TW202402776A - Phosphorus-containing (meth)acryloyl compound, method for producing the same, and flame-retardant resin composition comprising phosphorus-containing (meth)acryloyl compound, cured product, and laminate for electronic circuit board - Google Patents

Abstract

The present invention aims to provide a phosphorus-containing compound that can be used as a reactive phosphorus-based flame retardant, a curable resin composition comprising the phosphorus-containing compound, and a cured product of the curable resin composition. The phosphorus-containing compound has excellent solubility in a solvent and demonstrates excellent heat resistance and dielectric properties in a cured product.

Provided is a phosphorus-containing (meth)acryloyl compound represented by general formula (1):

wherein Y is a substituent represented by general formula (2) or (3) below, and at least one of Ys contains a substituent represented by general formula (3) below.

Description

Phosphorus-containing (meth)acrylyl compound, production method thereof, flame-retardant resin composition containing phosphorus-containing (meth)acrylyl compound, cured product, and laminate for electronic circuit substrate

The present invention relates to reactive phosphorus compounds, especially 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 electrical and electronic equipment due to their excellent mechanical properties and formability. However, most plastic materials are easily flammable, so in applications such as electrical/electronic products, OA equipment, communication equipment, etc., they must be made flame retardant to prevent heat ignition and fire safety.

As for the flame retardant technology of plastic materials, it is not limited to the type of resin and its use. Generally, additive flame retardants such as halogen flame retardants, inorganic flame retardants, and phosphorus flame retardants are added. However, this Among them, it has been pointed out that halogen-based flame retardants, mainly bromine-based, may become the source of dioxin, which is highly carcinogenic, and their use is being restricted in response to the current trend of reducing environmentally harmful substances. In addition, inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide have a flame retardant effect due to endothermic effects. However, in order to achieve sufficient flame retardancy, they must be added in large amounts, thereby reducing various properties of plastic molded products. s reason.

Therefore, most phosphorus-based flame retardants are used that do not produce harmful substances and can be flame-retardant by adding a small amount. However, even so, it is still inevitable to reduce the processability and glass transition temperature due to bleeding, etc. etc. on the characteristics.

In order to solve the problems of such additive flame retardants, reactive flame retardants containing phosphorus atoms that are flame retardant components and having reactive groups have been developed and widely used. As for reactive flame retardants that can be applied to epoxy resin compositions frequently used in the electronic/electrical fields, for example, Patent Document 1 discloses that hydroxymethyl bisphenol A is obtained by reacting bisphenol A with formaldehyde. , and then react 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter referred to as "DOPO") with it to obtain a phenolic resin, which can be used as a hardener for epoxy resin ; Patent Document 2 discloses that DOPO is reacted with quinones and then reacted with an epoxy resin to obtain a phosphorus-containing epoxy resin. These resins solve workability problems such as flame retardant bleeding and do not suffer from deterioration in thermal properties such as heat resistance. In this way, compared to additive flame retardants, the shortcomings of general additive flame retardants can be made up for by using reactive flame retardants. Therefore, many flame retardant epoxy resins are being developed.

However, in recent years, in the field of electronic/electrical materials that require flame retardancy, electronic devices represented by smartphones have been rapidly developed, and the requirements for resin components containing flame retardants have become higher. In particular, in the information/communication field, as the amount of information processing increases, signals are moving toward higher frequencies. In order to reduce transmission losses, resin components used in this field are strongly required to have low dielectric coefficients and low dielectric loss tangents. As a result, in the field of electronic/electrical materials represented by circuit boards, radically polymerizable resins that can achieve lower dielectric coefficients and lower dielectric loss tangents have begun to be widely used instead of epoxy resins. Therefore, not only reactivity is required Flame retardants whose bases are reactive with epoxy groups or epoxy resins are also required, and halogen-free flame retardants with low dielectric coefficient/low dielectric loss tangent that can react with free radical polymerizable resins are also required.

In addition, the resin composition used for circuit boards is used by impregnating base materials such as glass cloth, so it is required to be soluble in solvents. However, in fields where low dielectric is required, from the perspective of its impact on dielectric properties, It is preferable to use non-polar solvents such as toluene, in which precipitation must not be observed.

As for a halogen-free flame retardant with radically polymerizable functional groups, Patent Document 3 discloses a vinyl benzyl ether compound obtained from DOPO and chloromethylstyrene. However, since it is a monofunctional vinyl compound, there is still room for improvement from the viewpoint of heat resistance. 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 ( Meth)acrylyl compound. Although these compounds have excellent properties in terms of heat resistance and dielectric properties, they have strong crystallinity and precipitation is observed in low-polarity solvents, resulting in problems with handleability.

[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, the problem to be solved by the present invention is to provide a phosphorus-containing (meth)acryl compound, a flame-retardant resin composition, a cured product, and a laminate for an electronic circuit substrate. ) Acrylic compounds can be used as reactive phosphorus flame retardants and have excellent solvent solubility, and their cured products have excellent heat resistance and dielectric properties.

The inventors of the present invention studied the aforementioned subject in detail and found that a phosphorus-containing (meth)acrylyl compound having a specific structure and a cured product obtained by curing a composition containing the same have solubility, flame retardancy, heat resistance and dielectric properties. The properties are excellent, and the present invention is completed.

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

In the general formula (1), R1 and R2 are hydrogen, hydroxyl, a group represented by -OR or -R, and R is a hydrocarbon group having 2 to 40 carbon atoms. R1 and R2 may be the same or different, and R1 and R2 may form a ring structure together with the phosphorus atom. X in the formula represents a trivalent aromatic hydrocarbon group having 6 to 20 carbon atoms, and Y represents a substituent represented by the following general formula (2) or (3). However, at least one of Y contains a substituent represented by the following general formula (3).

In general formula (2), R3 is hydrogen or methyl.

In the general formula (3), R4 is hydrogen or methyl, and R5 is a hydrocarbon group from C1 to C20.

A phosphorus-containing composition comprising 5 to 95 parts by mass of the above-mentioned phosphorus-containing (meth)acrylyl compound and 5 to 95 parts by mass of (meth)acrylyl represented by the following general formula (4) base compound.

In the general formula (4), R1, R2, R3 and X are synonymous with the provisions in the general formula (1) and the general formula (3).

A method for producing the above-mentioned phosphorus-containing composition is to react a compound represented by the following general formula (5) with a compound containing one glycidyl ether group, and then use (meth)acrylic acid, (meth)acrylic acid Anhydride or halogenated (meth)acrylyl compound is used for (meth)acrylation.

In the general formula (5), R1, R2 and X are synonymous with those specified in the general formula (1).

A flame retardant resin composition is obtained by blending at least one of a thermosetting resin or a thermoplastic resin into the above-mentioned phosphorus-containing (meth)acryl compound or phosphorus-containing composition.

A laminated board for electronic circuit boards, which contains the above-mentioned flame-retardant resin composition as an essential component.

The phosphorus-containing (meth)acrylyl compound of the present invention has excellent solubility, and a cured product obtained by curing a composition containing the compound as an essential component exhibits low dielectric coefficient/dielectric It has a loss tangent and a small decrease in heat resistance. It can reduce transmission losses at high frequencies caused by the increase in information processing volume of electronic equipment, so it is very useful as a reactive phosphorus-based flame retardant.

