JP2010229311A - Curable resin composition, cured product thereof, and resin material for electronic part - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a curable resin composition capable of being adjusted in a varnish form without using an organic solvent and giving excellent heat-resistance, low dielectricity and low dielectric loss tangent to the cured product after the curing reaction. <P>SOLUTION: The curable resin composition includes an epoxy resin (A), an acid group-containing radical polymerizable monomer (B) and a radical polymerization initiator (C) as indispensable components. As the epoxy resin (A), the epoxy resin is used, which has each structure portion of a glycidyloxy group-containing aromatic hydrocarbon group (E), an alkoxyl group-containing condensed polycyclic aromatic hydrocarbon group (X) and a divalent hydrocarbon group (Y) such as a methylene group and has a structure that the glycidyloxy group-containing aromatic hydrocarbon group (E) and the alkoxyl group-containing condensed polycyclic aromatic hydrocarbon group (X) are bonded through the divalent hydrocarbon group (Y) such as the methylene group in the molecular structure. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention is capable of adjusting a varnish in a non-organic solvent system, and can obtain a cured product that exhibits excellent heat resistance and low dielectric constant and low dielectric loss tangent. , Interlayer insulation materials for build-up substrates, adhesive films for build-up, semiconductor sealing materials, die attach agents, flip-chip mounting underfill materials, grab top materials, liquid sealing materials for TCP, conductive adhesives, liquid crystal seals The present invention relates to a curable resin composition suitable as an insulating material for various electronic component materials such as a material, a flexible substrate coverlay, and a resist ink, and a cured product thereof.

  An epoxy resin composition containing an epoxy resin and its curing agent as essential components is excellent in various physical properties such as high heat resistance, moisture resistance, and dimensional stability. Electronic parts such as conductive paste, conductive adhesives such as conductive paste and other adhesives, liquid sealing materials such as underfill, liquid crystal sealing materials, flexible substrate coverlays, build-up adhesive films, paints, photoresist materials, Widely used in color materials, fiber reinforced composite materials, etc.

  On the other hand, in the field of printed wiring boards, development of non-solvent varnishes has been actively made in response to environmental loads such as VOC problems in recent years. For example, liquid epoxy resins represented by low molecular weight bisphenol type epoxy resins, acid anhydrides, and the like Non-solvent varnishes blended with epoxy resin curing agents typified by products are widely used. However, a cured product obtained by curing such a low molecular weight bisphenol type epoxy resin with a curing agent for epoxy resin does not have a sufficient heat resistance itself, and heat when using lead-free solder or mounting a high-frequency type semiconductor device. There was a problem of insufficient resistance to history.

  As an epoxy resin excellent in heat resistance such as reflow resistance of a cured product, an epoxy resin having a structure obtained by glycidyl etherification of a phenol resin obtained by polycondensation of methoxynaphthalene, phenols and formaldehyde is known ( Patent Document 1) below. However, this epoxy resin having a methoxynaphthalene skeleton in the molecular structure is excellent in heat resistance of cured products, but is solid at room temperature, so it can be applied to electronic materials such as copper-clad laminate insulation materials and build-up adhesive films. However, the use of organic solvents is unavoidable, the above-mentioned VOC problem remains, and the resistance to thermal history when applied to the above-mentioned electronic components compatible with lead-free solder has not reached a sufficient level. . Furthermore, in the technical field of electronic component materials such as copper-clad laminate insulating materials and build-up adhesive films, in recent years, signal speeds and frequencies have increased in various electronic devices. There is a demand for an insulating material that exhibits a low dielectric loss tangent while maintaining a dielectric constant. The dicyclopentadiene type epoxy resin has a relatively low dielectric constant and dielectric loss tangent of the cured product itself, and has good dielectric properties. However, it has not been sufficient for the extremely high required characteristics in recent years.

  On the other hand, as a varnish for non-solvent printed circuit boards, there is also a technology for mixing and varnishing vinyl ester resins obtained by reacting novolak-type epoxy resins and bisphenol-type epoxy resins with methacrylic acid with unsaturated monomers. (Patent Document 2 below). However, when a vinyl ester resin obtained by reacting a novolak epoxy resin with methacrylic acid is used, its varnish viscosity is remarkably high, impairing the impregnation of the glass cloth, and the printed wiring board productivity is low. It was. On the other hand, when a vinyl ester resin obtained by reacting a liquid bisphenol-type epoxy resin with methacrylic acid is used, the varnish viscosity is low, but the heat resistance is not sufficient.

