JP2010275414A - Phosphorus-containing phenol resin, method for producing the same, phosphorus-containing epoxy resin composition using the resin and cured product of the composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a useful phosphorus-containing phenol resin having less precipitation of a phosphate compound, and to provide a phosphorus-containing epoxy resin composition that uses the resin as an essential component and is mixed with an epoxy resin, and a cured product thereof. <P>SOLUTION: The phosphorus-containing phenol resin is obtained by reacting a compound represented by chemical formula (3) with an epoxy resin and has a phosphorus content of 2-9 wt.%. In the phosphorus-containing phenol resin, benzoquinone being a starting substance of the compound represented by chemical formula (3) has a value obtained by dividing a peak area (B) by a total area (C) of ≤8 area% in a peak area (A) on a chromatogram measured using gel permeation chromatography, the peak area (B) on a higher molecular side than the component of (A) and the total area (C) of the peak area (A) and the peak area (B). <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

The present invention relates to a phosphorus-containing phenolic resin having a low phosphorus compound precipitation, useful as a sealing material, a molding material, a casting material, an adhesive, an electrically insulating coating material, and the like used for electronic parts, a method for producing the same, The present invention relates to a phosphorus-containing epoxy resin composition containing an epoxy resin as an essential component and a cured product thereof.

Epoxy resins are widely used in electronic parts, electrical equipment, automobile parts, FRP, sports equipment and the like because of their excellent adhesiveness, heat resistance and moldability. In particular, copper-clad laminates and encapsulants used in electronic parts and electrical equipment are required to have flame resistance from the viewpoint of safety such as prevention of fire and delay, and brominated epoxy having these characteristics has been used in the past. Resin is used. Brominated epoxy resins are useful electrons and electrics because flame resistance is imparted by introducing halogen, especially bromine, into epoxy resins, and epoxy groups have high reactivity and excellent curability. It is positioned as a material.

However, looking at recent electronic devices, there is an increasing trend of weight reduction, size reduction, and circuit miniaturization. Under such demands, halides with a large specific gravity are not preferred from the viewpoint of recent weight reduction trends, and when used at high temperatures for a long period of time, the dissociation of halides occurs, thereby corroding fine wiring. There is a fear. Furthermore, harmful compounds such as halides are generated during the combustion of used electronic parts and electrical equipment, and the use of halogens has become a problem from the viewpoint of environmental safety.

Recently, as an alternative material, inorganic materials such as aluminum hydroxide, phosphorus compounds, nitrogen compounds, etc. have been studied, and in particular, flame retardant formulations using phosphorus compounds have recently been studied. Phosphoric acid esters and red phosphorus are disclosed as phosphorus compounds that make epoxy resin flame retardant, but phosphoric acid ester undergoes a hydrolysis reaction, so red phosphorus generates phosphoric acid in a high-temperature, high-humidity atmosphere, There is a problem in long-term reliability because it affects migration resistance. Therefore, flame retardancy using a compound represented by the chemical formula (3) disclosed in Non-Patent Documents 1 and 2 and Patent Document 1 having a molecular structure in which phosphoric acid is not liberated even in a high-temperature and high-humidity atmosphere has been studied. Yes.

Regarding a method for imparting flame retardancy using a compound represented by the chemical formula (3), a method of adding to a curable resin composition as a curing agent is disclosed in Patent Documents 2 to 4, and epoxy resin, cured It is described that the curable resin composition obtained by adding a predetermined amount of the compound represented by the chemical formula (3) to the agent and the curing accelerator and the cured product thereof have flame retardancy. Patent Document 5 describes that flame retardancy and heat resistance are improved by blending with an epoxy resin. However, since the compound represented by the chemical formula (3) has extremely high crystallinity and hardly dissolves in the solvent, it can be blended in an amount exceeding the amount where crystals do not precipitate in order to cure the epoxy resin uniformly. However, Patent Document 5 describes a problem that it is insufficient as a main component for imparting flame retardancy and can only be used to the extent that flame retardancy is assisted.

JP 60-126293 A JP 2000-212391 A Japanese Patent No. 3108212 JP 2001-041081 A JP 2002-249540 A Japanese Patent Laid-Open No. 2003-040969

I. G. M.M. Campbell and I.M. D. R. Stevens, Chemical Communications, pp. 505-506 (1966) (Zh. Obshch. Khim.), 42 (11), pages 2415-2418 (1972).

Accordingly, the present inventors have described a resin composition in which crystals of the compound represented by the chemical formula (3) do not precipitate even when the compound represented by the chemical formula (3) is blended with the epoxy resin as a main component in order to impart flame retardancy. As a result of various investigations, the present invention has been completed. The object of the present invention is to provide a phosphorus-containing phenol resin capable of blending an epoxy resin with a sufficient amount of the compound represented by the chemical formula (3) for imparting flame retardancy. A production method and a phosphorus-containing epoxy resin composition using the resin and a cured product thereof.

In order to solve the above-mentioned problems, the present inventors have conducted extensive research going back to the method for synthesizing the compound represented by the chemical formula (3). ) And a phosphorus-containing phenol resin having a remarkably low crystallinity, which has been a problem due to the reaction between the compound represented by the chemical formula (3) obtained by this production method and the epoxy resin, can be obtained. It was.

That is, the gist of the present invention is a compound represented by the following chemical formula (1)

と下記化学式（２）で示される化合物

And a compound represented by the following chemical formula (2)

とを反応して得られる下記化学式（３）で示される化合物

A compound represented by the following chemical formula (3) obtained by reacting with

と、エポキシ樹脂類を反応して得られる、リン含有量が２重量％〜９重量％のリン含有フェノール樹脂であって、前記化学式（１）で示される化合物は、ゲルパーミエーションクロマトグラフィーを用い、下記条件で測定されるクロマトグラム上のピーク面積（Ａ）と（Ａ）の成分より高分子側のピーク面積（Ｂ）およびピーク面積（Ａ）とピーク面積（Ｂ）の合計面積（Ｃ）において、ピーク面積（Ｂ）を合計面積（Ｃ）で除した値が８面積％以下であることを特徴とするリン含有フェノール樹脂である。

And a phosphorus-containing phenol resin having a phosphorus content of 2 to 9% by weight obtained by reacting epoxy resins, and the compound represented by the chemical formula (1) uses gel permeation chromatography. The peak area (B) on the polymer side from the components of the peak area (A) and (A) on the chromatogram measured under the following conditions, and the total area (C) of the peak area (A) and the peak area (B) In which the value obtained by dividing the peak area (B) by the total area (C) is 8 area% or less.

