KR20220007546A - Phosphorus-containing vinyl benzyl ether compound, production method thereof, flame-retardant resin composition containing same, and laminate for electronic circuit board - Google Patents

Abstract

The present invention relates to a phosphorus-containing vinyl benzyl ether compound providing a cured product with excellent heat resistance and dielectric properties, a flame-retardant resin composition including the same, and a cured product thereof. The present invention provides a phosphorus-containing vinyl benzyl ether compound represented by chemical formula (1). In chemical formula (1), each Y independently represents a hydroxyl group or a vinylbenzyloxy group represented by chemical formula (2).

Description

Phosphorus-containing vinylbenzyl ether compound, manufacturing method thereof, flame retardant resin composition containing the same, and laminate for electronic circuit boards TECHNICAL FIELD }

The present invention relates to a reactive phosphorus compound, particularly a phosphorus-containing vinylbenzyl ether compound, and is useful as a reactive flame retardant for plastic materials.

BACKGROUND ART Plastic materials are used in a wide range of applications from excellent mechanical properties and moldability to building materials and electrical and electronic equipment. However, since most plastic materials are easily combustible, flame retardancy is essential for safety against exothermic ignition and fire in applications used, for example, electrical/electronic products, OA equipment, and communication equipment.

As a flame retardant technology for plastic materials, addition type flame retardants, such as halogen flame retardants, inorganic flame retardants, and phosphorus flame retardants, are not limited to resin types and uses, but are generally used. However, among these, halogen-based flame retardants, mainly bromine-based, have been pointed out as potential sources of high carcinogenic dioxin generation, and are progressing toward limiting their use in response to the recent movement to reduce environmental load substances. In addition, inorganic flame retardants such as magnesium hydroxide and aluminum hydroxide have a flame retardant effect due to endothermic heat.

Therefore, many phosphorus-based flame retardants are used that do not generate harmful substances and can be flame retarded with a relatively small amount of addition, but, nevertheless, effects on properties such as a decrease in workability due to bleed-out and a decrease in glass transition temperature are unavoidable. .

In order to solve the problem of these additive-type flame retardants, a reactive flame retardant containing a phosphorus atom as a flame retardant component and having a reactive group has been developed and widely used. As a reactive flame retardant applicable to the epoxy resin composition widely used in the field of electronics and electricity, for example, in Patent Document 1, as a curing agent for an epoxy resin, bisphenol A and formaldehyde are reacted to form hydroxymethylbisphenol A A phenol resin obtained by reacting 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (hereinafter abbreviated as "DOPO") after obtaining is disclosed, and in Patent Document 2, DOPO and The phosphorus containing epoxy resin obtained by making it react with an epoxy resin after making quinones react is disclosed. In these resins, the problem of workability, such as bleed-out of a flame retardant, is solved, and deterioration of thermal characteristics, such as heat resistance, is not seen. In this way, compared with the additive-type flame retardant, by using the reactive flame retardant, it is generally possible to compensate for the drawbacks of the additive-type flame retardant, and thus many flame-retardant epoxy resins and the like have been developed.

However, in recent years, in the field of electronic/electrical materials in which flame retardancy becomes essential, the demand for the resin component containing the flame retardant is changing with the rapid evolution of electronic devices typified by smartphones. In particular, in the field of information and communication, a low dielectric constant and a low dielectric loss tangent are strongly required for resin components used in this field in order to increase the frequency of signals and to reduce transmission loss along with the increase in the amount of information processing. Therefore, in the field of electronic and electrical materials typified by circuit boards, radically polymerizable resins capable of lower dielectric constant and lower dielectric loss tangent have come to be widely used instead of epoxy resins. Therefore, not only the flame retardant in which a reactive group has reactivity with an epoxy group or an epoxy resin, but also a halogen-free flame retardant of the low dielectric constant and low dielectric loss tangent which can react with radically polymerizable resin is calculated|required.

As a halogen-free flame retardant which has a radically polymerizable functional group, the vinylbenzyl ether compound which contains a DOPO skeleton in patent document 3 and patent document 4 is disclosed. However, in terms of low dielectric constant and low dielectric loss tangent, it cannot be said to be a sufficient characteristic, and there is not yet a flame retardant containing a radically polymerizable group that satisfies thermal properties such as halogen-free flame retardancy and heat resistance and dielectric properties.

Japanese Patent Laid-Open No. 2013-166938 Japanese Laid-Open Patent Publication No. Hei 11-279258 Japanese Patent Laid-Open No. 2004-331537 Japanese Laid-Open Patent Publication No. 2004-277322

Accordingly, the problem to be solved by the present invention is to provide a phosphorus-containing compound useful as a reactive phosphorus-based flame retardant and excellent in heat resistance and dielectric properties in a cured product, a flame-retardant resin composition containing the same, and a cured product thereof .

As a result of earnestly examining the said subject, this inventor discovered that the phosphorus containing vinylbenzyl ether compound which has a specific structure is excellent in heat resistance and dielectric characteristic, and led to this invention.

That is, this invention is a phosphorus containing vinyl benzyl ether compound represented by following General formula (1).

[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 represents the number of substitutions and is each independently an integer of 0 to 4. However, m1+m2+m3+m4 ≥ 4. When ^two or more R ¹ , R ^{2 , R 3} , R ⁴ or R ⁵ exist, a plurality of R ¹ , R ² , R ³ , R ⁴ or R ⁵ may be the same or different.

