin component.

[0103] [Fluororesin] The resin composition of the present invention may contain a fluororesin for the purpose of improving the flame retardancy (particularly drip prevention performance) of the cured product (formed product). Examples of fluororesins include polytetrafluoroethylene (PTFE), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-ethylene copolymer (ETFE), poly(trifluorochloroethylene) (CTFE), and polyfluorovinylidene (PVdF). These may be used alone or in combination of two or more.

[0104] The amount of the fluororesin blended 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.

[0105] [Inorganic Filler] The resin composition of the present invention may contain an inorganic filler for the purpose of improving the flame retardancy (particularly drip prevention performance) and mechanical strength of the cured product (formed product). 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, glass fine powder, hollow glass, and fibrous aluminum titanate. Examples of suitable inorganic fillers include potassium metal salts (such as potassium titanate fibers and sodium titanate fibers), fibrous borates (such as aluminum borate fibers, magnesium borate fibers, and zinc borate fibers), 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, and flaky titanium dioxide. These may be used alone or in combination of two or more. In particular, to reduce 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, and amorphous silica. 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 size of 5 μm or less, adhesion to metal foil is improved when the resin composition is used in a metal-clad laminate, etc. Furthermore, the surface of the inorganic filler may be coated with a silane coupling agent in order to suppress deterioration of the resin component.

[0106] The amount of inorganic filler in the resin composition of the present invention is not particularly limited. In order to achieve a balance between improved flame retardancy and improved mechanical properties, the amount of inorganic filler is 0 to 800 parts by weight, preferably 1 to 600 parts by weight, and more preferably 10 to 400 parts by weight, per 100 parts by weight of the resin component.

[0107] [Additives] The resin composition of the present invention may contain various additives depending on the application, the type of resin component, etc., within a range that does not impair the desired physical properties. 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 fibers, polyparaphenylene benzobisoxazole fibers, etc.), silane coupling agents, waxes, fatty acids and metal salts thereof, mold 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, etc.), and the like. compounds, organic phosphorus-based peroxide decomposers, organic sulfur-based peroxide decomposers, etc.), fluorescent brighteners (stilbene derivatives, etc.), light stabilizers (hindered amine compounds, etc.), photosensitizers, gloss agents, metal deactivators (benzotriazole compounds, etc.), light-shielding agents (rutile titanium oxide, zinc oxide, chromium oxide, cerium oxide, etc.), quenchers (organic nickel, etc.), curing agents, curing accelerators, crosslinking agents, diluents, flowability modifiers, polymerization inhibitors, dyes, pigments, colorants, antifogging agents, antifungal agents, antibacterial agents, deodorizers, 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, anti-tracking agents, luminous agents, adhesives, pressure-sensitive adhesives, tackifiers, and various stabilizers. These may be used alone or in combination of two or more.

[0108] The amount of the additives to be added to 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.

[0109] The resin composition of the present invention can be produced by mixing and / or kneading the resin component, the phosphorus compound 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, the resin composition can be produced by mixing and / or kneading a mixture of liquid, powder, bead, flake, or pellet-like components using an extruder (such as a single-screw extruder or a twin-screw extruder), a kneader (such as a Banbury mixer, a pressure kneader, a two-roll mill, or a three-roll mill), or the like.

[0110] 4. Thermally Radical Curable Resin Composition The resin composition of the present invention (hereinafter referred to as the "thermally radically curable resin composition of the present invention") contains the phosphorus compound of the present invention and a thermally radically curable resin component. Furthermore, the thermally radically curable resin composition of the present invention may contain, in addition to the phosphorus compound of the present invention and the thermally radically curable resin component, other resin components, other flame retardants, crosslinking agents, radical polymerization initiators, inorganic fillers, stress relaxation agents, organic solvents, and additives as necessary. Furthermore, in the present invention, the term "resin composition" refers to the state of the mixture before curing.

[0111] [Thermal Radical Curable Resin Component] Examples of the thermal radical curable resin component (including resins in uncured and semi-cured states) used in the thermal radical curable resin composition of the present invention include polyphenylene ether resins, bismaleimide resins, bismaleimide-triazine resins, polyfunctional styrene compounds, polystyrene resins, polybutadiene resins, benzocyclobutene resins, polytetrafluoroethylene resins, and acrylic resins.

[0112] The polyphenylene ether resin may be, for example, a compound having a structure represented by formula (1).

[0113] (In the formula, R ａ are the same or different and represent 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 is usually an integer of 1 or more.

[0114] R ａExamples of the alkyl group having 1 to 6 carbon atoms represented by R include linear or branched alkyl groups having 1 to 6 carbon atoms, and specific examples include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-pentyl, and n-hexyl groups, with methyl being preferred. ａ Examples of the alkenyl group having 2 to 6 carbon atoms represented by R include linear or branched alkenyl groups having 2 to 6 carbon atoms, and specific examples thereof include vinyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, pentenyl, and hexenyl groups. ａ are the same or different and are preferably a hydrogen atom or a methyl group. n is preferably an integer of 1 to 400.

[0115] Examples of the compound having the structure represented by formula (1) include a compound having a structure represented by formula (1-1), a compound having a structure represented by formula (1-2), and a compound having a structure represented by formula (1-3).

[0116] (wherein n is the same as defined above).

[0117] (wherein n is the same as defined above).

[0118] (wherein n is the same as defined above).

[0119] The compound having the structure represented by formula (1) preferably has two or more structures represented by formula (1) in the molecule. Furthermore, 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, or a vinylbenzyl group). The crosslinkable group is preferably present at the terminal of the molecule of this compound.

[0120] A preferred embodiment of the compound having the structure represented by formula (1) is, for example, a compound represented by chemical formula (IV).

[0121] (In the formula, X ａ are the same or different and represent a hydrogen atom or a group represented by formula (2).ａ represents —O— or a group represented by formula (3). ａ is the same as above. n may be the same or different and is the same as above.

[0122] (In the formula, 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 are the same or different and represent an alkylene group having 1 to 10 carbon atoms, -C(=O)-, -Ph-, -Ph-CH ２ -or-Ph-CH ２ CH ２ - represents.)

[0123] (In the formula, 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 a single bond, an alkylene group having 1 to 6 carbon atoms which may be substituted with a phenyl group, 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 -(alkylene)-(phenylene)-(alkylene)-.

[0124] R ｂ , R ｃ and R ｄ Examples of the alkyl group having 1 to 3 carbon atoms represented by R include a methyl group, an ethyl group, an n-propyl group, and an isopropyl group. ｂ and R ｃ is preferably a hydrogen atom, and R ｄ is preferably a hydrogen atom or a methyl group.

[0125] Examples of the alkylene group having 1 to 10 carbon atoms represented by Z include a methylene group, a methylmethylene group, a dimethylene group, a trimethylene group, an ethylmethylene group, a dimethylmethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, a heptamethylene group, an octamethylene group, a nonamethylene group, and a decamethylene group. Z is -C(=O)-, -Ph-, -Ph-CH ２-or-Ph-CH ２ CH ２ - is preferred.

[0126] R ｅ Examples of the alkyl group having 1 to 6 carbon atoms represented by R include linear or branched alkyl groups having 1 to 6 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-pentyl group, and an n-hexyl group. ｅ Examples of the alkenyl group having 2 to 6 carbon atoms represented by R include linear or branched alkenyl groups having 2 to 6 carbon atoms, and specific examples thereof include vinyl, allyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, pentenyl, and hexenyl groups. ｅ Examples of the aryl group represented by R include a phenyl group, a 2-tolyl group, a 3-tolyl group, and a 4-tolyl group. ｅ is preferably a hydrogen atom or a methyl group.

