TW202202513A - Phosphorus-containing vinylbenzyl ether compound, method for producing the same, flame-retardant resin composition, and laminate for electronic circuit board A phosphorus-containing vinylbenzyl ether compound excellent in heat resistance and dielectric properties - Google Patents

Abstract

The present invention provides a phosphorus-containing vinylbenzyl ether compound excellent in heat resistance and dielectric properties in a cured product, a method for producing the same, a flame-retardant resin composition, and a laminate for an electronic circuit board. A phosphorus-containing vinylbenzyl ether compound represented by the following general formula (1). Here, Y is each independently a hydroxyl group or a vinylbenzyloxy group represented by the following formula (2).

Description

Phosphorus-containing vinylbenzyl ether compound, method for producing the same, flame-retardant resin composition, and laminate for electronic circuit board

The present invention relates to a reactive phosphorus compound, in particular to a phosphorus-containing vinylbenzyl ether compound and its manufacturing method, a flame retardant resin composition, a laminate for an electronic circuit substrate, and a reactive flame retardant plastic material. agents are useful.

Plastic materials are used in a wide range of applications (even building materials or electrical and electronic equipment) due to their excellent mechanical properties and formability. However, most plastic materials are easily combustible, so in applications such as electrical/electronic products, office automation equipment, or communication equipment, it is necessary to achieve flame retardancy for safety against heat generation and fire.

As a flame retardant technology for plastic materials, additive flame retardants such as halogen-based flame retardants, inorganic flame retardants, and phosphorus-based flame retardants are not limited to resin types and applications, and are common technologies. However, among these, halogen-based flame retardants, mainly bromine-based, have been pointed out as a potential source of dioxin, which is highly carcinogenic. Therefore, in response to recent efforts to reduce environmental load substances, the use of flame retardants is being restricted. developing. In addition, inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide have a flame retardant effect due to heat absorption, but in order to achieve sufficient flame retardant, they need to be added in large amounts, which reduces various properties of plastic molded products. s reason. Therefore, phosphorus-based flame retardants that do not generate harmful substances and can be flame-retardant by adding a relatively small amount are used in many cases, but even in this case, it is unavoidable that a drop in workability due to bleeding or the like, a drop in glass transition temperature, and the like cannot be avoided. effect on characteristics.

In order to solve the problems of these additive flame retardants, reactive flame retardants containing phosphorus atoms, which are flame retardant components, and having reactive groups have been developed and widely used. As a reactive flame retardant that can be applied to epoxy resin compositions frequently used in the electronic/electrical fields, for example, Patent Document 1 discloses a phenol resin obtained by , as a hardener for epoxy resins, bisphenol A and formaldehyde are reacted to obtain hydroxymethyl bisphenol A, and then it is combined with 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10- Oxide (hereinafter, abbreviated as "DOPO") is reacted, thereby obtained; in Patent Document 2, it is disclosed that DOPO (9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide) is reacted with quinones Phosphorus-containing epoxy resin obtained by reacting with epoxy resin after reaction. In these resins, the problem of processability such as bleeding of the flame retardant was solved, and the deterioration of thermal properties such as heat resistance was not observed. As described above, the use of reactive flame retardants can generally make up for the shortcomings of additive flame retardants compared to additive flame retardants, so a large number of flame retardant epoxy resins and the like have been developed.

However, in recent years, in the field of electronic/electrical materials that must have flame retardancy, the requirements for resin components containing flame retardants are changing to a higher level due to the rapid development of electronic devices such as smartphones. Especially in the field of information/communication, with the increase in the amount of information processing, the high frequency of the signal continues to develop. In order to reduce the transmission loss, the resin components used in this field are strongly required to have low dielectric constant and low dielectric loss tangent. . Therefore, in the field of electronic/electrical materials represented by circuit boards, instead of epoxy resins, radically polymerizable resins capable of realizing lower dielectric constant and lower dielectric loss tangent are widely used. Therefore, not only flame retardants having reactive groups reactive with epoxy groups or epoxy resins, but also halogen-free flame retardants with low dielectric constant and low dielectric loss tangent that can react with radically polymerizable resins are required. fuel. As a halogen-free flame retardant having a radically polymerizable functional group, Patent Document 3 and Patent Document 4 disclose vinylbenzyl ether compounds containing a DOPO skeleton. However, low dielectric constant and low dielectric loss tangent cannot be said to be sufficient properties, and there is no radical polymerizable group-containing flame retardant that satisfies thermal and dielectric properties such as halogen-free flame retardancy and heat resistance. . [Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2013-166938 [Patent Document 2] Japanese Patent Laid-Open No. 11-279258 [Patent Document 3] Japanese Patent Laid-Open No. 2004-331537 [Patent Document 4] Japanese Patent Laid-Open No. 2004-277322

[Problems to be Solved by Invention] Therefore, the problem to be solved by the present invention is to provide a phosphorus-containing vinylbenzyl ether compound which is useful as a reactive phosphorus-based flame retardant and has excellent heat resistance and dielectric properties in a cured product, and which contains the phosphorus-containing vinylbenzyl ether compound. A curable resin composition of a base ether compound and a cured product thereof.

[Technical means to solve the problem] The present inventors have intensively studied the above-mentioned problems, and as a result, they have found that a phosphorus-containing vinylbenzyl ether compound having a specific structure is excellent in heat resistance and dielectric properties, and completed the present invention.