FIG. 1 is a GPC chart showing the hydroxyl-containing phosphorus compound A obtained in Synthesis Example 2.

FIG. 2 is a GPC chart showing the hydroxyl-containing phosphorus compound B obtained in Synthesis Example 3.

FIG. 3 is a GPC chart showing the hydroxyl-containing phosphorus compound C obtained in Synthesis Example 4.

FIG. 4 is a GPC chart showing the hydroxyl-containing phosphorus compound D obtained in Synthesis Example 5.

FIG. 5 shows a GPC chart of the phosphorus-containing methacrylate compound A obtained in Example 1.

FIG. 6 shows a GPC chart of the phosphorus-containing methacryloyl compound B obtained in Example 2.

FIG. 7 shows a GPC chart of the phosphorus-containing methacryloyl compound C obtained in Example 3.

FIG. 8 is a GPC chart showing the phosphorus-containing methacryloyl compound D obtained in Example 4.

Hereinafter, the present invention will be described in detail.

In the description of the present invention, descriptions of acrylic resins, acrylic compounds, acrylic ester compounds, etc. are based on common practice. For example, both "acrylyl" and "methacrylyl" may be collectively referred to as "(meth) "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)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 formula (1), R1 and R2 are hydrogen, hydroxyl, a group represented by -OR or -R, and R is a hydrocarbon group having 2 to 40 carbon atoms. R1 and R2 may be the same or different, and R1 and R2 may form a ring structure together with the phosphorus atom. Preferably, R is a benzene ring group, and the benzene ring may also be substituted by an alkyl group having 1 to 3 carbon atoms.

In formula (1), X is a trivalent aromatic hydrocarbon group having 6 to 20 carbon atoms. Examples of aromatic hydrocarbon groups include benzene ring group, naphthalene ring group, biphenyl ring group, terphenyl ring group, and the like. The aromatic hydrocarbon group may be unsubstituted, or may have an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aryloxy group having 6 to 10 carbon atoms. , an aralkyl group having 7 to 12 carbon atoms or an aralkyloxy group having 7 to 12 carbon atoms as a substituent. The above-mentioned X is preferably a phenyl ring group, a naphthyl ring group, or an aromatic substituent obtained by substituting these with a methyl group or a 1-phenylethyl group.

In formula (1), Y is a substituent represented by the following formula (2) or the following formula (3). At least one of them contains a substituent represented by the following general formula (3).

In general formula (2), R3 is hydrogen or methyl.

In the general formula (3), R4 is hydrogen or methyl, and R5 is a hydrocarbon group from C1 to C20. Examples of the C1 to C20 hydrocarbon group include an aliphatic hydrocarbon group having a linear or branched structure, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group 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 anthracene. Key et al. When R5 contains an aromatic hydrocarbon group, the aromatic ring may or may not have a substituent. Examples of the substituent include a carboxyl group, an aliphatic hydrocarbon group, a acyl group, an alkoxy group, a cyano group, a hydroxyl group, a methacryloxy group, a vinyl benzyl ether group, a group formed by linking these substituents, and the like. When the aromatic hydrocarbon group has a substituent, the carbon number mentioned above does not include the carbon number of the substituent.

In formula (1), at least one of Y contains a substituent represented by general formula (3). Preferably, a phosphorus-containing (meth)acryl compound (bisubstituted product) in which both Y's are substituents represented by the general formula (3) and only one of the two Y's is represented by the general formula (3) A mixture of phosphorus-containing (meth)acrylyl compounds (1 substituents) with substituents. In this mixture, the presence ratio of the 2-substituted body is preferably 10 to 99 mol%, more preferably 20 to 95 mol%. In addition, although the unsubstituted form may also be contained, its content is preferably less than 50 mol%.

The composition of a phosphorus-containing (meth)acrylyl compound of the present invention contains a phosphorus-containing (meth)acrylyl compound represented by the above-mentioned general formula (1) and a (meth)acrylyl compound represented by the following general formula (4). Phosphorus-containing composition of meth)acrylyl compound. The compounds represented by general formula (1) include compounds represented by general formula (4).

The composition of the phosphorus-containing (meth)acrylyl compound of the present invention preferably contains 95 to 5 parts by mass of the compound represented by the general formula (1), and 5 to 95 parts by mass of the following general formula (4) represents a (meth)acrylyl compound. By including the (meth)acryl compound represented by the following general formula (4) within this range, the solubility is excellent and the heat resistance can be further improved.

In the general formula (4), R1, R2, R3 and X are synonymous with the provisions in the general formula (1) and the general formula (3).

In the composition of the phosphorus-containing (meth)acrylyl compound of the present invention, the phosphorus content rate is preferably 1.0 to 10.0 wt%, more preferably 2.0 to 8.0 wt%, and still more preferably 3.0 to 6.0 wt%.

The compound represented by the aforementioned general formula (1) and the resin composition containing the compound represented by the aforementioned general formula (1) and the aforementioned general formula (4) can be obtained by combining a hydroxyl-containing phosphorus compound represented by the following general formula (5) and It is obtained by reacting a compound containing one glycidyl group and then performing (meth)acrylation with (meth)acrylic acid, (meth)acrylic anhydride or a halogenated (meth)acrylyl compound.

In the general formula (5), R1, R2 and X are synonymous with those specified in the general formula (1). The hydroxyl-containing phosphorus compound represented by the general formula (5) can be obtained by the reaction of an organophosphorus compound having an active hydrogen directly bonded to a phosphorus atom and a quinone compound, as described in Japanese Patent Application Laid-Open No. Sho 61-236787 and Japanese Patent Application Laid-Open No. 05 -331179, Japanese Patent Application Laid-Open No. 05-39345, etc., and are synthesized by conventional methods. Examples of organophosphorus compounds include: dimethylphosphine, diethylphosphine, diphenylphosphine, etc.; examples of phosphine oxides include: dimethylphosphine oxide, diethylphosphine oxide, and diphenylphosphine oxide. substances, menthyl phenyl phosphinate, tert-butylphenylphosphine oxide, etc.; phosphate esters include: diethyl hydrogen phosphite, bis(2-ethyl hydrogen phosphite) Hexyl) ester, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, diphenyl hydrogen phosphite, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (HCA Sanguang Co., Ltd.), etc., but are not limited to these, and two or more types may be used. Specific examples of the quinone compound include 1,4-benzoquinone, 1,2-benzoquinone, 1,4-naphthoquinone, and the like. These quinones may be used alone or in mixture of two or more kinds, but are not limited to these.

The hydroxyl-containing phosphorus compound represented by the general formula (5) can be synthesized by the reaction of an organophosphorus compound having an active hydrogen directly bonded to a phosphorus atom and a quinone compound, as described above. However, this reaction sometimes occurs. Accordingly, a structure in which two phosphorus atoms represented by the following general formula (6) are added to a quinone compound is by-produced. However, this is not a compound that hinders the effects of the present invention, and there is no problem even if this compound is included.

