TW202402961A - Phosphorous-containing (meth)acryloyl compound, method for producing the same, flame retardant resin composition containing the same and laminate for electronic circuit board - Google Patents

Abstract

An objective of this invention is to provides a phosphorous-containing compound, a curable resin composition including the compound and a cured article of the resin composition, wherein the phosphorous-containing compound is useful to be a reactive phosphorous flame retardant, with excellent solvent solubility, and the cured article thereof is excellent in thermo-resistance and dielectric properties. This invention provides a phosphorous-containing (meth)acryloyl compound represented by the following general formula (1); In the general formula(1), R1, R2 are each hydrogen, hydroxyl group, or a group represented by -OR or -R, R is an alkyl group with a carbon number of 2 to 40; R1, R2 may be the same or different, and R1, R2 may form a ring structure with the phosphorous atom; R3 is C1 to C20 alkyl group; X in the formula is a substituent represented by the following general formula (2); In the general formula (2), R4 is hydrogen or methyl group.

Description

Phosphorus-containing (meth)acrylyl compound, its production method, flame-retardant resin composition containing the compound, and laminate for electronic circuit substrates

The present invention relates to reactive phosphorus compounds, particularly to (meth)acrylyl compounds containing phosphorus, which are suitable for use as reactive flame retardants for plastic materials.

Plastic materials are used in a wide range of applications including building materials and electronic and electrical machinery due to their excellent mechanical properties and formability. However, since most plastic materials are easy to burn, in the applications they are used for, such as electronic and electrical products, OA equipment, communication equipment, etc., in order to ensure safety against heat and fire, they must be made flame retardant.

In terms of flame retardant technology for plastic materials, the addition of additive flame retardants such as halogen-based flame retardants, inorganic-based flame retardants, and phosphorus-based flame retardants is widely used, not limited to resin types and uses. However, among these, halogen-based flame retardants, mainly bromine-based, have been pointed out as a possible source of dioxin, which is highly carcinogenic. Therefore, in response to the current trend of reducing environmentally hazardous substances, there is a move towards restricting their use. In addition, although inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide have a flame retardant effect due to heat absorption, they need to be added in large amounts to achieve flame retardancy, thus reducing various properties of plastic molded products. the reason.

Therefore, phosphorus-based flame retardants are often used that do not produce harmful substances and can achieve flame retardancy even when added in a relatively small amount. However, even so, it is difficult to avoid a decrease in processability or loss of workability due to bleeding, etc. It is the effect of the reduction of glass transition temperature on the characteristics.

In order to solve the problems of such additive flame retardants, a reactive flame retardant containing phosphorus atoms as a flame retardant component and having a reactive group has been developed and widely used. A reactive flame retardant that can be applied to epoxy resin compositions widely used in the field of electronics and motors. For example, Patent Document 1 discloses a method of reacting bisphenol A with formaldehyde to obtain hydroxymethyl bisphenol A. The phenol resin obtained by reacting with 9,10-dihydro-9-oxa-10-phosphophenanthrene-10-oxide (hereinafter referred to as "DOPO") is used as a hardener for epoxy resin. Patent Document 2 discloses a phosphorus-containing epoxy resin obtained by reacting DOPO with quinones and then reacting with an epoxy resin. In these resins, workability problems such as bleeding of the flame retardant are solved, and no deterioration in thermal properties such as heat resistance is observed. In this way, compared with additive flame retardants, the use of reactive flame retardants can generally make up for the shortcomings of additive flame retardants, so many flame retardant epoxy resins and the like have been developed.

However, in recent years, in the field of electronic and electrical materials for which flame retardancy is a necessary characteristic, due to the rapid evolution of electronic devices represented by smartphones, the requirements for resin components containing flame retardants have also moved to a higher level. Especially in the field of information and communication, as the amount of information processing increases, the frequency of signals is rapidly progressing. In order to reduce transmission losses, resin components used in this field are strongly required to have low dielectric constant and low loss tangent. Therefore, in the field of electronic and motor materials represented by circuit substrates, radical polymerization, which can further achieve low dielectric constant and low loss tangent, has gradually been widely used. Replace epoxy resin with a flexible resin. Therefore, not only the reactive group is an epoxy group or a flame retardant that is reactive with epoxy resin, but also a halogen-free halogen with low dielectric constant and low loss tangent that can react with free radical polymerizable resin is required. Flame retardant.

In addition, since the resin composition used in circuit boards is impregnated with base materials such as glass cloth, it is required to be soluble in solvents. However, in fields requiring low dielectric, toluene is used due to its impact on dielectric properties. Non-polar solvents such as these are preferred, so no precipitation should be observed in these solvents.

As a halogen-free flame retardant having a radically polymerizable functional group, Patent Document 3 discloses a vinyl benzyl ether compound obtained from DOPO and chloromethylstyrene. However, since DOPO compounds are hydrolyzed by alkali, when reacting with chloromethylstyrene, partial hydroxyl groups are generated due to hydrolysis, causing deterioration of dielectric properties. Patent Document 4 discloses a polyfunctional vinyl benzyl ether compound using an adduct of DOPO and quinones, and Patent Document 5 and Non-Patent Document 1 disclose a polyfunctional vinyl benzyl ether compound using an adduct of DOPO and quinones. Functional (meth)acrylyl compounds. Although these compounds have excellent properties in terms of heat resistance and dielectric properties, they are highly crystalline and may precipitate in low-polarity solvents, resulting in handling problems.

[Prior technical literature]

[Patent Document]

[Patent Document 1] Japanese Patent Application Laid-Open No. 2013-166938

[Patent Document 2] Japanese Patent Application Laid-Open No. 11-279258

[Patent Document 3] Japanese Patent Application Laid-Open No. 2004-277322

[Patent Document 4] Japanese Patent Application Laid-Open No. 2004-331537

[Patent Document 5] Japanese Patent Application Laid-Open No. 2014-156426

[Non-patent literature]

[Non-patent document 1]Ind. Eng. Chem. Res. 2013, 52, 12855-12864

Therefore, an object to be solved by the present invention is to provide a phosphorus-containing compound that is suitable for use as a reactive phosphorus-based flame retardant, has excellent solvent solubility, and has excellent heat resistance and dielectric properties in a cured product. A curable resin composition of the compound and a cured product of the resin composition.