（在通式（1）中，R¹ 、R² 、R³ 、R⁴ 及R⁵ 分別獨立地為直鏈或支鏈的碳數1～5的烷基；m1、m2、m3、m4及m5表示取代數，分別獨立地為0～4的整數；其中，m1+m2+m3+m4≧4；在存在多個R¹ 、R² 、R³ 、R⁴ 或R⁵ 的情況下，多個R¹ 、R² 、R³ 、R⁴ 或R⁵ 可相同也可不同； Y分別獨立地為羥基或下述式（2）所表示的乙烯基苄基氧基； [化2]

n1、n2、n3及n4表示取代數，分別獨立地為0～2的整數；其中，n1+n2+n3+n4≧1，Y中的至少一個為乙烯基苄基氧基；k為0～10的整數）That is, the present invention is a phosphorus-containing vinylbenzyl ether compound represented by the following general formula (1). [hua 1]

(In the general formula (1), R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a linear or branched alkyl group having 1 to 5 carbon atoms; m1, m2, m3, m4 and m5 represents the number of substitutions, and each independently is an integer of 0 to 4; wherein, m1+m2+m3+m4≧4; when there are multiple R ¹ , R ² , R ³ , R ⁴ or R ⁵ , more R ¹ , R ² , R ³ , R ⁴ or R ⁵ may be the same or different; Y is each independently hydroxyl or vinylbenzyloxy represented by the following formula (2);

n1, n2, n3 and n4 represent the number of substitutions, which are independently an integer from 0 to 2; wherein, n1+n2+n3+n4≧1, at least one of Y is vinylbenzyloxy; k is 0～ an integer of 10)

In the phosphorus-containing vinylbenzyl ether compound, n1 and n2 are preferably 1, and n3 and n4 are preferably 0.

（在通式（3）中，p1、p2、p3及p4表示取代數，分別獨立地為0～2的整數；其中，p1+p2+p3+p4≧1；R¹ 、R² 、R³ 、R4、R⁵ 、m1、m2、m3、m4、m5及k與通式（1）中的這些含義相同）The present invention is a method for producing a phosphorus-containing vinylbenzyl ether compound, which is to produce the phosphorus-containing vinylbenzyl ether compound as described in claim 1 or 2, characterized in that the following general formula (3) is used for the production of The indicated phosphorus-containing phenolic compounds are reacted with vinylbenzyl halides. [hua 3]

(In the general formula (3), p1, p2, p3, and p4 represent substitution numbers, and are each independently an integer of 0 to 2; wherein, p1+p2+p3+p4≧1; R ¹ , R ² , R ³ , R4, R5, m1, m2, m3, m4, m5 and k have the same meanings as those in the general formula ( ¹ ))

The present invention is a flame-retardant resin composition, which is characterized in that one or more kinds of thermosetting resins or thermoplastic resins are blended into the phosphorus-containing vinylbenzyl ether compound; further, the present invention is a kind of electronic circuit board. The laminated board is obtained using a flame-retardant resin composition.

[Effect of invention] The phosphorus-containing vinylbenzyl ether compound of the present invention exhibits an unprecedented low dielectric constant, low dielectric loss tangent, and a small decrease in heat resistance, which is used to reduce transmission in electronic equipment at high frequencies as the amount of information processing increases. Lost reactive phosphorus flame retardants are very useful.

Hereinafter, the present invention will be described in detail. In the description of the present invention, the phosphorus-containing vinylbenzyl ether compound or the phosphorus-containing phenol compound includes not only a single compound but also a mixture (resin).

The phosphorus-containing vinylbenzyl ether compound of the present invention is represented by the following general formula (1). [hua 4]

Among the phosphorus-containing vinylbenzyl ether compounds of the general formula (1), those in which the substituent Y is present at the para position with respect to the phosphate bond are preferred.

In formula (1), specific examples of the alkyl group in R ¹ , R ² , R ³ and R ⁴ include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, Tertiary butyl, n-pentyl, isopentyl, neopentyl, etc. Among these, a methyl group is particularly preferred from the viewpoints of reactivity in production and availability. R ¹ , R ² , R ³ , and R ⁴ are collectively represented by ^Rh (h is an integer of 1 or more and 4 or less), and when there are a plurality of each ^Rh , the respective ^Rh may be the same or different. In formula (1), m1, m2, m3, and m4 represent the number of substitutions of the alkyl group bonded to each benzene ring. Here, m1, m2, m3, and m4 are each independently an integer of 0 or more and 4 or less. Among them, m1+m2+m3+m4≧4, preferably m1+m2+m3+m4≧6. Among m1, m2, m3, and m4, it is preferable that m1 and m2 are each independently an integer of 1 or more and 3 or less, and m3 and m4 are each independently an integer of 0 or more and 3 or less. More preferably, m1, m2 and m5 are each independently 0 or 3, and m3 and m4 are each independently 0, 2 or 3. n1 and n2 are each independently 0 or 1, and n3 and n4 are each independently 0 or 1. The substitution positions of R ¹ , R ² , R ³ and R ⁴ on the benzene ring are not particularly limited. Preferably, the substituents of R ¹ , R ² , R ³ and R ⁴ are each independently present in the ortho position or the meta position with respect to the phosphate bond. More preferably, the substituents of R ¹ , R ² , R ³ and R ⁴ are each independently present in an ortho position or a meta position with respect to the phosphate bond, and at least one of R ¹ , R ² , R ³ and R ⁴ One of the substituents is present in the ortho position. By having one or more alkyl groups present at the ortho position with respect to the phosphate bond, the phosphate moiety is hydrophobicly shielded, and hydrolysis can also be suppressed.

In formula (1), Y is each independently a phenolic hydroxyl group or a vinylbenzyl ether group represented by formula (2). [hua 5]

In the formula (2), the substitution position of the vinyl group on the benzene ring is not particularly limited, but the meta-position or the para-position is preferred with respect to the bonding position of the methylene oxide chain. n1, n2, n3 and n4 represent the number of substitutions of the phenolic hydroxyl group bonded to each benzene ring or the substituent represented by the formula (2). Here, n1, n2, n3, and n4 are each independently an integer of 0 or more and 2 or less. However, at least one of n1, n2, n3 or n4 is 1 or more, and has at least one or more, preferably two or more vinylbenzyl ether groups represented by the formula (2) in the molecule. By having one or more vinylbenzyl ether groups represented by the formula (2), the flame retardant component is immobilized in the cured product, especially in the vinyl-based resin, does not bleed out, and can suppress heat resistance. decline. In the phosphorus-containing vinylbenzyl ether compound of the present invention, the substitution position of Y on the benzene ring is not particularly limited, but from the viewpoint of reactivity, it is preferably bonded to the para position with respect to the phosphate bond. In the formula (1), the number of substitutions bonded to one benzene ring is represented by the sum of the number of substitutions nh of Y and the number of substitutions mh of the alkyl group R ^h , mh+nh (h is an integer of 1 or more and 4 or less) . In each benzene ring, the sum of the substitution numbers mh+nh is 5 or less, preferably 4 or less.