JP 2006-274236 A Japanese Patent No. 3415610

  Therefore, the problem to be solved by the present invention can be adjusted to a varnish without using an organic solvent, and after the curing reaction, the cured product has excellent heat resistance, low dielectric constant and low It is an object of the present invention to provide a curable resin composition that gives a dielectric loss tangent, and a cured product that combines high heat resistance, low dielectric constant, and low dielectric loss tangent.

In order to solve the above problems, the present inventors have intensively studied, and as a result, glycidyloxy group-containing aromatic hydrocarbon group (E)
An alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X), and
Divalent hydrocarbon group (Y) selected from a methylene group, an alkylidene group, and an methylene group containing an aromatic hydrocarbon structure
And the glycidyloxy group-containing aromatic hydrocarbon group (E) and the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X) are the methylene group and the alkylidene group. , And epoxy resin (A) having a structure bonded through a divalent hydrocarbon group (Y) selected from aromatic hydrocarbon structure-containing methylene groups in the molecular structure, acid group-containing radical polymerizable monomer (B) and radical polymerization initiator (C) are used in combination, and these are cured continuously or simultaneously, so that curing by so-called in situ polymerization reaction is performed, that is, acid groups in the monomer (B) By reacting with an epoxy group in the polyfunctional epoxy resin (A) and polymerizing a radical polymerizable group derived from the monomer (B), so that it is liquid at room temperature before curing. After curing It found to express heat resistance and dielectric properties which, thus completing the present invention.

That is, the present invention is a curable resin composition comprising an epoxy resin (A), an acid group-containing radical polymerizable monomer (B), and a radical polymerization initiator (C) as essential components, the epoxy resin (A)
Glycidyloxy group-containing aromatic hydrocarbon group (E),
An alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X), and
Divalent hydrocarbon group (Y) selected from a methylene group, an alkylidene group, and an methylene group containing an aromatic hydrocarbon structure
And the glycidyloxy group-containing aromatic hydrocarbon group (E) and the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X) are the methylene group and the alkylidene group. In addition, the present invention relates to a curable resin composition having a molecular structure having a structure bonded via a divalent hydrocarbon group (Y) selected from methylene groups containing an aromatic hydrocarbon structure.

  The present invention further relates to a cured product obtained by in situ reaction of the resin composition for fiber-reinforced composite material.

  The present invention further provides a fiber reinforced composite comprising injecting and impregnating the resin composition for fiber reinforced composite material into a base material composed of reinforced fibers arranged in a mold, followed by in-situ curing. The present invention relates to a material manufacturing method.

  According to the present invention, it is possible to adjust to a varnish without using an organic solvent, and after the curing reaction, the cured product has excellent heat resistance and curability that provides a low dielectric constant and a low dielectric loss tangent. A resin composition and a cured product having both high heat resistance, low dielectric constant, and low dielectric loss tangent can be provided.

Hereinafter, the present invention will be described in detail.
The curable resin composition of the present invention has, as its thermosetting resin component, a polyfunctional epoxy resin (A) containing a naphthalene skeleton in the molecular structure, an acid group-containing radical polymerizable monomer (B), and The radical polymerization initiator (C) is an essential component. Then, by reacting these continuously or simultaneously, that is, the reaction between the epoxy group and the acid group and the polymerization reaction of the radical polymerizable group are performed simultaneously or continuously without distinguishing them as reaction steps. It is characterized by that. Curing by in-situ polymerization reaction in this way enables liquefaction in non-organic solvent systems or low viscosity during melting, while dramatically improving heat resistance and dielectric properties in cured products. Can be made.