The inventors of the present invention conducted careful research on the aforementioned subject and found that (meth)acrylyl compounds and compositions containing phosphorus having a specific structure are excellent in flame retardancy, heat resistance, solubility and dielectric properties, and thus completed the present invention. invention.

That is, the present invention is a phosphorus-containing (meth)acrylyl compound represented by the following general formula (1).

In the general formula (1), R ¹ and R ² are hydrogen, hydroxyl, a group represented by -OR or -R, and R is a hydrocarbon group with 2 to 40 carbon atoms; R ¹ and R ² can be the same or different, R ¹ and R ² can form a cyclic structure together with a phosphorus atom; R ³ is a hydrocarbon group from C1 to C20; X in the formula is a substituent represented by the following general formula (2).

In the general formula (2), R ⁴ is hydrogen or methyl.

A method for producing a phosphorus-containing (meth)acrylyl compound as described above, which involves reacting a compound represented by the following general formula (3) with a compound containing one glycidyl ether group, and then (Meth)acrylation is carried out from (meth)acrylic acid, (meth)acrylic anhydride or halogenated (meth)acrylyl compounds.

A flame-retardant resin composition is prepared by blending at least one thermosetting resin or thermoplastic resin with the above-mentioned phosphorus-containing (meth)acrylyl compound.

A cured product obtained by curing the above-mentioned flame-retardant resin composition, and a laminated body for an electronic circuit board containing the above-mentioned flame-retardant resin composition as an essential component.

The (meth)acrylyl compound containing phosphorus of the present invention has excellent solvent solubility. In addition, a cured product obtained by curing a composition containing this compound as an essential component exhibits a low dielectric constant, a low loss tangent, and is heat-resistant. The degree of degradation in performance is small, and it can reduce the transmission loss at high frequencies associated with the increase in information processing capacity of electronic equipment, so it is very suitable for use as a reactive phosphorus-based flame retardant.

The present invention will be described in detail below.

In the description of the present invention, acrylic resins, acrylic compounds, acrylic ester compounds, etc. are referred to in accordance with common conventions. For example, "acrylyl" and "methacrylyl" are sometimes collectively referred to as "(methacrylyl)". "Acrylyl", "acrylic acid" and "methacrylic acid" are collectively referred to as "(meth)acrylic acid", and both "acrylate" and "methacrylate" are collectively referred to as "(meth)acrylic acid" Acrylate".

The hydroxyl-containing phosphorus compound or the phosphorus-containing (meth)acrylyl compound includes not only a single compound but also a mixture (resin).

The phosphorus-containing (meth)acrylyl compound of the present invention is represented by the following general formula (1).

In the general formula (1), R ¹ and R ² are hydrogen, hydroxyl, a group represented by -OR or -R, and R is a hydrocarbon group having 2 to 40 carbon atoms. R ¹ and R ² may be the same or different, and R ¹ and R ² may form a cyclic structure together with a phosphorus atom. Preferably, R is a benzene ring group, and the benzene ring may be substituted by an alkyl group having 1 to 3 carbon atoms.

In formula (1), X is a substituent represented by the following formula (2). However, the phosphorus-containing (meth)acrylyl compound of the present invention may also be a mixture of unreacted products containing a compound in which X is a hydroxyl group as a raw material.

In formula (2), R ⁴ is hydrogen or methyl.

In the general formula (1), R ³ is a C1 to C20 hydrocarbon group. Examples of hydrocarbon groups from C1 to C20 include aliphatic hydrocarbon groups having a linear or branched structure, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups having 6 to 20 carbon atoms. Examples of the aliphatic hydrocarbon group include alkyl groups having 1 to 20 carbon atoms, and examples of the aromatic hydrocarbon group include phenyl, naphthyl, biphenyl, and anthracenyl groups. When R ³ contains an aromatic hydrocarbon group, the aromatic ring may or may not have a substituent. Examples of the substituent include carboxyl group, aliphatic hydrocarbon group, acyl group, alkoxy group, cyano group, hydroxyl group, methacryloxy group, vinyl benzyl ether group, and groups linked to these substituents. When the aromatic hydrocarbon group has a substituent, the carbon number of the substituent is not included in the above carbon number.

The phosphorus content of the phosphorus-containing (meth)acrylyl compound represented by the general formula (1) is preferably 1.0 to 10.0% by weight, more preferably 5.0 to 9.0% by weight, and more preferably 6.0 to 8.0% by weight. .

The compound represented by the general formula (1) can be obtained by reacting the compound represented by the following general formula (3) with a compound containing one glycidyl ether group, and then using (meth)acrylic acid, (meth) It is obtained by (meth)acrylation with acrylic anhydride or halogenated (meth)acrylyl compound.

In the general formula (3), R ¹ and R ² are synonymous with those specified in the general formula (1). The phosphorus compound represented by the general formula (3) may be an organic phosphorus compound having an active hydrogen directly bonded to a phosphorus atom. Examples thereof include dimethylphosphine, diethylphosphine, diphenylphosphine, etc. Examples of phosphine oxides include: dimethylphosphine oxide, diethylphosphine oxide, diphenylphosphine oxide, methylphenylphosphonate, tert-butylphenylphosphine oxide, etc. Phosphate esters can be Examples: diethyl hydrogen phosphite, bis(2-ethylhexyl) hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite, 9,10-dihydrogen phosphite -9-oxa-10-phosphine-10-oxide (manufactured by HCA Sanko Co., Ltd.), etc., but are not limited to these, and two or more types may be used.

Examples of compounds containing one glycidyl ether group include: ethyl glycidyl ether, butyl glycidyl ether, tert-butyl glycidyl ether, glycidyl isopropyl ether, 2-ethylhexyl glycidyl ether, Lauryl glycidyl ether, lauryl alcohol (EO) 15 glycidyl ether, C12 to 13 mixed alcohol glycidyl ether, 3-glycidyloxypropyl (dimethoxy) silane, glycidyl acrylate, allyl shrink Glyceryl ether, glycidyl methacrylate, 1,1,1,3,5,5,5-heptamethyl-3-(3-glycidyloxypropyl)trisiloxane, 1,2-cyclo Oxydecane glycidyl guaiacol ether (1,2-epoxydecane glycidyl guaiacol ether), phenyl glycidyl ether, o-cresolyl glycidyl ether, m-cresolyl glycidyl ether, p-cresolyl glycidyl ether Ethers such as cresolyl glycidyl ether, 4-tert-butylphenyl glycidyl ether, benzyl glycidyl ether, phenol (EO) 5 glycidyl ether, 4-glycidyloxycarbazole, 4-tert-butyl glycidyl benzylate, etc. are not limited to these, and two or more types may be used in combination. From the viewpoint of ease of acquisition, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, cresolyl glycidyl ether, and 4-tert-butylphenyl glycidyl ether are preferred.