Y is each independently a hydroxyl group or a vinylbenzyloxy group represented by the following formula (2).

[Formula 2]

n1, n2, n3 and n4 represent the number of substitutions and are each independently an integer of 0-2. However, n1+n2+n3+n4≥1, and at least one of Y is a vinylbenzyloxy group. k is an integer of 0 to 10.)

As for the said phosphorus containing vinylbenzyl ether compound, it is preferable that n1 and n2 are 1, and it is preferable that n3 and n4 are 0.

The present invention is a method for producing a phosphorus-containing vinylbenzyl ether compound according to claim 1 or 2, wherein a phosphorus-containing phenol compound represented by the following general formula (3) is reacted with vinylbenzyl halide.

[Formula 3]

(In the general formula (3), p1, p2, p3 and p4 represent a substitution number and are each independently an integer of 0 to 2. However, p1+p2+p3+p4 ≥ 1. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , 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 characterized by blending one or more of a thermosetting resin or a thermoplastic resin with the phosphorus-containing vinylbenzyl ether compound, and further, a laminate for an electronic circuit board obtained by using the flame-retardant resin composition.

The phosphorus-containing vinylbenzyl ether compound of the present invention exhibits an unprecedented low dielectric constant and dielectric loss tangent, has little decrease in heat resistance, and is a reactive type that reduces transmission loss at high frequencies accompanying an increase in information throughput of electronic devices. It is very useful as a phosphorus-based flame retardant.

1 is an FD-MS analysis result of phosphorus-containing vinylbenzyl ether A obtained in Example 1. FIG.
Fig. 2 is an FD-MS analysis result of the phosphorus-containing vinylbenzyl ether B obtained in Example 2.

Hereinafter, the present invention will be described in detail.

In the description of the present invention, the phosphorus-containing vinylbenzyl ether compound or phosphorus-containing phenolic 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).

[Formula 4]

In the phosphorus-containing vinylbenzyl ether compound of the general formula (1), the compound in which the substituent Y exists at the para position with respect to the phosphate ester bond is preferable.

^{Specific examples of the alkyl group for R 1} , R ² , R ³ and R ⁴ in formula (1) include, for example, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl , n-pentyl, isopentyl, neopentyl, and the like. Among these, a methyl group is especially preferable from a viewpoint of the reactivity in a manufacturing surface, and easiness of availability. By integrating the R ^1, R ^2, R ³ and R ⁴ R ^h is represented by (h is an integer of 1 to 4), if each of R ^h a plurality is present, each R ^h is may be the same or different do.

In Formula (1), m1, m2, m3, and m4 represent the substitution number of the said alkyl group couple|bonded with each benzene ring. Here, m1, m2, m3, and m4 are each independently an integer of 0 or more and 4 or less. However, m1+m2+m3+m4≥4, Preferably it is m1+m2+m3+m4≥6. In m1, m2, m3 and m4, preferably, 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.

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 at the ortho or 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 at the ortho or meta position with respect to the phosphate bond, and R ¹ , R ² , R ³ and R ^{At least one substituent of 4} is present in the ortho position. When one or more alkyl groups exist in an ortho position with respect to a phosphate ester bond, a phosphate ester site|part is hydrophobically shielded, and it becomes possible also to suppress hydrolysis.

In Formula (1), Y is each independently a phenolic hydroxyl group or a vinylbenzyl ether group represented by Formula (2).

[Formula 5]

In Formula (2), although the substitution position on the benzene ring of a vinyl group is not specifically limited, A meta position or a para position is preferable with respect to the bonding position of a methylene oxide chain|strand. n1, n2, n3 and n4 represent the substitution number of the phenolic hydroxyl group couple|bonded with each benzene ring, or the substituent represented by 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 n1, n2, n3 or n4 is 1 or more, and has at least 1 or more, preferably 2 or more vinylbenzyl ether groups represented by Formula (2) in a molecule|numerator. By having one or more vinyl benzyl ether groups represented by Formula (2), the flame-retardant component is particularly fixed in the vinyl resin in the cured product, and it is not possible to bleed out, and it becomes possible to suppress a decrease in heat resistance.

Among the phosphorus-containing vinylbenzyl ether compounds 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 at the para position with respect to the phosphate ester bond.

Formula (1), can be substituted, which combine on a single benzene ring, represented by the number of substitution of Y nh and mh + nh sum of substitution can mh of the alkyl group R ^h (h is an integer of 1 to 4). In each benzene ring, the sum mh+nh of the number of substitutions is 5 or less, Preferably it is 4 or less.

In Formula (1), R<^5> is a C1-C5 linear or branched alkyl group. Specific examples of the alkyl group for R ⁵ include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, and neopentyl. From the viewpoint of reactivity in production and ease of availability, a methyl group is particularly preferred. When R ⁵ is plural, 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 a phosphate ester bond. As an average value of k, it is 0 or more and 5.0 or less, Preferably it is 0 or more and 3.0 or less, More preferably, it is a number of 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 to 20% by weight, more preferably 2.0 to 10% by weight, and still more preferably 3.0 to 7.0% by weight.

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

[Formula 6]

In the general formula (3), p1, p2, p3, and p4 represent the number of hydroxyl group substitutions, 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 are common corresponding to Formula (1), and follow the detailed description above. .

The phosphorus content rate of the phosphorus containing phenol compound represented by General formula (3) becomes like this. Preferably it is 1.0 to 20 weight%, More preferably, it is 3.0 to 10 weight%, More preferably, it is 5.0 to 8.0 weight%. The hydroxyl equivalent is preferably 100 to 1000, more preferably 150 to 500, still more preferably 200 to 350.