(Measurement conditions for gel permeation chromatography)
As an analytical column, exclusion limit molecular weight 400,000, theoretical plate number 16,000, length 30 cm and exclusion limit molecular weight 60,000, theoretical plate number 16,000, length 30 cm, exclusion limit molecular weight 10,000, theoretical plate number 16,000 The length of 30 cm was used in series, the temperature of the column chamber was 40 ° C., an absorbance detector was used as the detector, the measurement wavelength was 400 nm, the flow rate of tetrahydrofuran was 1 ml / min as the eluent, and the sample was A 1% solution of tetrahydrofuran of the compound represented by the chemical formula (1) is prepared and measured.

The present invention not only has the effect that the phosphorus-containing phenol resin has no crystallinity and excellent solvent solubility, but also can obtain a phosphorus-containing phenol resin having good yield, hue, and appearance in a uniform manner. Moreover, the curable resin composition using the phosphorus-containing phenol resin of the present invention had flame retardancy and high heat resistance.

It is the chromatogram of the gel permeation chromatography of the compound shown by Chemical formula (1) used in the synthesis example 1 of this invention. The value obtained by dividing the peak area (B) by the total area (C) of the peak areas (A) and (B) is 13.2 area%. It is the chromatogram of the gel permeation chromatography of the compound shown by Chemical formula (1) used in the synthesis example 1 of this invention. A value obtained by dividing the peak area (B) by the total area (C) of the peak areas (A) and (B) is 3.9 area%.

Hereinafter, embodiments of the present invention will be described in detail.
The compound represented by the chemical formula (1) is not a stable compound as described above, and even when stored in a normal state such as room temperature, it changes with time and is converted into a compound having a large molecular weight. When the polymer component is quantified by the above-described analysis method for a commercially available product, the polymer component contains approximately 12 to 15% by area with respect to the total peak area. May exceed 8% by area. It has been found that this polymer component causes a side reaction in the step of producing the phosphorus-containing phenol compound represented by the formula (3), and causes a decrease in the purity of the resulting phosphorus-containing phenol compound. Therefore, the present inventors have increased the phosphorus-containing phenol compound represented by the formula (3) by using a compound in which the content of the polymer compound contained in the compound represented by the formula (1) is a specific amount or less. It was found to be obtained with high purity and high yield. It has been found that the phosphorus-containing phenolic resin of the present invention obtained by reacting the obtained phosphorus-containing phenolic compound with an epoxy resin does not affect productivity such as poor curing and delay in curing time.

The phosphorus-containing phenol compound represented by the chemical formula (3) used in the present invention is obtained by reacting the compound represented by the chemical formula (1) with the compound represented by the chemical formula (2). The compound represented by the chemical formula (1) The polymer component contained in is 8 area% or less with respect to the total peak area measured under specific conditions using gel permeation chromatography. Using a compound obtained by removing the polymer component contained in the compound represented by the chemical formula (1), the phosphorus-containing phenol compound represented by the chemical formula (3) is obtained by reacting the compound represented by the chemical formula (2). Further, the hue and appearance of the phosphorus-containing phenol resin obtained by reacting this phosphorus-containing phenol compound with an epoxy resin, that is, turbidity due to precipitation of crystals and turbidity due to fine gel-like substances, It becomes possible to remarkably improve the heat resistance of the cured product.

The content of the polymer component contained in the compound represented by the chemical formula (1) is 8 area% or less, preferably 6 area% or less, and more preferably 4 area% or less. A phosphorus-containing phenol compound represented by the chemical formula (3) obtained by reacting a compound represented by the chemical formula (1) with a compound represented by the chemical formula (2) and an epoxy resin, wherein the content of the compound exceeds 8 area%. The phosphorus-containing phenol resin obtained by reaction deteriorates in hue, and the phosphorus-containing epoxy resin composition obtained by blending the epoxy resin with the phosphorus-containing phenol resin as an essential component and the cured product also deteriorate in hue, Furthermore, turbidity derived from a fine gel-like substance is generated. Moreover, there exists a problem that the heat resistance of the hardened | cured material formed by hardening | curing with an epoxy resin falls.

The compound represented by the chemical formula (1) used in the present invention can reduce the content of the polymer component by purification operations such as extraction, washing, recrystallization, distillation, and sublimation after production. Even when the content exceeds 8 area% due to changes over time, the content can be reduced to 8 area% or less by purification operations such as extraction, washing, recrystallization, distillation, and sublimation. In particular, as an easy purification method, it is easy to use a difference in solubility between the compound represented by the chemical formula (1) and the polymer component in a solvent to filter the polymer component by filtration or the like. Is the method.

A method for producing the phosphorus-containing phenol compound represented by the chemical formula (3) is specifically exemplified. The compound represented by the chemical formula (1) and the compound represented by the chemical formula (2) are dissolved in a solvent in a separate container, and the solution of the compound represented by the chemical formula (1) is directly removed while filtering the polymer component through a filter. The polymer component is newly generated by adding dropwise to the solution of the compound represented by the chemical formula (2) over 10 minutes to 10 hours, preferably 10 minutes to 5 hours, more preferably 10 minutes to 3 hours, and sequentially reacting. The compound represented by the chemical formula (1) can be supplied to the reaction system without any problem.

In order to prevent the polymer component contained in the compound represented by the chemical formula (1) from dissolving and passing without being separated by filtration, the dissolution temperature and the filtration temperature should be 60 ° C. or lower, preferably 40 ° C. or lower. desirable. This reaction proceeds sequentially by dropping the filtered solution of the compound represented by the chemical formula (1) while maintaining the solution of the compound represented by the chemical formula (2) at 60 ° C. to 150 ° C., preferably 60 ° C. or higher. Can react by holding at 80 ° C. or higher, more preferably 100 ° C. or higher, to obtain a phosphorus-containing phenol compound represented by the chemical formula (3).