The reaction between the phosphorus compound having active hydrogen represented by the general formula (3) and the epoxy resin containing one glycidyl group can be carried out by a generally known method. That is, the epoxy resin is added to the phosphorus compound with active hydrogen, and the reaction is carried out under stirring at a reaction temperature of 100°C to 200°C, preferably 120°C to 180°C. When the reaction speed is slow, a catalyst may be used as necessary to improve productivity. Specific catalysts can be used: tertiary amines such as benzyldimethylamine; quaternary ammonium salts such as tetramethylammonium chloride; triphenylphosphine, tris(2,6-dimethoxyphenyl)phosphine, etc. Phosphines; phosphonium salts such as ethyltriphenylphosphonium bromide; imidazoles such as 2-methylimidazole (2-methyl Imidazole) and 2-ethyl-4-methylimidazole and other catalysts.

Regarding the reaction molar ratio between the phosphorus-containing compound represented by the general formula (3) and the epoxy resin containing one glycidyl group, the glycidyl group is 0.80 to 1.20 per mole of active hydrogen of the phosphorus compound. Mol, preferably 0.9 to 1.10 mol, more preferably 0.95 to 1.05 mol. When it is below 0.80, the unreacted phosphorus compound with active hydrogen increases in the compound. When it is above 1.20, the unreacted epoxy resin containing one glycidyl group increases in the compound, thus reducing the heat resistance and making the dielectric The characteristics are deteriorated, so it is not good.

A phosphorus-containing compound containing an alcoholic hydroxyl group obtained from the reaction of a phosphorus compound having active hydrogen represented by the general formula (3) and an epoxy resin containing one glycidyl group (hereinafter referred to as hydroxyl-containing phosphorus Compound), the reaction with (meth)acrylic acid, halogenated (meth)acrylyl group or (meth)acrylic anhydride is not particularly limited, and it can react with the usual (meth)acrylyl group of alcohol compound or phenol compound. Chemical reactions are carried out in the same way.

For example, when using (meth)acrylic acid, in the presence of a strong acid catalyst such as sulfuric acid, p-toluenesulfonic acid, methanesulfonic acid, etc., a phosphorus compound containing a hydroxyl group can be mixed with a ratio of 1 to 10 times (meth)acrylic acid relative to the hydroxyl group. It is produced by condensation reaction of acrylic acid. Since this reaction must be performed while discharging by-produced condensation water out of the system, the reaction solvent is a hydrocarbon solvent such as toluene that azeotropes with water, and the reaction liquid is heated to about 70 to 140°C.

In addition, the phosphorus-containing (meth)acrylyl compound of the present invention can be obtained by reacting a phosphorus compound containing a hydroxyl group with a halogenated (meth)acrylyl group or (meth)acrylic anhydride. Usable halogenated (meth)acrylyl groups include: fluorinated acrylyl group, chlorinated acrylyl group, bromide acrylyl group, iodinated acrylyl group and other halogenated acrylyl groups; fluorinated methacrylyl group , methacryloyl chloride, methacryloyl bromide, methacryloyl iodide and other halogenated methacrylyl groups.

In the implementation of the present invention, one type or a mixture of two or more types of halogenated (meth)acrylyl and (meth)acrylic anhydride can be used. In the present invention, from the viewpoint of ease of acquisition, chlorinated (meth)acrylic acid or/and (meth)acrylic anhydride is preferably used.

The amount of halogenated (meth)acrylyl group or/and (meth)acrylic anhydride is 0.8 to 5 moles, preferably 0.95 to 4 moles, relative to 1 mole of hydroxyl group of the phosphorus-containing phenolic compound used as a raw material. Ear. When the amount of halogenated (meth)acrylic acid or/and (meth)acrylic anhydride is lower than the above range, the resulting phosphorus-containing The heat resistance of the (meth)acrylyl compound decreases, and the residual amount of hydroxyl groups increases, which deteriorates the dielectric properties, so it is undesirable. When the dosage exceeds the above range, the efficiency of the kettle decreases and the cost increases, so it is undesirable. .

When halogenated (meth)acrylyl is used, hydrogen halide corresponding to the halogenated (meth)acrylic acid used is generated as a by-product. Therefore, it is preferable to use a basic compound in combination to capture the halogenated (meth)acrylyl group. The hydrogen halide produced reacts with it. The basic compound is not particularly limited, and examples thereof include trimethylamine, triethylamine, diisopropylethylamine, tri-n-propylamine, triisopropylamine, tributylamine, N-methyldiethylamine, and N-ethyldiamine. Methylamine, N-ethyldipentylamine and other aliphatic amines; N,N-dimethylaniline, diethylaniline and other aromatic amines; N,N-dimethylcyclohexylamine, N,N-diethylamine alicyclic amines such as cyclohexylamine; N,N-dimethylaminopyridine, N-methylmorpholine, diazabicycloundecene (DBU), diazabicyclononene (DBN), N - Heterocyclic amines such as methylpyridine and N-methylpyrrolidine; diamines such as tetramethylethylenediamine and triethylenediamine, etc. In terms of ease of acquisition, aliphatic amines such as trimethylamine and triethylamine, and pyridine are particularly preferred.

The amount of the basic compound used is, for example, 0.8 to 7 moles, preferably about 0.95 to 5 moles, based on 1 mole of hydroxyl group of the hydroxyl group-containing phosphorus compound used as a raw material. When the dosage of the tertiary amine is lower than the above range, the hydrogen halide will not be completely captured and corrosion of the reaction device will occur. When the dosage is higher than the above range, the cost will tend to increase.

