Phosphorus-containing vinyl benzyl ether compound and method for producing the same, resin composition and laminate for circuit board

Abstract

The present invention provides a vinyl benzyl ether compound having excellent low dielectric properties, heat resistance and halogen-free flame retardancy in a cured product and a method for producing the same, as well as a resin composition and a laminate for a circuit board using the vinyl benzyl ether compound, which impart excellent cured product properties (especially dielectric properties) in particular for use in printed wiring boards. The present invention is a phosphorus-containing vinyl benzyl ether compound represented by the following formula (1) obtained by reacting a specific phosphorus-containing phenol compound with a vinyl benzyl halide, and the resin composition containing the vinyl benzyl ether compound as an essential component has halogen-free flame retardancy and can obtain a cured product having excellent dielectric properties, heat resistance, etc.

Description

Technical Field

[0001] The present invention relates to a vinyl benzyl ether compound containing a phosphorus atom in the molecule, and to a flame-retardant resin composition containing the compound as an essential component, particularly a resin composition for producing a copper-clad laminate used in an electronic circuit substrate, or a sealing material, molding material, injection molding material, adhesive, electrical insulating coating, film material, etc. used in electronic parts, which requires flame retardancy or heat resistance. Background Art

[0002] Patent Document 1 discloses vinyl benzyl ethers of polyphenols such as bisphenol A and bisphenol S. Patent Document 2 discloses vinyl compounds that have been imparted with flame retardancy without using halogen. However, heat resistance is insufficient in some applications requiring high properties.

[0003] [Prior art literature]

[0004] [Patent Document]

[0005] [Patent Document 1] U.S. Patent No. 4,116,936

[0006] [Patent Document 2] Japanese Patent Publication No. 2004-331537 Summary of the invention

[0007] [Problems to be solved by the invention]

[0008] The problem to be solved by the present invention is to provide a vinyl benzyl ether compound having excellent low dielectric properties, heat resistance and halogen-free flame retardancy in a cured product, and a resin composition using the vinyl benzyl ether compound that imparts excellent cured product properties (especially dielectric properties) in particular for printed wiring board applications, a circuit board material, and a cured product thereof.

[0009] [Technical means to solve the problem]

[0010] In order to solve the above-mentioned problems, the present inventors have conducted intensive research on vinyl compounds having excellent heat resistance and halogen-free flame retardancy. As a result, they have found that phosphorus-containing vinyl compounds obtained by using phosphorus-containing phenol compounds having a specific structure and reacting them under specific reaction conditions have excellent heat resistance, thereby completing the present invention.

[0011] That is, the present invention is a phosphorus-containing vinyl benzyl ether compound represented by the following formula (1).

[0012] [Chemistry 1]

[0013]

[0014] In formula (1), R1 is a hydrocarbon group having 2 to 40 carbon atoms which may have a hetero atom, R 2 Each of them is independently a hydroxyl group or a vinylbenzyloxy group represented by the formula (2), and X is a trivalent aromatic hydrocarbon group having 6 to 20 carbon atoms.

[0015] The present invention also provides a method for producing a phosphorus-containing vinylbenzyl ether compound, comprising reacting 2.0 to 4.0 mol of a vinylbenzyl halide with 1 mol of a phosphorus-containing phenol compound represented by the following formula (3) and / or the following formula (4).

[0016] [Chemistry 2]

[0017]

[0018] In formula (3) and formula (4), R 1 and X are respectively the same as R of the formula (1) 1 and X have the same meaning.

[0019] The phosphorus-containing phenol compound is preferably at least one selected from the group consisting of 10-(dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 8-benzyl-10-(dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and 8-benzyl-10-(dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide.

[0020] The basic compound is preferably used in an amount of 0.5 mol to 5 mol based on 1 mol of the vinylbenzyl halide.

[0021] The present invention also provides a resin composition comprising the phosphorus-containing vinyl benzyl ether compound as an essential component and a thermosetting resin and / or a thermoplastic resin.

[0022] The present invention also provides a laminate for an electronic circuit board, comprising the phosphorus-containing vinyl benzyl ether compound as an essential component, and a laminate for an electronic circuit board, comprising the resin composition.

[0023] [Effects of the Invention]

[0024] The phosphorus-containing vinyl benzyl ether compound of the present invention does not contain halogen and has flame retardancy, and its cured product has excellent physical properties, especially dielectric loss tangent. In addition, since it also contains a compound having three vinyl groups, it has good heat resistance, and can also be used in laminated boards for electronic circuit substrates, etc., which require high excellent heat resistance and dielectric properties. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 : is the gel permeation chromatogram of the phosphorus-containing vinyl benzyl ether compound obtained in Example 1.