In formula (1), R ⁵ is a linear or branched alkyl group having 1 or more and 5 or less carbon atoms. Specific examples of the alkyl group in R ⁵ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, and neopentyl group. Wait. From the viewpoints of reactivity in production and availability, a methyl group is particularly preferred. When there are plural R ^5s , each R ⁵ may be the same or different. In formula (1), m5 is an integer of 0 or more and 4 or less. In formula (1), k is an integer of 0 or more and 10 or less, and represents the number of repetitions of the phosphate bond. The average value of k is 0 or more and 5.0 or less, preferably 0 or more and 3.0 or less, more preferably 0 or more and 2.5 or less.

The phosphorus content of the phosphorus-containing vinylbenzyl ether compound represented by the general formula (1) is preferably 1.0% by weight to 20% by weight, more preferably 2.0% by weight to 10% by weight, and still more preferably 3.0% by weight to 3.0% by weight. 7.0% by weight.

在通式（3）中，p1、p2、p3、p4表示羥基的取代數，分別獨立地為0以上且2以下的整數，p1+p2+p3+p4≧1，較佳的是p1+p2+p3+p4≧2。 式（3）中，R¹ 、R² 、R³ 、R⁴ 、R⁵ 、m1、m2、m3、m4、m5及k與式（1）對應而相通，以上述詳細說明為准。The phosphorus-containing vinylbenzyl ether compound of the present invention can be obtained by reacting a phosphorus-containing phenol compound represented by the general formula (3) with a vinylbenzyl halide. [hua 6]

In the general formula (3), p1, p2, p3, and p4 represent the substitution numbers of hydroxyl groups, each independently an integer of 0 or more and 2 or less, p1+p2+p3+p4≧1, preferably p1+p2 +p3+p4≧2. In formula (3), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , m1 , m2 , m3 , m4 , m5 and k correspond to formula (1), and the above detailed description shall prevail.

The phosphorus content of the phosphorus-containing phenol compound represented by the general formula (3) is preferably 1.0% by weight to 20% by weight, more preferably 3.0% by weight to 10% by weight, and still more preferably 5.0% by weight to 8.0% by weight . The hydroxyl equivalent is preferably 100 to 1000, more preferably 150 to 500, and still more preferably 200 to 350.

Specific examples of the phosphorus-containing phenol compound represented by the formula (3) include compounds represented by the following formulae (4) to (7), for example. [hua 7]

The phosphorus-containing phenol compound represented by the formula (3) can be obtained by a general method for producing an aromatic phosphate ester, and as an example of a reaction form, phosphorus oxychloride (phosphorus oxychloride) and phenols are used. For the esterification reaction of raw materials, the corresponding phosphoric acid ester can be obtained by dehydrochlorination reaction. Moreover, since the phosphorus-containing phenol compound of Formula (3) has one or more phenolic hydroxyl groups, it is required that one or more of the phenols as a raw material be a benzene compound having a plurality of hydroxyl groups.

The phosphorus-containing vinylbenzyl ether compound of the present invention can be obtained by reacting a phosphorus-containing phenol compound represented by formula (3) with a vinylbenzyl halide.

Examples of vinylbenzyl halide used in the present invention include p-vinylbenzyl chloride, m-vinylbenzyl chloride, p-vinylbenzyl bromide, m-vinylbenzyl bromide, and the like. , but not limited to these, and may be used alone or in combination of two or more. Commercially available products include CMS-14 (manufactured by AGC Seimi Chemical Co., Ltd., p-vinylbenzyl chloride), CMS-P (manufactured by AGC Seimi Chemical Co., Ltd., mixture of p-vinylbenzyl chloride and m-vinylbenzyl chloride) etc.

The compounding ratio of the phosphorus-containing phenol compound and the vinylbenzyl halide is 0.80 mol to 4.0 mol of the vinylbenzyl halide, preferably 0.95, relative to 1 mol of the hydroxyl group in the phosphorus-containing phenol compound. mol to 2.0 mol, more preferably 1.0 mol to 1.5 mol. When the amount of vinylbenzyl halide is less than 0.8 mol relative to 1 mol of the phosphorus-containing phenolic compound, the number of remaining hydroxyl groups increases and heat resistance decreases, and when it exceeds 4.0 mol, the unreacted vinylbenzyl halide is halogenated. The residual amount of the substance increases, or the side-reacted polymer becomes too much.

In the reaction between the phosphorus-containing phenol compound represented by the formula (3) and the vinylbenzyl halide, it is preferable to react with the halogen of the vinylbenzyl halide to promote the reaction with the phosphorus-containing phenol compound. , while adding basic compounds. Examples of the basic compound include hydroxides of alkali metals such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; hydroxides of alkaline earth metals such as calcium hydroxide and magnesium hydroxide; and alkalis such as sodium carbonate and potassium carbonate. Basic compounds such as metal carbonates. Among them, alkali metal carbonates are preferred from the viewpoint of the effect of promoting the reaction and the inhibition of hydrolysis. Moreover, it may be used alone or in combination of two or more. In addition, it may be used as a solid, or may be used as a solution such as an aqueous solution, but an aqueous solution is preferred. The usage-amount of the basic compound is 0.5 mol to 5.0 mol, preferably 1 mol to 4 mol, more preferably 1.2 mol to 3 mol per 1 mol of vinylbenzyl halide. . When the usage-amount of a basic compound is less than 0.5 mol, reaction cannot fully progress. On the other hand, if it exceeds 5.0 mol, for example, a large amount of acid required for neutralization is required, which is not economical.

In the reaction, if necessary, a catalyst may be used. Examples of catalysts used include tertiary amines such as benzyldimethylamine; quaternary amine salts such as tetramethylammonium chloride, tetramethylammonium bromide, and tetrabutylammonium bromide; triphenyl amines Phosphines such as phosphine, tris(2,6-dimethoxyphenyl)phosphine; benzyltriphenylphosphonium chloride, tetrabutylphosphonium bromide, ethyltriphenylphosphonium bromide, tetrabutyl iodide Phosphonium salts such as phosphonium; or various catalysts such as imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole are not limited to these, and may be used alone or in combination of two or more. The usage-amount of a catalyst is 10 weight part or less with respect to 100 weight part of raw materials.