When the reaction is carried out by (meth)acrylic anhydride, a catalyst does not need to be used. However, when the reaction is difficult to proceed, an ester catalyst, an acid catalyst, an alkali catalyst, or a Lewis acid catalyst can be used. Here, examples of the ester catalyst include alkali metal salts such as sodium and potassium of lower carboxylic acids such as sodium acetate, potassium propionate, and sodium (meth)acrylate. Examples of the acid catalyst include inorganic acids such as sulfuric acid and boric acid; organic acids such as methane sulfonic acid and p-toluenesulfonic acid. In addition, if the alkali catalyst is an organic base, examples thereof include nitrogen-containing aliphatic compounds such as triethylamine and triethylenediamine; nitrogen-containing aromatic heterocyclic compounds such as pyridine and 4-(dimethylamino)pyridine, etc. . Examples of the Lewis acid catalyst include aluminum chloride, zinc chloride, and the like.

Relative to the (meth)acrylic anhydride used, the amount of catalyst is preferably 10% or less, more preferably 5% or less. When a catalyst is used, if the temperature is higher than the above range, removal of the catalyst will take time. In addition, the catalyst may easily remain in the product, resulting in deterioration of characteristics.

烷、乙酸乙酯、乙腈、苯、甲苯、二甲苯、二氯甲烷、三氯甲烷、四氯化碳、二甲基甲醯胺、二甲基乙醯胺、二甲基亞碸、六甲基磷酸三醯胺、水等溶劑，可視需要組合此等來使用。 In the reaction between a phosphorus compound containing a hydroxyl group and a halogenated (meth)acrylyl group or/and (meth)acrylic anhydride, it is preferred to use an organic solvent as the reaction solvent and carry out the reaction in a solution. The solvent that can be used is not particularly limited as long as it has no reactivity with the phosphorus compound containing a hydroxyl group and the halogenated (meth)acrylic acid or/and (meth)acrylic anhydride. Examples include: tetrahydrofuran, dihydrofuran

Alkane, ethyl acetate, acetonitrile, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, dimethylformamide, dimethylacetamide, dimethylsulfoxide, hexamethyl Triamide phosphate, water and other solvents can be used in combination as needed.

In the reaction between phosphorus compounds containing hydroxyl groups and halogenated (meth)acrylic acid or/and (meth)acrylic anhydride, the reaction temperature is preferably -50 to 150°C. When the reaction is carried out at high temperatures, there is a possibility of polymerization. High, so -25 to 100℃ is especially preferred. In addition, the reaction time is appropriately set according to the set reaction temperature, and is preferably set in the range of 1 to 48 hours.

The reaction of a phosphorus compound containing a hydroxyl group with (meth)acrylic acid, halogenated (meth)acrylyl or (meth)acrylic anhydride can also be carried out in the presence of a polymerization inhibitor. By adding a polymerization inhibitor, it is possible to prevent the polymerization of (meth)acrylic acid, halogenated (meth)acrylyl, (meth)acrylic anhydride, or (meth)acrylic acid ester that is the target product supplied to the reaction. And the situation of by-product oligomers. The polymerization inhibitor is not particularly limited, and commonly known ones can be used, except hydroquinone, hydroxymonomethyl ether, t-Butyl Catechol, and t-butyl p-phenylene. In addition to organic compounds such as diphenols, 4-methoxyphenol, 4-methoxy-1-naphthol, and phenothiazine, copper compounds such as copper chloride and copper sulfide can also be used in combination. Wait and use.

After the reaction is completed, the reaction liquid (reaction mixture) obtained may be subjected to distillation of the reaction solvent, solvent substitution, etc. if necessary, and may be washed with water, etc., or treated with activated carbon or silica. By purifying by means such as gel chromatography, the target (meth)acrylyl compound of the present invention can be obtained.

Next, a flame-retardant resin composition containing the phosphorus-containing (meth)acrylyl compound of the present invention as an essential component and blending a curable resin or a thermoplastic resin will be described.

Examples of the curable resin include unsaturated polyester resin, curable maleimide resin, epoxy resin, polycyanate resin, phenol resin, and those having one or more polymerizable unsaturated hydrocarbon groups in the molecule. The one or more vinyl compounds, etc. are preferably epoxy resins and one or more vinyl compounds having one or more polymerizable unsaturated hydrocarbon groups in the molecule.

When the curable resin is an epoxy resin, it is preferably one or more epoxy resins selected from epoxy resins having two or more epoxy groups in one molecule. Examples of the epoxy resin include: cresol-novolac type epoxy resin, triphenylmethane type epoxy resin, biphenyl epoxy resin, naphthalene type epoxy resin, bisphenol A type epoxy resin and bisphenol F type epoxy resin. Oxygen resin, etc. These can be used individually or in combination of 2 or more types. By using such an epoxy resin, it is possible to minimize the impact on the excellent dielectric properties and fluidity of the curable resin composition of the present invention, thereby fully improving the heat resistance of the cured product. and tightness.

(Benzoxazine)系硬化劑、氰酸酯系硬化劑等。此等可使用1種或組合2種以上而使用。 In addition, when an epoxy resin is contained, a hardener may be used in addition to the epoxy resin. The curing agent is not particularly limited, and examples thereof include: phenol-based curing agents, amine-based compounds, amide-based compounds, acid anhydride-based compounds, naphthol-based curing agents, active ester-based curing agents, benzo

(Benzoxazine)-based hardener, cyanate ester-based hardener, etc. These can be used 1 type or in combination of 2 or more types.

Furthermore, when formulating epoxy resin, a hardening accelerator may be used as needed. Examples include amines, imidazoles, organic phosphines, Lewis acids, etc. The amount added is usually in the range of 0.2 to 5 parts by weight relative to 100 parts by weight of the epoxy resin.

When the curable resin is one or more vinyl compounds (hereinafter also referred to as vinyl compounds) having one or more polymerizable unsaturated hydrocarbon groups in the molecule, the type is not particularly limited. That is, the vinyl compounds may be those that can form crosslinks and be hardened by reacting with the phosphorus-containing (meth)acrylyl compound of the present invention. The polymerizable unsaturated hydrocarbon group is preferably a carbon-carbon unsaturated double bond, and is particularly preferably a compound having two or more carbon-carbon unsaturated double bonds in the molecule.