[0026] Figure 2 This is the infrared absorption spectrum of the phosphorus-containing vinyl benzyl ether compound obtained in Example 1. DETAILED DESCRIPTION

[0027] The present invention is described in detail. The phosphorus-containing vinylbenzyl ether compound of the present invention is represented by the above formula (1). Moreover, in one molecule, there are 1 to 3 vinylbenzyloxy groups represented by the above formula (2), and the average number is 1.5 to 3, preferably 1.7 to 2.9, and more preferably 1.9 to 2.8.

[0028] In formula (1), X is a trivalent aromatic hydrocarbon group having 6 to 20 carbon atoms. Examples of the aromatic hydrocarbon group include a benzene ring group, a naphthalene ring group, a biphenyl ring group, and a terphenyl ring group.

[0029] The aromatic hydrocarbon group may be unsubstituted or may have, as a substituent, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aryloxy group having 6 to 10 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an aralkyloxy group having 7 to 12 carbon atoms. The alkyl group or alkoxy group having 1 to 6 carbon atoms may be linear, branched, or cyclic, and examples thereof include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an isopropyl group, a sec-butyl group, a tert-butyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, an isohexyl group, a cyclohexyl group, a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, an n-pentyloxy group, an n-hexyloxy group, an isopropoxy group, a sec-butoxy group, a tert-butoxy group, an isopentyloxy group, a neopentyloxy group, a tert-pentyloxy group, an isohexyloxy group, a cyclopentyloxy group, and a cyclohexyloxy group. Examples of the aryl group or aryloxy group having 6 to 10 carbon atoms include phenyl, tolyl, ethylphenyl, o-xylyl, propylphenyl, mesityl, naphthyl, indanyl, phenoxy, tolyloxy, ethylphenoxy, xylyloxy, propylphenoxy, mesityloxy, and naphthyloxy. Examples of the aralkyl group or aralkyloxy group having 7 to 11 carbon atoms include benzyl, methylbenzyl, dimethylbenzyl, trimethylbenzyl, phenethyl, 1-phenylethyl, 2-phenylisopropyl, naphthylmethyl, benzyloxy, methylbenzyloxy, dimethylbenzyloxy, trimethylbenzyloxy, phenethyloxy, 1-phenylethyloxy, 2-phenylisopropyloxy, and naphthylmethyloxy.

[0030] The X is preferably a benzene ring group, a naphthyl ring group, or an aromatic ring group substituted with a methyl group or a 1-phenylethyl group.

[0031] In formula (1), R 1is a hydrocarbon group having 2 to 40 carbon atoms which may have a heteroatom, and may be any of a linear, branched, or cyclic structure, preferably a group having an aromatic ring structure, and particularly preferably a biphenyl structure represented by the following formula (5). 1 In the case of having an aromatic ring structure, the aromatic ring may have a substituent having 1 to 10 carbon atoms. As the substituent having 1 to 10 carbon atoms, for example, an alkyl having 1 to 6 carbon atoms, an alkoxy having 1 to 6 carbon atoms, an aryl having 6 to 10 carbon atoms, an aryloxy having 6 to 10 carbon atoms, an aralkyl having 7 to 10 carbon atoms, or an aralkyloxy having 7 to 10 carbon atoms, and specifically, the substituents exemplified above are mentioned, preferably a methyl group, a cyclohexyl group, a phenyl group, a tolyl group, and a benzyl group, and more preferably a methyl group, a phenyl group, and a benzyl group. Furthermore, as heteroatoms, oxygen atoms and the like can be exemplified, which may be contained between carbon atoms constituting a hydrocarbon chain or a hydrocarbon ring.

[0032] [Chemistry 3]

[0033]

[0034] In formula (5), R 3 Each of them is independently a hydrocarbon group having 1 to 10 carbon atoms, and j is independently an integer of 0 to 4, preferably 0 to 2, and more preferably 0 or 1. When a substituent is included, the total number of carbon atoms is 12 to 40.

[0035] In formula (1), R 2 Each of the above R is independently a hydroxyl group or a vinylbenzyloxy group represented by the above formula (2). In the formula (1), there is one vinylbenzyloxy group, and according to the two R 2 The compound may be a hydroxyl group or a vinylbenzyloxy group, and the number of the vinylbenzyloxy groups present is 1, 2 or 3 based on the total number.

[0036] By controlling the reaction conditions described below, the ratio of the hydroxyl groups of the phosphorus-containing phenol compound as the raw material to be converted into vinylbenzyloxy groups can be adjusted, and the ratio of R in the phosphorus-containing vinylbenzyl ether compound obtained can be adjusted. 2 For example, if the amount of vinylbenzyl halide used is increased relative to the phosphorus-containing phenol compound as a raw material, the ratio of the vinylbenzyloxy group increases.