As a specific example of the phosphorus containing phenol compound represented by Formula (3), the compound represented by the following Formula (4) - (7) is mentioned, for example.

[Formula 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 an example of the reaction form is an esterification reaction using phosphorus oxychloride (phosphoryl chloride) and phenols as raw materials. , a corresponding phosphoric acid ester can be obtained by a dehydrochlorination reaction. Moreover, since the phosphorus containing phenol compound of Formula (3) has one or more phenolic hydroxyl groups, it is calculated|required that one or more of the phenols which are raw materials are benzene compounds which have two or more hydroxyl groups.

The phosphorus containing vinyl benzyl ether compound of this invention can be obtained by reaction of the phosphorus containing phenol compound and vinylbenzyl halide represented by Formula (3).

Examples of the vinylbenzyl halide used in the present invention include, but are not limited to, p-vinylbenzyl chloride, m-vinylbenzyl chloride, p-vinylbenzyl bromide, m-vinylbenzyl bromide, and the like. , may be used independently, or two or more types may be mixed and used for it. Commercially available products include CMS-14 (manufactured by AGC Semi Chemical Co., Ltd., p-vinyl benzyl chloride), CMS-P (manufactured by AGC Semi Chemical Co., Ltd., a mixture of p-vinyl benzyl chloride and m-vinyl benzyl chloride) and the like. can

Vinylbenzyl halide is 0.8-4.0 mol, 0.95-2.0 mol is preferable, and, as for the compounding ratio of a phosphorus containing phenol compound and vinylbenzyl halide, with respect to 1 mol of hydroxyl groups in a phosphorus containing phenol compound, 1.0-1.5 mol is more preferable. When the amount of vinylbenzyl halide is less than 0.8 mol with respect to 1 mol of the phosphorus-containing phenol compound, the number of residual hydroxyl groups increases and heat resistance decreases, and when it exceeds 4.0 mol, the residual amount of unreacted vinylbenzyl halide increases, or side reaction of the polymer becomes excessively large.

In the reaction of the phosphorus-containing phenol compound represented by the formula (3) and vinylbenzyl halide, it is preferable to react with the halogen of vinylbenzyl halide and to add an alkaline compound in order to accelerate the reaction with the phosphorus-containing phenol compound. Examples of the alkaline 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 alkaline compounds such as carbonates of alkali metals such as sodium carbonate and potassium carbonate. have. Among them, carbonates of alkali metals are preferable from the viewpoints of the accelerating effect of the reaction and suppression of hydrolysis. Moreover, it may be used independently and may use 2 or more types together. Moreover, although you may use with solid or you may use with solutions, such as aqueous solution, aqueous solution is preferable. The usage-amount of an alkaline compound is 0.5-5.0 mol with respect to 1 mol of vinylbenzyl halide, 1-4 mol is preferable, and its 1.2-3 mol is more preferable. When the amount of the alkaline compound used is less than 0.5 mol, the reaction is not sufficiently performed. On the other hand, when it exceeds 5.0 mol, it is economically unpreferable, such as a large amount of acid required for neutralization is needed.

A catalyst can also be used for reaction as needed. Examples of the catalyst to be used include tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, and tetrabutylammonium bromide, triphenylphosphine, tris( Phosphines such as 2,6-dimethoxyphenyl) phosphine, phosphonium salts such as benzyltriphenylphosphonium chloride, tetrabutylphosphonium bromide, ethyltriphenylphosphonium bromide, and tetrabutylphosphonium iodide; Although various catalysts, such as imidazoles, such as 2-methylimidazole and 2-ethyl- 4-methylimidazole, are mentioned, It is not limited to these, You may use independently and may use 2 or more types together. . The amount of the catalyst used is 10 parts by weight or less with respect to 100 parts by weight of the raw material.

The solvent used for the reaction is not particularly limited, and hydrocarbons such as hexane, heptane, octane, decane, dimethylbutane, pentene, cyclohexane, methylcyclohexane, benzene, toluene, xylene, and ethylbenzene, methanol, and ethanol Alcohols such as , propanol, butanol, amyl alcohol, pentanol, hexanol, methyl amyl alcohol, heptanol, cyclohexanol, benzyl alcohol, furfuryl alcohol, ethyl ether, isopropyl ether, butyl ether, diisoamyl ether Ethers such as methylphenyl ether, ethylphenyl ether, amylphenyl ether, ethylbenzyl ether, dioxane, methylfuran, tetrahydrofuran, acetone, methylacetone, methylethylketone, methylpropylketone, methylbutylketone, methylamylketone , diethyl ketone, ethyl butyl ketone, dipropyl ketone, ketones such as cyclohexanone, methyl cellosolve, methyl cellosolve acetate, ethyl cellosolve, cellosolve acetate, ethylene glycol isopropyl ether, diethylene glycol Although dimethyl ether, methyl ethyl carbitol, propylene glycol monomethyl ether, dimethylformamide, dimethyl sulfoxide, etc. are mentioned, It is not limited to these, You may use individually, or you may use it in mixture of 2 or more types. In addition, when the salt generated in the reaction is removed by washing with water, it is preferable to use a solvent capable of separating the aqueous layer. For example, benzene, toluene, xylene, methyl ethyl ketone, methyl isobutyl ketone, etc. are mentioned.