  The epoxy resin (A) used in the present invention can take any combination of the structures shown in the specific examples of the structural sites (E), (X), and (Y). The molecular structure of the phenol resin composed of such constituent parts is such that the glycidyloxy group-containing aromatic hydrocarbon group (E), the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X), the methylene group, etc. When each structural unit of (Y) is represented by “E”, “X”, “Y”, the following structural site A1

であらわされる構造部位を必須として分子構造内に含むものであるが、更に具体的には、下記構造式Ａ２及びＡ３で表される構造、

The structure represented by the formula is essentially included in the molecular structure, more specifically, structures represented by the following structural formulas A2 and A3,

で表される構造を繰り返し単位とするノボラック構造の分子末端に、下記構造式Ａ６ Structural formula A4 or A5

At the molecular end of the novolak structure having the structure represented by

で表される構造を有する構造、その他下記構造式Ａ７〜Ａ１０

And other structural formulas A7 to A10 shown below

で表される構造を繰り返し単位とする交互共重合体構造が挙げられる。

The alternating copolymer structure which makes the structure represented by repeating unit a repeating unit is mentioned.

  In the present invention, the epoxy resin (A) can have various structures as described above. By having the structure represented by the structural formula A6 at the molecular end, the dielectric loss tangent of the cured epoxy resin is obtained. Can be significantly reduced. Accordingly, an epoxy resin having the structure of the structural formula A3 or an epoxy resin having the structure represented by the structural formula A6 at the molecular end thereof and having the repeating unit of A4 or A7 is particularly preferable. From the standpoint of the effect of the above, an epoxy resin having the structure of the structural formula A3 or an epoxy resin having the structure represented by the structural formula A6 at the molecular end of the A4 as a repeating unit is preferable. .

  Here, the glycidyloxy group-containing aromatic hydrocarbon group (E) specifically includes glycidyloxybenzenes, glycidyloxynaphthalenes, and aromatic nuclei represented by the following structural formulas E1 to E16. A compound having an alkyl group as a substituent is preferable in that it has excellent flame retardancy.

  Here, each structure becomes a monovalent aromatic hydrocarbon group when the structure is located at the molecular end as in the structural formula A2. In addition, among the structures listed above, those having two or more bonding positions with other structural sites on the naphthalene skeleton may be on the same nucleus or on different nuclei. There may be.

  Next, the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X) contained in the epoxy resin (A) structure is a monovalent aromatic having an alkoxy group as a substituent on the condensed polycyclic aromatic nucleus. A hydrocarbon group, specifically, an alkoxynaphthalene structure represented by the following structural formulas X1 to X11 or an alkoxyanthracene structure represented by the following structural formula X12.

  Here, each structure becomes a monovalent aromatic hydrocarbon group when the structure is located at the molecular end. In addition, among the structures listed above, those having two or more bonding positions with other structural sites on the naphthalene skeleton may be on the same nucleus or on different nuclei. There may be.

  Among the alkoxy group-containing condensed polycyclic aromatic hydrocarbon groups (X) described in detail above, those having an alkoxynaphthalene type structure from the viewpoint that the flame retardancy of the cured epoxy resin is particularly good. Preferably, a naphthalene structure having a methoxy group or an ethoxy group as a substituent, represented by the structural formulas X1 to X10, and the like, in view of the fact that in recent years it is possible to design a halogen-free material that is highly required in the field of electronic components Furthermore, it is preferably an aromatic hydrocarbon group formed from a structure having a methyl group as a substituent.

  Next, each structural site of the divalent hydrocarbon group (Y) selected from the above-mentioned methylene group, alkylidene group, and aromatic hydrocarbon structure-containing methylene group includes methylene group and alkylidene group as ethylidene group. Group, 1,1-propylidene group, 2,2-propylidene group, dimethylene group, propane-1,1,3,3-tetrayl group, n-butane-1,1,4,4-tetrayl group, n-pentane A -1,1,5,5-tetrayl group is mentioned. In addition, examples of the aromatic hydrocarbon structure-containing methylene group include the following Y1 to Y4 structures.