Commercially available products can also be used as the hydroxyl-containing phosphorus compound represented by the above general formula (5), and diphenylphosphinohydroquinone (PPQ Bukheung Chemical Industry) and 10-(2,5-dihydroxyphenyl) can be purchased. -10H-9-oxa-10-phosphenanthrene-10-oxide (HCA-HQ Sanko Chemical), 10-(2,5-dihydroxynaphthyl)-10H-9-oxa-10-phospha Phenanthrene-10-oxide, 1,4-cyclooctylphosphonohydroquinone, 1,5-cyclooctylphosphonohydroquinone (CPHO-HQ), etc.

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)methylsilane, glycidyl acrylate, ethylene Propyl glycidyl ether, glycidyl methacrylate, 1,1,1,3,5,5,5-heptamethyl-3-(3-glycidyloxypropyl)trisiloxane, 1 , 2-epoxydecane glycidyl guaiacol ether, phenyl glycidyl ether, o-cresol-based glycidyl ether, m-cresol-based glycidyl ether, p-cresol-based glycidyl ether and other cresol groups Glycidyl ether, 4-tert-butylphenyl glycidyl ether, benzyl glycidyl ether, phenol (EO) 5 glycidyl ether, 4-glycidyloxycarbazole, 4-tert-butylbenzoic acid glycidyl ether Glyceride, etc., but are not limited to these, and two or more types may be used in combination. From the viewpoint of easy availability, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, cresolyl glycidyl ether, and 4-tert-butylphenyl glycidyl ether are preferred.

The reaction between the phosphorus-containing phenolic compound represented by the above general formula (5) and the epoxy resin containing one glycidyl group can be carried out by a conventional method. That is, when the epoxy resin is added to the hydroxyl-containing phosphorus compound, the reaction temperature is preferably 100°C to 200°C, more preferably 120°C to 180°C, and the reaction is carried out with stirring. If the reaction speed is slow, a catalyst can be used as needed to improve productivity. Specific catalysts include tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, triphenylphosphine, and ginseng(2,6-dimethoxyphenyl)phosphine. Various catalysts such as phosphines, phosphonium salts such as ethyltriphenylphosphonium bromide, and imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole.

Regarding the reaction molar ratio between the phosphorus-containing phenolic compound represented by the above general formula (5) and the epoxy resins containing one glycidyl group, the glycidyl group is 0.05 to 1 mole of the hydroxyl group of the hydroxyl-containing phosphorus compound. 1.00 mol, preferably 0.10 to 0.95 mol, more preferably 0.20 to 0.80 mol. If it is 0.05 or less, the number of compounds of the general formula (4) will increase and the solubility will be insufficient, which is undesirable.

A phosphorus-containing compound containing an alcoholic hydroxyl group (hereinafter referred to as a hydroxyl-containing phosphorus compound) obtained by reacting a phosphorus-containing compound represented by the aforementioned general formula (5) with an epoxy resin containing a glycidyl group and (methane) The reaction of acrylic acid, halogenated (meth)acrylyl, or (meth)acrylic anhydride is not particularly limited, and can be carried out in the same manner as a general (meth)acrylation reaction of an alcohol compound or a phenol compound.

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 an amount of 1 to 10 times ( Meth)acrylic acid is produced by condensation reaction. This reaction must be carried out while removing by-produced condensation water out of the system. Therefore, it is carried out by using a hydrocarbon solvent such as toluene that azeotropes with water as the reaction solvent and heating the reaction liquid to about 70 to 140°C. .

The phosphorus-containing (meth)acrylyl compound of the present invention can be obtained by reacting a hydroxyl-containing phosphorus compound with a halogenated (meth)acrylyl group or (meth)acrylic anhydride. Halogenated (methyl)propylene Examples of the acrylic group include fluorinated acrylyl group, chlorinated acrylyl group, bromide acrylyl group, iodinated acrylyl group and other halogenated acrylyl groups, fluorinated methacryloyl group, and chlorinated methacryloyl group. halogenated methacrylyl groups such as bromide methacrylyl group, iodinated methacrylyl group, etc.

In the implementation of the present invention, one type or a mixture of two or more types may be used as the halogenated (meth)acrylyl group or (meth)acrylic anhydride. In the present invention, from the viewpoint of easy availability, (meth)acrylyl chloride or/and (meth)acrylic anhydride is preferably used.

The usage amount of the halogenated (meth)acrylyl group or/and (meth)acrylic anhydride is 0.8 to 5 moles, preferably 0.95 to 4 moles, based on 1 mole of hydroxyl group of the phosphorus-containing phenolic compound used as a raw material. More. If the usage amount of (meth)acrylic acid halide or/and (meth)acrylic anhydride is lower than the above range, the heat resistance of the obtained phosphorus-containing (meth)acrylyl compound will decrease, and the residual amount of hydroxyl groups will increase. , causing the dielectric properties to deteriorate, which is undesirable. If the usage amount is higher than the above range, the efficiency of the kettle will decrease and the cost will increase, which is undesirable.

啉、二氮雜雙環十一烯(DBU)、二氮雜雙環壬烯(DBN)、N-甲基吡啶、N-甲基吡咯啶等雜環胺；四甲基乙二胺、三乙二胺等二胺等。尤其是三甲基胺、三乙基胺等脂肪族胺、吡啶，因為容易取得而較佳。 When a halogenated (meth)acrylyl group is used, hydrogen halide corresponding to the (meth)acrylic acid halide used is generated as a by-product. Therefore, it is preferable to capture the generated hydrogen halide with a basic compound. react. The basic compound is not particularly limited, and examples thereof include: trimethylamine, triethylamine, diisopropylethylamine, tri-n-propylamine, triisopropylamine, tributylamine, and N-methyl - Aliphatic amines such as diethylamine, N-ethyl-dimethylamine, N-ethyl-dipentylamine; N,N-dimethylaniline, diethylaniline and other aromatic amines; N, Alicyclic amines such as N-dimethyl-cyclohexylamine, N,N-diethyl-cyclohexylamine; N,N-dimethylaminopyridine, N-methyl

Heterocyclic amines such as pholine, diazabicycloundecene (DBU), diazabicyclononene (DBN), N-methylpyridine, N-methylpyrrolidine; tetramethylethylenediamine, triethylenediamine Amine etc. Diamine etc. In particular, aliphatic amines such as trimethylamine and triethylamine, and pyridine are preferred because they are easy to obtain.

The amount of the basic compound used is, for example, 0.8 to 7 moles, preferably about 0.95 to 5 moles per mole of hydroxyl group of the phosphorus-containing phenolic compound used as a raw material. If the level of tertiary amine used is less than If the temperature exceeds the above range, the hydrogen halide cannot be completely captured, resulting in corrosion of the reaction device. If the temperature exceeds the above range, the cost will tend to increase.

When reacting with (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 methanesulfonic acid and p-toluenesulfonic acid. Furthermore, if the alkali catalyst is an organic base, examples thereof include nitrogen-containing aliphatic compounds such as triethylamine and triethylenediamine, and nitrogen-containing aromatic compounds such as pyridine and 4-(dimethylamino)pyridine. cyclic compounds, etc. Examples of the Lewis acid catalyst include aluminum chloride, zinc chloride, and the like.