You may carry out the reaction in presence of a polymerization inhibitor. By adding the polymerization inhibitor, it is possible to prevent the vinylbenzyl halide or the target product, the vinylbenzyl ether compound, from being polymerized to form an oligomer. A known polymerization inhibitor can be used without limitation, hydroquinone, hydroxymonomethyl ether, t-butylcatechol, t-butylhydroquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, phenol In addition to organic compounds, such as nothiazine, copper compounds, such as copper chloride and copper sulfide, etc. are mentioned, You may use combining these.

After completion of this reaction, the obtained reaction solution (reaction mixture) is subjected to distillation removal of the reaction solvent, solvent substitution, etc., if necessary, followed by washing with water, activated carbon treatment, silica gel chromatography, etc. By purification, the target product, the vinyl benzyl ether compound of the present invention, can be extracted.

Next, a flame retardant resin composition comprising the phosphorus-containing vinylbenzyl ether compound of the present invention as an essential component and blending one or more of a curable resin and/or a thermoplastic resin 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 a phosphorus-containing vinylbenzyl ether compound may be blended with respect to 100 parts by weight of the total amount of the curable resin and the thermoplastic resin. Preferably it is 50-250 weight part, More preferably, it is 70-230 weight part.

Examples of the curable resin include unsaturated polyester resins, curable maleimide resins, epoxy resins, polycyanate resins, phenol resins, and one or more vinyl compounds having one or more polymerizable unsaturated hydrocarbon groups in the molecule. and preferably an epoxy resin, at least one vinyl compound having at least one polymerizable unsaturated hydrocarbon group in the molecule.

When curable resin is an epoxy resin, it is preferable that it is 1 or more types of epoxy resins chosen from the epoxy resin which has two or more epoxy groups in 1 molecule. As such an epoxy resin, a cresol novolak-type epoxy resin, a triphenylmethane-type epoxy resin, a biphenyl epoxy resin, a naphthalene-type epoxy resin, a bisphenol A-type epoxy resin, a bisphenol F-type epoxy resin, etc. are mentioned. These may be used independently and may be used in combination of 2 or more type. By using such an epoxy resin, it is thought that the influence on the outstanding dielectric property and fluidity|liquidity which the flame-retardant resin composition of this invention has is minimized, and the heat resistance and adhesiveness of hardened|cured material can fully be improved.

In addition, when containing an epoxy resin, you may use a hardening|curing agent other than an epoxy resin. The curing agent is not particularly limited, and for example, a phenol-based curing agent, an amine-based compound, an amide-based compound, an acid anhydride-based compound, a naphthol-based curing agent, an active ester-based curing agent, a benzoxazine-based curing agent, a cyanate ester-based curing agent, etc. can be heard You may use these 1 type or in combination of 2 or more types.

In addition, when mix|blending 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 to 5 parts by weight with respect to 100 parts by weight of the epoxy resin.

As the curable resin, in the case of one or more vinyl compounds having one or more polymerizable unsaturated hydrocarbon groups in the molecule (hereinafter also referred to as vinyl compounds), the type is not particularly limited. That is, what is necessary is just to form bridge|crosslinking and harden|cure vinyl compounds by making them react with the phosphorus containing vinyl benzyl ether compound of this invention. It is more preferable that the polymerizable unsaturated hydrocarbon group is a carbon-carbon unsaturated double bond, and a compound having two or more carbon-carbon unsaturated double bonds in the molecule is more preferable.

The average number of carbon-carbon unsaturated double bonds per molecule of vinyl compounds as the curable resin (the number of vinyl groups (including substituted vinyl groups; also referred to as the number of terminal double bonds)) varies depending on the Mw of the vinyl compounds. , For example, it is preferable that it is 1-20, and it is more preferable that it is 2-18. When the number of these terminal double bonds is too small, it tends to be difficult to obtain a sufficient heat resistance of the cured product. Moreover, when there are too many terminal double bonds, the reactivity becomes high too much, for example, there exists a possibility that the storage stability of curable resin composition may fall, and there exists a possibility that problems, such as the fluidity|liquidity of curable resin composition falling, may arise.

Examples of the vinyl compounds include trialkenyl isocyanurate compounds such as triallyl isocyanurate (TAIC), modified polyphenylene ethers (PPE) whose ends are modified with (meth)acryloyl groups or styryl groups, molecules Polyfunctional (meth)acrylate compounds having two or more (meth)acryloyl groups in the molecule, vinyl compounds (polyfunctional vinyl compounds) having two or more vinyl groups in the molecule, such as polybutadiene, and styrene, divinylbenzene, etc. A vinylbenzyl compound etc. are mentioned. Among these, those having two or more carbon-carbon double bonds in the molecule are preferable, and specific examples thereof include TAIC, polyfunctional (meth)acrylate compounds, modified PPE resins, polyfunctional vinyl compounds and divinylbenzene compounds. can When these are used, it is thought that bridge|crosslinking is formed more suitably by hardening reaction, and the heat resistance of the hardened|cured material of curable resin composition can be improved more. In addition, these may be used independently and may be used in combination of 2 or more type. 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 the thermoplastic resin include polystyrene, polyphenylene ether resin, polyetherimide resin, polyethersulfone resin, PPS resin, polycyclopentadiene resin, polycycloolefin resin, and known thermoplastic resins. Elastomers (eg, styrene-ethylene-propylene copolymer, styrene-ethylene-butylene copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, hydrogenated styrene-butadiene copolymer, hydrogenated styrene-isoprene copolymer etc.) or rubbers (for example, polybutadiene, polyisoprene). Preferably, polyphenylene ether resin (unmodified|denatured) and hydrogenated styrene-butadiene copolymer are mentioned.