[0037] Regarding the two R in formula (1) 2 , preferably at least one is a vinylbenzyloxy group, especially in the phosphorus-containing vinylbenzyl ether compound of formula (1), the two R 2 The content of the component consisting entirely of vinylbenzyloxy groups (compound having 3 vinylbenzyloxy groups) is preferably 0.5% by mass or more, more preferably 5% by mass or more.

[0038] The phosphorus-containing vinylbenzyl ether compound represented by the formula (1) is obtained by reacting the phosphorus-containing phenol compound represented by the formula (3) and / or the formula (4) with a vinylbenzyl halide.

[0039] The phosphorus-containing phenol compound represented by formula (4) has a phosphorus-containing heterocyclic ring and can be obtained by the reaction method described in Japanese Patent Laid-Open Nos. 60-126293, 61-236787, and 05-331179.

[0040] Specific examples of the phosphorus-containing phenolic compound represented by formula (4) include 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide (e.g., HCA-HQ, manufactured by Sanko Chemical Co., Ltd.), 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide (e.g., HCA-NQ, manufactured by Sanko Chemical Co., Ltd.), 8-benzyl-10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and 8-benzyl-10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide.

[0041] Furthermore, by subjecting the phosphorus-containing phenolic compounds represented by the formula (4) to an addition reaction of water, the phosphorus-containing heterocyclic ring is opened to obtain phosphorus-containing phenolic compounds represented by the formula (3) corresponding to the compounds of the formula (4).

[0042] These phosphorus-containing phenol compounds may be used alone or in combination of two or more, and are not limited thereto.

[0043] Examples of the vinylbenzyl halide used in the present invention include p-vinylbenzyl chloride, m-vinylbenzyl chloride, p-vinylbenzyl bromide, and m-vinylbenzyl bromide, but are not limited thereto and may be used alone or in combination of two or more. Examples of commercially available products include CMS-14 (p-vinylbenzyl chloride, manufactured by AGC Seimichemical Co., Ltd.), CMS-P (a mixture of p-vinylbenzyl chloride and m-vinylbenzyl chloride, manufactured by AGC Seimichemical Co., Ltd.).

[0044] The reaction of a phosphorus-containing phenol compound and a vinylbenzyl halide is a reaction of a polyphenol and a vinylbenzyl halide, and can be carried out according to a known method. For example, there is a method in which an alkali metal hydroxide is added or dropped in batches to a phosphorus-containing phenol compound and a vinylbenzyl halide in an appropriate solvent and reacted, and the generated metal halide is separated by filtration or washing with water. Alternatively, there is also a method in which a phosphorus-containing phenol compound and an alkali metal hydroxide are prepared, and vinylbenzyl halide is added or dropped in batches to react, and the generated metal halide is separated by filtration or washing with water.

[0045] Regarding the mixing ratio of the phosphorus-containing phenol compound and the vinylbenzyl halide, the vinylbenzyl halide is 2.0 mol to 4.0 mol, preferably 2.2 mol to 3.8 mol, and more preferably 2.5 mol to 3.5 mol, relative to 1 mol of the phosphorus-containing phenol compound. If the vinylbenzyl halide is less than 2.0 mol relative to 1 mol of the phosphorus-containing phenol compound, a polyfunctional compound having three vinyl groups can hardly be obtained. In addition, if it exceeds 4.0 mol, the remaining amount of unreacted vinylbenzyl halide increases, or the polymer of the side reaction is excessive.

[0046] The solvent used in the reaction is not particularly limited, and examples thereof include hydrocarbons such as hexane, heptane, octane, decane, dimethylbutane, pentene, cyclohexane, methylcyclohexane, benzene, toluene, xylene, and ethylbenzene; or alcohols such as methanol, ethanol, propanol, butanol, amyl alcohol, amyl alcohol, hexanol, methyl amyl alcohol, heptanol, cyclohexanol, benzyl alcohol, and furfuryl alcohol; or ethyl ether, isopropyl ether, butyl ether, diisoamyl ether, methyl phenyl ether, ethyl phenyl ether, amyl phenyl ether, ethyl benzyl ether, dioxane, methyl furan, and the like. The solvent may be methyl ether, ...

[0047] In this specification, the so-called alkaline compound refers to a compound that reacts with the halogen of the raw material vinylbenzyl halide to promote the reaction with the phosphorus-containing phenol compound, and is shown as: alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, or alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, or alkali metal carbonates such as sodium carbonate and potassium carbonate. Among them, alkali metal hydroxides are preferred. In addition, it can be used alone or in combination of two or more. In addition, it can be used in solid form or in the form of a solution such as an aqueous solution, preferably an aqueous solution. Relative to 1 mol of vinylbenzyl halide, the amount of the alkaline compound used is 0.5 mol to 5.0 mol, preferably 1 mol to 3 mol, and more preferably 1.2 mol to 2 mol. When the amount of the alkaline compound used is less than 0.5 mol, the reaction does not proceed fully. On the other hand, if it exceeds 5.0 mol, a large amount of acid required for neutralization is required, which is not preferred in terms of economy.