[0127] Examples of alkylene groups having 1 to 6 carbon atoms and optionally substituted with a phenyl group, represented by W, include a methylene group, a methylmethylene group, a dimethylmethylene group, a phenylmethylene group, a phenylmethylmethylene group, and a diphenylmethylene group. Examples of cycloalkylene groups represented by W include a cyclohexane-1,1-diyl group. Examples of alkenediyl groups having 2 to 6 carbon atoms and optionally substituted with a halogen atom, represented by W, include ethylene-1,1-diyl and 2,2-dichloroethylene-1,1-diyl. Examples of -(alkylene)-(phenylene)-(alkylene)- represented by W include -(alkylene having 1 to 3 carbon atoms)-(phenylene)-(alkylene having 1 to 3 carbon atoms)-. Examples of the alkylene group having 1 to 3 carbon atoms include a methylene group, a methylmethylene group, a dimethylene group, a trimethylene group, an ethylmethylene group, and a dimethylmethylene group, and preferably a dimethylmethylene group. Examples of the phenylene group include a 1,2-phenylene group, a 1,3-phenylene group, and 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).

[0128] Y ａ represents a group represented by formula (3) (wherein R ｅ represents a hydrogen atom or a methyl group, and W represents an alkylene group having 1 to 3 carbon atoms.

[0129] Preferred examples of the compound represented by chemical formula (IV) include a compound represented by chemical formula (IV-1), a compound represented by chemical formula (IV-2), and a compound represented by chemical formula (IV-3).

[0130] (In the formula, R ａ , R ｄ , R ｅ , W and n are the same as above.)

[0131] (In the formula, R ａ , R ｂ , R ｃ , R ｄ, R ｅ , W and n are the same as above.)

[0132] (In the formula, R ａ , R ｅ , W and n are the same as above.)

[0133] These polyphenylene ether resins can be synthesized according to or in accordance with known methods, for example, those described in US Pat. No. 4,059,568 and The Journal of Organic Chemistry (1969), 34, 297-303.

[0134] Furthermore, commercially available polyphenylene ether resins can also be used as the polyphenylene ether resin. Examples of commercially available products include "SA9000-111 (trade name)" manufactured by SABIC, and "OPE-2St (trade name)" and "OPE-2EA (trade name)" manufactured by Mitsubishi Gas Chemical Company. These polyphenylene ether resins may be used alone or in combination of two or more.

[0135] 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. The weight average molecular weight can be measured using gel permeation chromatography (GPC) in styrene equivalent terms.

[0136] The bismaleimide resin is a compound having two maleimide groups in the molecule, and refers to a bismaleimide compound before curing. Examples of the bismaleimide resin include an aliphatic bismaleimide compound and an aromatic bismaleimide compound.

[0137] 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, and 1,11-bismaleimide-3,6,9-trioxaundecane.

[0138] 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, and N,N'-(methylenedi-p-phenylene)bismaleimide. 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'-(benzylidene di-p-phenylene)bismaleimide, N,N'-[methylenebis(3-chloro-4-phenylene)]bismaleimide, N,N'-[methylene 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 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.

[0139] Commercially available bismaleimide resins can also be used. Examples of commercially available bismaleimide resins include "BMI-689 (trade name)," "BMI-1500 (trade name)," "BMI-2500 (trade name)," and "BMI-3000J (trade name)" manufactured by Designer Molecules Inc.; "BMI-1000 (trade name)," "BMI-2300 (trade name)," "BMI-4000 (trade name)," and "BMI-5100 (trade name)" manufactured by Daiwa Kasei Kogyo; "MIR-3000-70MT (trade name)" and "MIR-5000 (trade name)" manufactured by Nippon Kayaku; and "BMI (trade name)," "BMI-70 (trade name)," and "BMI-80 (trade name)" manufactured by K.I. Kasei. These bismaleimide resins may be used alone or in combination of two or more.

[0140] The bismaleimide-triazine resin is not particularly limited as long as it is a prepolymer containing a maleimide compound and a cyanate ester compound as main components. Examples include a resin obtained by heating and melting 2,2-bis(4-cyanatophenyl)propane and bis(3-ethyl-5-methyl-4-maleimidophenyl)methane to polymerize, and a resin obtained by heating and melting a novolac-type cyanate ester resin and bis(3-ethyl-5-methyl-4-maleimidophenyl)methane to polymerize, followed by dissolving the resulting resin in methyl ethyl ketone.

[0141] Examples of polyfunctional styrene compounds 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, compounds represented by chemical formula (VI), and divinylbenzene polymers (oligomers) having vinyl groups on the side chains.

[0142] (In the formula, Y ｂ are the same or different and represent -(alkylene having 1 to 3 carbon atoms)-(divalent organic group having a cyclic structure)-(alkylene having 1 to 3 carbon atoms)-, and p represents an integer of 1 to 10.

[0143] Examples of the alkylene group 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, etc. Examples of the divalent organic group having a cyclic structure include a phenylene group, a xylylene group, a naphthylene group, a tolylene group, a biphenylene group, a group containing an indane structure, and a group containing a cycloolefin structure.

[0144] Preferred examples of the compound represented by chemical formula (VI) include a compound represented by chemical formula (VI-1) and a compound represented by chemical formula (VI-2).

[0145] (In the formula, p represents an integer of 1 to 10.)

[0146] (In the formula, p represents an integer of 1 to 10.)

[0147] An example of the polystyrene resin is a compound having a structure represented by formula (4).

[0148] (In the formula, R ｆ , R ｇ and R ｈ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0149] R ｆ , R ｇ and R ｈ Examples of the alkyl group having 1 to 6 carbon atoms represented by the formula (I) include linear or branched alkyl groups having 1 to 6 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-pentyl group, and an n-hexyl group.

[0150] Examples of compounds having a structure represented by formula (4) include compounds having a structure represented by formula (4-1) and compounds having a structure represented by formula (4-2).

[0151]

[0152]

[0153] The compound having the structure represented by formula (4) preferably has a structure represented by formula (5) in the molecule. This compound may be a polymer in which the structure represented by formula (4) and the structure represented by formula (5) are randomly bonded, or may be a block copolymer or a random copolymer.

[0154] (In the formula, R ｉ , R ｊ and R ｋ are the same or different and represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ｌ represents an aryl group.

[0155] R ｉ , R ｊ and R ｋ Examples of the alkyl group having 1 to 6 carbon atoms represented by the formula (I) include linear or branched alkyl groups having 1 to 6 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-pentyl group, and an n-hexyl group.

[0156] R ｌ Examples of the aryl group represented by the formula (I) include unsubstituted or substituted aryl groups with an alkyl group or the like, and specific examples thereof include a methylphenyl group, an ethylphenyl group, a propylphenyl group, a butylphenyl group, a t-butylphenyl group, a vinylphenyl group, a naphthyl group, an ethylnaphthyl group, a biphenylyl group, and an ethylbiphenylyl group.

[0157] Examples of the structure represented by formula (5) include a structure represented by formula (5-1), a structure represented by formula (5-2), and a structure represented by formula (5-3).

[0158]

[0159]

[0160]

[0161] A compound having a structure represented by formula (4) may have a structure represented by formula (6) in the molecule. This compound may be a polymer in which the structure represented by formula (4) and the structure represented by formula (6) are randomly bonded, or may be a block copolymer, or may be a random copolymer. Furthermore, this compound may be a polymer in which the structure represented by formula (4), the structure represented by formula (5), and the structure represented by formula (6) are randomly bonded, or may be a block copolymer, or may be a random copolymer.

[0162] (In the formula, R ｍ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group, or a benzyl group.

[0163] R ｍ Examples of the alkyl group having 1 to 18 carbon atoms represented by the formula (I) include linear or branched alkyl groups having 1 to 18 carbon atoms, and specific examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, an n-pentyl group, an n-hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, an undecyl group, a dodecyl group, a tridecyl group, a tetradecyl group, a pentadecyl group, a hexadecyl group, a heptadecyl group, and an octadecyl group.