The solvent not containing a carbonyl group used when dissolving the compound represented by the chemical formula (1) or (2) is not a solvent for the compound represented by the chemical formula (1), the chemical formula (2), or the chemical formula (3). Active ones having a boiling point of 35 ° C. to 150 ° C. and a dielectric constant of 10 or less, more preferably 5 or less are preferred. Specific examples include hydrocarbons such as toluene, xylene and n-hexane, and ethers such as dioxane. These solvents are not limited to those listed here, and two or more of them may be used. Those having a carbonyl group such as ketones are not preferred because they may react with the compound represented by the formula (2).

Moreover, the solvent which melt | dissolves the compound shown by Chemical formula (1), and the solvent which melt | dissolves the compound shown by Chemical formula (2) may each differ. However, in any case, the difference in solubility between the compound represented by the chemical formula (1) and the polymer component is important, and a particularly important factor for controlling the difference is to dissolve the compound represented by the chemical formula (1). Selection of the solvent species to be used and the dissolution temperature. Furthermore, the means for reducing the content of the polymer component to a specific amount or less is not limited to filtration, and purification methods such as recrystallization and sublimation may be used.

After completion of the reaction, since the compound represented by the chemical formula (3) is precipitated, the compound represented by the chemical formula (3) is separated by a solid-liquid separator. At this time, since the compound represented by the chemical formula (1) or the chemical formula (2) is dissolved in a trace amount in the solvent, the purity can be further improved by washing the separated compound represented by the chemical formula (3) with the solvent. I can do it. In addition, ionic impurities can be reduced by washing with water.

Epoxy resins used for obtaining a phosphorus-containing phenol resin by reacting a phosphorus-containing phenol compound represented by the chemical formula (3) obtained in high purity and high yield with an epoxy resin are two glycidyl per molecule. Those with groups are desirable. When obtaining a phosphorus-containing phenol resin using an epoxy resin having three or more glycidyl groups in one molecule, depending on the blending, there is a possibility of gelation during the reaction. It is possible to use. Specifically, Epototo YDC-1312, Epotot ZX-1027 (Hydroquinone type epoxy resin manufactured by Toto Kasei Co., Ltd.), Epotot ZX-1251 (Biphenol type epoxy resin manufactured by Toto Kasei Co., Ltd.), Epototo YD-127, Epototo YD-128 , Epototo YD-8125, Epototo YD-825GS, Epototo YD-011, Epototo YD-900, Epototo YD-901 (BPA type epoxy resin manufactured by Tohto Kasei Co., Ltd.), Epototo YDF-170, Epototo YDF-8170, Epototo YDF- 870GS, Epototo YDF-2001 (BPF type epoxy resin manufactured by Toto Kasei Co., Ltd.), Epototo YDPN-638 (Phenol novolac type epoxy resin manufactured by Toto Kasei Co., Ltd.), Epototo YDCN- 701 (Cresol novolak type epoxy resin manufactured by Toto Kasei Co., Ltd.), Epototo ZX-1201 (Bisphenol fluorene type epoxy resin manufactured by Toto Kasei Co., Ltd.), NC-3000 (Biphenylaralkylphenol type epoxy resin manufactured by Nippon Kayaku Co., Ltd.), EPPN -501H, EPPN-502H (Nippon Kayaku Co., Ltd. polyfunctional epoxy resin) Epototo ZX-1355 (Tohto Kasei Co., Ltd. naphthalenediol type epoxy resin), Epototo ESN-155, Epototo ESN-185V, Epototo ESN-175 ( Β-naphthol aralkyl epoxy resin manufactured by Toto Kasei Co., Ltd.), Epototo ESN-355, Epototo ESN-375 (Naphthalene all aralkyl epoxy resin manufactured by Toto Kasei), Epototo E Epoxy resin produced from a phenolic compound such as a polyhydric phenol resin such as N-475V, Epototo ESN-485 (α-naphthol aralkyl epoxy resin manufactured by Toto Kasei Co., Ltd.) and epihalohydrin, Epotot YH-434, Epototo YH- 434GS (Toto Kasei Co., Ltd., diaminodiphenylmethanetetraglycidylamine) and other epoxy compounds produced from epihalohydrin, Epototo YD-171 (Toto Kasei Co., Ltd., dimer acid type epoxy resin) and other carboxylic acids and epihalohydrin Epoxy resin produced from EPOTOTO FX-289B, EPOTOTO FX-305 (Phosphorus-containing epoxy resin made by Toto Kasei Co., Ltd.), Phenotote ERF-001 (Phosphorus-containing phenoxy made by Toto Kasei Co., Ltd.) Examples include phosphorus-containing epoxy resins obtained by reacting an epoxy resin such as fat) with a modifier such as a phosphorus-containing phenol compound. Or two or more types may be used.

When a phosphorus-containing phenol compound is obtained by reacting a phosphorus-containing phenol compound represented by the chemical formula (3) obtained with high purity and high yield with an epoxy resin, other than the phosphorus-containing phenol compound represented by the chemical formula (3) You may use together phenols in the range which does not impair the characteristic. The phenols used here are preferably those having two or more phenolic hydroxyl groups in one molecule. If one having one phenolic hydroxyl group in one molecule and no other active functional group is used, heat resistance and flame retardancy may be affected. Specific examples of phenols include bisphenols typified by bisphenol A and bisphenol F, phenols such as biphenol, naphthalene diol, hydroquinone, resorcinol and catechol, novolak resins and resole resins typified by phenol novolac, and xylylene skeletons. Aralkyl resins having the above and (reaction product of a compound represented by the chemical formula (2) and naphthoquinone) and the like, but are not limited to these and may be used alone or 2 More than one type may be used.

As a method for synthesizing a phosphorus-containing phenol resin obtained by reacting a phosphorus-containing phenol compound represented by the chemical formula (3) obtained with high purity and high yield with an epoxy resin, ordinary polyfunctional phenols and epoxy are used. Similar to the reaction with the resins, the phosphorus-containing phenol compound represented by the formula (3) and the epoxy resin are charged, and the mixture is melted and heated to perform the reaction with stirring. The reaction temperature is 100 ° C to 200 ° C. When this reaction is slow, productivity can be improved by using a catalyst as necessary. Moreover, when the viscosity at the time of reaction is high, a solvent can be used as needed.