The amount of catalyst used is preferably 10% or less, and more preferably 5% or less based on the (meth)acrylic anhydride used. If the catalyst is used above the above range, it will take time to remove the catalyst, and the catalyst will 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、氯仿、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，可因應需求將此等組合使用。 In the reaction between the hydroxyl-containing phosphorus compound and the 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 phenolic compound and (meth)acrylic acid halide or/and (meth)acrylic anhydride. Examples include: tetrahydrofuran, dihydrofuran,

Alkane, ethyl acetate, acetonitrile, benzene, toluene, xylene, methylene chloride, chloroform, carbon tetrachloride, dimethylformamide, dimethylacetamide, dimethyltrisoxide, hexamethylphosphoric acid Triamide, water and other solvents can be used in combination according to needs.

In the reaction between a hydroxyl-containing phosphorus compound and (meth)acrylic acid halide or/and (meth)acrylic anhydride, the reaction temperature is preferably -50 to 150°C. If the reaction is carried out at a high temperature, polymerization will occur. The possibility becomes high, so -25 to 100°C is more preferable. In addition, the reaction time can be appropriately set according to the set reaction temperature, and is preferably set in the range of 1 to 48 hours.

(phenothiazine)等有機化合物以外，還可列舉氯化銅、硫化銅等銅化合物等，亦可將此等組合使用。 The reaction of the hydroxyl-containing phosphorus compound 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, (meth)acrylic acid, halogenated (meth)acrylyl, (meth)acrylic anhydride, and (meth)acrylic acid ester, which are the target products, can be prevented from polymerizing and causing side effects. Oligomers are produced. Polymerization inhibitors can be those known in the art without limitation, and examples include hydroquinone, hydroxymonomethyl ether, tert-butylcatechol, tert-butylhydroquinone, 4-methoxyphenol, 4-Methoxy-1-naphthol, thiophene

In addition to organic compounds such as phenothiazine, copper compounds such as copper chloride and copper sulfide may also be used in combination.

After the reaction is completed, the reaction solution (reaction mixture) obtained can be subjected to distillation of the reaction solvent, solvent replacement, etc. as required, and can be refined by means such as washing with water, activated carbon treatment, and silica gel chromatography. The target (meth)acryl compound of the present invention can be taken out.

Next, the flame retardancy of the composition containing the phosphorus-containing (meth)acrylyl compound or 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 explained. Resin composition.

In the flame retardant resin composition of the present invention, the blending ratio is not particularly limited. For example, 10 to 300 parts by weight of phosphorus-containing (methane) may be blended relative to 100 parts by weight of the total amount of the curable resin and the thermoplastic resin. (meth)acrylyl compound or a phosphorus-containing (meth)acrylyl compound. Preferably it is 20 to 200 parts by weight, more preferably 50 to 150 parts by weight.

Examples of the curable resin include unsaturated polyester resin, curable maleimide resin, epoxy resin, polycyanate resin, phenolic resin, and one having one or more polymerizable unsaturated hydrocarbon groups in the molecule. The above 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 per molecule. Examples of this epoxy resin include: cresol novolak type epoxy resin, triphenylmethane type epoxy resin, biphenyl epoxy resin, naphthalene type epoxy resin, bisphenol A type epoxy resin and bisphenol F type ring Oxygen resin, etc. These can be used individually or in combination of 2 or more types. It is believed that by using such an epoxy resin, the excellent dielectric properties and fluidity of the curable resin composition of the present invention are minimally affected, and the heat resistance and adhesion of the cured product can be fully improved.

系硬化劑、氰酸酯系硬化劑等。此等可使用1種或將2種以上組合使用。 When epoxy resin is included, 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-based curing agents, etc.

Hardener, cyanate ester hardener, etc. These can be used 1 type or in combination of 2 or more types.

Furthermore, when blending epoxy resin, a hardening accelerator can also be used according to needs. For example, amines, imidazoles, organic phosphines, Lewis acids, etc. The added amount is usually in the range of 0.2 to 5 parts by weight relative to 100 parts by weight of 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 harden by reacting with the phosphorus-containing (meth)acrylyl compound of the present invention. More preferably, the polymerizable unsaturated hydrocarbon group is a carbon-carbon unsaturated double bond, and more preferably, it is a compound having two or more carbon-carbon unsaturated double bonds in the molecule.

The average number of carbon-carbon unsaturated double bonds (the number of vinyl groups (including substituted vinyl groups), also called the number of terminal double bonds) per molecule of vinyl compounds that are curable resins is based on the vinyl compound. Mw varies depending on the class, but for example, it is preferably 1 to 20, and more preferably 2 to 18. If the number of terminal double bonds is too small, it will tend to be difficult to obtain a cured product having sufficient heat resistance. Also, if the terminal double bond If the amount is too large, the reactivity will be too high, and problems such as a decrease in the storage stability of the curable resin composition or a decrease in the fluidity of the curable resin composition may occur.

Examples of the above-mentioned vinyl compounds include: triallyl isocyanate compounds such as triallyl isocyanate (TAIC), modified polyphenylene ether (PPE) whose terminals are modified with (meth)acrylyl groups or styrene groups. ), multifunctional (meth)acrylate compounds with two or more (meth)acrylyl groups in the molecule, vinyl compounds with more than two vinyl groups in the molecule such as polybutadiene (polyfunctional ethylene base compounds) and vinyl benzyl compounds such as styrene, divinylbenzene, etc. Among them, those having two or more carbon-carbon double bonds in the molecule are preferred. Specific examples include: TAIC, multifunctional (meth)acrylate compounds, modified PPE resins, multifunctional vinyl compounds, and bis(meth)acrylate compounds. Vinylbenzene compounds, etc. It is thought that if these are used, crosslinking will be more ideally formed due to the curing reaction, and the heat resistance of the cured product of the curable resin composition can be further improved. Moreover, these may be used individually or in combination of 2 or more types. Moreover, a compound having one carbon-carbon unsaturated double bond in the molecule may 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).

Examples of the thermoplastic resin include polystyrene, polyphenylene ether resin, polyether imide resin, polyether styrene resin, PPS resin, polycyclopentadiene resin, polycycloolefin resin, etc., as well as known thermoplastic elastomers. (For example, 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.