[0048] In the reaction, catalyst can also be used as needed.As the catalyst used, for example, tertiary amines such as benzyldimethylamine, or quaternary ammonium salts such as tetramethylammonium chloride and tetramethylammonium bromide, or phosphines such as triphenylphosphine and tri(2,6-dimethoxyphenyl)phosphine, or phosphonium salts such as benzyltriphenylphosphonium chloride, tetrabutylphosphonium bromide, ethyltriphenylphosphonium bromide, tetrabutylphosphonium iodide, or various catalysts such as imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole, are not limited to these, can be used alone, and can also be used in combination of two or more.Relative to 100 mass parts of raw materials, the usage amount of the catalyst is less than 10 mass parts, preferably less than 5 mass parts.

[0049] The reaction temperature is preferably 30°C to 150°C, more preferably 50°C to 90°C. If the reaction temperature is high, polymerization is carried out by the reaction of the vinyl group. If the reaction temperature is too low, the reaction does not proceed and the efficiency is poor. Various chromatography methods or infrared spectroscopy (IR), ultraviolet spectroscopy (UV), etc. can be used to track the reaction. For example, the end point can be determined by measuring the residual amount of the vinylbenzyl halide of the raw material or the peak of the functional group related to the reaction.

[0050] In the production method of the present invention, depending on whether the phosphorus-containing phenol compound represented by the formula (4) is used as a raw material or the reaction conditions, a phosphorus-containing vinyl benzyl ether compound represented by the following formula (6) may be produced as a by-product.

[0051] [Chemistry 4]

[0052]

[0053] In formula (6), R 1, R 2 and X are respectively the same as R of the formula (1) 1 , R 2 and X have the same meaning.

[0054] In the production method of the present invention, the phosphorus compound represented by the following formula (7) and / or formula (8) may be reacted with quinones to obtain the phosphorus-containing phenol compound represented by the above formula (3) and / or formula (4), and then the compound may be reacted with a vinylbenzyl halide without separation and purification. In this case, the reaction product of the residual raw material phosphorus compound and the vinylbenzyl halide may be produced as a by-product.

[0055] [Chemistry 5]

[0056]

[0057] In formula (7) and formula (8), R 1 R of the formula (1) 1 For the same meaning.

[0058] In the reaction product obtained by the manufacturing method of the present invention, there is a case where the compound represented by the formula (6) is also produced as a by-product together with the phosphorus-containing vinyl benzyl ether compound represented by the formula (1) of the present invention. As long as the effect of the present invention is not hindered, the mixture containing these by-products can also be used. In this case, the content of the by-product is less than 30% by mass, more preferably less than 20% by mass. The reaction product can also be refined by distillation, etc., so as to separate and remove these by-products.

[0059] The obtained phosphorus-containing vinyl benzyl ether compound has free radical polymerizability, so it can be polymerized by light irradiation or heating to obtain a cured product. As shown in formula (1) and formula (2), R 2 The polymerization inhibitor may be vinylbenzyloxy or hydroxyl, and the hydroxyl group may be used for curing. In addition, a polymerization inhibitor may be added in advance during storage. Examples of the polymerization inhibitor include quinones, hydroquinones, phenols, various copper salts, amidines, hydrazines, and the like. More specifically, toluenequinone, hydroquinone, copper naphthenate, hydrazine hydrochloride, and the like are exemplified, but are not limited to these, and may be used alone or in combination of two or more.

[0060] In the curable resin composition containing the phosphorus-containing vinyl benzyl ether compound as an essential component, a radical polymerization initiator may be used as necessary. Examples of the usable radical polymerization initiator include methyl ethyl ketone peroxide, cyclohexanone peroxide, methyl acetate peroxide, acetylacetone peroxide, cumene hydroperoxide, benzoyl peroxide, tert-butyl peroxybenzoate, etc., but are not limited to these, and may be used alone or in combination of two or more.