これらの中でも誘電効果に優れる点、更に有機溶剤へ溶解させた際の粘度が低い点から、とりわけメチレン基であることが好ましい。
従って、エポキシ樹脂（Ａ）は、特に下記構造式（１）

Among these, a methylene group is particularly preferable because of its excellent dielectric effect and its low viscosity when dissolved in an organic solvent.
Accordingly, the epoxy resin (A) particularly has the following structural formula (1)

（式中、Ｅはグリシジルオキシ基含有芳香族炭化水素基を、Ｘはアルコキシ基含有縮合多環式芳香族炭化水素基、Ｘ’はアルコキシ基含有縮合多環式芳香族炭化水素基又はグリシジルオキシ基含有芳香族炭化水素基を表し、ｎは繰り返し単位で１〜１００の整数である。）で表される構造を有するものがとりわけ好ましい。
ここで、Ｘ’のアルコキシ基含有縮合多環式芳香族炭化水素基又はグリシジルオキシ基含有芳香族炭化水素基とは、Ｘ’が任意にアルコキシ基含有縮合多環式芳香族炭化水素基（Ｘ）又はグリシジルオキシ基含有芳香族炭化水素基（Ｅ）であることを示すものである。

(In the formula, E represents a glycidyloxy group-containing aromatic hydrocarbon group, X represents an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group, and X ′ represents an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group or glycidyloxy. A group-containing aromatic hydrocarbon group is preferred, and n is a repeating unit and is preferably an integer of 1 to 100).
Here, the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group or the glycidyloxy group-containing aromatic hydrocarbon group represented by X ′ is an X ′ is optionally an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X Or a glycidyloxy group-containing aromatic hydrocarbon group (E).

  In addition, when the epoxy resin (A) has a structure represented by the structural formula (1), the resin usually contains the following structural formula (1 ′).

（式中、Ｅはグリシジルオキシ基含有芳香族炭化水素基（Ｅ）を表す。）
で表される化合物が含まれることになるが、その含有率はエポキシ樹脂（Ａ）中、５質量％以下となる割合、特に１．０〜３．５質量％なる範囲であることが難燃性の点から好ましい。

(In the formula, E represents a glycidyloxy group-containing aromatic hydrocarbon group (E).)
In the epoxy resin (A), the content ratio is 5% by mass or less, particularly 1.0 to 3.5% by mass flame retardant. From the viewpoint of sex.

  In the present invention, as the main component of the epoxy resin (A), the following structural formula

（式中、Ｅはグリシジルオキシ基含有芳香族炭化水素基を表す。）
で表される構造単位を繰り返し単位とする主骨格の末端にＸはアルコキシ基含有縮合多環式芳香族炭化水素基を導入すること該エポキシ樹脂（Ａ）の硬化物の難燃性を飛躍的に改善できる。

(In the formula, E represents a glycidyloxy group-containing aromatic hydrocarbon group.)
Introducing an alkoxy group-containing condensed polycyclic aromatic hydrocarbon group to the terminal of the main skeleton having the structural unit represented by the formula as a repeating unit, the flame retardancy of the cured product of the epoxy resin (A) is dramatically improved Can be improved.

  The value of n in the structural formula (1) is the number of repeating units derived from GPC measurement. Here, the conditions for the GPC measurement are specifically as follows.

[GPC measurement conditions]
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “H _XL -L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (Differential refraction diameter)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.
(Polystyrene used)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).

  The value of n thus determined is in the range of 1 to 100 as described above. In particular, in the present invention, the content of the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group present at the molecular end is high. From the point that the flame retardant effect becomes remarkable, the range of 1 to 50 is particularly preferable.

  The glycidyloxy group-containing aromatic hydrocarbon group (E) described in detail above, particularly those having a methyl group as a substituent on the aromatic nucleus can give particularly excellent flame retardancy to the cured epoxy resin itself, This makes it possible to design halogen-free materials that are highly demanded in the field of electronic components.

  In addition to the structure represented by the structural formula (1), the epoxy resin (A) is a phenol in which the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (B) in the structural formula (1) is adjacent. It may contain a compound having a cyclic structure produced by a dealcoholization reaction with a functional hydroxyl group.

  Specifically, the epoxy resin (A) is the total mass of the compound of n = 1, the compound of n = 2, the compound of n = 3, and the compound of n = 4 in the structural formula (1). The value obtained by dividing the total mass of all the compounds represented by the structural formula (1) is 0.3 to 0.8, in addition to the flame retardancy of the cured product, This is preferable from the viewpoint that dielectric properties such as dielectric constant and low dielectric loss tangent are good.

  In addition, the epoxy resin (A) has a good curability of the composition when the epoxy equivalent is high, and the flame retardancy of the cured product is good when the epoxy equivalent is low. Accordingly, the epoxy equivalent is 200 to 600 g / eq. In the range of 250 to 550 g / eq. It is preferable that it is the range of these.