The average number of carbon-carbon unsaturated double bonds per molecule of vinyl compounds that are curable resins (the number of vinyl groups (including substituted vinyl groups). It is also called the number of terminal double bonds.) is due to ethylene Depending on the Mw of the base compound, the number is preferably 1 to 20, and particularly preferably 2 to 18. If the number of terminal double bonds is too small, it will tend to be difficult to obtain sufficient heat resistance of the cured product. In addition, when the number of terminal double bonds is too large, the reactivity may become too high, which may cause defects such as a decrease in the storage stability of the curable resin composition or a decrease in the fluidity of the curable resin composition.

Examples of vinyl compounds include: isotrienyl isocyanurate compounds such as triallyl isocyanurate (TAIC), modified polystyrene whose terminals are modified with (meth)acrylyl groups or styrene groups. Ether (PPE), polyfunctional (meth)acrylate compounds with two or more (meth)acrylyl groups in the molecule, polybutadiene, etc. Generally, ethylene with two or more vinyl groups in the molecule base compounds (polyfunctional vinyl compounds), and vinyl benzyl compounds such as styrene and divinylbenzene. Among them, those with more than two carbon-carbon double bonds in the molecule are preferred. Specifically, TAIC, multifunctional (meth)acrylate compounds, modified PPE resins, multifunctional vinyl compounds, and Divinylbenzene compounds, etc. When using these, it can be considered to form crosslinks more appropriately through the curing reaction, thereby further improving the curability of the resin. The heat resistance of the hardened material of the composition. In addition, these can be used individually or in combination of 2 or more types. In addition, compounds having one carbon-carbon unsaturated double bond in the molecule can also be used together. Examples of compounds having one carbon-carbon unsaturated double bond in the molecule include compounds having one vinyl group in the molecule (monovinyl compounds).

Thermoplastic resins include, for example, polystyrene, polyphenylene ether resin, polyether imide resin, polyether styrene resin, PPS resin, polycyclopentadiene resin, polycycloolefin resin, etc., or known thermoplastic elastic resins. body (such as styrene-ethylene-propylene copolymer, styrene-ethylene-butylene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, hydrogenated styrene-butadiene copolymer , hydrogenated styrene-isoprene copolymer, etc.), or rubber (such as polybutadiene, polyisoprene). Preferred examples include unmodified or modified polyphenylene ether resin and hydrogenated styrene-butadiene copolymer.

The flame-retardant resin composition of the present invention may also contain a radical polymerization initiator (polymerization catalyst or cross-linking agent) that generates free radicals by light and/or heat. Examples of the photopolymerization initiator include benzoins such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether; acetophenone, 2,2-diethoxy-2 -Phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropan-1-one , diethoxyacetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropan-1-one and other benzene esters Ketones; anthraquinones such as 2-ethyl Anthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, 2-pentylanthraquinone; 2,4-diethylthiophene Thioxanthones such as 2,4-diethyl Thioxanthone, 2-isopropylthioxanthone, and 2-chlorothioxanthone; ketals such as acetophenone dimethyl ketal and benzyl dimethyl ketal Ketones; diphenyl ketones such as Benzophenone, 4-benzyl-4'-methyldiphenyl sulfide, 4,4'-bismethylaminodiphenylketone; 2 , 4,6-trimethylbenzyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzyldiphenyl)-phenylphosphine oxide and other phosphine oxides.

Thermal free radical initiators include: benzyl peroxide, cumene hydroperoxide, 2,5-dihydroperoxy-2,5-dimethylhexane, 2,5-dimethyl-2, 5-Di(tert-butylperoxy)hexyne-3, di(tert-butyl) peroxide, tert-butylcumyl peroxide, 1,3-bis(butylperoxycumyl) methyl)benzene, α,α'-bis(tert-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-di(tert-butylperoxy)hexane , dicumyl peroxide, di(tert-butylperoxy)isophthalate, tert-butylperoxybenzoate, 2,2-bis(tert-butylperoxy)butane , 2,2-bis(tert-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzylperoxy)hexane, bis(trimethylsilyl peroxide) peroxide), trimethylsilyl peroxide, triphenylsilyl peroxide and other peroxides, but are not limited to these. In addition, although it is not a peroxide, 2,3-dimethyl-2,3-diphenylbutane can also be used as a free radical polymerization initiator. However, the invention is not limited to these examples, and two or more radical initiators may be used in combination.

The compounding amount of the radical polymerization initiator is preferably 0.01 to 10 parts by weight, and particularly preferably 0.1 to 5 parts by weight based on 100 parts by weight of the (meth)acryl compound containing phosphorus.

The flame-retardant resin composition of the present invention must contain a phosphorus-containing (meth)acrylyl compound represented by the general formula (1) as a reactive flame retardant, and the phosphorus content rate based on the composition is preferably 0.5. to 5.0% by weight, preferably 1.0 to 4.0% by weight.

A filler can be blended into the flame-retardant resin composition of the present invention. Examples of the filler include those added in order to improve the heat resistance or flame retardancy of the cured product of the curable resin composition. Generally known fillers can be used, but are not particularly limited. In addition, by containing fillers, heat resistance, dimensional stability, flame retardancy, etc. can be further improved. Specific examples include: silica such as spherical silica; metal oxides such as aluminum oxide, titanium oxide, and mica; metal hydroxides such as aluminum hydroxide and magnesium hydroxide; talc, aluminum borate, barium sulfate, and carbonic acid Calcium etc. When metal hydroxides such as aluminum hydroxide and magnesium hydroxide are used, they function as flame retardant auxiliaries and ensure flame retardancy even if the phosphorus content is low. Preferred among them is dioxide Silicon, mica and talc, especially spherical silicon dioxide. In addition, these can be used individually by 1 type or in combination of 2 or more types.

The filler can be used directly, or it can be surface-treated with a silane coupling agent such as epoxy silane type or amine silane type. From the viewpoint of reactivity with the radical polymerization initiator, the silane coupling agent is preferably a vinyl silane type, a methacryloxy silane type, a propylene oxy silane type, and a styrene silane type silane coupling agent. This improves the bonding strength with metal foil or the layer-to-layer bonding strength between resins. In addition, it is also possible to add the above-mentioned silane coupling agent by an integral blending method without performing surface treatment on the filler in advance.