You may mix|blend a radical polymerization initiator (a polymerization catalyst thru|or a crosslinking agent) with the resin composition of this invention. Examples of the radical initiator include benzoyl peroxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne- 3, di-t-butyl peroxide, t-butylcumyl peroxide, 1,3-bis(butylperoxyisopropyl)benzene, α,α'-bis(t-butylperoxy-m-isopropyl)benzene , 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, dicumyl peroxide, di-t-butylperoxyisophthalate, t-butylperoxybenzoate, 2,2-bis(t -Butylperoxy)butane, 2,2-bis(t-butylperoxy)octane, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, di(trimethylsilyl)peroxide, trimethylsilyltri Peroxides such as phenylsilyl peroxide, but are not limited thereto. Moreover, although it is not a peroxide, 2, 3- dimethyl-2, 3- diphenyl butane can also be used as a radical polymerization initiator. However, it is not limited to these examples, You may use combining 2 or more types of radical initiators.

To [ the compounding quantity of a radical polymerization initiator / 100 weight part of phosphorus containing vinylbenzyl ether compounds ], Preferably it is 0.01-10 weight part, More preferably, it is 0.1-5 weight part.

A filler can be mix|blended with the flame-retardant resin composition of this invention. Examples of the filler include those added in order to increase heat resistance and flame retardancy of the flame retardant resin composition and cured product thereof, and a known filler can be used, but is not particularly limited. Moreover, heat resistance, dimensional stability, a flame retardance, etc. can be improved further by containing a filler. Specific examples include silica such as spherical silica, metal oxides such as alumina, titanium oxide and mica, metal hydroxides such as aluminum hydroxide and magnesium hydroxide, talc, aluminum borate, barium sulfate, and calcium carbonate. When metal hydroxides, such as aluminum hydroxide and magnesium hydroxide, are used, it acts as a flame retardant auxiliary agent, and a phosphorus content rate can ensure flame retardance at least. Among these, silica, mica, and talc are preferable, and spherical silica is more preferable. In addition, these may be used individually by 1 type, and may be used in combination of 2 or more type.

Although the filler may be used as it is, what surface-treated with silane coupling agents, such as an epoxysilane type or an aminosilane type, may be used. As this silane coupling agent, the silane coupling agent of a vinylsilane type, a methacryloxysilane type, an acryloxysilane type, and a styrylsilane type is preferable from a reactive viewpoint with a radical polymerization initiator. Thereby, the adhesive strength with metal foil and the interlayer adhesive strength of resin become high. In addition, instead of the method of surface-treating a filler beforehand, you may add and use the said silane coupling agent by the integral blend method.

The content of the filler is preferably 10 to 200 parts by weight, preferably 30 to 150 parts by weight, based on 100 parts by weight in total of the solid content (including organic components such as monomers and flame retardants, and excluding solvents) excluding the filler. do.

The resin composition of the present invention may further contain additives other than the above. Examples of the additive include defoaming agents such as silicone-based anti-foaming agents and acrylic acid ester-based anti-foaming agents, heat stabilizers, antistatic agents, ultraviolet absorbers, dyes and pigments, lubricants, and dispersing agents such as wetting and dispersing agents.

The flame-retardant resin composition of the present invention or a cured product obtained by curing the same can be used as a molded product, a laminate, a cast product, an adhesive, a coating film, or a film. For example, the cured product of the semiconductor encapsulation material is a mold or a molded product, and as a method of obtaining a cured product for such use, a flame retardant resin composition is molded using a mold, a transfer molding machine, an injection molding machine, etc., and then again 80 to A hardened|cured material can be obtained by heating at 230 degreeC for 0.5 to 10 hours.

The flame-retardant resin composition of this invention can also be used as a prepreg. When manufacturing a prepreg, it can prepare in the form of a varnish for the objective of making it impregnate to the base material (fibrous base material) for forming a prepreg, or set it as the circuit board material which forms a circuit board, It can be set as resin varnish. This resin varnish is suitable for circuit boards, and can be used as a varnish for circuit board materials. In addition, specifically, a printed wiring board, a printed circuit board, a flexible printed wiring board, a build-up wiring board, etc. are mentioned as the use of the circuit board material here.

As an organic solvent used for said resin varnish, if hardening reaction is not inhibited, 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; Polar solvents, such as dimethylacetamide and dimethylformamide; Aromatic hydrocarbon solvents, such as toluene and xylene, etc. are mentioned, It is also possible to use these 1 type or in mixture of 2 or more types. From the viewpoint of dielectric properties, aromatic hydrocarbons such as benzene, toluene and xylene are preferable.

When producing 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, particularly preferably 20 to 100 parts by weight of the flame-retardant resin composition of the present invention. to 500 parts by weight.

As the base material used for producing the prepreg, a known material is used, but for example, a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. is each alone, or It is used in combination of two or more types. A coupling agent can be used for these base materials in order to improve the adhesiveness in the interface of resin and a base material as needed. As a coupling agent, common things, such as a silane coupling agent, a titanate coupling agent, an aluminum type coupling agent, and a zircoaluminate coupling agent, can be used.