啉基丙烷-1-酮等苯乙酮類；2-乙基蒽醌、2-第三丁基蒽醌、2-氯蒽醌、2-戊基蒽醌等蒽醌類；2,4-二乙基硫雜蒽酮、2-異丙基硫雜蒽酮、2-氯硫雜蒽酮等硫雜蒽酮(thioxanthone)類；苯乙酮二甲基縮酮、苯偶醯二甲基縮酮(benzil dimethylketal)等縮酮類；二苯基酮(benzophenone)、4-苯甲醯基-4’-甲基二苯基硫化物、4,4’-雙甲基胺基二苯基酮等二苯基酮類；2,4,6-三甲基苯甲醯基二苯基膦氧化物、雙(2,4,6-三甲基苯甲醯基)-苯基膦氧化物等膦氧化物類等。就熱自由基起始劑而言，有過氧化苯甲醯、氫過氧化異丙苯、2,5-二氫過氧化-2,5-二甲基己烷、2,5-二甲基-2,5-二(第三丁基過氧基)己炔-3、過氧化二-第三丁基、過氧化第三丁基異丙苯基、1,3-雙(丁基過氧基異丙基)苯、α,α’-雙(第三丁基過氧基-間異丙基)苯、2,5-二甲基-2,5-二(第三丁基過氧基)己烷、過氧化二異丙苯基、過氧間苯二甲酸二-第三丁酯、過氧苯甲酸第三丁酯、2,2-雙(第三丁基過氧基)丁烷、2,2-雙(第三丁基過氧基)辛烷、2,5-二甲基-2,5-二(苯甲醯基過氧基)己烷、過氧化二(三甲基矽基)、過氧化三甲基矽基三苯基矽基等過氧化物，但不限定於此等。又，2,3-二甲基-2,3-二苯基丁烷雖非過氧化物，但亦可作為自由基聚合起始劑使用。然而，並不限於此等例子，亦可將自由基起始劑組合2種以上而使用。 The flame-retardant resin composition of the present invention may also be blended with a radical polymerization initiator (polymerization catalyst or cross-linking agent) that generates free radicals by light and/or heat. Examples of photopolymerization initiators 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-benzene Propan-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-

Acetophenones such as linylpropan-1-one; anthraquinones such as 2-ethylanthraquinone, 2-tert-butylanthraquinone, 2-chloroanthraquinone, 2-pentylanthraquinone; 2,4- Thioxanthone (thioxanthone) such as diethyl thioxanthone, 2-isopropyl thioxanthone, 2-chlorothioxanthone; acetophenone dimethyl ketal, benzildimethyl ketal Ketals such as benzil dimethylketal; benzophenone, 4-benzyl-4'-methyldiphenyl sulfide, 4,4'-bismethylaminodiphenyl Ketones and other diphenyl ketones; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide Phosphine oxides, etc. As far as thermal radical initiators are concerned, there are 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(butylperoxy isopropyl)benzene, α,α'-bis(tert-butylperoxy-m-isopropyl)benzene, 2,5-dimethyl-2,5-bis(tert-butylperoxy) )hexane, dicumyl peroxide, di-tert-butyl peroxyisophthalate, tert-butyl peroxybenzoate, 2,2-bis(tert-butylperoxy)butane , 2,2-bis(tert-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, bis(trimethylperoxide) Silicone), trimethylsilyl peroxide, triphenylsilyl peroxide and other peroxides, but are not limited to these. Moreover, although 2,3-dimethyl-2,3-diphenylbutane is not a peroxide, it can also be used as a radical polymerization initiator. However, the invention is not limited to these examples, and two or more radical initiators may be used in combination.

The blending amount of the radical polymerization initiator is preferably 0.01 to 10 parts by weight, more preferably 0.1 to 5 parts by weight relative to 100 parts by weight of the resin component.

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. The phosphorus content ratio of the composition is preferably 0.5 to 5.0. % by weight, more preferably 1.0 to 4.0% by weight.

The flame retardant resin composition of the present invention may also contain a filler. Examples of fillers include those added to improve heat resistance and flame retardancy, and conventional fillers can be used without particular limitation. In addition, by containing a filler, 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 additives, ensuring flame retardancy even if the phosphorus content is low. Among them, silica, mica and talc are preferred, and spherical silica is more preferred. In addition, one of these may be used alone, or two or more types may be used in combination.

The filler may be used directly, or may be surface-treated with a silane coupling agent such as an epoxy silane type or an amino silane type. From the viewpoint of reactivity with the radical polymerization initiator, the silane coupling agent is preferably a vinyl silane type, a methacryloxysilane type, an acryloxysilane type, or a styrene type silane coupling agent. Silane type silane coupling agent. Thereby, the bonding strength with the metal foil and the interlayer bonding strength between resins are improved. Alternatively, the silane coupling agent may be added 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, more preferably 30 to 150 parts by mass, based on a total of 100 parts by mass of solid components other than the filler (including organic components such as monomers and flame retardants, excluding solvents).

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, dyes or pigments, lubricants, dispersants such as wetting and dispersing agents, etc. .

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, a cast product, an adhesive, a coating, or a film. For example, hardened materials of semiconductor sealing materials As a method of obtaining a hardened product for this purpose as a castable or molded product, the curable resin composition can be molded using a casting or transfer molding machine, an injection molding machine, etc., and further heated at 80 to 230°C for 0.5 to 230°C. 10 hours to obtain a hardened product.

The flame-retardant resin composition of the present invention can also be used as a prepreg. When producing a prepreg, it can be prepared in a varnish state for the purpose of impregnating the base material (fibrous base material) used to form the prepreg, or for the purpose of using it as a circuit board material that will form a circuit board. For resin varnish. This resin varnish is suitable for circuit substrates and can be used as a varnish for circuit substrate materials. In addition, specific uses of the circuit board material described here include printed wiring boards, printed wiring boards, flexible printed wiring boards, build-up wiring boards, and the like.

The organic solvent used in the above-mentioned resin varnish is not particularly limited as long as it does not inhibit the curing reaction. Examples include ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, propyl acetate, and butyl acetate; dimethylacetamide, and dimethylformamide. Polar solvents such as toluene and xylene and aromatic hydrocarbon solvents such as toluene and xylene can be used alone or in a mixture of two or more. 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, more 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 material used when making the prepreg can use conventional materials. For example, glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper and other base materials can be used alone, or Use 2 or more types together. Among these base materials, with the purpose of improving the adhesion of the interface between the resin and the base material, coupling agents can also be used according to needs. 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 a 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 as many times as required. In addition, at this time, multiple solutions with different compositions and concentrations can be used to repeatedly impregnate, and finally the desired resin composition and resin amount can be adjusted. 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 component.

The curable resin composition of the present invention can also be used as a laminated board. When forming a laminate using prepregs, one or more prepregs are laminated and a metal foil is arranged on one or both sides to form a laminate, and the laminate is heated/pressurized to integrate the laminates. Here, as the metal foil, single, alloy, or composite metal foils such as copper, aluminum, brass, and nickel can be used. The conditions for heating and pressurizing the laminated product are as long as the conditions for curing the curable resin composition are appropriately adjusted and the heating and pressurizing is carried out. However, if the pressurizing pressure is too low, the inside of the resulting laminated board may be damaged. Air bubbles may remain, resulting in a decrease in electrical characteristics, so it is best to apply pressure that satisfies formability conditions. For example, the temperature can be set to 180 to 250°C, the pressure can be set to 49.0 to 490.3N/cm ² (5 to 50kgf/cm ² ), and the heating and pressurizing time can be set to 40 to 240 minutes. The single-layer laminated board thus obtained can be further used as an inner layer material to produce a multilayer board. In this case, a circuit is first formed on the laminated board 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. On one or both sides of the circuit forming surface of the inner layer material, an insulating layer is formed with a resin sheet, a metal foil with resin, or a prepreg, and a conductor layer is formed on the surface of the insulating layer to form a multilayer board.

The curable composition of the present invention can also be used in a build-up film. A method of producing a build-up film from the resin composition of the present invention includes, for example, 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 thus formed can be used as a build-up film for multilayer printed wiring boards.