[0164] R ｍ Examples of the cycloalkyl group having 5 to 8 carbon atoms represented by the formula (I) include a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group.

[0165] R ｍ Examples of the aryl group represented by the formula (I) include unsubstituted or substituted aryl groups, and specific examples thereof include a phenyl group, a 4-hydroxyphenyl group, a 4-acetylphenyl group, a 4-methoxyphenyl group, a 4-ethoxyphenyl group, a 4-chlorophenyl group, and a 4-bromophenyl group.

[0166] A preferred embodiment of the compound having the structure represented by formula (4) is a compound containing a structural unit represented by formula (4-1) in the molecule and further containing at least one of a structural unit represented by formula (5-1) and a structural unit represented by formula (5-2). This compound may be a block copolymer or a random copolymer. The molar contents of the structural unit represented by formula (4-1), the structural unit represented by formula (5-1), and the structural unit represented by formula (5-2) are preferably 1 to 92 mol%, 0 to 54 mol%, and 0 to 89 mol%, respectively. The average number of structural units represented by formula (4-1) is preferably 1 to 350, the average number of structural units represented by formula (5-1) is preferably 0 to 160, and the average number of structural units represented by formula (5-2) is preferably 0 to 270.

[0167] As the polystyrene resin, commercially available polystyrene resins can also be used. Examples of commercially available products include "ODV-XET (X03) (trade name)," "ODV-XET (X04) (trade name)," and "ODV-XET (X05) (trade name)" manufactured by Nippon Steel Chemical & Material Co., Ltd. These polystyrene resins may be used alone or in combination of two or more.

[0168] The weight average molecular weight (Mw) of the polystyrene resin is preferably 1500 to 40000, and more preferably 1500 to 35000. The weight average molecular weight can be measured using gel permeation chromatography (GPC) in terms of styrene.

[0169] Examples of polybutadiene resins include compounds having at least one of the polybutadiene structures represented by formula (7), (8), and (9). These polybutadiene structures include not only structures formed by polymerizing butadiene, but also structures formed by hydrogenating a polybutadiene structure. In these compounds, the polybutadiene structure may be contained in the main chain or in a side chain.

[0170] (In the formula, m represents the number of repeating units and is usually an integer of 1 or more.)

[0171] (In the formula, m represents the number of repeating units and is usually an integer of 1 or more.)

[0172] (In the formula, m represents the number of repeating units and is usually an integer of 1 or more.)

[0173] A compound having at least one of the polybutadiene structures represented by formula (7), (8), and (9) may have the structure represented by formula (6) in its molecule. This compound may be a polymer, a block copolymer, or a random copolymer in which at least one of the polybutadiene structures represented by formula (7), (8), and (9) and the structure represented by formula (6) are randomly bonded.

[0174] Other polybutadiene resins include, for example, butadiene homopolymer, epoxy-modified polybutadiene, butadiene-styrene-random copolymer, and maleic acid-modified polybutadiene.

[0175] As the polybutadiene resin, commercially available polybutadiene resins can also be used. Examples of commercially available products include "Ricon 130 (trade name)", "Ricon 131 (trade name)", "Ricon 142 (trade name)", "Ricon 150 (trade name)", "Ricon 152 (trade name)", "Ricon 153 (trade name)", "Ricon 156 (trade name)", and "Ricon 157 (trade name)" manufactured by Cray Valley; "B-1000 (trade name)", "B-2000 (trade name)", and "B-3000 (trade name)" (butadiene homopolymers) manufactured by Nippon Soda; "Ricon 100 (trade name)" and "Ricon 181 (trade name)" (butadiene-styrene-random copolymers) manufactured by Cray Valley; "Ricon 130MA8 (trade name)", "Ricon 130MA13 (trade name)", "Ricon 130MA20 (trade name)", and "Ricon 156MA17 (trade name)" (maleic acid modified polybutadiene), etc. These polybutadiene resins may be used alone or in combination of two or more.

[0176] The number average molecular weight (Mn) of the polybutadiene resin is preferably 500 to 10,000, and more preferably 1,000 to 6,000. The number average molecular weight can be measured using gel permeation chromatography (GPC) in terms of styrene.

[0177] The benzocyclobutene resin is not particularly limited as long as it has two or more benzocyclobutene groups bonded directly or via an organic group.

[0178] In the thermally radically curable resin composition of the present invention, the above-mentioned thermally radically curable resin components may be used alone or in combination of two or more.

[0179] [Other Resin Components] In addition to the thermoradical curable resin component, the thermoradical curable resin composition of the present invention may contain, if necessary, a resin component (other resin component) other than the thermoradical curable resin component. Examples of the other resin component include the above-mentioned resin component, a styrene-based block copolymer, etc.

[0180] Examples of styrene block copolymers include styrene-butadiene block copolymers, styrene-butadiene-styrene block copolymers (SBS), styrene-isoprene block copolymers, styrene-ethylene / butylene-styrene block copolymers (SEBS), styrene-(ethylene-ethylene / propylene)-styrene block copolymers (SEEPS), styrene-ethylene / propylene-styrene block copolymers (SEPS), etc. These may be used alone or in combination of two or more.

[0181] Commercially available styrene-based block copolymers can be used. Examples of commercially available products include "Tufprene (trade name)," "Asaprene T (trade name)," and "Tuftec (trade name)" manufactured by Asahi Kasei; "Elastomer AR (trade name)" manufactured by Aronkasei; "Kraton G (trade name)" and "Califlex (trade name)" manufactured by Kraton Polymer Japan; "JSR-TR (trade name)," "TSR-SIS (trade name)," and "Dynaron (trade name)" manufactured by JSR; "Denka STR (trade name)" manufactured by Denka; "Quintac (trade name)" manufactured by Nippon Zeon; "Esporex SB Series (trade name)" manufactured by Sumitomo Chemical; "Septon (trade name)" and "Hybra (trade name)" manufactured by Kuraray; "Sumiflex (trade name)" manufactured by Sumitomo Bakelite; and "Leostomer (trade name)" and "Actimer (trade name)" manufactured by Riken Technos. These styrene-based block copolymers may be used alone or in combination of two or more types.

[0182] The amount of the other resin components in the thermal radical curable resin composition of the present invention is not particularly limited, and is generally 0 to 1,000 parts by weight, preferably 1 to 800 parts by weight, and more preferably 10 to 700 parts by weight, per 100 parts by weight of the thermal radical curable resin component.

[0183] [Flame Retardant] In addition to the phosphorus compound of the present invention, the thermoradical curable resin composition of the present invention may, if necessary, contain other flame retardants as described in the above section 3. Flame Retardant and Resin Composition.

[0184] The amount of the phosphorus compound of the present invention in the thermal radical curable resin composition of the present invention is not particularly limited, and is 1 to 200 parts by weight, preferably 1 to 160 parts by weight, and more preferably 2 to 150 parts by weight, per 100 parts by weight of the resin components (total of the thermal radical curable resin component and other resin components). The amount of the other flame retardant in the thermal radical curable resin composition of the present invention is also not particularly limited, and is 0 to 100 parts by weight, preferably 1 to 80 parts by weight, and more preferably 10 to 40 parts by weight, per 100 parts by weight of the resin components (total of the thermal radical curable resin component and other resin components).

[0185] [Crosslinking Agent] The thermally radically curable resin composition of the present invention may contain a crosslinking agent to the extent that the effects of the resin composition can be exhibited. Examples of crosslinking agents include monobenzyl diallyl isocyanurates such as mono(alkyl having 6 to 20 carbon atoms)diallyl isocyanurate, 1-benzyl-3,5-diallyl isocyanurate, and 1-(4-vinylbenzyl)-3,5-diallyl isocyanurate, tris(4-vinylbenzyl)isocyanurate, tris(4-vinylbenzyloxy)triazine, triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, triallyl trimellitate, and the aforementioned polyfunctional styrene compounds. These may be used alone or in combination of two or more.