[0061] In the resin composition of the present invention, various other curable resins or thermoplastic resins can be formulated. As the curable resin, for example, epoxy resin, vinyl benzyl ether compound other than the present invention, polyester resin, etc. can be listed, and as the thermoplastic resin, polyethylene, polypropylene, acrylonitrile-butadiene-styrene (ABS) resin, polystyrene, methacrylic resin, polycarbonate, polyphenylene ether, polyphenylene sulfide, etc. can be listed, but they are not limited to these, and can be used alone or in combination of two or more. In the curable resin composition in which the phosphorus-containing vinyl benzyl ether compound represented by formula (1) is an essential component, when such other resins are used in combination, the main purpose of the phosphorus-containing vinyl benzyl ether compound represented by formula (1) is to impart flame retardancy, and therefore, relative to 100 parts by mass of the phosphorus-containing vinyl benzyl ether compound represented by formula (1), it is sufficient to use other resins in an amount less than 1900 parts by mass. In other words, when the phosphorus-containing vinyl benzyl ether compound of the present invention is used as a flame retardant in a resin composition containing an epoxy resin or the like as a main component, it only needs to be blended in an amount of 5% by mass or more in the composition (solid content).

[0062] In addition, various fillers can be mixed in the resin composition of the present invention as needed. Examples of fillers include aluminum hydroxide, magnesium hydroxide, talc, calcined talc, clay, kaolin, titanium oxide, glass powder, silica balloons, glass fibers, pulp fibers, synthetic fibers, ceramic fibers, etc., but are not limited to these and can be used alone or in combination of two or more. Pigments can also be mixed.

[0063] The properties of the composition of the present invention were evaluated. As a result, it was found that a cured product of the resin composition containing a phosphorus-containing vinyl benzyl ether compound obtained by reacting a phosphorus-containing phenol compound with a vinyl benzyl halide as an essential component has flame retardancy without containing a halide, does not dissociate the halogen at high temperatures, exhibits a low dielectric constant of 3.2 or less, a low dielectric loss tangent of 0.006 or less, and is also excellent in heat resistance.

[0064] [Example]

[0065] The present invention is specifically described by way of examples and comparative examples, but the present invention is not limited thereto. Unless otherwise specified, "parts" represent parts by mass, and "%" represents mass %. Regarding the measurement method, the following methods are used for measurement. The unit of equivalent is "g / eq.".

[0066] Phosphorus content: Sulfuric acid, hydrochloric acid and perchloric acid are added to the sample, heated and wet ashed, so that all phosphorus atoms are converted into orthophosphoric acid. Metavanadate and molybdate are reacted in a sulfuric acid acid solution, and the absorbance of the generated phosphovanadomolybdic acid complex at 420nm is measured, and the phosphorus atom content obtained based on the calibration curve prepared in advance using potassium dihydrogen phosphate is expressed in %. Furthermore, the phosphorus content of the laminate is expressed as the content relative to the resin component of the laminate. That is, it is the phosphorus content of the resin composition.

[0067] Flammability: Based on UL94 (safety certification standard of Underwriters Laboratories Inc.). Five test pieces were tested and judged based on the total duration of flame combustion after the first and second exposure to flame (5 pieces, 2 times each, a total of 10 times of exposure to flame), using the same standard judgment criteria, namely V-0, V-1, and V-2.

[0068] Glass transition temperature (Tg): It is expressed as the peak top temperature of tan δ when measured by a dynamic viscoelasticity measuring apparatus (EXSTAR6000 DMS6100 manufactured by SII NanoTechnology Co., Ltd.) under the condition of a temperature increase of 5° C. / min.

[0069] Relative dielectric constant and dielectric loss tangent: The relative dielectric constant and dielectric loss tangent were determined at a frequency of 1 GHz using a material analyzer (manufactured by AGILENT Technologies) in accordance with IPC-TM-650 2.5.5.9 by a capacitance method.

[0070] Field Desorption Mass Spectrometry (FD-MS) analysis: The solution was dissolved in tetrahydrofuran (manufactured by Kanto Chemical, for high performance liquid chromatography) and measured using a mass spectrometer (manufactured by JEOL Ltd., JMS-T100GCV).

[0071] GPC (Gel Permeation Chromatography): A column (TSKgelG4000H manufactured by Tosoh Corporation) connected in series to a main body (HLC-8220GPC manufactured by Tosoh Corporation) was used. XL 、TSKgelG3000H XL 、TSKgelG2000H XL) instrument, and the column temperature was set to 40°C. In addition, tetrahydrofuran (THF) was used as the eluent, and the flow rate was set to 1 mL / min, and a differential refractive index detector was used as the detector. The measurement sample was a sample obtained by dissolving 0.1 g of the sample in 10 mL of THF and filtering it with a microfilter using 50 μL. Data processing was performed using GPC-8020 Model II Version 6.00 manufactured by Tosoh Co., Ltd.

[0072] IR (infrared absorption spectrum): A Fourier transformation infrared spectrophotometer (Perkin Elmer Precisely, Spectrum One FT-IR Spectrometer 1760X) was used, and a KRS-5 unit was used. A sample dissolved in THF was applied to the unit, dried, and the wave number 650 cm was measured. -1 ~4000cm -1 The absorbance.