[Example]

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

Physical property measurements in the synthesis examples and examples were performed by the following methods.

(1) Phosphorus content: Add sulfuric acid, hydrochloric acid, and perchloric acid to the sample, heat and perform wet ashing to convert all phosphorus atoms into orthophosphoric acid. React metavanadate and molybdate in an acidic solution of sulfuric acid, measure the absorbance of the produced phosphovanadium molybdate complex at 420 nm, and express the result in % by using a calibration line prepared in advance using potassium dihydrogen phosphate. Out the phosphorus atom content rate.

(2) Solvent solubility: In a varnish adjusted to a solid content of 50% by mass using toluene as a solvent, 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: Use differential scanning calorimetry to measure and determine it by shifting from the baseline at a heating rate of 10°C/min.

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

(5) Flame retardancy: evaluated by vertical method in accordance with UL94. The evaluation system is recorded as V-0, V-1, and V-2.

(Synthesis example 1)

340 parts of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 660 parts of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide were added to a glass separable flask equipped with a stirring device, a thermometer, a cooling tube, and a nitrogen gas introduction device. of toluene, dissolved at 80°C. While paying attention to the reaction heat, 245 parts of 1,4-naphthoquinone were added in portions. The reaction was continued, the temperature was raised to 110°C, and the reaction was further performed. 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 doing this three times, circulate the hot air Dry in a ring oven to obtain a light yellow powder of phosphorus-containing phenolic compound 10-(2,5-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide (DOPO-NQ ).

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

置入具備攪拌裝置、溫度計、迪安-斯塔克裝置及氮氣導入裝置的玻璃製可分離式燒瓶中，於110℃進行溶解。加入0.47份的三苯基膦，一邊去除甲苯，一邊進一步加熱至160℃，進行反應5小時。以GPC確認反應的終點，確認原料的DOPO-NQ及苯基縮水甘油醚的峰消失後，以真空泵實施減壓至1kPa，將甲苯餾除，得到233份的含羥基之磷化合物A。測量含磷率，結果為4.7%。從GPC分析的結果來看，含羥基之磷化合物A中，包含91%的由2莫耳之苯基縮水甘油醚對於1莫耳之DOPO-NQ反應而成之化合物(下述結構式) Mix 130 parts of DOPO-NQ, 121 parts of toluene as solvent, and 105 parts of phenyl glycidyl ether

It was placed in a glass separable flask equipped with a stirring device, a thermometer, a Dean-Stark device and a nitrogen introduction device, and dissolved at 110°C. 0.47 parts of triphenylphosphine was added, and while removing toluene, the mixture was further heated to 160°C and reacted for 5 hours. After confirming the end point of the reaction using GPC and confirming that the peaks of DOPO-NQ and phenyl glycidyl ether of the raw materials disappeared, the pressure was reduced to 1 kPa with a vacuum pump, and toluene was distilled off to obtain 233 parts of hydroxyl-containing phosphorus compound A. The phosphorus content was measured and the result was 4.7%. Judging from the results of GPC analysis, the hydroxyl-containing phosphorus compound A contains 91% of a compound formed by the reaction of 2 moles of phenyl glycidyl ether with 1 mole of DOPO-NQ (the following structural formula)

、以及9%的由1莫耳之苯基縮水甘油醚對於1莫耳之DOPO-NQ反應而成的化合物，並未包含DOPO-NQ。反應GPC圖表如圖1所示。

, and 9% of the compound formed by the reaction of 1 mole of phenyl glycidyl ether with 1 mole of DOPO-NQ, but did not contain DOPO-NQ. The reaction GPC chart is shown in Figure 1.

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

Except for changing the usage amount of phenyl glycidyl ether to 52 parts and changing the usage amount of triphenylphosphine to 0.36 parts, the same operation as Synthesis Example 2 was performed to obtain 180 parts of hydroxyl-containing phosphorus. Compound B. The phosphorus content rate was measured and the result was 6.1%. From the results of GPC analysis, it was confirmed that the hydroxyl-containing phosphorus compound B contained 36% of a compound obtained by reacting 2 moles of phenyl glycidyl ether with 1 mole of DOPO-NQ (the following structural formula)

、31%的由1莫耳之苯基縮水甘油醚對於1莫耳之DOPO-NQ反應而成的化合物、以及32%的DOPO-NQ。反應GPC圖表如圖2所示。

, 31% of a compound formed by the reaction of 1 mole of phenyl glycidyl ether with 1 mole of DOPO-NQ, and 32% of DOPO-NQ. The reaction GPC chart is shown in Figure 2.

(Synthesis Example 4) Synthesis of hydroxyl-containing phosphorus compound C

代替苯基縮水甘油醚，將三苯基膦的使用量變更為0.40份，除此之外，進行與合成例2相同的操作，得到200份的含羥基之磷化合物C。測量含磷率，結果為5.4%。從GPC分析的結果確認含羥基之磷化合物C包含32%的由2莫耳之4-第三丁基苯基縮水甘油醚對於1莫耳之DOPO-NQ反應而成的化合物(下述結構式) Use 72 parts of 4-tert-butylphenyl glycidyl ether of the following structural formula

Except for changing the usage amount of triphenylphosphine to 0.40 parts instead of phenyl glycidyl ether, the same operation as Synthesis Example 2 was performed to obtain 200 parts of hydroxyl-containing phosphorus compound C. The phosphorus content was measured and the result was 5.4%. From the results of GPC analysis, it was confirmed that the hydroxyl-containing phosphorus compound C contained 32% of a compound obtained by reacting 2 moles of 4-tert-butylphenyl glycidyl ether with 1 mole of DOPO-NQ (the following structural formula )

、35%的由1莫耳之4-第三丁基苯基縮水甘油醚對於1莫耳之DOPO-NQ反應而成的化合物、以及31%的DOPO-NQ。GPC圖表如圖3所示。

, 35% of a compound formed by the reaction of 1 mole of 4-tert-butylphenyl glycidyl ether with 1 mole of DOPO-NQ, and 31% of DOPO-NQ. The GPC chart is shown in Figure 3.

(Synthesis Example 5) Synthesis of hydroxyl-containing phosphorus compound D

代替苯基縮水甘油醚，將三苯基膦的使用量變更為0.39份，除此之外，進行與合成例2相同的操作，得到193份的含羥基之磷化合物D。測量含磷率，結果為5.9%。從GPC分析的結果確認含羥基之磷化合物D包含32%的2莫耳之2-乙基己基縮水甘油醚對於1莫耳之DOPO-NQ反應而成的化合物(下述結構式) Use 65 parts of 2-ethylhexyl glycidyl ether of the following structural formula

Except for changing the usage amount of triphenylphosphine to 0.39 parts instead of phenyl glycidyl ether, the same operation as Synthesis Example 2 was performed to obtain 193 parts of hydroxyl-containing phosphorus compound D. The phosphorus content rate was measured and the result was 5.9%. From the results of GPC analysis, it was confirmed that the hydroxyl-containing phosphorus compound D contains a compound obtained by reacting 32% of 2 moles of 2-ethylhexyl glycidyl ether with 1 mole of DOPO-NQ (the following structural formula)

、32%的1莫耳之2-乙基己基縮水甘油醚對於1莫耳之DOPO-NQ反應而成的化合物、以及37%的DOPO-NQ。反應GPC圖表如圖4所示。

, 32% of a compound formed by reacting 1 mole of 2-ethylhexyl glycidyl ether with 1 mole of DOPO-NQ, and 37% DOPO-NQ. The reaction GPC chart is shown in Figure 4.