As a method of obtaining a prepreg, after making a base material impregnate the said resin varnish, the method of drying is mentioned. Impregnation is carried out by dipping (dipping), application or the like. It is also possible to repeat the impregnation a plurality of times if necessary, and at this time, it is also possible to repeat the impregnation using a plurality of solutions having different compositions and concentrations to finally adjust the resin composition and amount of the resin to be desired. After impregnation, a prepreg can be obtained by heat-drying at 100-180 degreeC for 1 to 30 minutes. Here, it is preferable that the amount of resin in a prepreg sets it as 30 to 80 weight% of resin content.

The flame retardant resin composition of the present invention. It can also be used as a laminated board. When a laminate is formed using a prepreg, one or a plurality of prepregs are laminated, a metal foil is disposed on one side or both sides to form a laminate, and the laminate is heated and pressurized to form a laminated body. Here, as metal foil, single, alloy, composite metal foils, such as copper, aluminum, brass, and nickel, can be used. As the conditions for heat and pressurizing the laminate, heat and pressurization may be performed by appropriately adjusting the conditions for curing the flame retardant resin composition. When the pressure of pressurization is too low, bubbles remain inside the obtained laminate, and when the electrical properties are lowered Therefore, it is preferable to pressurize under conditions that satisfy moldability. For example, the temperature can be set to 180 to 250° C., the pressure to be 49.0 to 490.3 N/cm 2 (5 to 50 kgf/cm 2 ), and the heat and press time can be set to 40 to 240 minutes, respectively. Moreover, a multilayer board can be produced using the single-layer laminated board obtained in this way as an inner layer material. In this case, first, circuit formation is performed on the laminate by an additive method, a subtractive method, or the like, and the formed circuit surface is treated with an acid solution to perform blackening treatment to obtain an inner layer material. A multilayer board is formed by forming an insulating layer with a resin sheet, a metal foil with a resin, or a prepreg on one or both circuit formation surfaces of this inner layer material, and forming a conductor layer on the surface of the insulating layer.

In addition, the flame retardant composition of the present invention may be used in a build-up film. As for the method of manufacturing a buildup film from the resin composition of this invention, the method of apply|coating and drying the said resin varnish on a support film, and forming a film-form insulating layer is mentioned, for example. The film-form insulating layer formed in this way can be used as a buildup film for multilayer printed wiring boards.

Example

Next, although an Example demonstrates this invention, this invention is not limited by these. All parts in each example are parts by weight.

In addition, the measurement of the physical property in a synthesis example and an Example was performed by the method shown below.

(1) Hydroxyl equivalent: Measured in accordance with JIS K 0070 standard. Specifically, using a potentiometric titrator, using 1,4-dioxane as a solvent, acetylation is carried out with 1.5 mol/L acetyl chloride, and excess acetyl chloride is decomposed with water to 0.5 mol/L-hydroxylated Titrated with potassium.

(2) Phosphorus content: Sulfuric acid, hydrochloric acid and perchloric acid were added to the sample, heated to wet incineration, and all phosphorus atoms were converted to orthophosphoric acid. Phosphorus atom content obtained by reacting metavanadate and molybdate in an acidic sulfuric acid solution, measuring the absorbance at 420 nm of the produced phosphorus vanadmolybdic acid complex, and using a calibration curve prepared in advance using potassium dihydrogen phosphate. was expressed as %.

(3) Electric field desorption mass spectrometry (FD-MS): The molecular weight was measured by JMS-T100GCV by JEOL.

(4) Glass transition temperature: It was calculated|required from the baseline shift at the temperature increase rate of 10 degreeC/min using differential scanning calorimetry.

(5) Relative dielectric constant and dielectric loss tangent: The dielectric constant and dielectric loss tangent at a frequency of 1 GHz were determined by the capacitance method using a material analyzer (manufactured by AGILENT Technologies) in accordance with the IPC-TM-650 2.5.5.9 standard.

(6) Flame retardancy: In accordance with UL94, the vertical method evaluated. Evaluation was described as V-0, V-1, and V-2. Those for which flame retardancy was not obtained were marked as N.C (not classified) except for classification.

(7) Tackiness: In order to confirm the presence or absence of bleed-out, the tackiness was confirmed by accelerating the sample surface after hardening. Those without tags were evaluated as ○ and those with tags as ×.

(Synthesis Example 1) Synthesis of phosphorus-containing phenol A

1500 g of phosphorus oxychloride, 471 g of phenol, and 1.2 g of magnesium chloride as a catalyst were charged to a 2-liter 4-neck flask equipped with a stirrer, a thermometer, and a hydrochloric acid recovery device (condenser to which a water scrubber was connected).

While stirring the obtained mixed solution, it was made to react by heating it up to 90 degreeC gradually over about 3 hours, and the generated hydrogen chloride (hydrochloric acid gas) was collect|recovered with a water scrubber. Then, the pressure in a flask was reduced gradually to 12 kPa at 120 degreeC, unreacted phosphorus oxychloride, phenol, and hydrogen chloride by-produced were removed, and 1055 g of monophenyl phosphoro dichloridate (MPC) was obtained.

In a 2-liter 4-neck flask equipped with a stirrer, thermometer, dropping funnel and condenser, 822 g of 2,3,5-trimethylhydroquinone, 6.3 g of aluminum chloride as a catalyst, and 1000 g of 1,2-dichlorobenzene as a solvent were added charged. Moreover, the said MPC 570g was filled in the dropping funnel.