The solvent used in the reaction is not particularly limited, and examples thereof include hexane, heptane, octane, decane, dimethylbutane, pentene, cyclohexane, methylcyclohexane, benzene, toluene, Hydrocarbons such as xylene and ethylbenzene; methanol, hexanol, propanol, butanol, amyl alcohol, amyl alcohol, hexanol, methyl amyl alcohol, heptyl alcohol, cyclohexanol, benzyl alcohol, furfuryl alcohol, etc. Alcohols; ethyl ether, isopropyl ether, butyl ether, diisoamyl ether, methyl phenyl ether, ethyl phenyl ether, amyl phenyl ether, ethyl benzyl ether, dioxane, Ethers such as methyl furan and tetrahydrofuran; acetone, methyl acetone, methyl ethyl ketone, methyl propyl ketone, methyl butyl ketone, methyl amyl ketone, diethyl ketone, ethyl butyl ketone, Dipropyl ketone, cyclohexanone and other ketones; or methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, cellosolve acetate, ethylene glycol isopropyl ether, diethyl Glycol dimethyl ether, methyl ethyl carbitol, propylene glycol monomethyl ether, dimethylformamide, dimethyl sulfoxide, etc. are not limited to these, and may be used alone or in combination of two or more. use. Moreover, when removing the salt produced|generated by reaction by water washing, it is preferable to use the solvent which can liquid-separate an aqueous layer. For example, benzene, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, etc. are mentioned.

The reaction can also be carried out in the presence of a polymerization inhibitor. By adding a polymerization inhibitor, the vinylbenzyl halide used for the reaction or the vinylbenzyl ether compound which is the target product is polymerized and an oligomer can be prevented from by-producing. As the polymerization inhibitor, known substances can be used without limitation, and examples include hydroquinone, hydroxymonomethyl ether, tertiary butyl catechol, tertiary butyl hydroquinone, 4-methoxyphenol, Organic compounds such as 4-methoxy-1-naphthol and phenothiazine, and copper compounds such as copper chloride and copper sulfide, etc., may be used in combination.

After the completion of the reaction, the obtained reaction solution (reaction mixture) is, if necessary, subjected to distillation removal of the reaction solvent, solvent replacement, etc., and purification by methods such as washing with water, activated carbon treatment, silica gel chromatography, etc., The target vinylbenzyl ether compound of the present invention can be extracted.

Next, a flame-retardant resin composition in which one or more of a curable resin and/or a thermoplastic resin is blended with the phosphorus-containing vinylbenzyl ether compound of the present invention as an essential component will be described.

In the flame-retardant resin composition of the present invention, the blending ratio is not particularly limited, but for example, 10 to 300 parts by weight of phosphorus-containing vinylbenzyl ether is blended with respect to 100 parts by weight of the total amount of the curable resin and the thermoplastic resin. compound. It is preferably 50 parts by weight to 250 parts by weight, more preferably 70 parts by weight to 230 parts by weight.

Examples of curable resins include unsaturated polyester resins, curable maleimide resins, epoxy resins, polycyanate resins, phenol resins, and one or more types of polymerizable unsaturated hydrocarbon groups having one or more in the molecule. The vinyl compounds and the like 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, etc. These may be used alone or in combination of two or more. It is considered that by using such an epoxy resin, the effects on the excellent dielectric properties and fluidity of the flame-retardant resin composition of the present invention can be minimized, and the heat resistance and adhesion of the cured product can be sufficiently improved sex.

Furthermore, when an epoxy resin is contained, a hardener other than an epoxy resin may be used. 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, benzoxazine-based curing agents, and cyanide-based curing agents. Ester-based hardener, etc. These can be used alone or in combination of two or more.

Furthermore, when mixing an epoxy resin, a hardening accelerator can be used as needed. For example, amines, imidazoles, organic phosphines, Lewis acids and the like. The addition amount is usually in the range of 0.2 parts by weight to 5 parts by weight with respect 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 thereof is not particularly limited. That is, the vinyl compounds may be cross-linked and cured by reacting with the phosphorus-containing vinylbenzyl ether compound of the present invention. More preferably, the polymerizable unsaturated hydrocarbon group is a compound having a carbon-carbon unsaturated double bond, and still more preferably 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)) per molecule of vinyl compounds as curable resins; also referred to as the number of terminal double bonds) is based on vinyl groups Although Mw of a compound differs, for example, 1 to 20 are preferable, and 2 to 18 are more preferable. When the number of terminal double bonds is too small, it tends to be difficult to obtain sufficient heat resistance as heat resistance of a cured product. Furthermore, when the number of terminal double bonds is too large, the reactivity becomes too high, and there is a possibility that 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 vinyl compounds include triallyl isocyanurate (TAIC) and other trienyl isocyanurate compounds, and compounds whose terminals are modified with a (meth)acryloyl group or a styryl group. Modified polyphenylene ether (PPE), polyfunctional (meth)acrylate compounds having two or more (meth)acryloyl groups in the molecule, such as polybutadiene, etc. having two or more in the molecule Vinyl compounds of vinyl (polyfunctional vinyl compounds), vinylbenzyl compounds such as styrene and divinylbenzene, and the like. Among them, compounds having two or more carbon-carbon double bonds in the molecule are preferred, and specific examples thereof include TAIC, polyfunctional (meth)acrylate compounds, modified PPE resins, polyfunctional vinyl compounds, and divinyl compounds. Benzene compounds, etc. It is considered that when these are used, the crosslinking is more preferably formed by the curing reaction, and the heat resistance of the cured product of the curable resin composition can be further improved. In addition, these may be used individually or in combination of 2 or more types. Moreover, you may use together the compound which has one carbon-carbon unsaturated double bond in a molecule|numerator. As a compound which has one carbon-carbon unsaturated double bond in a molecule|numerator, the compound (monovinyl compound) etc. which have one vinyl group in a molecule|numerator are mentioned.

Examples of thermoplastic resins include polystyrene, polyphenylene ether resin, polyetherimide resin, polyether sulfite resin, polyphenylene sulfide (PPS) resin, polycyclopentadiene resin, polycyclic Olefin resins, etc., or known thermoplastic elastomers (such as styrene-ethylene-propylene copolymers, styrene-ethylene-butylene copolymers, styrene-butadiene copolymers, styrene-isoprene copolymers , hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer, etc.), or rubbers (eg polybutadiene, polyisoprene). Preferable examples include polyphenylene ether resin (unmodified) and hydrogenated styrene-butadiene copolymer.