Specific examples of the catalyst include tertiary amines such as benzyldimethylamine, quaternary ammonium salts such as tetramethylammonium chloride, phosphines such as triphenylphosphine and tris (2,6-dimethoxyphenyl) phosphine, Various catalysts such as phosphonium salts such as phenylphosphonium bromide and imidazoles such as 2-methylimidazole and 2-ethyl-4-methylimidazole can be used. Specific examples of the reaction solvent include benzene, toluene, xylene, cyclopentanone, cyclohexanone and the like. However, the reaction solvent is not limited to these, and may be used alone or in combination of two or more.

The phosphorus content of the phosphorus-containing phenol resin of the present invention is preferably 2% to 9% by weight, more preferably 2.5% to 8.5% by weight. If the phosphorus content in the phosphorus-containing phenol resin is 2% by weight or less, flame retardancy may not be maintained. Further, when the phosphorus content exceeds 9% by weight, a large amount of the phosphorus-containing phenol compound remains. Therefore, when this is blended into a solution, the phosphorus-containing phenol compound represented by the formula (3) may be precipitated. is there. Therefore, it is desirable to adjust the phosphorus content to 2 to 9% by weight.

The epoxy resin used in the curable resin composition comprising the phosphorus-containing phenol resin of the present invention as an essential component and blended with an epoxy resin preferably has at least two glycidyl groups in one molecule. Specifically, Epototo YDC-1312, Epotot ZX-1027 (Hydroquinone type epoxy resin manufactured by Toto Kasei Co., Ltd.), Epotot ZX-1251 (Biphenol type epoxy resin manufactured by Toto Kasei Co., Ltd.), Epototo YD-127, Epototo YD-128 , Epototo YD-8125, Epototo YD-825GS, Epototo YD-011, Epototo YD-900, Epototo YD-901 (BPA type epoxy resin manufactured by Tohto Kasei Co., Ltd.), Epototo YDF-170, Epototo YDF-8170, Epototo YDF- 870GS, Epototo YDF-2001 (BPF type epoxy resin manufactured by Toto Kasei Co., Ltd.), Epototo YDPN-638 (Phenol novolac type epoxy resin manufactured by Toto Kasei Co., Ltd.), Epototo YDCN 701 (Cresol novolak type epoxy resin manufactured by Toto Kasei Co., Ltd.), Epototo ZX-1201 (Bisphenol fluorene type epoxy resin manufactured by Toto Kasei Co., Ltd.), NC-3000 (Biphenylaralkylphenol type epoxy resin manufactured by Nippon Kayaku Co., Ltd.), EPPN -501H, EPPN-502H (polyfunctional epoxy resin manufactured by Nippon Kayaku Co., Ltd.) Epototo ZX-1355 (Naphthalenediol type epoxy resin manufactured by Tohto Kasei Co., Ltd.), Epototo ESN-155, Epototo ESN-185V, Epototo ESN-175 ( Β-naphthol aralkyl epoxy resin manufactured by Toto Kasei Co., Ltd.), Epototo ESN-355, Epototo ESN-375 (Genotol aralkyl epoxy resin manufactured by Toto Kasei Co., Ltd.), Epototo ES Epoxy resin produced from a phenolic compound such as a polyhydric phenol resin such as N-475V, Epototo ESN-485 (α-naphthol aralkyl epoxy resin manufactured by Toto Kasei Co., Ltd.) and epihalohydrin, Epotot YH-434, Epototo YH- 434GS (Toto Kasei Co., Ltd., diaminodiphenylmethanetetraglycidylamine) and other epoxy compounds produced from epihalohydrin, Epototo YD-171 (Toto Kasei Co., Ltd., dimer acid type epoxy resin) and other carboxylic acids and epihalohydrin Epoxy resin manufactured from EPOTOTO FX-289B, EPOTOTO FX-305 (Phosphorus-containing epoxy resin manufactured by Toto Kasei Co., Ltd.), Phenotote ERF-001 (Phosphorus-containing phenoxy tree manufactured by Toto Kasei Co., Ltd.) ) And phosphorus-containing epoxy resins obtained by epoxy resin by reacting with the modifying agent, such as phosphorus-containing phenol compound such as including but may be used in combination of two or more kinds is not limited thereto.

The curable resin composition comprising the phosphorus-containing phenolic resin of the present invention as an essential component and an epoxy resin is blended excessively with respect to the phosphorus-containing phenolic compound as necessary, and an excess epoxy group You may use the hardening | curing agent for making it react. As the curing agent, various phenol resins, acid anhydrides, amines, hydrazides, acidic polyesters, aminotriazines, and other conventionally used curing agents for epoxy resins can be used. Only one type of curing agent may be used alone, or two or more types may be used.

Curing of tertiary amines, quaternary ammonium salts, phosphines, imidazoles, etc., if necessary, in a curable resin composition comprising the phosphorus-containing phenol resin of the present invention as an essential component and an epoxy resin or the like. An accelerator can be blended.
An organic solvent can also be used for viscosity adjustment in the curable resin composition containing the phosphorus-containing phenol resin of the present invention as an essential component and an epoxy resin or the like. Examples of the organic solvent that can be used include ethers such as ethylene glycol monomethyl ether, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol and ethanol, and aromatic hydrocarbons such as benzene and toluene. Among these solvents, only one kind may be used or two or more kinds may be used, and the epoxy resin concentration can be blended in the range of 30 to 80% by weight.
The curable resin composition comprising the phosphorus-containing phenol compound of the present invention as an essential component and an epoxy resin may be blended with a filler as necessary. Specific examples include inorganic fillers such as aluminum hydroxide, magnesium hydroxide, talc, calcined talc, clay, kaolin, titanium oxide, glass powder, fine powder silica, fused silica, crystalline silica, silica balloon, etc. May be blended. About these, a well-known and usual thing can be used, and it may be used independently and may use 2 or more types together. Generally, the reason for using an inorganic filler is an improvement in impact resistance.