[0186] The amount of the crosslinking agent in the thermally radically curable resin composition of the present invention is not particularly limited, and is 0 to 200 parts by weight, preferably 5 to 150 parts by weight, and more preferably 10 to 100 parts by weight, per 100 parts by mass of the resin components (the total of the thermally radically curable resin component and other resin components).

[0187] The thermally radically curable resin composition of the present invention may further contain other components, as necessary, such as the above-mentioned radical polymerization initiator, the above-mentioned inorganic filler, the stress relaxation agent, the organic solvent, and the above-mentioned additives.

[0188] [Radical Polymerization Initiator] The radical polymerization initiator may be any of those described in the above section 3. Flame Retardant and Resin Composition. The amount of radical polymerization initiator in the thermally radically curable resin composition of the present invention is not particularly limited, and is 0.001 to 10 parts by weight, preferably 0.01 to 8 parts by weight, and more preferably 0.1 to 5 parts by weight, per 100 parts by weight of the resin components (the total of the thermally radically curable resin component and other resin components).

[0189] [Inorganic Filler] The inorganic filler may be any of those described in the above section 3. Flame Retardant and Resin Composition. The amount of inorganic filler in the thermally curable resin composition of the present invention is not particularly limited, and is 0 to 800 parts by weight, preferably 1 to 600 parts by weight, and more preferably 10 to 400 parts by weight, per 100 parts by weight of the resin components (total of the thermally curable resin component and other resin components).

[0190] [Stress Relaxant] The stress relaxation agent is not particularly limited, and examples thereof include silicone resin particles. The average particle diameter of the stress relaxation agent is preferably 10 μm or less. By using a stress relaxation agent having such an average particle diameter, adhesion to metal foil is improved when the thermo-radical curable resin composition of the present invention is used in a metal-clad laminate or the like.

[0191] The amount of the stress relaxation agent to be added in the thermally radically 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, per 100 parts by mass of the resin components (the total of the thermally radically curable resin component and other resin components).

[0192] [Organic Solvent] The organic solvent is not particularly limited as long as it can dissolve or disperse the thermally 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; and chlorinated hydrocarbon solvents such as trichloroethylene. These may be used alone or in combination of two or more. The thermally curable resin composition of the present invention containing an organic solvent can be used to produce a prepreg by impregnating a substrate as a resin varnish, as described below.

[0193] The amount of organic solvent in the thermo-radical curable resin composition of the present invention may be adjusted depending on the operation of applying or impregnating / applying the resin varnish to a substrate, and is 30 to 1,000 parts by weight, preferably 100 to 500 parts by weight, per 100 parts by mass of the resin component (total of the thermo-radical curable resin component and other resin components).

[0194] [Additives] The additives described in the above section 3. Flame retardant and resin composition can be used as the additives. The amount of the additives to be added to the thermally 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, per 100 parts by weight of the resin components (total of the thermally curable resin component and other resin components).

[0195] The thermoradical curable resin composition of the present invention can be produced by mixing and / or kneading the thermoradical curable resin component, the phosphorus compound of the present invention, and, if necessary, other resin components, other flame retardants, crosslinking agents, radical polymerization initiators, inorganic fillers, stress relaxation agents, organic solvents, and additives by a known method. For example, the composition can be produced by mixing and / or kneading a mixture of liquid, powder, bead, flake, or pellet-like components using an extruder (such as a single-screw extruder or a twin-screw extruder), a kneader (such as a Banbury mixer, a pressure kneader, a two-roll mill, or a three-roll mill), or the like.

[0196] 5. Uses of the Resin Composition of the Present Invention The resin composition described in the above 3. and the thermo-radical curable resin composition described in the above 4. (hereinafter, both will be collectively referred to as "the resin composition of the present invention") can be suitably used in applications such as prepregs, resin-coated metal foils, thermosetting resin films, metal-clad laminates, printed wiring boards, resin boards, semiconductor devices, and adhesives.

[0197] [Prepreg] The prepreg of the present invention will now be described. When using the resin composition of the present invention to produce a prepreg for use in 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 soluble in an organic solvent (each component contained in the resin composition of the present invention) is added to an organic solvent and dissolved. Heating may be performed as necessary. Then, components insoluble in an organic solvent (each component contained in the resin composition of the present invention), such as an inorganic filler, are added as needed, and the mixture is dispersed using a ball mill, bead mill, planetary mixer, roll mill, or the like until a predetermined dispersion state is achieved, thereby preparing the resin composition of the present invention in the form of a varnish.

[0198] 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. The semi-cured product is the resin composition of the present invention in a partially cured state (B-staged state).

[0199] The prepreg of the present invention may be a prepreg comprising a semi-cured product of the resin composition of the present invention (a resin composition in a B-stage state) and a substrate, or may be a prepreg comprising the resin composition of the present invention before curing (a resin composition in an A-stage) and a substrate.

[0200] Examples of substrates used for prepregs include 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. Examples of glass cloth materials include ordinary E-glass, as well as D-glass, S-glass, NE-glass, quartz glass, and L-glass. The use of glass cloth results in a laminated board with excellent mechanical strength. Flattened glass cloth is preferred. Flattening can be achieved, for example, by continuously pressing the glass cloth with a press roll at an appropriate pressure to compress the yarns flat. Examples of the thickness of the substrate include 0.02 to 0.3 mm.

[0201] The proportion of the base material in the prepreg is 20 to 80% by weight, preferably 25 to 70% by weight, of the entire prepreg.

[0202] Examples of methods for producing prepregs include a method in which the resin composition of the present invention is prepared in a varnish form and then impregnated or coated onto a substrate. Examples of impregnation and coating methods include immersing the substrate (dipping), coating using a roll, die coating, bar coating, or the like, and spraying using a sprayer. This impregnation and coating can be repeated multiple times as needed. It is also possible to repeat impregnation and coating using multiple resin compositions with different resin component concentrations. After impregnation and coating, the substrate may be dried or heated.

[0203] The substrate impregnated with or 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 semi-cured (B-stage) prepreg.

[0204] Table 1 shows a preferred blend example (excluding organic solvents) when the resin composition of the present invention is used for a prepreg.

[0205]

[0206] By using such prepregs, it is possible to produce metal-clad laminates and printed wiring boards that have excellent electrical properties (for example, dielectric properties), heat resistance, flame retardancy, adhesive strength, and chemical resistance.

[0207] [Resin-Coated Metal Foil] 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. The resin-coated metal foil of the present invention may also comprise another layer between the resin layer and the metal foil.

[0208] As described above, the resin layer may be a semi-cured product of the resin composition of the present invention (a resin composition in a B-stage state) or the resin composition of the present invention before curing (a resin composition in an A-stage state). The resin layer may or may not contain a substrate. The substrate may be the same as the substrate of the prepreg.

[0209] Examples of the metal foil include copper foil and aluminum foil, and the thickness of the copper foil is about 12 to 70 μm.

[0210] Examples of methods for producing the resin-coated metal foil of the present invention include a method in which the resin composition of the present invention prepared in the form of a varnish as described above is applied to a metal foil. The application method is not particularly limited as long as it is a method that can apply the resin composition of the present invention to the metal foil. Examples include application methods using a roll, die coater, bar coater, etc., and spraying methods using a sprayer. After application, the composition may be dried or heated.

[0211] 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 resin-coated metal foil in a semi-cured state (B-stage state).