The MPC in the dropping funnel was dripped over 2 hours, heating to the temperature of 110 degreeC, stirring the mixed solution in a four neck flask, and maintaining at the same temperature (110 degreeC). It heated gradually to 160 degreeC after completion|finish of dripping, and it stirred for 4 hours, and obtained the reaction product. Then, it cooled to 105 degreeC, the pressure in the flask was gradually reduced to 6.3 kPa, and hydrogen chloride by-produced was removed.

The obtained reaction product was washed with diluted hydrochloric acid and water, then neutralized with an aqueous sodium carbonate solution, and washed again with water. Then, it heated to the temperature of 150 degreeC, and it pressure-reduced to 1 kPa, and water and 1,2-dichlorobenzene were collect|recovered. Further, under a reduced pressure of 1 kPa, steam distillation was performed at a temperature of 110°C to distill off the low-boiling point component, and then cooled to room temperature to obtain 1195 g of a black-brown solid phosphorus-containing phenol compound A. The phosphorus content of the compound A as the obtained mixture was 6.5%, and the hydroxyl equivalent was 272 g/eq.

(Synthesis Example 2) Synthesis of phosphorus-containing phenol B

A 2-liter 4-neck flask equipped with a stirrer, a thermometer and a hydrochloric acid recovery device (condenser to which a water scrubber is connected) was charged with 1500 g of phosphorus oxychloride, 611 g of 2,6-dimethylphenol, and 1.2 g of magnesium chloride as a catalyst. .

While stirring the obtained mixed solution, it was reacted by heating to a temperature of 110°C gradually over about 3 hours, and the generated hydrogen chloride (hydrochloric acid gas) was recovered with a water scrubber. Thereafter, the pressure in the flask was gradually reduced to 12 kPa at 120°C, unreacted phosphorus oxychloride, phenol, and hydrogen chloride by-products were removed to obtain 1200 g of mono2,6-dimethylphenylphosphorodichloridate. .

A 2-liter 4-neck 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 200 g of toluene as a solvent. Further, 203 g of the mono2,6-dimethylphenylphosphorodichloridate was charged into the dropping funnel.

The mixed solution in the 4-neck flask was heated to a temperature of 20°C while stirring, and the mono2,6-dimethylphenylphosphorodichloridate in the dropping funnel was added dropwise over 2 hours while maintaining the same temperature (20°C). After completion|finish of dripping, it heated to 65 degreeC, and it stirred for 5 hours, and obtained the reaction product. The obtained reaction product was washed with dilute hydrochloric acid and water, heated to a temperature of 150° C., reduced pressure to 2 kPa, water, toluene, and low-boiling components were distilled off, and cooled to room temperature to obtain 330 g of a blackish-brown solid phosphorus-containing phenol compound B. The phosphorus content of the compound B as the obtained mixture was 6.5%, and the hydroxyl equivalent was 272 g/eq.

(Example 1) Synthesis of phosphorus-containing vinylbenzyl ether compound A

In a glass separable flask equipped with a stirring device, a thermometer, and a cooling tube, 200.0 g of phosphorus-containing phenol compound A and 133.2 g of diethylene glycol dimethyl ether were charged, and the mixture was heated and dissolved at 75°C in a nitrogen atmosphere. After adding CMS-P 134.0g and becoming uniform, 10.0g of tetrabutylammonium bromide, 222.4g of 50% potassium carbonate aqueous solution were added, and reaction was performed for 10 hours.

Then, the reaction liquid was concentrated, and after melt|dissolving in 674.4 g of toluene, the reaction liquid was neutralized with 10% sodium dihydrogen phosphate aqueous solution, and water wash|cleaning was performed. Furthermore, 340.0 g of toluene solutions of phosphorus containing vinylbenzyl ether compound A were obtained by dehydrating, filtration, and concentrating a solvent again. The obtained compound A was analyzed by FD-MS, and since a peak having a molecular weight of 674 was confirmed, it was confirmed that the compound having the following structure was the main component. In addition, the phosphorus content was 4.7%.

[Formula 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 and 133.2 g of diethylene glycol dimethyl ether were charged, and the mixture was heated and dissolved at 75° C. in a nitrogen atmosphere. After adding CMS-P 128.6g and becoming uniform, 8.2g of tetrabutylammonium bromide, 213.4g of 50% potassium carbonate aqueous solution were added, and reaction was performed for 15 hours.

Then, the reaction liquid was concentrated, and after melt|dissolving in 665.0 g of toluene, the reaction liquid was neutralized with 10% sodium dihydrogen phosphate aqueous solution, and water wash|cleaning was performed. Furthermore, by dehydrating, filtration, and concentrating a solvent again, 381.5 g of toluene solutions of the phosphorus containing vinyl benzyl ether compound B were obtained. The obtained compound B was analyzed by FD-MS, and from the point which confirmed the peak of molecular weight 704, it confirmed that the compound of the following structure was a main component. In addition, the phosphorus content was 4.6%.