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

Place 100 parts of hydroxyl-containing phosphorus compound A, 100 parts of tetrahydrofuran, and 51 parts of triethylamine into a glass separable flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping funnel. After dissolving, place it on ice. Cool in the bath to below 5°C. In a nitrogen atmosphere, 35 parts of methacrylyl chloride of the following structural formula was added dropwise over 1 hour.

，進一步持續反應2小時，以GPC確認原料的峰消失。

, the reaction was further continued for 2 hours, and the disappearance of the peak of the raw material was confirmed by GPC.

Then, the reaction liquid was concentrated and dissolved in 271 parts of toluene, and then washed in the order of sodium carbonate aqueous solution and water. After washing with water, dehydration and filtration were performed, and the solvent was further concentrated to adjust the solid content concentration to 50%, thereby obtaining 205 parts of a toluene solution of the phosphorus-containing methacryloyl compound A. Contains phosphorus The rate is 4.1%. From the results of GPC analysis, it was confirmed that the phosphorus-containing methacrylyl compound A contained 92% of methacrylamide derived from a compound obtained by reacting 2 moles of phenyl glycidyl ether with 1 mole of DOPO-NQ. Cyl compound (the following structural formula)

、8%的源自於由1莫耳之苯基縮水甘油醚對於1莫耳之DOPO-NQ反應而成之化合物的甲基丙烯醯基化合物，並不包含源自於DOPO-NQ的甲基丙烯醯基化合物。GPC圖表如圖5所示。

, 8% of methacrylic compounds derived from the reaction of 1 mole of phenyl glycidyl ether with 1 mole of DOPO-NQ, excluding methyl groups derived from DOPO-NQ Acrylyl compound. The GPC chart is shown in Figure 5.

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

Place 100 parts of hydroxyl-containing phosphorus compound B, 100 parts of tetrahydrofuran, and 48 parts of triethylamine into a glass separable flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping funnel, and dissolve them in ice. Cool in the bath to below 5°C. In a nitrogen atmosphere, 45 parts of methacrylyl chloride was added dropwise over 1 hour, and the reaction was continued for another 2 hours, and it was confirmed by GPC that the peak of the raw material disappeared.

Then, the reaction liquid was concentrated and dissolved in 294 parts of toluene, and then washed and concentrated in the same manner as in Example 1 to obtain 214 parts of a toluene solution of phosphorus-containing methacryloyl compound B with a solid content concentration of 50%. The solid content concentration is 50% and the phosphorus content is 5.1%. From the results of GPC analysis, it was confirmed that the phosphorus-containing methacrylyl compound B contained 37% of methacrylamide derived from the reaction of 2 moles of phenyl glycidyl ether with 1 mole of DOPO-NQ. Cyl compound (the following structural formula)

、28%的源自於由1莫耳之苯基縮水甘油醚對於1莫耳之DOPO-NQ反應而成之化合物的甲基丙烯醯基化合物、以及32%的源自於DOPO-NQ的甲基丙烯醯基化合物。GPC圖表如圖6所示。

, 28% of methacrylic compounds derived from the reaction of 1 mole of phenyl glycidyl ether with 1 mole of DOPO-NQ, and 32% of methacrylates derived from DOPO-NQ. Acrylyl compound. The GPC chart is shown in Figure 6.

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

Place 100 parts of phosphorus-containing phenolic compound C, 100 parts of tetrahydrofuran, 33 parts of triethylamine, and 2.4 parts of 4 in a glass separable flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping funnel. -Dimethylaminopyridine, dissolved at room temperature. In a nitrogen atmosphere, 61 parts of methacrylic anhydride with the following structural formula was added dropwise over 1 hour.

，進一步於50℃持續反應6小時，以GPC確認原料的峰消失。

, further continued the reaction at 50° C. for 6 hours, and confirmed by GPC that the peak of the raw material disappeared.

Then, the reaction liquid was concentrated and dissolved in 210 parts of toluene, and then washed and concentrated in the same manner as in Example 1 to obtain 220 parts of a toluene solution of phosphorus-containing methacryloyl compound C with a solid content concentration of 50%. The phosphorus content is 4.4%. From the results of GPC analysis, it was confirmed that the phosphorus-containing methacryl compound C contained 34% derived from the reaction of 2 moles of 4-tert-butylphenyl glycidyl ether with 1 mole of DOPO-NQ. Methacrylyl compound of the compound (the following structural formula)

、37%的源自於由1莫耳之4-第三丁基苯基縮水甘油醚對於1莫耳之DOPO-NQ反應而成之化合物的甲基丙烯醯基化合物、以及27%的源自於DOPO-NQ的甲基丙烯醯基化合物。GPC圖表如圖7所示。

, 37% of methacrylic compounds derived from the reaction of 1 mole of 4-tert-butylphenyl glycidyl ether with 1 mole of DOPO-NQ, and 27% Methacrylyl compound based on DOPO-NQ. The GPC chart is shown in Figure 7.

(Example 4) Synthesis of phosphorus-containing methacryloyl compound D

Place 100 parts of hydroxyl-containing phosphorus compound D, 100 parts of tetrahydrofuran, and 47 parts of triethylamine into a glass separable flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping funnel, and dissolve them in ice. Cool in the bath to below 5°C. In a nitrogen atmosphere, 45 parts of methacrylyl chloride was added dropwise over 1 hour, and the reaction was continued for another 2 hours, and it was confirmed by GPC that the peak of the raw material disappeared.

Then, the reaction liquid was concentrated and dissolved in 305 parts of toluene, and then washed and concentrated in the same manner as in Example 1 to obtain 235 parts of a toluene solution of the phosphorus-containing methacryloyl compound D with a solid content concentration of 50%. The phosphorus content is 4.4%. From the results of GPC analysis, it was confirmed that the phosphorus-containing methacryl compound D contained 33% of a compound derived from the reaction of 2 moles of 2-ethylhexyl glycidyl ether with 1 mole of DOPO-NQ. Methacrylyl compound (the following structural formula)

、29%的源自於由1莫耳之2-乙基己基縮水甘油醚對於1莫耳之DOPO-NQ反應而成之化合物的甲基丙烯醯基化合物、以及35%的源自於DOPO-NQ的甲基丙烯醯基化合物。GPC圖表如圖8所示。

, 29% of the methacryl compound derived from the reaction of 1 mole of 2-ethylhexyl glycidyl ether with 1 mole of DOPO-NQ, and 35% of the methacryl compound derived from DOPO- Methacrylyl compound of NQ. The GPC chart is shown in Figure 8.

(Comparative example 1)

Place 100 parts of DOPO-NQ, 233 parts of tetrahydrofuran, and 72 parts of triethylamine in a glass detachable flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping funnel, dissolve them, and cool them in an ice bath. to below 5℃. Under a nitrogen atmosphere, 62 parts of methacrylyl chloride was added dropwise over 1 hour, and the reaction was continued for 2 hours.