[0212] Preferred formulations (excluding organic solvents) 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 above). Furthermore, preferred formulations (excluding organic solvents) when the resin composition of the present invention is used for a resin-coated metal foil not containing a substrate are shown in Table 2.

[0213]

[0214] By using such a resin-coated metal foil, it is possible to produce a metal-clad laminate or a printed wiring board that has excellent electrical properties (e.g., dielectric properties), heat resistance, flame retardancy, adhesive strength, and chemical resistance.

[0215] [Thermosetting Resin Film] The thermosetting resin film of the present invention will be described. The thermosetting resin film of the present invention can be produced by forming the resin composition of the present invention into a desired shape. For example, the thermosetting resin film of the present invention can be produced by applying the resin composition of the present invention onto a support and then drying it. The support is not particularly limited, and examples include metal foils such as copper and aluminum, and organic films such as polyester resins, polyethylene resins, and polyethylene terephthalate resins (PET). The support may be subjected to a release treatment with a silicone-based compound or the like. The resin composition of the present invention can be used in various shapes, and the shape is not particularly limited.

[0216] The method for applying the resin composition of the present invention to a support is not particularly limited, but from the viewpoint of thinning and controlling the film thickness, gravure coating, slot die coating, doctor blade coating, etc. The slot die coating can provide an uncured film of the resin composition (thermosetting resin film of the present invention) having a thickness of 5 to 300 μm after heat curing.

[0217] Drying conditions can be appropriately set depending on the type and amount of organic solvent used in the resin composition of the present invention, the coating thickness, etc. For example, drying conditions can be set to 50 to 120°C and 1 to 60 minutes. The thermosetting resin film of the present invention obtained in this manner has good storage stability. The thermosetting resin film can be peeled off from the support at any desired time.

[0218] The thermosetting resin film of the present invention can be cured, for example, at 150 to 230°C for 30 to 180 minutes. The thermosetting resin film of the present invention can be cured after sandwiching the thermosetting resin film between substrates on which wiring such as copper foil is formed, or after appropriately laminating a thermosetting resin film on which wiring such as copper foil is formed. The thermosetting resin film can also be used as a coverlay film to protect wiring on a substrate, and the curing conditions for this are similar. The thermosetting resin film of the present invention can also be suitably used for flexible copper-clad laminates (FCCLs) for flexible printed circuit boards (FPCs), copper-clad laminates (CCLs) for multilayer substrates, build-up materials, and the like.

[0219] Preferred formulation examples (excluding organic solvents) when the resin composition of the present invention is used in a thermosetting resin film are shown in Table 3. 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.

[0220]

[0221] [Metal-clad laminate] The metal-clad laminate of the present invention will be described. The 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. The metal-clad laminate comprises a metal foil on the surface of the insulating layer. The metal-clad laminate may also comprise another layer between the insulating layer and the metal foil. The insulating layer may or may not comprise a substrate. The substrate may be the same as the substrate of the prepreg. The metal foil may be the same as the metal foil of the resin-coated metal foil.

[0222] Examples of methods for producing metal-clad laminates include the method using the prepreg described above. Methods for producing metal-clad laminates using prepregs include stacking one or more prepregs, then stacking a metal foil such as copper foil on both or either of the upper and lower surfaces of the prepreg, and then heat-pressing and molding the resulting laminate to form an integrated laminate. This method allows for the production of laminates clad on both or one side with metal foil. Heat-press conditions can be appropriately set depending on the thickness of the metal-clad laminate to be produced and the composition of the resin composition used in the prepreg. For example, conditions such as a temperature of 170 to 220°C, a pressure of 1.5 to 5.0 MPa, and a time of 60 to 150 minutes can be used. Metal-clad laminates can also be produced without using prepregs. Examples include a method in which a varnish-like resin composition of the present invention is applied to a metal foil to form a layer containing the resin composition of the present invention on the metal foil, followed by heat-pressure molding, or a method in which a thermosetting resin film is cured using a metal foil as a support.

[0223] Preferred formulations (excluding organic solvents) when the resin composition of the present invention is used in a metal-clad laminate containing a substrate are the same as those for the prepreg described above (see Table 1 above). Also, preferred formulations (excluding organic solvents) when the resin composition of the present invention is used in a metal-clad laminate not containing a substrate are the same as those for the resin-coated metal foil not containing a substrate described above (see Table 2 above).

[0224] By using such a metal-clad laminate, it is possible to produce a printed wiring board that is excellent in electrical properties (for example, dielectric properties, etc.), heat resistance, flame retardancy, adhesive strength, and chemical resistance.

[0225] [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 comprises wiring on the surface of the insulating layer. The printed wiring board of the present invention may also comprise another layer between the insulating layer and the wiring. The insulating layer may or may not comprise a substrate. The substrate may be the same as the substrate of a prepreg. 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 resin film of the present invention, and thus has excellent electrical properties (e.g., dielectric properties, etc.) and high flame retardancy.

[0226] The wiring is not particularly limited as long as it is wiring that can be provided on a printed wiring board. For example, wiring formed by partially removing a metal foil laminated on an insulating layer can be used. In addition, wiring formed by a subtractive method, an additive method, a semi-additive method, a chemical mechanical polishing (CMP), a trench method, an inkjet method, a squeegee method, a transfer method, or the like can be used.

[0227] Examples of methods for producing printed wiring boards include a method using the above-mentioned metal-clad laminate. Methods for producing printed wiring boards using metal-clad laminates include a method of forming a circuit by etching the metal foil on the surface of the metal-clad laminate. This method allows for the production of a printed wiring board in which a conductor pattern is provided as a circuit on the surface of the metal-clad laminate.

[0228] Preferred formulations (excluding organic solvents) when the resin composition of the present invention is used in a printed wiring board containing a substrate in the insulating layer are the same as those for the prepreg described above (see Table 1 above).Preferable formulations (excluding organic solvents) when the resin composition of the present invention is used in a printed wiring board containing no substrate in the insulating layer are the same as those for the resin-coated copper foil containing no substrate described above (see Table 2 above).

[0229] The printed wiring board obtained in this manner has excellent electrical properties (e.g., dielectric properties, etc.), heat resistance, flame retardancy, and chemical resistance, and is sufficiently prevented from peeling off of the circuit. Furthermore, even when it is used in the form of a package to which a semiconductor chip is bonded, it is easy to mount, has consistent quality, and is excellent in signal speed and impedance.

[0230] [Resin Plate] The resin composition of the present invention can also be used as a resin plate cured into a plate shape. For example, a resin plate can be obtained by applying the resin composition of the present invention in a varnish form to a plate, drying it, and then curing it. Further, the resin plate can also be an unclad plate obtained by removing the metal foil from the metal-clad laminate.

[0231] [Semiconductor Device] The use of the resin composition of the present invention in a semiconductor device will be described. A semiconductor device can be manufactured by using and curing the resin composition of the present invention or the thermosetting resin film of the present invention. This semiconductor device is suitable for high-frequency applications because it has excellent electrical properties (e.g., dielectric properties) and 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. A semiconductor device refers to any device that can function by utilizing semiconductor properties, and includes electronic components, semiconductor circuits, modules incorporating these, electronic devices, etc.

[0232] [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 metals, inorganic materials, and resin materials. In particular, the adhesive is preferred as an adhesive between a metal and a material selected from metals, inorganic materials, and resin materials.

[0233] Examples of the metal include copper, aluminum, titanium, nickel, tin, iron, silver, gold, and alloys thereof. Among these metals, copper is preferred. Examples of the metal form include plates, foils, and plated films made of these metals.

[0234] Examples of the inorganic material include silicon, ceramic, 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 flake graphite (natural graphite), expanded graphite, expanded graphite (synthetic graphite), activated carbon, carbon fibers, carbon black, etc. Among these inorganic materials, silicon, ceramics (alumina, silicon carbide, aluminum nitride, silicon nitride, barium titanate, etc.), glass, and inorganic salts are preferred.