Moreover, when metal hydroxides, such as aluminum hydroxide and magnesium hydroxide, are used, it acts as a flame retardant aid and can ensure flame retardancy even if the phosphorus content is low. Particularly when the blending amount is 10% or more, the effect of impact resistance is high. However, if the blending amount exceeds 150%, the adhesiveness, which is a necessary item for use in a laminated board, is lowered. Moreover, organic fillers, such as fiber fillers, such as glass fiber, a pulp fiber, a synthetic fiber, a ceramic fiber, fine particle rubber, and a thermoplastic elastomer, can also be contained in the said resin composition. Similarly, these are not limited to these, and well-known and conventional ones can be used, and these may be used alone or in combination of two or more.

Examples of the electronic circuit board material obtained from the curable resin composition as described above include a resin sheet, a metal foil with a resin, a prepreg, and a laminate. The method for producing the resin sheet is not particularly limited. For example, a phosphorus-containing epoxy resin composition as described above is preferably used for a carrier film that does not dissolve in a curable resin composition such as a polyester film or a polyimide film. After applying to a thickness of 5 to 100 μm, it is dried by heating at 100 to 200 ° C. for 1 to 40 minutes to form a sheet. A resin sheet is generally formed by a method called a casting method. At this time, if the sheet to which the phosphorus-containing epoxy resin composition is applied is previously subjected to a surface treatment with a release agent, the molded resin sheet can be easily peeled off. Here, the thickness of the resin sheet is preferably 5 to 80 μm.

Next, the resin-coated metal foil obtained from the curable resin composition as described above will be described. As the metal foil, copper, aluminum, brass, nickel or the like alone, alloy, or composite metal foil can be used. It is preferable to use a metal foil having a thickness of 9 to 70 μm. The method for producing a flame retardant resin composition containing a phosphorus-containing phenol resin and a metal foil with a resin from the metal foil is not particularly limited. For example, the curable resin composition is formed on one surface of the metal foil. A resin varnish whose viscosity is adjusted with a solvent is applied using a roll coater or the like, and then dried by heating to semi-cure the resin component (B-stage) to form a resin layer. In semi-curing the resin component, for example, it can be dried by heating at 100 to 200 ° C. for 1 to 40 minutes. Here, as for the thickness of the resin part of metal foil with resin, it is desirable to form in 5-110 micrometers.

Next, the prepreg obtained using the curable resin composition as described above will be described. As the sheet-like substrate, inorganic fibers such as glass, or woven or non-woven fabrics of organic fibers such as polyester, polyamine, polyacryl, polyimide, Kevlar, etc. can be used, but it is not limited thereto. The method for producing the prepreg from the curable resin composition and the substrate is not particularly limited. For example, the substrate is immersed in a resin varnish whose viscosity is adjusted with a solvent of the epoxy resin composition and impregnated. It is obtained by heat-drying and semi-curing (B-stage) the resin component. For example, it can be heat-dried at 100 to 200 ° C. for 1 to 40 minutes. Here, the amount of resin in the prepreg is preferably 30 to 80% by weight based on the whole.

Next, a method for producing a laminate using the above resin sheet, metal foil with resin, prepreg and the like will be described. When a prepreg is used to form a laminate, one or more prepregs are laminated, a metal foil is placed on one or both sides to form a laminate, and this laminate is heated and pressurized to be laminated and integrated. . Here, as the metal foil, a single, alloy, or composite metal foil of copper, aluminum, brass, nickel or the like can be used. The conditions for heating and pressurizing the laminate may be adjusted as appropriate under the conditions for curing the curable resin composition, and heating and pressurizing. However, if the pressure at the time of pressurization is too low, bubbles are formed inside the resulting laminate. May remain and electrical characteristics may deteriorate, so it is preferable to apply pressure under conditions that satisfy moldability.

For example, the temperature can be set to 160 to 220 ° C., the pressure can be set to 0.5 to 5 MPa, and the heating and pressing time can be set to 40 to 240 minutes. Furthermore, a multilayer board can be produced by using the single-layer laminated board thus obtained as an inner layer material. In this case, first, a circuit is formed 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 a blackening process to obtain an inner layer material. An insulating layer is formed with a resin sheet, a metal foil with resin, or a prepreg on one or both sides of the inner layer material, and a multilayer plate is formed by forming a conductor layer on the surface of the insulating layer. Is.

When forming an insulating layer with a resin sheet, a resin sheet is arrange | positioned on the circuit formation surface of several inner-layer material, and a laminated body is formed. Or a resin sheet is arrange | positioned between the circuit formation surface of an inner-layer material, and metal foil, and a laminated body is formed. Then, the laminate is heated and pressed to be integrally formed, thereby forming a cured product of the resin sheet as an insulating layer and forming a multilayered inner layer material. Alternatively, the inner layer material and the metal foil as the conductor layer are formed by using a cured resin sheet as an insulating layer. Here, as a metal foil, the thing similar to what was used for the laminated board used as an inner layer material can also be used.

Further, the heating and pressing can be performed under the same conditions as the formation of the inner layer material. When an insulating layer is formed by applying a resin to a laminate, the outermost circuit forming surface resin of the inner layer material is a phosphorus-containing epoxy resin composition or a flame-retardant epoxy resin composition containing a phosphorus-containing epoxy resin. Preferably, after coating to a thickness of 5 to 100 μm, it is dried by heating at 100 to 200 ° C. for 1 to 90 minutes to form a sheet. It is generally formed by a method called a casting method. The thickness after drying is preferably 5 to 80 μm. A printed wiring board can be formed by further forming via holes and circuits on the surface of the multilayer laminate formed as described above by an additive method or a subtractive method.

Further, by repeating the above method using this printed wiring board as an inner layer material, a multilayer board can be formed. When the insulating layer is formed of a metal foil with resin, the metal foil with resin is overlapped on the circuit formation surface of the inner layer material so that the resin layer of the metal foil with resin faces the circuit formation surface of the inner layer material. Arrange to form a laminate. Then, by heating and pressing this laminate to integrally form it, a cured product of the resin layer of the resin-coated metal foil is formed as an insulating layer, and the outer metal foil is formed as a conductor layer. Here, the heat and pressure molding can be performed under the same conditions as the formation of the inner layer material.