Then, the reaction solution was concentrated, dissolved in 318 parts of toluene, washed and concentrated in the same manner as in Example 1, and prepared into a toluene solution with a solid content concentration of 50%, thereby obtaining 235 parts of phosphorus-containing methacrylamide. Compound E (the following structural formula)

的溶液。含磷率為6.2%。

The solution. The phosphorus content is 6.2%.

(Comparative example 2)

Synthesis was performed according to Synthesis Example 1 of Patent Document 3. Specifically, 150 parts of 9,10-dihydro-9-oxa-10-phospha as a phosphorus compound was placed in a glass separable flask equipped with a stirring device, a thermometer, a cooling tube, and an oxygen introduction device. Phernanthrene-10-oxide, 70 parts of toluene as reaction solvent, 20 parts of isopropyl alcohol, 120 parts of CMS-P as vinyl benzyl halide, 2.7 parts of tetramethyl chloride as catalyst Ammonium, heat and dissolve. Thereafter, 127 parts of a 48.5% aqueous sodium hydroxide solution of an alkali metal was added in portions while paying attention to the temperature rise due to the heat generated by the reaction. Keep the reaction at 70°C to 80°C and follow the remaining amount of CMS-P by gas chromatography. After confirming that the residual amount of CMS-P has been reduced and sufficient reaction has occurred, dilute it with toluene. Neutralize with hydrochloric acid and filter to remove generated sodium chloride. Further wash with water to remove ionic impurities. Dehydration and solvent removal were performed by heating and pressure reduction, and a toluene solution with a solid content concentration of 50% was prepared to obtain phosphorus-containing vinyl benzyl compound A (the following structural formula)

的溶液。測量所得之化合物的含磷率，結果為9.3%。

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

(Comparative example 3)

According to Synthesis Example 1 of Patent Document 3, synthesis was further performed using 1,4-naphthoquinone. Specifically, 340 was placed in a glass separable flask equipped with a stirring device, a thermometer, a cooling tube, and an oxygen introduction device. 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 660 parts of toluene were dissolved at 80°C. While paying attention to the reaction heat, 245 parts of 1,4-naphthoquinone were added in portions. The reaction was continued, the temperature was raised 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 doing this three times, dry it in a hot air circulation oven. 93.5 parts of the obtained light yellow powder of the phosphorus-containing phenolic compound 10-(2,5-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide and 140.5 parts of were added as Dimethylsterine as solvent, 93.5 parts of methyl isobutyl ketone, 77.8 parts of CMS-P as vinyl benzyl halide, 0.20 parts of tetramethylammonium chloride as catalyst, 74.2 parts of A 48.5% sodium hydroxide aqueous solution as an alkali metal and 0.16 parts of trimethylhydroquinone as a polymerization inhibitor were neutralized with 35% hydrochloric acid until the pH became 5 to 6, and the lower water layer was separated and removed. While adjusting the pH to 7 to 6 with an aqueous sodium dihydrogen phosphate solution, washing with water and separation and removal of the water layer were repeated 3 to 5 times. Perform reflux dehydration and filter the solution, recover the solvent and prepare a toluene solution with a solid content concentration of 50% to obtain phosphorus-containing vinyl benzyl ether compound B (the following structural formula)

的溶液。所得之化合物的含磷率為4.2%。

The solution. The phosphorus content of the obtained compound was 4.2%.

<Solubility test>

A solubility test was performed using the 50% toluene solutions prepared in Examples 1 to 4 and Comparative Examples 1 to 3. The results are shown in Table 1.

[Table 1]

Examples 5 to 12, Comparative Examples 4 to 8

<Preparation of curable resin composition and production of cured product>

Various components were blended in the proportions in Tables 2 and 3 to prepare a varnish, which was applied on a PET film and dried in an oven at 130° C. for 5 minutes to prepare a film of the resin composition. Next, the film is pulverized to obtain powder of the resin composition. Then, the powder was sandwiched into a stainless steel mirror plate together with a spacer, and molded using a vacuum oven at 210° C. for 90 minutes 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>

Varnish was prepared by blending various components in the proportions in Tables 2 and 3. The resin varnish was impregnated into glass cloth (manufactured by Nitto Bo Co., Ltd.; type 7628; model H258), and then heated at 130° C. for 5 minutes. This is dried to obtain a prepreg.

8 pieces of the obtained prepregs were stacked, and copper foil (manufactured by Mitsui Metals & Mining Co., Ltd., 3EC-III, thickness 35 μm) was laminated on top and bottom, and the process was carried out under the temperature conditions of 130°C × 15 minutes + 190°C × 80 minutes. 2MPa vacuum pressure was applied to obtain a laminated board with a thickness of 1.6mm. The copper foil was etched and cut to obtain a flame retardant test piece. The flame retardancy was evaluated using this flame retardant test piece, and is shown in Table 2 and Table 3.

[Table 2]

[table 3]

OPE-2St: Terminal styrene-based modified polyphenylene ether resin manufactured by Mitsubishi Gas Chemical Co., Ltd.

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

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

[Industrial availability]

The phosphorus-containing (meth)acrylyl compound of the present invention can be used in a wide range of applications including building materials or electrical and electronic equipment, especially in electrical/electronic products, OA equipment, communication equipment, etc., as a reactive phosphorus-based flame retardant. The agent is very useful.

Claims (6)

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

In the general formula (1), R1 and R2 are hydrogen, hydroxyl, -OR or -R, and R is a hydrocarbon group with 2 to 40 carbon atoms; R1 and R2 can be the same or different, and R1 and R2 can also be the same as phosphorus. The atoms together form a cyclic structure; X in the formula represents a trivalent aromatic hydrocarbon group with 6 to 20 carbon atoms, and Y is a substituent represented by the following general formula (2) or (3); but at least one of Y Contains a substituent represented by the following general formula (3):

In general formula (2), R3 is hydrogen or methyl;

In the general formula (3), R4 is hydrogen or methyl, and R5 is a hydrocarbon group from C1 to C20. A composition of phosphorus-containing (meth)acrylyl compounds, which contains: The phosphorus-containing (meth)acrylyl compound as described in claim 1; and A phosphorus-containing (meth)acrylyl compound represented by the following general formula (4);

In the general formula (4), R1, R2, R3 and X are synonymous with the provisions in the general formula (1) and the general formula (3). A method for producing a phosphorus-containing (meth)acrylyl compound as described in claim 1, which involves reacting a compound represented by the following general formula (5) with a compound containing one glycidyl ether group, (meth)acrylation with (meth)acrylic acid, (meth)acrylic anhydride or halogenated (meth)acrylyl compound;

In the general formula (5), R1, R2 and X are synonymous with those specified in the general formula (1). A flame-retardant resin composition obtained by blending at least one thermosetting resin or thermoplastic resin into the phosphorus-containing (meth)acrylyl compound described in claim 1. A hardened product obtained by hardening the flame-retardant resin composition according to claim 4. A laminated board for electronic circuit boards, which contains the flame-retardant resin composition according to claim 4 as an essential component.

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