[0073] The vinylbenzyl halide, phosphorus-containing phenol compound, and other materials used in the following examples are as follows.

[0074] ·CMS-P: A mixture of p-vinylbenzyl chloride and m-vinylbenzyl chloride (manufactured by AGC Seimi Chemical Co., Ltd.)

[0075] ·CMS-14: p-vinylbenzyl chloride (manufactured by AGC Seimi Chemical Co., Ltd.)

[0076] HCA=NQ: 10-(2,7-dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Chemical Co., Ltd., phosphorus content 8.3%)

[0077] · HCA-HQ: 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Chemical Co., Ltd., phosphorus content 9.6%)

[0078] · HCA: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (manufactured by Sanko Chemical Co., Ltd., phosphorus content 14.4%)

[0079] NQ: 1,4-naphthoquinone (manufactured by Kawasaki Chemical Co., Ltd., 4% water content)

[0080] TBAB: catalyst, tetrabutylammonium bromide (reagent)

[0081] TMAC: catalyst, tetramethylammonium chloride (reagent)

[0082] Perbutyl P: Free radical polymerization initiator, 1,4-bis[(tert-butylperoxy)isopropyl]benzene (manufactured by NOF Corporation)

[0083] AO-60: Antioxidant, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (manufactured by ADEKA Co., Ltd.)

[0084] Example 1

[0085] In a reaction apparatus equipped with a stirring device, a thermometer, and a cooling tube, 187 parts of HCA=NQ as a phosphorus-containing phenol compound, 244 parts of CMS-P as a vinyl benzyl halide (3.2 mol per 1 mol of the phosphorus-containing phenol compound), 8.6 parts of TBAB as a catalyst, and 162 parts of diethylene glycol dimethyl ether as a solvent were added, and the temperature was raised to 75°C. At 75°C, while paying attention to heat generation, 392 parts of a 49% sodium hydroxide aqueous solution as an alkali metal (3.0 mol per 1 mol of the vinyl benzyl halide) were added dropwise over 5 hours. After the addition was completed, the reaction temperature was maintained at 75°C, while the residual amount of the vinyl benzyl halide was tracked by gas chromatography, and the reaction was continued until the reaction was fully reacted. Thereafter, the pressure was reduced and the solvent and water were recovered. 870 parts of toluene were added for dilution. 160 parts of ion exchange water were added, and the pH was neutralized with 35% hydrochloric acid until the pH value was 5-6. The water layer was separated and removed while standing. Repeat the washing with water for 3 to 5 times, and separate and remove the water layer. Reduce pressure at 75°C and reflux for dehydration. Filter and then recover the solvent. The phosphorus-containing vinyl benzyl ether compound (resin 1) obtained is a dark brown solid. The GPC chart of resin 1 is shown in Figure 1 In the example, IR is shown in Figure 2 As a result of FD-MS analysis, 508.2 as a monofunctional vinyl resin, 624.3 as a difunctional vinyl resin, and 740.2 as a trifunctional vinyl resin were confirmed, and the average number of vinylbenzyloxy groups was 2.0. The phosphorus content was 4.1%.

[0086] After 100 parts of the obtained phosphorus-containing vinyl benzyl ether compound was uniformly dissolved in 100 parts of toluene, 0.5 parts of Perbutyl P and 0.2 parts of AO-60 were added to the solution and uniformly mixed to obtain a resin composition varnish.

[0087] The obtained resin composition varnish is impregnated in glass cloth (manufactured by Nitto Bosho Co., Ltd., WEA7628XS13, 0.18 mm thick), and then heated at 130°C for 5 minutes, thereby drying to obtain a prepreg. Copper foil (manufactured by Mitsui Mining and Smelting Co., Ltd., HS1-M2-VSP, thickness 35 μm, Rz: 1.2 μm) is overlapped on the upper and lower sides of 8 sheets of the obtained prepreg, and vacuum pressing of 2 MPa is performed under the temperature conditions of 130°C for 130 minutes + 210°C for 180 minutes to obtain a 1.6 mm thick laminate. Both sides of the obtained laminate are etched to obtain a test piece for flame retardancy measurement. The glass transition temperature and flame retardancy results of the laminate are shown in Table 1.

[0088] In addition, the obtained prepreg was loosened and made into a powdered prepreg powder that passed 100 meshes using a sieve. The obtained prepreg powder was placed in a fluororesin mold and vacuum pressed at 2MPa under the temperature conditions of 130°C for 130 minutes + 210°C for 180 minutes to obtain a 50mm square 12mm thick test piece. The results of the relative dielectric constant and dielectric loss tangent of the test piece are shown in Table 1.