[0235] 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 resin, fluorine-containing resin, polyether resin, polyetherimide resin, polyether ether ketone resin, polyester resin, silicone resin, liquid crystal resin, etc., and these may be mixed or modified and 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.

[0236] Materials can be bonded using an adhesive by known methods, specifically, (1) a method in which an adhesive is applied to the surface of a material selected from metals, inorganic materials, and resin materials, and another material is pressure-bonded to part or all of the applied adhesive to bond (cure), and (2) a method in which a sheet of semi-cured adhesive is attached to the surface of a material selected from metals, inorganic materials, and resin materials, and another material is pressure-bonded to part or all of the other surface of the adhesive to bond (cure).

[0237] The adhesive can be cured by a known method. Examples include a method of applying heat and pressure using a heat press, or a method of first drying the applied adhesive and then heat treating it. Heating and pressing conditions can be, for example, a temperature of 50 to 300°C (particularly, 80 to 250°C), a pressure of 0.1 to 50 MPa (particularly, 0.5 to 10 MPa), and a time of about 1 minute to 10 hours (particularly, about 30 minutes to 5 hours).

[0238] The adhesive of the present invention can be used to bond two materials, particularly two materials of different properties, and can therefore be suitably used in various electronic devices such as electrical or electronic components, semiconductor wafers, printed wiring boards, and flexible metal-clad laminates.

[0239] A preferred example of the composition (excluding the organic solvent) when the resin composition of the present invention is used as an adhesive is the same as that for the thermosetting resin film described above (see Table 3 above).

[0240] In this specification, the terms "comprise" and "have" include the concepts of "consist essentially of" and "consist of."

[0241] The present invention will be described in more detail below with reference to examples, but the present invention is not limited thereto. The main raw materials used in Examples 1 to 5 are as follows.

[0242] [Main raw materials] ・Phosphoryl chloride (Fujifilm Wako Pure Chemical Industries) ・2,2-bis(4-hydroxy-3-methylphenyl)propane (see chemical formula (II-10), Tokyo Chemical Industry Co., Ltd.) ・2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane (see chemical formula (II-11), Tokyo Chemical Industry Co., Ltd.) ・2,7-naphthalenediol (see chemical formula (II-4), Tokyo Chemical Industry Co., Ltd.) ・4,4'-dihydroxybiphenyl (see chemical formula (II-6), Tokyo Chemical Industry Co., Ltd.) ・2,6-dimethyl-4-vinylphenol (see chemical formula (III-3), synthesized according to the method described in Royal Society Open Science (2022), 9(4), 220014) ・2-vinylphenol (see chemical formula (III-9), Organic Letters (2012), 14(18), 4722-4725.) Triethylamine (Fujifilm Wako Pure Chemical Industries, Ltd.) Potassium t-butoxide (Tokyo Chemical Industry Co., Ltd.) Sodium hydroxide (Fujifilm Wako Pure Chemical Industries, Ltd.) Tetrahydrofuran (Fujifilm Wako Pure Chemical Industries, Ltd.) Toluene (Fujifilm Wako Pure Chemical Industries, Ltd.)

[0243] The main raw materials used in the evaluation tests are as follows: [Main raw materials] (i) Thermal radical curing resin component Polyphenylene ether resin (manufactured by Mitsubishi Gas Chemical Company, trade name "OPE-2St 2200", molecular weight: 2200) (ii) Flame retardant Phosphoric acid, (1-methylethylidene)bis(2-methyl-4,1-phenylene)tetrakis(2,6-dimethyl-4-vinylphenyl) ester (see chemical formula (I-53), Example 1. Hereinafter referred to as "Flame retardant 1") Phosphoric acid, (1-methylethylidene)bis(2-methyl-4,1-phenylene)tetrakis(2-vinylphenyl) ester (see chemical formula (I-51), Example 3. Hereinafter referred to as "Flame retardant 2") Phosphoric acid, 2,7-naphthalenediyltetrakis(2,6-dimethyl-4-vinylphenyl) ester (see chemical formula (I-38), Example 4. Hereinafter referred to as "Flame retardant 3")

[0047] Phosphoric acid, [1,1'-biphenyl]-4,4'-diyltetrakis(2,6-dimethyl-4-vinylphenyl) ester (see chemical formula (I-42), Example 5; hereinafter referred to as "Flame Retardant 4") Tris(4-vinylphenyl) phosphate (see chemical formula (V), synthesized in accordance with the method described in Chinese Patent Application Publication No. 109762115; hereinafter referred to as "Flame Retardant 5") Tris(2-allylphenyl) phosphate (see chemical formula (VII), synthesized in accordance with the method described in Chinese Patent Application Publication No. 109762115; hereinafter referred to as "Flame Retardant 6") Triallyl isocyanurate (see chemical formula (VIII), manufactured by Tokyo Chemical Industry Co., Ltd.; hereinafter referred to as "Flame Retardant 7") Tetrakis(2,6-dimethylphenyl)1,3-phenylene bisphosphate (see chemical formula (IX), manufactured by Daihachi Chemical Industry Co., Ltd., trade name "PX-200"; hereinafter referred to as "Flame Retardant 8")

[0244]

[0245] (iii) Radical polymerization initiator: α,α'-di(t-butylperoxy)diisopropylbenzene (manufactured by NOF Corporation, trade name "Perbutyl P") (iv) Organic solvent: Toluene (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0246] The evaluation tests (methods for evaluating flame retardancy, methods for measuring glass transition temperature and dielectric properties) employed in the examples and comparative examples are as follows.

[0247] (1) Evaluation of Flame Retardancy The resin composition was applied to a 25 μm-thick polyimide film using a bar coater so that the dried coating would have a thickness of 50±5 μm, and toluene was distilled off until a constant weight was reached. The film was then heat-treated at 150°C for 30 minutes and then at 190°C for 1 hour to produce an evaluation film. The flame retardancy of this evaluation film was evaluated in accordance with the UL94 VTM test method for the vertical flame test of the US UL standard.

[0248] (2) Measurement of Glass Transition Temperature (Tg) The resin composition was poured into a mold set to a thickness of 1 mm using a 1 mm silicone spacer, and then the toluene was distilled off until constant weight was reached in a fan oven heated to 80°C. The mixture was then heated at 120°C for 30 minutes, 150°C for 30 minutes, and 190°C for 1 hour to obtain a 1 mm thick plate-shaped cured product. A 20 mm long x 5 mm wide x 1 mm thick test piece cut from the cured product was placed in the solid torsion jig of a dynamic viscoelasticity measuring apparatus (DMA) (UBM's "Rheosol-G5000") and subjected to dynamic viscoelasticity measurements over a temperature range of 50 to 300°C at a heating rate of 5°C / min, a frequency of 1 Hz, and a strain of 0.08%. The glass transition temperature (unit: °C) was defined as the peak-top temperature of the loss modulus. The higher the glass transition temperature, the more excellent the heat resistance of the cured product. The glass transition temperatures were rated as "A" for those of 230°C or higher, "B" for those of 190°C or higher but lower than 230°C, and "C" for those lower than 190°C.

[0249] (3) Measurement of Dielectric Properties (Dielectric Loss Tangent Df) The resin composition was poured into a mold set to a thickness of 1 mm using a 1 mm thick silicone spacer, and then the toluene was distilled off until a constant weight was reached in a fan oven heated to 80 ° C. The mixture was then heated at 120 ° C. for 30 minutes, 150 ° C. for 30 minutes, and 190 ° C. for 1 hour to obtain a 1 mm thick plate-shaped cured product. A test piece measuring 50 mm long x 2 mm wide x 1 mm thick was cut from the cured product and dried at 200 ° C. for 3 hours. The dielectric properties (dielectric loss tangent Df) were measured at a measurement frequency (10 GHz) using a network analyzer (Agilent Technologies "E8361A"). The smaller the dielectric loss tangent Df, the better the dielectric properties of the cured product. The dielectric loss tangent Df was rated as "A" when it was less than 0.0040, and "B" when it was 0.0040 or more.