In the resin composition of the present invention, a radical polymerization initiator (polymerization catalyst or crosslinking agent) may be formulated. As radical initiators, there are benzyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5 - Di(tert-butyl peroxide)hexyn-3, di-tert-butyl peroxide, tert-butyl cumyl peroxide, 1,3-bis(butyl isopropyl peroxide) benzene , α,α'-bis(tert-butylperoxide-m-isopropyl)benzene, 2,5-dimethyl-2,5-bis(tert-butylperoxide)hexane, dicumyl peroxide compound, di-tert-butylperoxide, tert-butylperoxybenzoate, 2,2-bis(tert-butylperoxide)butane, 2,2-bis( tert-butyl peroxide)octane, 2,5-dimethyl-2,5-bis(benzyl peroxide)hexane, bis(trimethylsilyl)peroxide, trimethyl Peroxides such as silyltriphenylsilyl peroxide, but not limited to these. Furthermore, although not a peroxide, 2,3-dimethyl-2,3-diphenylbutane can also be used as a radical polymerization initiator. However, it 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, more preferably 0.1 to 5 parts by weight, relative to 100 parts by weight of the phosphorus-containing vinylbenzyl ether compound.

A filler can be formulated into the flame-retardant resin composition of the present invention. As a filler, the filler etc. which are added in order to improve the heat resistance or flame retardance of a flame-retardant resin composition and its hardened|cured material, etc. are mentioned, Although a well-known filler can be used, it does not specifically limit. Moreover, heat resistance, dimensional stability, flame retardance, etc. can be further improved by containing a filler. Specifically, silica such as spherical silica, alumina, titania, and metal oxides such as mica, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, talc, aluminum borate, and barium sulfate may be mentioned. , and calcium carbonate, etc. When metal hydroxides such as aluminum hydroxide and magnesium hydroxide are used, they function as flame retardant aids, and flame retardancy can be ensured even when the phosphorus content is small. Among them, silica, mica, and talc are preferred, and spherical silica is more preferred. Moreover, these may be used individually by 1 type, and may be used in combination of 2 or more types.

The filler may be used as it is, or a filler surface-treated with a silane coupling agent such as an epoxysilane type or an aminosilane type may be used. As the silane coupling agent, from the viewpoint of reactivity with a radical polymerization initiator, vinylsilane type, methacrylooxysilane type, acryloxysilane type, and styrylsilane type are preferable type of silane coupling agent. Thereby, the adhesive strength with the metal foil or the interlayer adhesive strength between resins improves. In addition, the above-mentioned silane coupling agent can be added and used by an integral blend method rather than a method in which the filler is surface-treated in advance.

The content of the filler is preferably 10 parts by weight to 200 parts by weight with respect to 100 parts by weight of the total of the solid content (including organic components such as monomers and flame retardants, and the solvent is removed) from which the filler is removed, and more Preferably it is 30 weight part - 150 weight part.

The resin composition of the present invention may further contain additives other than those described above. Examples of additives include antifoaming agents such as silicone-based antifoaming agents and acrylate-based antifoaming agents, heat stabilizers, antistatic agents, ultraviolet absorbers, dyes or pigments, lubricants, and dispersants such as wetting and dispersing agents. Wait.

The flame-retardant resin composition of the present invention or a cured product obtained by curing it can be used as a molded product, a laminate, a molded product, an adhesive, a coating film, or a film. For example, the cured product of the semiconductor sealing material is an injection-molded product or a molded product, and as a method for obtaining the cured product for the above-mentioned use, the flame-retardant resin composition can be molded using injection molding, a transfer molding machine, an injection molding machine, or the like, Furthermore, it heats at 80 degreeC - 230 degreeC for 0.5 hour - 10 hours, and the hardened|cured material is obtained.

The flame-retardant resin composition of the present invention can also be used as a prepreg. When manufacturing a prepreg, it can be prepared in the form of a varnish for the purpose of impregnating a base material (fibrous base material) for forming a prepreg or making a circuit board material for forming a circuit board. Made of resin varnish. This resin varnish is suitable for circuit board applications, and can be used as a varnish for circuit board materials. In addition, as the use of the circuit board material mentioned here, a printed wiring board, a printed wiring board, a flexible printed wiring board, a build-up wiring board, etc. are specifically mentioned.

As an organic solvent used for the said resin varnish, if it does not inhibit a hardening reaction, it will not specifically limit. For example, ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; esters such as ethyl acetate, propyl acetate, and butyl acetate; dimethylacetamide and dimethylformamide Isopolar solvents; aromatic hydrocarbon solvents such as toluene and xylene; these can be used alone or in combination of two or more. From the viewpoint of dielectric properties, aromatic hydrocarbons such as benzene, toluene, and xylene are preferred.

When making the resin varnish, the amount of the organic solvent used is preferably 5 to 900 parts by weight, more preferably 10 to 700 parts by weight, relative to 100 parts by weight of the flame retardant resin composition of the present invention, Particularly preferred is 20 parts by weight to 500 parts by weight.

As the base material used for preparing the prepreg, known materials can be used, and for example, glass fibers, carbon fibers, polyester fibers, polyamide fibers, alumina fibers, paper, etc. can be used alone or in combination of two or more kinds. substrate. For these substrates, if necessary, a coupling agent can be used for the purpose of improving the adhesiveness at the interface between the resin and the substrate. As the coupling agent, common coupling agents such as silane coupling agents, titanate coupling agents, aluminum-based coupling agents, and zirconium-aluminum coupling agents can be used.

As a method of obtaining a prepreg, the method of impregnating a base material with the said resin varnish, and drying it is mentioned. The impregnation is performed by dipping, coating, or the like. The impregnation may be repeated as many times as necessary, and in this case, the impregnation may be repeated with a plurality of solutions having different compositions or concentrations to adjust to the final desired resin composition and resin amount. After the impregnation, a prepreg can be obtained by heating and drying at 100° C. to 180° C. for 1 minute to 30 minutes. Here, the amount of resin in the prepreg is preferably 30% by weight to 80% by weight of the resin component.