[0089] Example 2

[0090] In the same apparatus as in Example 1, 162 parts of HCA-HQ as a phosphorus-containing phenol compound, 7.8 parts of TBAB as a catalyst, and 140 parts of diethylene glycol dimethyl ether as a solvent were added, and the temperature was raised to 75°C. At 75°C, 202 parts of a 50% potassium hydroxide aqueous solution as an alkali metal (1.2 mol per 1 mol of vinyl benzyl halide) were added dropwise while paying attention to heat generation. While the reaction temperature was maintained at 65°C to 75°C, 229 parts of CMS-14 as a vinyl benzyl halide (3.0 mol per 1 mol of the phosphorus-containing phenol compound) were added over 3 hours. After the addition was completed, the reaction temperature was maintained at 75°C, and the residual amount of vinyl benzyl halide was tracked by gas chromatography, and the reaction was continued until the reaction was fully reacted. Thereafter, the pressure was reduced and the solvent and water were recovered. 785 parts of toluene were added for dilution. 160 parts of ion exchange water were added, and the pH was neutralized with 35% hydrochloric acid until the pH value was 5 to 6. Allow to stand and separate the water layer. Repeat 3 to 5 times of water washing and separation of the water layer. Reduce pressure at 75°C and perform reflux dehydration. Filter and then recover the solvent. The phosphorus-containing vinyl benzyl ether compound (resin 2) obtained is a light yellow semi-solid substance. As for the results of FD-MS analysis, 458.2 as a monofunctional vinyl resin, 574.2 as a difunctional vinyl resin, and 690.2 as a trifunctional vinyl resin were confirmed, and the average number of vinyl benzyloxy groups was 1.9. The phosphorus content was 4.6%.

[0091] A resin composition varnish, a prepreg, and a laminate were obtained by the same operation as in Example 1. Table 1 shows the measurement results of the glass transition temperature, flame retardancy, relative dielectric constant, and dielectric loss tangent.

[0092] Example 3

[0093] 108 parts of HCA and 162 parts of diethylene glycol dimethyl ether were added to the same apparatus as in Example 1, and the temperature was raised to 75°C. While paying attention to the heat generated by the reaction, 55.8 parts of NQ were added in batches. After the reaction was continued at 85°C for 30 minutes, the temperature was raised to 110°C, and the reaction was further carried out for 2 hours. The temperature was lowered to 75°C, and 191 parts of CMS-P as a vinyl benzyl halide (2.5 mol per 1 mol of the phosphorus-containing phenol compound generated by the reaction of HCA and NQ) and 7.1 parts of TBAB as a catalyst were added and mixed. While paying attention to the heat generated at 75°C, 205 parts of a 49% aqueous sodium hydroxide solution as an alkali metal (2.0 mol per 1 mol of the vinyl benzyl halide) were added dropwise over 5 hours. After the addition was completed, the reaction temperature was maintained at 75°C, and the amount of the remaining vinyl benzyl halide was monitored by gas chromatography, and the reaction was continued until the reaction was fully reacted. Thereafter, the pressure was reduced and the solvent and water were recovered. Add 830 parts of toluene for dilution. Add 160 parts of ion exchange water and neutralize with 35% hydrochloric acid until the pH value is 5-6. Let stand and separate the water layer. Repeat 3 to 5 times of water washing and separation and removal of the water layer. Reduce pressure at 75°C and reflux dehydration. Filter and then recover the solvent. The obtained phosphorus-containing vinyl benzyl ether compound (resin 3) is a dark brown solid. As for the results of FD-MS analysis, 508.2 as a monofunctional vinyl resin, 624.3 as a difunctional vinyl resin, and 740.2 as a trifunctional vinyl resin were confirmed, and the average number of vinyl benzyloxy groups was 1.7. The phosphorus content is 4.6%.

[0094] A resin composition varnish, a prepreg, and a laminate were obtained by the same operation as in Example 1. Table 1 shows the measurement results of the glass transition temperature, flame retardancy, relative dielectric constant, and dielectric loss tangent.

[0095] Comparative Example 1

[0096] In the same apparatus as in Example 1, except that HCA=NQ as a phosphorus-containing phenol compound was 187 parts, CMS-14 was 114 parts (1.5 mol relative to 1 mol of the phosphorus-containing phenol compound), TBAB was 6.0 parts, 49% sodium hydroxide aqueous solution was 183 parts (3.0 mol relative to 1 mol of the vinylbenzyl halide), and toluene was 640 parts, the same operation as in Example 1 was carried out to obtain a phosphorus-containing vinylbenzyl ether compound (resin H1) in the form of a dark brown solid. As a result of FD-MS analysis, 508.2 as a monofunctional vinyl resin and 624.3 as a difunctional vinyl resin were confirmed, but 740.2 as a trifunctional vinyl resin was not confirmed. The average number of vinylbenzyloxy groups was 1.4. The phosphorus content was 5.6%.