When an insulating layer is formed with a prepreg, a laminate is formed by arranging one or a plurality of prepregs laminated on the circuit forming surface of the inner layer material, and further arranging a metal foil on the outside thereof. . Then, the laminate is heated and pressed to be integrally formed, whereby a cured product of the prepreg is formed as an insulating layer, and the outer metal foil is formed as a conductor layer. Here, as a metal foil, the thing similar to what was used for the laminated board used as an inner layer board can also be used. Further, the heating and pressing can be performed under the same conditions as the formation of the inner layer material. A printed wiring board can be formed by further forming via holes and circuits on the surface of the multilayer laminate formed as described above by an additive method or a subtractive method. Further, by repeating the above method using this printed wiring board as an inner layer material, a multilayer board can be formed.

EXAMPLES The present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited to these. The content of the polymer component contained in the chemical formula (1) was connected to the GPC-8220 gel permeation chromatograph manufactured by Tosoh Corporation in the order of TSK-GEL SuperH4000, SuperH3000 and SuperH2000 manufactured by Tosoh Corporation. The temperature of the column chamber was 40 ° C., an absorbance detector was used as a detector, and the wavelength was measured at 400 nm. Further, tetrahydrofuran was used as an eluent at a flow rate of 1 ml / min, and a sample was measured by preparing a 1% tetrahydrofuran solution of a substance represented by the chemical formula (1).
When measuring a solution such as a filtrate, an arbitrary amount of the solution was weighed, and tetrahydrofuran was added so that the component of p-benzoquinone was about 1% by weight to prepare a sample. The prepared sample was analyzed immediately after preparation. The injection volume was measured by adjusting to an amount that does not saturate the detector and does not impair the quantitativeness even with a broad peak. The injection volume in this apparatus was 200 μl.

In addition, the purity of the compound represented by the chemical formula (3) in the phosphorus-containing phenol compound represented by the chemical formula (3) obtained by the reaction was measured using HPLC, and the chemical formula (3 The peak area of the compound represented by An Agilent 1100 series device manufactured by Hewlett Packard was used, and a CD005 column of Cadenza CD-C18 manufactured by Imtakt was used. Using a mixed solution of water / acetic acid / ammonium acetate = 790/10/2 (parts by weight) and tetrahydrofuran / acetonitrile = 1/1 (volume ratio) as an eluent, sample measurement was started with a mixed solution of 30%. The gradient was performed so that the mixed solution became 80% in 8 minutes. Thereafter, the mixed solution was taken as 100%, and the measurement was completed when 24 minutes had elapsed from the start. The flow rate was 1 ml / min, and measurement was performed at a wavelength of 266 nm using an ultraviolet-visible detector. The injection volume was measured by adjusting it to an amount that does not saturate the detector and does not impair quantitativeness even if it is a minute peak. The injection volume in this apparatus was 5 μl.

The appearance of the phosphorus-containing phenol compound represented by the chemical formula (3) was judged by APHA colorimetric method (JIS K6901) after dissolving in ethylene glycol to give a 6% by weight solution. The yield of the phosphorus-containing phenol compound represented by the chemical formula (3) was calculated from the yield based on the blended compound represented by the chemical formula (2) with a theoretical amount of 100%.

The content of the phenol compound represented by the general formula (3) contained in the phosphorus-containing phenol resin obtained by reacting the phenol compound represented by the general formula (3) with the epoxy resin was measured according to the following procedure. Tosoh Co., Ltd. GPC-8220 gel permeation chromatograph was connected and used in the order of Tosoh Co., Ltd. TSK-GEL SuperH4000, SuperH3000, SuperH2000 as an analytical column. The temperature in the column chamber was 40 ° C., and measurement was performed using a refractive index (RI) detector as a detector. Further, tetrahydrofuran was used as an eluent at a flow rate of 1 ml / min, and a sample was measured by preparing a 1% tetrahydrofuran solution of a phosphorus-containing phenol resin.

As a laminate evaluation, a phosphorus-containing phenol resin obtained by reacting a phosphorus-containing phenol compound represented by the chemical formula (3) with an epoxy resin, an epoxy resin, and 2-ethyl-4-methylimidazole (Shikoku Chemical Industries) as a curing accelerator 2E4MZ manufactured by Co., Ltd. was dissolved in a solvent of 2-methoxyethanol and methyl ethyl ketone, and after aging treatment at 60 ° C. for 1 hour, a phosphorus-containing epoxy resin composition was obtained. Further, this phosphorus-containing epoxy resin composition was impregnated into a glass cloth (WEA 7628 107 XS13 manufactured by Nitto Boseki Co., Ltd.) and dried for 7 minutes using a hot air circulation oven at 150 ° C. to obtain a semi-cured prepreg. It was. Four of these were laminated, sandwiched between copper foils (3EC-III manufactured by Mitsui Metal Mining Co., Ltd.), and cured using a vacuum hot press machine at 170 ° C. for 70 minutes and a pressure of 2 MPa. The flame retardancy test was performed according to the UL-94 standard.

Synthesis example 1
To a five-necked glass separable flask equipped with a stirrer, thermometer, condenser, nitrogen inlet, and raw material inlet, HCA (manufactured by Sanko Co., Ltd. 3, 4, 5,6, -dibenzo-1,2-oxaphosphane-2-oxide) and 60.0 parts by weight of toluene were charged, stirred in a nitrogen atmosphere, and heated and dissolved at 80 ° C. In another flask, 30.30 parts by weight of PBQ (p-benzoquinone manufactured by Yancheng Fengyang Chemical Industry Co., Ltd.), which is a compound represented by the chemical formula (1), and 270 parts by weight of toluene are blended, and 20 ° C. And dissolved. A 1% solution was prepared using PBQ powder before dissolution, and the peak area (B) was quantified. As a result, it was 13.2 area%. The toluene solution of benzoquinone was filtered through a membrane filter having a pore size of 1 μm, charged into the HCA toluene solution over 2 hours, and then reacted at 80 ° C. for 30 minutes. At this time, PBQ was prepared using a filtered solution of PBQ so that PBQ was a 1% solution of tetrahydrofuran, and the peak area (B) was quantified. As a result, it was 3.9 area%. After 30 minutes, the temperature was raised to the reflux temperature of toluene, and the reaction was carried out for 90 minutes.