The content of the filler is preferably 10 to 200 parts by mass, particularly preferably 30 to 150 parts by mass, relative to a total of 100 parts by mass of solid content (including organic components such as monomers and flame retardants, excluding solvents) excluding fillers. .

The flame-retardant resin composition of the present invention may further contain additives other than those mentioned above. Examples of additives include defoaming agents such as silicone-based defoaming agents and acrylate-based defoaming agents, heat stabilizers, antistatic agents, ultraviolet absorbers, dispersants such as dyes or pigments, smoothing agents, and moist dispersants. wait.

The cured product obtained by curing the flame-retardant resin composition of the present invention can be used as a molded product, a laminated product, an injection molded product, an adhesive, a coating, or a film. For example, a cured product of a semiconductor packaging material is an injection molded product or a molded product. A method for obtaining a cured product for this purpose is to use an injection molding or transfer molding machine, an injection molding machine, etc. to mold a curable resin composition, and then The cured product is obtained by heating at 80 to 230°C for 0.5 to 10 hours.

The flame-retardant resin composition of the present invention can also be used as a prepreg. When manufacturing a prepreg, it can be prepared into a varnish for the purpose of impregnating the base material (fibrous base material) used to form the prepreg or the circuit board material forming the circuit board. For resin varnish. This resin varnish Suitable for circuit boards and can be used as varnish for circuit board materials. The use of the circuit board material here specifically includes printed wiring boards, printed wiring boards, flexible printed wiring boards, build-up wiring boards, and the like.

The organic solvent used in the resin varnish is not particularly limited as long as it does not inhibit the hardening reaction. Examples include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, propyl acetate, and butyl acetate; and polar solvents such as dimethylacetamide and dimethylformamide. ; Aromatic hydrocarbon solvents such as toluene and xylene can be used alone or in a mixture of two or more types. From the viewpoint of dielectric properties, aromatic hydrocarbons such as benzene, toluene, and xylene are preferred.

When making a resin varnish, the amount of organic solvent used is preferably 5 to 900 parts by weight, particularly preferably 10 to 700 parts by weight, and particularly preferably 20 to 700 parts by weight relative to 100 parts by weight of the curable resin composition of the present invention. 500 parts by weight.

The base materials used when making prepregs are generally known materials, such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper and other base materials, either alone or in combination. . In these base materials, a coupling agent may also be used for the purpose of improving the adhesion at the interface between the resin and the base material, if necessary. As the coupling agent, general ones such as silane coupling agent, titanate coupling agent, aluminum-based coupling agent, and zircoaluminate coupling agent can be used.

A method of obtaining a prepreg includes a method of impregnating the base material with the resin varnish and then drying the base material. Impregnation is performed by dipping, coating, etc. The impregnation can also be repeated multiple times as necessary. In addition, at this time, multiple solutions with different compositions or concentrations can be used to repeat the impregnation, and the impregnation can be adjusted to the final desired resin composition and resin amount. After impregnation, the prepreg can be obtained by heating and drying at 100 to 180° C. for 1 to 30 minutes. Here, the amount of resin in the prepreg is preferably 30 to 80% by weight of the resin content.

The curable resin composition of the present invention can also be used as a laminated body. When using prepregs to form a laminated body, one or a plurality of prepregs are laminated and metal foil is placed on one or both sides to form a laminated body, and then the laminated body is heated and pressurized to form a laminated body. . Here, as the metal foil, a single metal foil, an alloy metal foil, or a composite metal foil such as copper, aluminum, brass, or nickel can be used. The conditions for heating and pressurizing the laminate can be appropriately adjusted under the conditions for hardening the curable resin composition. However, if the pressure is too low, air bubbles will remain inside the resulting laminate. , sometimes leading to a decrease in electrical characteristics, it is best to press under conditions that satisfy formability. For example, the temperature can be set to 180 to 250°C, the pressure to 49.0 to 490.3N/cm ² (5 to 50kgf/cm ² ), and the heating and pressurizing time to 40 to 240 minutes. Furthermore, the obtained single-layered laminate can be used as an inner layer material to produce a multilayer board. In this case, a circuit is first formed on the laminate by an additive method or a subtractive method, and the surface of the formed circuit is treated with an acid solution to perform a blackening treatment to obtain an inner layer material. Then, an insulating layer is formed on the circuit forming surface on one or both sides of the inner layer using a resin sheet, metal foil with resin, or prepreg, and a conductor layer is formed on the surface of the insulating layer to form a multilayer board. .

In addition, the curable composition of the present invention can also be used as a build-up film. An example of a method for producing a build-up film from the resin composition of the present invention is a method of applying the above-mentioned resin varnish on a support film and drying it to form a film-like insulating layer. The film-like insulating layer formed in this way can be used as a build-up film for multilayer printed wiring boards.

[Example]

Next, the present invention will be explained through examples, but the present invention is not limited thereto. Parts in each example are parts by weight.

The physical properties in the synthesis examples and examples were measured by the methods shown below.

(1) Phosphorus content: Add sulfuric acid, hydrochloric acid, and perchloric acid to the sample, then heat and perform wet ashing to turn all phosphorus atoms into orthophosphoric acid. React metavanadate and molybdate in a sulfuric acid solution, and measure the absorbance of the generated phosphovanadium molybdate complex at 420 nm, and then use a calibration curve prepared in advance using potassium dihydrogen phosphate, Express the obtained phosphorus atom content rate in %.

(2) Solvent solubility: In a varnish using toluene as a solvent and adjusted to a solid content of 50% by mass, a case where no precipitation occurred after one week was judged as ○, and a case where precipitation was observed was judged as ×.

(3) Glass transition temperature: determined from the baseline shift using differential scanning thermal analysis at a temperature rise rate of 10°C/min.

(4) Relative dielectric constant and loss tangent: According to the IPC-TM-6502.5.5.9 specification, use a material analyzer (manufactured by AGILENT Technologies) and use the capacitance method to determine the dielectric constant and loss tangent at a frequency of 1 GHz. .

(5) Flame retardancy: evaluated by vertical method according to UL94. The evaluation system is recorded in N.C. (Non Classified), V-0, V-1, and V-2.