The flame-retardant resin composition of the present invention can also be used as a laminate. When a prepreg is used to form a laminate, one or more prepreg bulk layers are formed, and metal foils are arranged on one or both sides to form a laminate, and the laminate is integrated by heating and pressing. 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 laminate may be appropriately adjusted under the conditions for curing the flame-retardant resin composition to perform heating and pressing. However, if the pressing pressure is too low, the resulting laminate may not In the case where air bubbles remain inside and the electrical properties are lowered, it is preferable to pressurize under the condition that the formability is satisfied. For example, the temperature can be set to 180°C to 250°C, the pressure can be set to 49.0 N/cm ² to 490.3 N/cm ² (5 kgf/cm ² to 50 kgf/cm ² ), and the heating and pressurization time can be set to 40 minutes to 240 minutes. Furthermore, a multilayer board can be produced using the single-layer laminate obtained in the above-described manner as an inner layer material. In such a case, first, a circuit is formed on a laminated board by an additive method, a subtractive method, or the like, and the surface of the formed circuit is treated with an acid solution to perform a blackening treatment to obtain an inner layer material. An insulating layer is formed using a resin sheet, a metal foil with resin, or a prepreg on the circuit forming surfaces of one side or both sides of the inner layer material, and a conductor layer is formed on the surface of the insulating layer, thereby forming an insulating layer. Multilayer board.

Furthermore, the flame-retardant composition of the present invention can also be used for a build-up film. As a method of producing a build-up film from the resin composition of the present invention, for example, the above-mentioned resin varnish is applied on a support film and dried to form a film-like insulating layer. The thus-formed film-like insulating layer can be used as a build-up film for a multilayer printed wiring board. [Example]

Next, although an Example demonstrates this invention, this invention is not limited to these. The parts in each example are parts by weight. In addition, the physical property measurement in a synthesis example and an Example was performed by the method shown below. (1) Hydroxyl Equivalent: Measured according to Japan Industrial Standards (JIS) K 0070 standard. Specifically, using a potentiometric titration apparatus, 1,4-dioxane was used as a solvent, acetylation was performed with 1.5 mol/L acetyl chloride, and excess acetyl chloride was decomposed with water, and 0.5 mol/L- Potassium hydroxide for titration. (2) Phosphorus content ratio: Sulfuric acid, hydrochloric acid, and perchloric acid were added to the sample, followed by heating and wet incineration, so that all phosphorus atoms became orthophosphoric acid. Metavanadate and molybdate were reacted in an acidic solution of sulfuric acid, and the absorbance at 420 nm of the phosphovanadomolybdic acid complex formed was measured and expressed in %. It was obtained from a calibration curve prepared in advance using potassium dihydrogen phosphate. the phosphorus atom content. (3) Field desorption mass spectrometry (FD-MS): The molecular weight was measured using JMS-T100GCV manufactured by JEOL Ltd. (4) Glass transition temperature: measured using differential scanning calorimetry and obtained from a baseline shift at a temperature increase rate of 10° C./min. (5) Relative dielectric constant and dielectric loss tangent: According to the IPC-TM-650 2.5.5.9 standard, use a material analyzer (manufactured by AGILENT Technologies), and use the capacitance method to find the dielectric at a frequency of 1 GHz. Electric constant and dielectric loss tangent. (6) Flame retardancy: According to UL94, it evaluated by the vertical method. Evaluations are marked with V-0, V-1, V-2. If flame retardancy cannot be obtained, it will be marked as N.C (not classified) without distinction. (7) Viscosity: In order to confirm the presence or absence of exudation, the adhesiveness of the surface of the hardened sample was confirmed by palpation. Those without stickiness were judged as ○, and those with stickiness were judged as ×.

(Synthesis Example 1) Synthesis of Phosphorus-Containing Phenolic Compound A A 2-liter four-neck flask equipped with a stirrer, a thermometer, and a hydrochloric acid recovery device (a condenser connected to a scrubber) was filled with 1,500 g of phosphorus oxychloride, 471 g of phenol, and 1.2 g of magnesium chloride as a catalyst. . While stirring the obtained mixed solution, the mixture was gradually heated and raised to a temperature of 90° C. for about 3 hours, and the reaction was carried out, and the generated hydrogen chloride (hydrochloric acid gas) was recovered by a water scrubber. Then, the pressure in the flask was gradually reduced to 12 kPa at 120°C to remove unreacted phosphorus oxychloride, phenol, and by-produced hydrogen chloride to obtain monophenyl phosphoro dichloridate (MPC) 1055 g. A 2-liter four-necked flask equipped with a stirrer, a thermometer, a dropping funnel, and a condenser was charged with 822 g of 2,3,5-trimethylhydroquinone, 6.3 g of aluminum chloride as a catalyst, and 2,3,5-trimethylhydroquinone as a solvent. 1,2-Dichlorobenzene 1000 g. Then, the dropping funnel was filled with 570 g of the above-mentioned MPC. While stirring the mixed solution in the four-necked flask, the MPC in the dropping funnel was added dropwise over two hours while heating to a temperature of 110°C and maintaining at the same temperature (110°C). After the dropwise addition, the mixture was gradually heated to 160° C. and stirred for 4 hours to obtain a reaction product. Then, it cooled to 105 degreeC, the pressure in the flask was gradually reduced to 6.3 kPa, and the hydrogen chloride by-produced was removed. The obtained reaction product was washed with dilute hydrochloric acid and water, neutralized and washed with an aqueous sodium carbonate solution, and washed with water again. Then, it heated to the temperature of 150 degreeC, pressure-reduced to 1 kPa, and collect|recovered water and 1, 2- dichlorobenzene. Furthermore, steam distillation was performed at a temperature of 110° C. under a reduced pressure of 1 kPa to distill off low-boiling components, and the mixture was cooled to room temperature to obtain 1195 g of a black-brown solid phosphorus-containing phenolic compound A. The phosphorus content of Compound A as the obtained mixture was 6.5%, and the hydroxyl group equivalent was 272 g/eq.