[Formula 9]

(Comparative Example 1)

It synthesized according to the synthesis example of patent document 3. Specifically, 340 parts of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, toluene 660 in a glass separable flask equipped with a stirring device, a thermometer, a cooling tube, and an oxygen gas introduction device. parts were poured and dissolved at 80°C. 245 parts of 1,4-naphthoquinone were added in portions, paying attention to the reaction exotherm. The reaction was continued, the temperature was raised to 110°C, and the reaction was carried out again. After 3 hours, a slurry solution in which dark brown crystals were precipitated was obtained. The crystals were separated by filtration, and the crystals were dispersed in 500 parts of methanol. After performing this operation 3 times, drying was performed in a hot air circulation oven. 93.5 parts of the obtained pale yellow powder of the phosphorus-containing phenolic compound 10-(2,5-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 140.5 parts of dimethyl sulfoxide as a solvent; 93.5 parts of methyl isobutyl ketone, 77.8 parts of CMS-P as vinylbenzyl halide, 0.20 parts of tetramethylammonium chloride as a catalyst, 74.2 parts of 48.5% sodium hydroxide aqueous solution as an alkali metal, 0.16 parts of trimethylhydroquinone as a polymerization inhibitor, It neutralized with 35% hydrochloric acid until pH was set to 5-6, and the lower aqueous layer was separated and removed. Washing with water and separating and removing the water layer were repeated 3 to 5 times while adjusting the pH to 7 to 6 with an aqueous sodium dihydrogen phosphate solution. Reflux dehydration was performed, solution filtration was performed, solvent collection|recovery was performed, and the phosphorus containing vinyl benzyl ether compound C was obtained. The phosphorus content of the obtained compound was 4.2%.

(Comparative Example 2)

It synthesized according to the synthesis example of patent document 4. Specifically, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide 150 as a phosphorus compound in a glass separable flask equipped with a stirring device, a thermometer, a cooling tube, and an oxygen gas introduction device Part, 70 parts of toluene as a reaction solvent, 20 parts of isopropyl alcohol, 120 parts of CMS-P as vinylbenzyl halide, and 2.7 parts of tetramethylammonium chloride as a catalyst were injected and heated to dissolve. Thereafter, 127 parts of a 48.5% aqueous sodium hydroxide solution as an alkali metal was charged in portions, paying attention to the temperature rise due to the reaction exotherm. The reaction was carried out by maintaining the temperature at 70°C to 80°C, and the residual amount of CMS-P was traced by gas chromatography. The residual amount of CMS-P decreased, it was confirmed that the reaction was sufficiently performed, and the mixture was diluted with toluene. Neutralization was carried out with hydrochloric acid, and the resulting sodium chloride was removed by filtration. Furthermore, water washing was performed to remove ionic impurities. Dehydration and solvent removal were performed by heating and reduced pressure to obtain the phosphorus-containing vinylbenzyl compound D in the form of a pale yellow solid. As a result of measuring the phosphorus content of the said compound D, it was 9.3 %.

Examples 3 to 6, Comparative Examples 3 to 11

<Adjustment of flame retardant resin composition and production of cured product>

A varnish was prepared by blending various components in the ratio of Table 1, applied on a PET film, and dried in an oven at 130° C. for 5 minutes to prepare a film of a resin composition. Next, the powder of the resin composition was obtained by grind|pulverizing this film. Further, a sample of the cured product was obtained by sandwiching this powder on a stainless steel mirror plate together with a spacer, and molding the powder at 210 DEG C for 90 minutes using a vacuum oven.

<Preparation of flame-retardant test piece>

A varnish was prepared by blending various components in the proportions shown in Table 1, and after impregnating this resin varnish into a glass cloth (manufactured by Nitto Spinning Co., Ltd.; 7628 type; product number H258), it was dried by heating at 130° C. for 5 minutes, and a prepreg got

8 sheets of prepreg obtained and copper foil (manufactured by Mitsui Metals Mining Co., Ltd., 3EC-III, thickness 35 µm) were superimposed on top and bottom, and vacuum pressing was performed at 2 MPa under the temperature conditions of 130 ° C. × 15 minutes + 190 ° C. × 80 minutes. Thus, a laminated sheet having a thickness of 1.6 mm was obtained. A flame-retardant test piece was obtained by etching and cutting copper foil.

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

TXP: Trizyrenyl phosphate manufactured by Daihachi Chemical Industry Co., Ltd., phosphorus content 9.5%

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

Perbutyl P: 1,3-bis(butylperoxyisopropyl)benzene manufactured by Nichiyo Co., Ltd.

The results are shown in Table 2.

Claims (5)

A phosphorus-containing vinylbenzyl ether compound 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 represents the number of substitutions and is each independently an integer of 0 to 4. However, m1+m2+m3+m4 ≥ 4. When ^two or more R ¹ , R ^{2 , R 3} , R ⁴ or R ⁵ exist, a plurality of R ¹ , R ² , R ³ , R ⁴ or R ⁵ may be the same or different.
Y is each independently a hydroxyl group or a vinylbenzyloxy group represented by the following formula (2).

n1, n2, n3 and n4 represent the number of substitutions and are each independently an integer of 0-2. However, n1+n2+n3+n4≥1, and at least one of Y is a vinylbenzyloxy group. k is an integer of 0 to 10.) The method of claim 1,
A phosphorus-containing vinylbenzyl ether compound, wherein n1 and n2 are 1 and n3 and n4 are 0. 3. The method of claim 1 or 2,
A method for producing a phosphorus-containing vinylbenzyl ether compound, comprising reacting a phosphorus-containing phenol compound represented by the following general formula (3) with a vinylbenzyl halide.

(In the general formula (3), p1, p2, p3 and p4 represent a substitution number and are each independently an integer of 0 to 2. However, p1+p2+p3+p4 ≥ 1. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , m1, m2, m3, m4, m5 and k have the same meanings as those in the general formula (1).) A flame-retardant resin composition comprising at least one of a thermosetting resin or a thermoplastic resin blended with the phosphorus-containing vinylbenzyl ether compound according to claim 1 or 2. The laminated board for electronic circuit boards obtained using the flame-retardant resin composition of Claim 4.

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