[0250] Example 1 Synthesis of phosphoric acid, (1-methylethylidene)bis(2-methyl-4,1-phenylene)tetrakis(2,6-dimethyl-4-vinylphenyl) ester (chemical formula (I-53)) 3.22 g (21.0 mmol) of phosphoryl chloride and 10 mL of tetrahydrofuran were placed in a 100 mL reactor and cooled to −70°C with stirring. While maintaining the temperature at −70 to −50°C, a mixed solution of 2.56 g (10.0 mmol) of 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2.12 g (21.0 mmol) of triethylamine, and 20 mL of tetrahydrofuran was added. The mixture was then stirred at −70°C for 1 hour, heated to 25°C, and stirred for 2 hours to obtain reaction mixture (1). Subsequently, a 300 mL reactor was charged with 10.37 g (70.0 mmol) of 2,6-dimethyl-4-vinylphenol, 60 mL of toluene, and 10 mL of tetrahydrofuran, and the mixture was cooled to -10°C with stirring. While maintaining the temperature at -10 to 0°C, 7.74 g (69.0 mmol) of potassium t-butoxide was added, and the temperature was then raised to 5°C and the mixture was stirred for 1 hour. Subsequently, the mixture was cooled to -10°C, and while maintaining the temperature at -10 to 0°C, reaction mixture (1) was added. Thereafter, the temperature was raised to 25°C and the mixture was stirred for 14 hours. This reaction solution was washed with a 5% aqueous sodium hydroxide solution and then washed with water, and the organic layer was concentrated to obtain 6.23 g of a pale yellow liquid (yield 66.5%).

[0251] This pale yellow liquid １ The H-NMR spectrum data was as follows: 1 H-NMR (CDCl3) δ: 7.11-7.18 (m, 2H), 7.06 (s, 8H), 6.92-6.97 (m, 4H), 6.60 (dd, 4H), 5.65 (d, 4H), 5.19 (d, 4H), 2.30 (s, 24H), 2.16 (s, 6H), 1.57 (s, 6H). The IR spectrum data of this pale yellow liquid was as shown in Figure 1. From these spectrum data, the obtained pale yellow liquid was identified as the compound represented by the above chemical formula (I-53).

[0252] Example 2 Synthesis of phosphoric acid, (1-methylethylidene)bis(2,6-dimethyl-4,1-phenylene)tetrakis(2,6-dimethyl-4-vinylphenyl) ester (chemical formula (I-62)) 3.37 g (22.0 mmol) of phosphoryl chloride and 10 mL of tetrahydrofuran were placed in a 100 mL reactor and cooled to −70°C with stirring. While maintaining the temperature at −70 to −50°C, a mixed solution of 2.84 g (10.0 mmol) of 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 2.23 g (22.0 mmol) of triethylamine, and 20 mL of tetrahydrofuran was added. The mixture was then stirred at −70°C for 8 hours, heated to 25°C, and stirred for 14 hours to obtain reaction mixture (2). Subsequently, a 300 mL reactor was charged with 10.37 g (70.0 mmol) of 2,6-dimethyl-4-vinylphenol, 60 mL of toluene, and 10 mL of tetrahydrofuran, and the mixture was cooled to -10°C with stirring. While maintaining the temperature at -10 to 0°C, 7.74 g (69.0 mmol) of potassium t-butoxide was added, and the temperature was then raised to 5°C and the mixture was stirred for 1 hour. The mixture was cooled to -10°C, and while maintaining the temperature at -10 to 0°C, reaction mixture (2) was added. The temperature was then raised to 25°C and the mixture was stirred for 14 hours. This reaction solution was washed with a 5% aqueous sodium hydroxide solution and then washed with water, and the organic layer was concentrated. The resulting concentrate was purified by column chromatography (chloroform) to obtain 2.83 g of a white solid (yield 29.3%).

[0253] This white solid １ The H-NMR spectrum data was as follows: 1 H-NMR (CDCl) δ: 7.06 (s, 8H), 6.83 (s, 4H), 6.60 (dd, 4H), 5.65 (d, 4H), 5.19 (d, 4H), 2.29 (s, 24H), 2.26 (s, 12H), 1.57 (s, 6H). The IR spectrum data of this white solid was as shown in Figure 2. From these spectrum data, the obtained white solid was identified as the compound represented by the title chemical formula (I-62).

[0254] Example 3 Synthesis of phosphoric acid, (1-methylethylidene)bis(2-methyl-4,1-phenylene)tetrakis(2-vinylphenyl) ester (chemical formula (I-51)) 3.22 g (21.0 mmol) of phosphoryl chloride and 10 mL of tetrahydrofuran were placed in a 100 mL reactor and cooled to −70°C with stirring. While maintaining the temperature at −70 to −50°C, a mixed solution of 2.56 g (10.0 mmol) of 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2.12 g (21.0 mmol) of triethylamine, and 20 mL of tetrahydrofuran was added. The mixture was then stirred at −70°C for 1 hour, heated to 25°C, and stirred for 2 hours. Subsequently, the mixture was cooled to -10°C, and while maintaining the temperature at -10 to 0°C, a mixed solution of 7.21 g (60.0 mmol) of 2-vinylphenol, 6.56 g (64.8 mmol) of triethylamine, and 20 mL of tetrahydrofuran was added. The temperature was then raised to 25°C and the mixture was stirred for 14 hours. Toluene was added to this reaction solution, and the mixture was washed with a 5% aqueous sodium hydroxide solution and then with water, and the organic layer was concentrated. The obtained concentrate was purified by column chromatography (chloroform) to obtain 2.87 g of a yellow liquid (yield 34.8%).

[0255] This yellow liquid １ The H-NMR spectrum data was as follows: 1 H-NMR (DMSO-d6) δ: 7.71 (d, 4H), 7.33-7.38 (m, 4H), 7.26-7.31 (m, 8H), 7.12-7.17 (m, 4H), 7.03-7.07 (m, 2H), 6.73 (dd, 4H), 5.84 (d, 4H), 5.27 (d, 4H), 2.07 (s, 6H), 1.60 (s, 6H). The IR spectrum data of this yellow liquid was as shown in Figure 3. From these spectral data, the obtained yellow liquid was identified as the compound represented by the above chemical formula (I-51).

[0256] Example 4 Synthesis of phosphoric acid, 2,7-naphthalenediyltetrakis(2,6-dimethyl-4-vinylphenyl) ester (chemical formula (I-38)) A 100 mL reactor was charged with 6.29 g (41.0 mmol) of phosphoryl chloride and 20 mL of tetrahydrofuran, and the mixture was cooled to −70°C with stirring. While maintaining the temperature at −70 to −50°C, a mixed solution of 3.20 g (20.0 mmol) of 2,7-naphthalenediol, 4.15 g (41.0 mmol) of triethylamine, and 20 mL of tetrahydrofuran was added. The mixture was then stirred at −70°C for 1 hour, then heated to 25°C and stirred for 2 hours to obtain reaction mixture (3). Subsequently, a 300 mL reactor was charged with 20.75 g (140 mmol) of 2,6-dimethyl-4-vinylphenol, 90 mL of toluene, and 20 mL of tetrahydrofuran, and the mixture was cooled to −10°C with stirring. While maintaining the temperature at -10 to 0°C, 15.48 g (138.0 mmol) of potassium t-butoxide was added, and then the temperature was raised to 5°C and stirred for 1 hour. Subsequently, the mixture was cooled to -10°C, and while maintaining the temperature at -10 to 0°C, reaction mixture (3) was added. The temperature was then raised to 25°C and stirred for 14 hours. This reaction liquid was washed with a 5% aqueous sodium hydroxide solution and then with water, and the organic layer was concentrated. The obtained concentrate was purified by column chromatography (chloroform) to obtain 8.53 g of a yellow liquid (yield 50.7%).