After completion of the reaction, it was gradually cooled and filtered at 70 ° C. This was washed with toluene and dried to obtain a white powder of a phosphorus-containing phenol compound. The hue was APHA50. Moreover, the HPLC purity of the obtained phosphorus-containing phenol compound was 98.5%, and the yield was 93.5%. FIG. 1 shows a chromatogram using gel permeation chromatography of PBQ powder. FIG. 2 shows a chromatogram using gel permeation chromatography of a solution obtained by filtering PBQ. The phosphorus-containing phenol compound represented by the chemical formula (3) thus obtained was designated as A.

Synthesis example 2
Except that PBQ was filtered through a membrane filter having a pore size of 10 μm, the same operation as in Synthesis Example 1 was performed to obtain a white powder of a phosphorus-containing phenol compound. The hue was APHA120. It was 4.4 area% as a result of preparing and making PBQ into a 1% solution of tetrahydrofuran using a filtered solution of PBQ and quantifying the peak area (B). Moreover, the HPLC purity of the obtained phosphorus-containing phenol compound was 98.6%, and the yield was 93.0%. The obtained phosphorus-containing phenol compound represented by the chemical formula (3) was defined as B.

Synthesis example 3
A light brown powder of a phosphorus-containing phenol compound was obtained in the same manner as in Synthesis Example 1 except that PBQ was filtered through a membrane filter having a pore size of 20 μm. The hue was APHA200. Using a filtered solution of PBQ, PBQ was prepared to be a 1% solution of tetrahydrofuran, and the peak area (B) was quantified. As a result, it was 6.9 area%. Moreover, the HPLC purity of the obtained phosphorus-containing phenol compound was 98.4%, and the yield was 93.4%. The obtained phosphorus-containing phenol compound represented by the chemical formula (3) was defined as C.

Synthesis example 4
A 5 neck glass separable flask equipped with a stirrer, thermometer, condenser, nitrogen inlet, and raw material inlet is charged with 60.00 parts by weight of HCA and 410 parts by weight of toluene and stirred in a nitrogen atmosphere. And dissolved at 80 ° C. Charge 30.30 parts by weight of PBQ having a peak area (B) of 13.2% by area. After 30 minutes, the temperature was raised to the reflux temperature of toluene, and the reaction was continued for 90 minutes. Thereafter, the same as in Synthesis Example 1 As a result, a brown powder of a phosphorus-containing phenol compound was obtained. The hue was APHA450. Moreover, the HPLC purity of the obtained phosphorus-containing phenol compound was 92.4%, and the yield was 93.8%. The appearance was a brown powder and contained black massive particles. The obtained phosphorus-containing phenol compound represented by the chemical formula (3) was defined as D.

Synthesis example 5
60.0 parts by weight of HCA and 410 parts by weight of toluene are charged into a five-necked glass separable flask equipped with a stirrer, thermometer, cooling pipe, nitrogen inlet, and raw material inlet, and stirred in a nitrogen atmosphere. And dissolved at 80 ° C. 27.0 parts by weight of PBQ were charged without purification, and after 30 minutes had elapsed, the temperature was raised to the reflux temperature of toluene and the reaction was carried out for 90 minutes. Thereafter, the same operation as in Synthesis Example 1 was carried out, followed by phosphorus-containing phenol. A brown powder of the compound was obtained. The obtained phosphorus-containing phenol compound was recrystallized with methyl cellosolve to obtain a white powder. The obtained phosphorus-containing phenol compound represented by the chemical formula (3) was defined as E. The HPLC purity of the obtained phosphorus-containing phenol compound was 99.8%, and the yield was 52.0%.

Example 1
73.0 parts by weight of the phosphorus-containing phenol compound A represented by the chemical formula (3) obtained in Synthesis Example 1 in the same apparatus as in Synthesis Example 1, and Epototo YDF-170 (bisphenol F type manufactured by Tohto Kasei Co., Ltd.) as an epoxy resin 27.0 parts by weight of epoxy resin) and 100.0 parts by weight of cyclohexanone as a reaction solvent were added, and dehydration was performed at 140 ° C. for 1 hour. Next, 0.03 part by weight of triphenylphosphine (made by Hokuko Chemical Co., Ltd.) was added as a reaction catalyst, the reaction was performed at the reflux temperature of cyclohexanone for 6 hours, and after cooling, cyclohexanone was added to make the resin content 50% by weight. Adjusted as follows. The appearance of the obtained phosphorus-containing phenol resin solution was 2 as evaluated by the Gardner method, and no turbidity was observed. The phosphorus content of the phosphorus-containing phenol resin obtained by removing cyclohexanone by heating was 7.0% by weight. The content rate of the phosphorus containing phenol compound shown by Chemical formula (3) by a gel permeation chromatograph was 19.1 area%. This was designated as phenol resin F.

Example 2
The procedure was the same as in Example 1 except that the phosphorus-containing phenol compound B represented by the chemical formula (3) obtained in Synthesis Example 2 was used. The appearance of the obtained phosphorus-containing phenol resin solution was 3 as evaluated by the Gardner method, and no turbidity was observed. The phosphorus content of the phosphorus-containing phenol resin obtained by removing cyclohexanone by heating was 7.0% by weight. The content rate of the phosphorus containing phenol compound shown by Chemical formula (3) by a gel permeation chromatograph was 18.9 area%. This was designated as phenol resin G.

Example 3
The procedure was the same as in Example 1 except that the phosphorus-containing phenol compound C represented by the chemical formula (3) obtained in Synthesis Example 3 was used. The appearance of the obtained phosphorus-containing phenol resin solution was 6 as evaluated by the Gardner method, and no turbidity was observed. The phosphorus content of the phosphorus-containing phenol resin obtained by removing cyclohexanone by heating was 7.0% by weight. The content of the phosphorus-containing phenol compound represented by the chemical formula (3) by gel permeation chromatography was 20.9 area%. This was designated as phenol resin H.

Comparative Example 1
The procedure was the same as in Example 1 except that the phosphorus-containing phenol compound D represented by the chemical formula (3) obtained in Synthesis Example 4 was used. The appearance of the obtained phosphorus-containing phenol resin solution was 18 or more as evaluated by the Gardner method, and turbidity was also observed. The phosphorus content of the phosphorus-containing phenol resin obtained by removing cyclohexanone by heating was 7.0% by weight. The content of the phosphorus-containing phenol compound represented by the chemical formula (3) by gel permeation chromatography was 22.1 area%. This was designated as phenol resin I.