(Synthesis Example 2) Synthesis of Phosphorus-Containing Phenolic Compound B A 2-liter four-neck flask equipped with a stirrer, a thermometer, and a hydrochloric acid recovery device (a condenser connected to a water scrubber) was filled with 1,500 g of phosphorus oxychloride and 611 g of 2,6-dimethylphenol as a catalyst. of magnesium chloride 1.2 g. While stirring the obtained mixed solution, the mixture was gradually heated and raised to a temperature of 110° C. for about 3 hours, and the reaction was carried out, and the generated hydrogen chloride (hydrochloric acid gas) was recovered with a water scrubber. Then, the pressure in the flask was gradually reduced to 12 kPa at 120°C, and unreacted phosphorus oxychloride, phenol, and by-produced hydrogen chloride were removed to obtain mono-2,6-dimethylphenyl dichloride phosphate 1200 g. A 2-liter four-necked flask equipped with a stirrer, a thermometer, a dropping funnel, and a condenser was charged with 320 g of 2,3,5-trimethylhydroquinone, 135 g of pyridine as a hydrogen chloride scavenger, and 320 g of pyridine as a solvent. Toluene 200 g. Furthermore, the dropping funnel was filled with 203 g of the above-mentioned mono-2,6-dimethylphenyl phosphoric acid dichloride. The mixed solution in the four-necked flask was heated to a temperature of 20°C and maintained at the same temperature (20°C) while stirring the mixed solution in the four-necked flask. Dimethyl phenyl ester. After the dropwise addition, the mixture was heated to 65°C and stirred for 5 hours to obtain a reaction product. The obtained reaction product was washed with dilute hydrochloric acid and water, heated to a temperature of 150°C, decompressed to 2 kPa, distilled to remove water, toluene, and low-boiling components, and cooled to room temperature to obtain a dark brown solid. Phosphorus-containing phenolic compound B 330 g. The phosphorus content of Compound B as the obtained mixture was 6.5%, and the hydroxyl group equivalent was 272 g/eq.

(Example 1) Synthesis of Phosphorus-Containing Vinylbenzyl Ether Compound A A glass-made separable flask equipped with a stirring device, a thermometer, and a cooling tube was charged with 200.0 g of phosphorus-containing phenolic compound A, and diethylene glycol dimethylformaldehyde. 133.2 g of ether was heated to 75°C under nitrogen atmosphere and dissolved. 134.0 g of CMS-P was added, 10.0 g of tetrabutylammonium bromide and 222.4 g of a 50% potassium carbonate aqueous solution were added after uniformity, and the reaction was carried out for 10 hours. Next, the reaction liquid was concentrated and dissolved in 674.4 g of toluene. The reaction liquid was neutralized with a 10% aqueous sodium dihydrogen phosphate solution, and washed with water. Furthermore, dehydration and filtration were performed, and the solvent was further concentrated, whereby 340.0 g of a toluene solution of phosphorus-containing vinylbenzyl ether compound A was obtained. The obtained compound A was analyzed by FD-MS, and a peak with a molecular weight of 674 was confirmed, thereby confirming that the compound having the following structure was the main component. Moreover, the phosphorus content rate was 4.7%. [hua 8]

(Example 2) Synthesis of Phosphorus-Containing Vinylbenzyl Ether Compound B In a glass separable flask equipped with a stirring device, a thermometer, a cooling tube, and a dropping funnel, 200 g of phosphorus-containing phenolic compound B, diethyl 133.2 g of glycol dimethyl ethers were heated to 75°C under nitrogen atmosphere and dissolved. 128.6 g of CMS-P was added, 8.2 g of tetrabutylammonium bromide and 213.4 g of 50% potassium carbonate aqueous solution were added after uniformity, and the reaction was carried out for 15 hours. Next, the reaction liquid was concentrated and dissolved in 665.0 g of toluene, then the reaction liquid was neutralized with a 10% aqueous sodium dihydrogen phosphate solution, and washed with water. Furthermore, dehydration and filtration were carried out, and the solvent was further concentrated to obtain 381.5 g of a toluene solution of phosphorus-containing vinylbenzyl ether compound B. The obtained compound B was analyzed by FD-MS, and the peak of the molecular weight of 704 was confirmed, whereby it was confirmed that the compound having the following structure was the main component. Moreover, the phosphorus content rate was 4.6%. [Chemical 9]

(Comparative Example 1) The synthesis was carried out according to the synthesis example of Patent Document 3. Specifically, 340 parts of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide was charged into a glass-made separation flask equipped with a stirring device, a thermometer, a cooling tube, and an oxygen introduction device. , 660 parts of toluene, dissolved at 80°C. 245 parts of 1, 4- naphthoquinone were added in batches while paying attention to the heat of reaction. The reaction was continued, the temperature was raised to 110°C, and the reaction was further carried out. After 3 hours, a slurry solution in which dark brown crystals were deposited was obtained. The crystals were separated by filtration and dispersed in 500 parts of methanol. After performing this operation three times, drying was performed using a hot air circulating oven. 93.5 parts of 10-(2,5-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, a phosphorus-containing phenolic compound obtained as a pale yellow powder, as a solvent, were added 140.5 parts of methylidene, 93.5 parts of methyl isobutyl ketone, 77.8 parts of CMS-P as vinylbenzyl halide, 0.20 parts of tetramethylammonium chloride as catalyst, 48.5% hydroxide as alkali metal 74.2 parts of sodium aqueous solution and 0.16 part of trimethylhydroquinone as a polymerization inhibitor were neutralized with 35% hydrochloric acid to pH 5-6, and the lower aqueous 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 aqueous layer are repeated 3 to 5 times. Reflux dehydration was performed, and the solution was filtered to recover the solvent, and phosphorus-containing vinylbenzyl ether compound C was obtained. The phosphorus content of the obtained compound was 4.2%.