(Synthesis Example 1) Synthesis of hydroxyl-containing phosphorus compound A

Put 150 parts of 9,10-dihydro-9-oxa-10-phosphine-10-oxide of the following structural formula and 65 parts of toluene into a glass equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen introduction device. Make a detachable flask and dissolve at 80°C.

Then, 105 parts of phenyl glycidyl ether of the following structural formula was put into a glass separable flask equipped with a stirring device, a thermometer, a Dean-Stark device, and a nitrogen introduction device.

The temperature was raised to 110°C, 0.51 part of triphenylphosphine was added, and the temperature was further heated to 160°C while removing toluene, and the reaction was carried out for 5 hours. Then, the pressure was reduced to 1 kPa with a vacuum pump to completely distill off the toluene, and 250 parts of the hydroxyl-containing phosphorus compound A having the following structural formula was obtained.

The phosphorus content was measured and the result was 8.4%.

(Synthesis Example 2) Synthesis of hydroxyl-containing phosphorus compound B

Use 143 parts of 4-tert-butylphenyl glycidyl ether of the following structural formula to replace phenyl glycidyl ether,

Except for changing the usage amount of triphenylphosphine to 0.59 parts, the same operation as Synthesis Example 1 was performed to obtain 290 parts of hydroxyl-containing phosphorus compound B.

The phosphorus content was measured and the result was 7.2%.

(Synthesis Example 3) Synthesis of hydroxyl-containing phosphorus compound C

Use 129 parts of 2-ethylhexyl glycidyl ether of the following structural formula to replace phenyl glycidyl ether,

Except for changing the usage amount of triphenylphosphine to 0.56 parts, the same operation as Synthesis Example 1 was performed to obtain 275 parts of hydroxyl-containing phosphorus compound C.

The phosphorus content was measured and the result was 7.5%.

(Example 1) Synthesis of phosphorus-containing methacryloyl compound A

160 parts of phosphorus compound A containing a hydrogen group, 160 parts of tetrahydrofuran, and 75 parts of triethylamine were put into a glass separable flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping funnel. After dissolving, use an ice bath to Cool to below 5°C. Under nitrogen atmosphere, 70 parts of methacrylic acid chloride with the following structural formula was added dropwise within 1 hour, and then the reaction was continued for 2 hours.

Then, the reaction solution was concentrated and dissolved in 442 parts of toluene, and then washed with sodium carbonate aqueous solution and water in sequence. After washing with water, dehydration and filtration are performed, and the solvent is further concentrated to reduce the solid content concentration It was adjusted to 50%, and 340 parts of toluene solutions of the phosphorus-containing methacryloyl compound A of the following structural formula were obtained.

The phosphorus content is 7.2%.

(Example 2) Synthesis of phosphorus-containing methacryloyl compound B

150 parts of phosphorus compound B containing a hydrogen group, 150 parts of tetrahydrofuran, 36 parts of triethylamine, and 2.7 parts of 4-dimethylaminopyridine were put into a glass separable device equipped with a stirring device, a thermometer, a cooling tube, and a dropping funnel. flask and dissolve at room temperature. Under nitrogen atmosphere, 67 parts of methacrylic anhydride with the following structural formula was added dropwise within 1 hour, and then the reaction was continued at 50°C for 6 hours.

Then, the reaction solution was concentrated and dissolved in 442 parts of toluene, and then washed and concentrated in the same manner as in Example 1 to obtain 314 parts of a toluene solution of phosphorus-containing methacryloyl compound B with a solid content concentration of 50%.

The phosphorus content is 6.5%.

(Example 3) Synthesis of phosphorus-containing methacryloyl compound C

Put 150 parts of phosphorus compound C containing hydrogen groups, 150 parts of tetrahydrofuran, 38 parts of triethylamine, and 2.8 parts of 4-dimethylaminopyridine into a glass separable device equipped with a stirring device, a thermometer, a cooling tube, and a dropping funnel. flask and dissolve at room temperature. Under nitrogen atmosphere, 70 parts of methacrylic anhydride was added dropwise within 1 hour, and then the reaction was continued at 50°C for 6 hours.

Then, the reaction solution was concentrated and dissolved in 444 parts of toluene, and then washed and concentrated in the same manner as in Example 1 to obtain 316 parts of a toluene solution of phosphorus-containing methacryloyl compound C with a solid content concentration of 50%.

The phosphorus content is 6.8%.

(Comparative Example 1) Synthesis of phosphorus-containing methacryloyl compound D

Put 100 parts of DOPO-NQ of the following structural formula, 233 parts of tetrahydrofuran, and 72 parts of triethylamine into a glass separable flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping funnel.

After dissolving, cool to below 5°C in an ice bath. Under nitrogen atmosphere, 62 parts of methacrylic acid chloride was added dropwise within 1 hour, and then the reaction was continued for 2 hours.

Next, the reaction solution was concentrated and dissolved in 318 parts of toluene, washed and concentrated in the same manner as in Example 1, and adjusted to a toluene solution with a solid content concentration of 50% to obtain phosphorus-containing methacryloyl compound E. 235 parts of solution.

The phosphorus content is 6.2%.

(Comparative Example 2) Synthesis of Vinyl Benzyl Compound A Containing Phosphorus

It was synthesized according to Synthesis Example 1 of Patent Document 3. Specifically, 150 parts of 9,10-dihydro-9-oxa-10-phosphine-10-oxide as the phosphorus compound, 70 parts of toluene as the reaction solvent, 20 parts of isopropyl alcohol, and ethylene halide were used. 120 parts of benzyl-based AGC SEIMI CHEMICAL CMS-P and 2.7 parts of tetramethylammonium chloride as a catalyst were put into a glass separable flask equipped with a stirring device, a thermometer, a cooling tube, and an oxygen introduction device, and carried out Dissolve with heat. Then, 127 parts of a 48.5% sodium hydroxide aqueous solution as an alkali metal was added in batches while paying attention to the temperature rise due to the heat generated by the reaction. The reaction was carried out at 70°C to 80°C, and the remaining amount of CMS-P was tracked by gas chromatography. After confirming that the remaining amount of CMS-P has been reduced and that it has fully reacted, dilute it with toluene. Neutralize with hydrochloric acid and filter to remove the sodium chloride generated. This is followed by water washing to remove ionic impurities. Dehydration and solvent removal were performed by heating and reducing pressure, and the solution was adjusted to a toluene solution with a solid content concentration of 50%, thereby obtaining a solution of vinyl benzyl compound A containing phosphorus.