Comparative Example 2
The same procedure as in Example 1 was performed except that the phosphorus-containing phenol compound E represented by the chemical formula (3) obtained in Synthesis Example 5 was used. The appearance of the obtained phosphorus-containing phenol resin solution was 2 as evaluated by the Gardner method, and turbidity due to the compound represented by the chemical formula (3) was observed. The phosphorus content of the phosphorus-containing phenol resin obtained by removing cyclohexanone by heating was 7.0% by weight. The content rate of the phosphorus containing phenol compound shown by Chemical formula (3) by a gel permeation chromatograph was 19.8 area%. This was designated as phenol resin J.

Example 4
Epototo YDF-170 as an epoxy resin, phenol resin solution F obtained in Example 1 as a curing agent, and 2-ethyl-4-methylimidazole are blended in predetermined amounts shown in Table 3, and methyl ethyl ketone / methyl cellosolve = 1. / 1 (part by weight) solution was blended so as to have a predetermined resin content. The obtained epoxy resin composition solution was impregnated with glass cloth, and this was heated and dried in a hot air circulation oven at 150 ° C. for 8 minutes to obtain a semi-cured prepreg. Four of these were laminated and cured using a vacuum hot press at 170 ° C. for 70 minutes to obtain a laminate.

Comparative Example 3 and Comparative Example 4
A laminate was obtained in the same procedure as in Example 4 except that the phenol resins I and J obtained in Comparative Examples 1 and 2 were used as the curing agent. The results are summarized in Table 3.

Table 1 shows the dissolution color, purity, and yield of the phosphorus-containing phenol compounds obtained in Synthesis Examples 1 to 5. Table 2 shows the appearance of the phenol resins obtained in Examples 1 to 3 and Comparative Examples 1 and 2 in a cyclohexanone solution. Table 3 shows the curing reactivity of the epoxy resin compositions of Example 4 and Comparative Examples 3 and 4, the appearance of the resulting laminate, and the glass transition temperature.

  As shown in Table 1, it can be seen that by reducing the polymer content of the compound of Chemical Formula 1, the purity of the resulting phenol compound represented by Chemical Formula 3 is high and the yield is also high.

  Table 2 shows the results of synthesizing a phosphorus-containing phenol resin obtained by reacting the phenol compound represented by Chemical Formula 3 with an epoxy resin. As a result, the hue of the phenol resin could be improved by using the phenol compound represented by the chemical formula 3 obtained by lowering the polymer content of the compound of the chemical formula 1. Moreover, when the phenol compound shown by Chemical formula 3 was obtained using the compound of Chemical formula 1 containing many high molecular weight components, the turbidity by a gel-like substance was confirmed visually by the phenol resin solution. This turbidity indicates that the resin solution is not uniform, and there is a high possibility that it will not be able to meet the demand for fine wiring mainly in the field of electronic materials. In addition, when the phenol compound E shown by Chemical formula 3 which recrystallized is used, the turbidity by the crystal | crystallization of the phenol compound E shown by Chemical formula 3 exists, and there exists a problem that it cannot harden | cure uniformly. Furthermore, since the yield of the phenol compound E represented by the chemical formula 3 is extremely low, it is not economical.

In Table 3, the result of the epoxy resin varnish which mix | blended the obtained phosphorus containing phenol resin, an epoxy resin, a hardening accelerator (2E4MZ), and a solvent was shown. As a result, the epoxy resin varnish of Example 4 was not turbid, but Comparative Examples 3 and 4 were turbid due to the phenol resin used. Moreover, it turns out that Example 4 without turbidity has a high glass transition temperature compared with Comparative Examples 3 and 4 with turbid epoxy resin varnish, and a uniform cured product can be obtained.

From the above, the present invention can obtain a phosphorus-containing phenol resin with significantly reduced crystallization, a non-turbid epoxy resin composition using the phenol resin, and a uniform cured product.

The phosphorus-containing phenol resin according to the present invention can be used as a flame-retardant phosphorus-containing phenol resin useful as a sealing material, a molding material, a casting material, an adhesive, an electrical insulating coating material, etc. used for electronic parts. By mixing this with an epoxy resin, an epoxy resin composition for producing a copper-clad laminate, a film material, a copper foil with resin, and the like used for an electronic circuit board can be obtained.

Claims (4)

Compound represented by the following chemical formula (1)

And a compound represented by the following chemical formula (2)

A compound represented by the following chemical formula (3) obtained by reacting with

And a phosphorus-containing phenol resin having a phosphorus content of 2 to 9% by weight obtained by reacting epoxy resins, and the compound represented by the chemical formula (1) uses gel permeation chromatography. The peak area (B) on the polymer side from the components of the peak area (A) and (A) on the chromatogram measured under the following conditions, and the total area (C) of the peak area (A) and the peak area (B) A phosphorus-containing phenol resin, wherein a value obtained by dividing the peak area (B) by the total area (C) is 8 area% or less.
(Measurement conditions for gel permeation chromatography)
As an analytical column, exclusion limit molecular weight 400,000, theoretical plate number 16,000, length 30 cm and exclusion limit molecular weight 60,000, theoretical plate number 16,000, length 30 cm, exclusion limit molecular weight 10,000, theoretical plate number 16,000 The length of 30 cm was used in series, the temperature of the column chamber was 40 ° C., an absorbance detector was used as the detector, the measurement wavelength was 400 nm, the flow rate of tetrahydrofuran was 1 ml / min as the eluent, and the sample was Measured by preparing a 1% solution of the compound represented by chemical formula (1) in tetrahydrofuran. The compound represented by the chemical formula (1) is dissolved in a solvent not containing a carbonyl group and filtered, so that the value obtained by dividing the peak area (B) by the total area (C) is 8 area% or less. The manufacturing method of the phosphorus containing phenol resin of Claim 1 to do. A phosphorus-containing epoxy resin composition comprising the phosphorus-containing phenol resin according to claim 1 as an essential component and an epoxy resin. A cured product obtained by curing the phosphorus-containing epoxy resin composition according to claim 3.

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