[0097] A resin composition varnish, a prepreg, and a laminate were obtained by the same operation as in Example 1. Table 1 shows the measurement results of the glass transition temperature, flame retardancy, relative dielectric constant, and dielectric loss tangent.

[0098] Comparative Example 2

[0099] In the same apparatus as in Example 1, except that 155 parts of diphenylphosphinylhydroquinone as the phosphorus-containing phenol compound was used, the same operation as in Example 2 was carried out to obtain a dark brown solid phosphorus-containing vinyl benzyl ether compound (resin H2). The phosphorus content was 5.7%.

[0100] A resin composition varnish, a prepreg, and a laminate were obtained by the same operation as in Example 1. Table 1 shows the measurement results of the glass transition temperature, flame retardancy, relative dielectric constant, and dielectric loss tangent.

[0101] Comparative Example 3

[0102] A bromine-containing vinyl benzyl ether compound (resin H3) was obtained by performing the same operation as in Example 2 except that 170 parts of tetrabromobisphenol A was used instead of the phosphorus-containing phenol compound, 90 parts of toluene as a reaction solvent, 97.9 parts of CMS-P as a vinyl benzyl halide, 0.9 parts of TMAC as a catalyst, and 83.1 parts of a 49% aqueous sodium hydroxide solution as an alkali metal. The average number of vinyl benzyloxy groups was 2.0. The bromine content was 42%.

[0103] A resin composition varnish, a prepreg, and a laminate were obtained by the same operation as in Example 1. Table 1 shows the measurement results of the glass transition temperature, flame retardancy, relative dielectric constant, and dielectric loss tangent.

[0104] [Table 1]

[0105]

[0106] According to Table 1, the phosphorus-containing vinyl resin of the present invention has flame retardancy without containing halogen, and its cured product has excellent dielectric properties, especially excellent heat resistance.

Claims

1. A phosphorus-containing vinyl benzyl ether compound represented by the following formula (1): The phosphorus-containing vinyl benzyl ether compound is obtained by reacting 2.5 to 3.5 mol of a vinyl benzyl halide with 1 mol of at least one of the phosphorus-containing phenol compounds represented by the following formula (3) and the following formula (4) under the premise that 5 parts by mass or less of a catalyst is used relative to 100 parts by mass of a raw material, heating the mixture to 50° C. to 90° C., and then reacting 0.5 to 5 mol of a basic compound relative to 1 mol of the vinyl benzyl halide. The product obtained by the reaction has 1 to 3 vinylbenzyloxy groups represented by the following formula (2) in one molecule, and the average number is 1.5 to 3. The product obtained by the reaction contains at least a compound having three vinylbenzyloxy groups represented by the formula (2) in one molecule, In formula (1), formula (3) and formula (4), R 1 is a hydrocarbon group having 2 to 40 carbon atoms which may have a hetero atom, R 2 Each independently represents a hydroxyl group or a vinylbenzyloxy group represented by the formula (2), and X represents a trivalent aromatic hydrocarbon group having 6 to 20 carbon atoms.

2. A method for producing a phosphorus-containing vinylbenzyl ether compound, comprising: reacting 2.5 to 3.5 mol of a vinylbenzyl halide with respect to 1 mol of at least one of the phosphorus-containing phenol compounds represented by the following formula (3) and the following formula (4) under the premise that 5 parts by mass or less of a catalyst is used relative to 100 parts by mass of a raw material, heating the mixture to 50° C. to 90° C., and then adding 0.5 to 5 mol of a basic compound relative to 1 mol of the vinylbenzyl halide. In formula (3) and formula (4), R 1 is a hydrocarbon group having 2 to 40 carbon atoms which may have a hetero atom, and X is a trivalent aromatic hydrocarbon group having 6 to 20 carbon atoms.

3. The method for producing a phosphorus-containing vinyl benzyl ether compound according to claim 2, wherein the phosphorus-containing phenol compound is at least one selected from the group consisting of 10-(dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 8-benzyl-10-(dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and 8-benzyl-10-(dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide.

4. A resin composition comprising the phosphorus-containing vinyl benzyl ether compound according to claim 1 as an essential component and at least one of a thermosetting resin and a thermoplastic resin.

5. A laminate for an electronic circuit board, comprising the phosphorus-containing vinyl benzyl ether compound according to claim 1 as an essential component. 6 . A laminate for an electronic circuit board, which is produced by using the resin composition according to claim 4 .

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