The phosphorus content of the obtained compound was measured and found to be 9.3%.

(Comparative Example 3) Synthesis of Vinyl Benzyl Compound B Containing Phosphorus

The synthesis was performed according to Synthesis Example 1 of Patent Document 4, and further using 1,4-naphthoquinone. Specifically, 340 parts of 9,10-dihydro-9-oxa-10-phosphinephenanthrene-10-oxide and 660 parts of toluene were put into a glass-made container equipped with a stirring device, a thermometer, a cooling tube, and an oxygen introduction device. separate flask and perform dissolution at 80°C. While paying attention to the reaction heat, 245 parts of 1,4-naphthoquinone were added in batches. The reaction was continued, the temperature was increased to 110°C and the reaction was further carried out. After 3 hours, a slurry solution with dark brown crystals precipitated was obtained. The crystals were separated by filtration and dispersed in 500 parts of methanol. After repeating this operation three times, dry it in a hot air circulation oven. To the obtained light yellow powder, 93.5 parts of the phosphorus-containing phenolic compound 10-(2,5-dihydroxynaphthyl)-10H-9-oxa-10-phosphinophene-10-oxide and dimethyl as a solvent were added. 140.5 parts of vinyl benzene, 93.5 parts of methyl isobutyl ketone, 77.8 parts of CMS-P manufactured by AGC SEIMI CHEMICAL Co., Ltd. as the halogenated vinyl benzyl group, 0.20 parts of tetramethylammonium chloride as the catalyst, and 48.5% of the alkali metal 74.2 parts of sodium hydroxide aqueous solution and 0.16 parts of trimethylhydroquinone as a polymerization inhibitor were neutralized with 35% hydrochloric acid until the pH became 5 to 6, and then the lower water layer was separated and removed. Wash with water while adjusting the pH to 7 to 6 with a sodium dihydrogen phosphate aqueous solution, and repeat the water layer separation and removal 3 to 5 times. The solvent was recovered by performing reflux dehydration and filtration of the solution, and the solution was adjusted to a toluene solution with a solid content concentration of 50% to obtain a solution of vinyl benzyl ether compound B containing phosphorus.

The phosphorus content of the obtained compound was measured and found to be 4.2%.

〈Solubility test〉

The solubility test was performed using the 50% toluene solution prepared in Examples 1 to 3 and Comparative Examples 1 to 3. The results are shown in Table 1.

[Table 1]

Examples 4 to 9, Comparative Examples 4 to 12

〈Preparation of curable resin composition and production of cured product〉

Prepare various ingredients according to the ratios in Tables 2 and 3, and use toluene to make a varnish with a solid content of 50%. Then apply it on the PET film and dry it in an oven at 130°C for 5 minutes to make a resin composition. membrane of matter. This film is then pulverized to obtain powder of a resin composition. Then, this powder was sandwiched between a stainless steel mirror plate and a spacer, and molded at 210° C. for 90 minutes using a vacuum oven to obtain a sample of the hardened product. The glass transition temperature and dielectric properties were evaluated using this hardened material sample, and are shown in Table 2 and Table 3.

〈Preparation of flame-retardant test pieces〉

Various ingredients were prepared according to the ratios in Tables 2 and 3, and a varnish with a solid content of 50% was made from toluene. The resin varnish was impregnated into glass cloth (manufactured by Nitto Bo Co., Ltd.; type 7628; model number H258). ), then heated at 130° C. for 5 minutes to dry and obtain a prepreg.

The 8 prepregs obtained were stacked, and copper foil (manufactured by Mitsui Metals & Mining Co., Ltd., 3EC-III, thickness 35 μm) was stacked on the upper and lower sides, and the temperature conditions were 130°C × 15 minutes + 190°C × 80 minutes. Vacuum molding at 2 MPa was performed to obtain a 1.6 mm thick laminated body. The copper foil was etched and cut to obtain a flame retardant test piece. The flame retardancy was evaluated using this flame retardancy test piece, and is shown in Table 2 and Table 3.

[Table 2]

[table 3]

OPE-2St: Made by Mitsubishi Gas Chemical Co., Ltd. End-modified polyphenylene ether resin with styrene group

PX-200: Aromatic condensed phosphate ester made by Daihachi Chemical Industry Co., Ltd., phosphorus content 9.0%

Perbutyl P: 1,3-bis(butylperoxyisopropyl)benzene manufactured by NOF Corporation

[Industrial applicability]

The phosphorus-containing (meth)acrylyl compound of the present invention can be used in a wide range of applications covering building materials and electronic and electrical equipment, especially in electronic and electrical products, OA equipment, communication equipment, etc., and is extremely suitable as a reactive phosphorus It is a flame retardant.

Claims (5)

A (meth)acrylyl compound containing phosphorus is represented by the following general formula (1),

In the general formula (1), R ¹ and R ² are hydrogen, hydroxyl, a group represented by -OR or -R, and R is a hydrocarbon group having 2 to 40 carbon atoms; R ¹ and R ² can be the same or different, R ¹ and R ² can be combined with a phosphorus atom to form a cyclic structure; R ³ is a hydrocarbon group from C1 to C20; X in the formula is a substituent represented by the following general formula (2);

In the general formula (2), R ⁴ is hydrogen or methyl. A method for producing the phosphorus-containing (meth)acrylyl compound described in claim 1, by combining a compound represented by the following general formula (3) and a compound containing 1 glycidyl ether After reacting the base compound, (meth)acrylation is performed by (meth)acrylic acid, (meth)acrylic anhydride or halogenated (meth)acrylyl compound.

In the general formula (3), R ¹ and R ² are synonymous with those specified in the general formula (1). A flame-retardant resin composition prepared by blending at least one thermosetting resin or thermoplastic resin with the phosphorus-containing (meth)acrylyl compound described in claim 1. A hardened product obtained by hardening the flame-retardant resin composition according to claim 3. A laminated body for electronic circuit boards, which contains the flame-retardant resin composition according to claim 3 as an essential component.