[0257] This yellow liquid １ The H-NMR spectrum data was as follows: 1 H-NMR (CDCl3) δ: 7.70 (d, 2H), 7.41-7.44 (m, 2H), 7.14-7.27 (m, 2H), 7.08 (s, 8H), 6.64 (dd, 4H), 5.64 (d, 4H), 5.21 (d, 4H), 2.33 (s, 24H). The IR spectrum data of this yellow liquid was as shown in Figure 4. From these spectrum data, the obtained yellow liquid was identified as the compound represented by the above chemical formula (I-38).

[0258] Example 5 Synthesis of phosphoric acid, [1,1'-biphenyl]-4,4'-diyltetrakis(2,6-dimethyl-4-vinylphenyl) ester (chemical formula (I-42)) 31.43 g (205.0 mmol) of phosphoryl chloride and 150 mL of tetrahydrofuran were placed in a 500 mL reactor and cooled to -70°C with stirring. While maintaining the temperature at -70 to -50°C, a mixed solution of 18.62 g (100.0 mmol) of 4,4'-dihydroxybiphenyl, 20.74 g (205.0 mmol) of triethylamine, and 100 mL of tetrahydrofuran was added. The mixture was then stirred at -70°C for 1 hour, heated to 25°C, and stirred for 2 hours to obtain reaction mixture (4). Subsequently, a 3000 mL reactor was charged with 311.22 g (2100 mmol) of 2,6-dimethyl-4-vinylphenol, 600 mL of toluene, and 400 mL of tetrahydrofuran, and the mixture was cooled to -10°C with stirring. While maintaining the temperature at -10 to 0°C, 232.27 g (2070 mmol) of potassium t-butoxide was added, and the temperature was then raised to 5°C and the mixture was stirred for 1 hour. Subsequently, the mixture was cooled to -10°C, and while maintaining the temperature at -10 to 0°C, reaction mixture (4) was added. The temperature was then raised to 25°C and the mixture was stirred for 14 hours. This reaction solution was washed with a 5% aqueous sodium hydroxide solution and then washed with water, and the organic layer was concentrated. The resulting concentrate was purified by column chromatography (chloroform) to obtain 63.33 g of a yellow liquid (yield 73.1%).

[0259] This yellow liquid １ The H-NMR spectrum data was as follows: 1 H-NMR (CDCl3) δ: 7.38-7.41 (m, 4H), 7.08-7.13 (m, 4H), 7.06 (s, 8H), 6.61 (dd, 4H), 5.68 (d, 4H), 5.22 (d, 4H), 2.35 (s, 24H). The IR spectrum data of this yellow liquid was as shown in Figure 5. From these spectrum data, the obtained yellow liquid was identified as the compound represented by the above chemical formula (I-42).

[0260] Example 6 A resin composition was prepared by mixing 70 parts by weight of OPE-2St 2200 as a thermo-radical curable resin component, 30 parts by weight of Flame Retardant 1 as a flame retardant, 1 part by weight of Perbutyl P as a radical polymerization initiator, and 100 parts by weight of toluene as an organic solvent. This resin composition was subjected to evaluation tests (evaluation of flame retardancy, measurement of glass transition temperature, and dielectric properties), and the obtained test results are shown in Table 4.

[0261] [Examples 7 to 9] Resin compositions having the formulations shown in Table 4 were prepared in the same manner as in Example 6, and evaluation tests were carried out on these resin compositions. The test results obtained are as shown in Table 4.

[0262] Comparative Examples 1 to 5 Resin compositions having the formulations shown in Table 5 were prepared in the same manner as in Example 6, and evaluation tests were carried out on these resin compositions. The test results obtained are as shown in Table 5.

[0263]

[0264]

[0265] Tables 4 and 5 confirm that when flame retardants 1 to 4 were used as flame retardants (Examples 6 to 9), the cured products had higher flame retardancy than when no flame retardant was used (Comparative Example 1) or when a conventional flame retardant was used (Comparative Example 4). Furthermore, when flame retardants 1 to 4 were used as flame retardants (Examples 6 to 9), the cured products had higher glass transition temperatures (Tg) than when no flame retardant was used (Comparative Example 1) or when a conventional flame retardant was used (Comparative Examples 3 to 5). Additionally, when flame retardants 1 to 4 were used as flame retardants (Examples 6 to 9), the cured products had lower dielectric dissipation factors Df than when no flame retardant was used (Comparative Example 1) or when a conventional flame retardant was used (Comparative Example 2). Therefore, it is believed that the inclusion of the flame retardant of the present invention in a resin composition can result in cured products with excellent flame retardancy, heat resistance, and electrical properties.

[0266] The resin composition containing the phosphorus compound of the present invention is expected to give a cured product having low thermal expansion (low CTE) and excellent flame retardancy, heat resistance, electrical properties, and moisture absorption resistance, and is therefore suitable as a material for printed wiring boards, adhesives, etc.

Claims

1. A phosphorus compound represented by chemical formula (I): (In the formula, R １ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an aryl group which may be substituted with an alkyl group having 1 to 10 carbon atoms or a phenyl group. ２ represents an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an aryl group which may be substituted with an alkyl group having 1 to 10 carbon atoms or a phenyl group; R ２ When there are multiple Y, they may be the same or different. １ represents a phenylene group which may be substituted with an alkyl group having 1 to 10 carbon atoms, a naphthylene group, or a group represented by formula (A); n may be the same or different and represents an integer of 0 to 3. (In the formula, R ３ are the same or different and each represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, an alkynyl group having 2 to 10 carbon atoms, or an aryl group which may be substituted with an alkyl group having 1 to 10 carbon atoms or a phenyl group. ２ represents a single bond, an alkylene group having 1 to 15 carbon atoms which may be substituted with a phenyl group, a cycloalkylene group having 5 to 15 carbon atoms, a cycloalkylidene group having 5 to 15 carbon atoms which may be substituted with an alkyl group having 1 to 10 carbon atoms, a phenylene group, an adamantane-1,3-ylene group, an adamantane-2-ylidene group, an oxygen atom, a sulfur atom, a sulfinyl group, a sulfonyl group, or a fluoren-9-ylidene group.

2. A method for synthesizing a phosphorus compound according to claim 1, characterized in that the compound represented by the chemical formula (II) is reacted with phosphoryl chloride, and then the resulting mixture is reacted with a vinylphenol compound represented by the chemical formula (III). (In the formula, Y １ is the same as above.) (In the formula, R １ , R ２ and n is the same as above.) 3. A method for synthesizing a phosphorus compound according to claim 1, characterized in that a vinylphenol compound represented by the chemical formula (III) is reacted with phosphoryl chloride, and then a compound represented by the chemical formula (II) is reacted therewith. (In the formula, R １ , R ２ and n is the same as above.) (In the formula, Y １ is the same as above.) 4. A flame retardant containing the phosphorus compound according to claim 1.

5. A resin composition containing the phosphorus compound according to claim 1 and a resin component.

6. A prepreg comprising the resin composition according to claim 5 and a substrate.

7. A resin-coated metal foil comprising a resin layer containing the resin composition according to claim 5 or a semi-cured product of said resin composition, and a metal foil.

8. A thermosetting resin film formed from the resin composition according to claim 5.

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

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

11. An adhesive comprising the resin composition according to claim 5.

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