(Comparative Example 2) The synthesis was carried out according to the synthesis example of Patent Document 4. Specifically, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10, which is a phosphorus compound, was placed in a glass-made separation flask provided with a stirring device, a thermometer, a cooling tube, and an oxygen introducing device. -150 parts of oxides, 70 parts of toluene as a reaction solvent, 20 parts of isopropyl alcohol, 120 parts of CMS-P as a vinylbenzyl halide, and 2.7 parts of tetramethylammonium chloride as a catalyst, heated to dissolve. Then, 127 parts of a 48.5% sodium hydroxide aqueous solution as an alkali metal was charged in batches while paying attention to the temperature rise due to the heat generation of the reaction. The reaction was carried out while maintaining at 70°C to 80°C, and the residual amount of CMS-P was tracked by gas chromatography. It was confirmed that the residual amount of CMS-P was reduced, and the reaction was sufficiently advanced, and then diluted with toluene. It neutralized with hydrochloric acid, and filtered and removed the produced|generated sodium chloride. Further, washing with water is performed to remove ionic impurities. Dehydration and solvent removal were performed by heating under reduced pressure to obtain phosphorus-containing vinylbenzyl compound D as a pale yellow solid. The phosphorus content of the compound D was measured and found to be 9.3%.

Example 3 to Example 6, Comparative Example 3 to Comparative Example 11 <Preparation of flame retardant resin composition and preparation of cured product> A varnish was produced by mixing various components in the ratio of Table 1, apply|coating this to a polyethylene terephthalate film, and drying it in 130 degreeC oven for 5 minutes, the film of the resin composition was produced. Next, by pulverizing this film, a powder of the resin composition is obtained. Further, this powder was sandwiched with a spacer on a mirror plate made of stainless steel, and molded using a vacuum oven at 210° C. for 90 minutes to obtain a sample of a cured product. <Preparation of flame retardancy test pieces> A varnish was prepared by blending various components in the ratios shown in Table 1, and the resin varnish was impregnated in glass cloth (manufactured by Nitto Textile Co., Ltd.; 7628 type; model H258), followed by heating at 130° C. for 5 minutes. Dry to obtain a prepreg. The obtained 8 prepregs were stacked on top and bottom of copper foils (manufactured by Mitsui Metals & Mining Co., Ltd., 3EC-III, thickness 35 μm), and subjected to 2 MPa vacuum pressing to obtain a 1.6 mm thick laminate. By etching and cutting the copper foil, a flame-retardant test piece was obtained.

[Table 1] Example 3 Example 4 Example 5 Example 6 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 OPE-2St 34.6 56.4 32.0 54.6 100.0 33.0 55.4 65.0 76.6 60.5 73.7 66.8 77.9 Phosphorus-containing vinylbenzyl ether compound A 65.4 43.6 Phosphorus-containing vinylbenzyl ether compound B 68.0 45.4 Phosphorus-containing vinylbenzyl ether compound C 67.0 44.6 Phosphorus-containing vinylbenzyl ether compound D 35.0 23.4 TXP 39.5 26.3 PX-200 33.2 22.1 Perbutyl P (phr) 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 *Numerical values indicate the amount of preparation (solid content value), and were varnished using 100 parts by weight of toluene as a solvent.

OPE-2St: Terminal styrene modified polyphenylene ether resin manufactured by Mitsubishi Gas Chemical Co., Ltd. TXP: Trixylenyl phosphate, manufactured by Daeba Chemical Industry Co., Ltd., with a phosphorus content of 9.5% PX-200: manufactured by Daeba Chemical Industry Co., Ltd. Aromatic condensed phosphoric acid ester, phosphorus content 9.0% Perbutyl P: 1,3-bis(butyl isopropyl peroxide) benzene manufactured by NOF Corporation

The results are shown in Table 2.

[Table 2] Example 3 Example 4 Example 5 Example 6 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 Comparative Example 9 Comparative Example 10 Comparative Example 11 Glass transition temperature (℃) 165 163 167 173.9 167.1 163 157.5 150 154.8 86.1 104.6 97.7 116.7 Dielectric constant 2.70 2.65 2.64 2.58 2.57 3.05 2.82 3.20 2.75 2.65 2.67 2.67 2.64 Dielectric Loss Tangent 0.0029 0.0027 0.0025 0.0024 0.0026 0.0031 0.0032 0.0039 0.0036 0.0020 0.0022 0.0016 0.0018 flame retardancy V-0 V-0 V-0 V-0 NC V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 sticky ○ ○ ○ ○ ○ ○ ○ ○ ○ × × × ○

without

1 shows the results of field desorption mass spectrometry (FD-MS) analysis of phosphorus-containing vinylbenzyl ether compound A obtained in Example 1. 2 is the FD-MS analysis result of the phosphorus-containing vinylbenzyl ether compound B obtained in Example 2. FIG.

Claims (5)

A phosphorus-containing vinylbenzyl ether compound, characterized in that it is represented by the following general formula (1);

In the general formula (1), R ¹ , R ² , R ³ , R ⁴ and R ⁵ are each independently a linear or branched alkyl group having 1 to 5 carbon atoms; m1, m2, m3, m4 and m5 Indicates the number of substitutions, each independently an integer of 0 to 4; wherein, m1+m2+m3+m4≧4; when there are multiple R ¹ , R ² , R ³ , R ⁴ or R ⁵ , multiple R ¹ , R ² , R ³ , R ⁴ or R ⁵ may be the same or different; Y is each independently hydroxyl or vinylbenzyloxy represented by the following formula (2);

n1, n2, n3 and n4 represent the number of substitutions, which are independently an integer from 0 to 2; wherein, n1+n2+n3+n4≧1, at least one of Y is vinylbenzyloxy; k is 0～ An integer of 10. The phosphorus-containing vinylbenzyl ether compound according to claim 1, wherein n1 and n2 are 1, and n3 and n4 are 0. A method for producing a phosphorus-containing vinylbenzyl ether compound, comprising producing the phosphorus-containing vinylbenzyl ether compound as claimed in claim 1 or claim 2, wherein the following general formula (3) is used to represent The phosphorus-containing phenolic compound reacts with vinylbenzyl halide;

In the general formula (3), p1, p2, p3 and p4 represent substitution numbers, which are each independently an integer of 0 to 2; wherein, p1+p2+p3+p4≧1; R ¹ , R ² , R ³ , R4, R5, m1, m2, m3, m4, m5 and k have the same meanings as those in the general formula ( ¹ ). A flame-retardant resin composition prepared by blending at least one of a thermosetting resin or a thermoplastic resin with the phosphorus-containing vinylbenzyl ether compound according to claim 1 or claim 2. A laminate for an electronic circuit board obtained by using the flame-retardant resin composition according to claim 4.

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