  Further, the epoxy resin (A) has a molar ratio of the glycidyloxy group-containing aromatic hydrocarbon group (E) to the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (B). / The latter = 30/70 to 98/2 is preferable because the flame retardancy of the cured product is further improved.

The epoxy resin (A) detailed above can be produced through the following first to third stages.
First stage: A hydroxy group-containing aromatic compound (x1) and formaldehyde are charged, and a methylolation reaction is carried out in the presence of an alkali catalyst.
Second stage: After neutralizing the alkali catalyst with a neutralizing agent, an alkoxy group-containing condensed polycyclic aromatic compound (x2) is charged and reacted under an acid catalyst to obtain a phenol resin.
Third stage: A target epoxy resin is produced by reacting the phenol resin obtained in the second stage with epihalohydrin.

  As described above, the first stage is a process for producing methylol by reacting the hydroxy group-containing aromatic compound (x1) with formaldehyde in the presence of an alkali catalyst. Specific examples of the hydroxy group-containing aromatic compound (x1) used herein include unsubstituted phenols such as phenol, resorcinol and hydroquinone, cresol, phenylphenol, ethylphenol, n-propylphenol, iso-propylphenol, t -Monosubstituted phenols such as butylphenol, disubstituted phenols such as xylenol, methylpropylphenol, methylbutylphenol, methylhexylphenol, dipropylphenol, dibutylphenol, mesitol, 2,3,5-trimethylphenol, 2,3, Examples thereof include trisubstituted phenols such as 6-trimethylphenol, and naphthols such as 1-naphthol, 2-naphthol, and methylnaphthol. Two or more of these may be used in combination.

  Among these, as described above, 1-naphthol, 2-naphthol, cresol, and phenol are particularly preferable from the viewpoint of flame retardancy of the cured product.

  The alkali catalyst used in the first stage is not particularly limited, but an alkali metal or alkaline earth metal hydroxide is preferable. For example, lithium hydroxide, sodium hydroxide, potassium hydroxide, hydroxide Examples include calcium and magnesium hydroxide. The amount used is preferably in the range of 0.1 to 3.0 times the number of moles of the charged hydroxy group-containing aromatic compound (x1).

  The first stage reaction can be performed, for example, with stirring under a temperature condition of 0 to 80 ° C.

  Next, the second stage neutralizes the reaction solution by adding a neutralizing agent to the reaction liquid obtained in the first stage, and then charges the alkoxy group-containing condensed polycyclic aromatic compound (x2), This is a step of obtaining a phenol resin by reacting under an acid catalyst. The neutralizing agent used here is not particularly limited, and examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid, and trifluoride. Examples thereof include Lewis acids such as boron fluoride, anhydrous aluminum chloride, and zinc chloride.

  Further, the alkoxy group-containing condensed polycyclic aromatic compound (x2) used in the second step is specifically 1-methoxynaphthalene, 2-methoxynaphthalene, 1-methyl-2-methoxynaphthalene, 1-methoxy- 2-methylnaphthalene, 1,3,5-trimethyl-2-methoxynaphthalene, 2,6-dimethoxynaphthalene, 2,7-dimethoxynaphthalene, 1-ethoxynaphthalene, 1,4-dimethoxynaphthalene, 1-t-butoxynaphthalene , 1-methoxyanthracene and the like. Among these, 2-methoxynaphthalene is preferable because the effect of improving the flame retardancy in the cured epoxy resin is particularly remarkable.

  The acid catalyst used in the second stage is not particularly limited, but examples thereof include inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid and oxalic acid, Examples include Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. The amount used is preferably in the range of 0.1 to 5% by mass relative to the total mass of the raw materials charged.

  Here, the reaction charge ratio of the hydroxy group-containing aromatic compound (x1), the alkoxy group-containing condensed polycyclic aromatic compound (x2) and formaldehyde in the first step and the second step is the hydroxy group-containing aromatic system. The molar ratio (x1) / (x2) between the compound (x1) and the alkoxy group-containing aromatic compound (x2) is 30/70 to 98/2, and the hydroxy group-containing aromatic compound (x1) The ratio of the total number of moles of the alkoxy group-containing condensed polycyclic aromatic compound (x2) and the number of moles of formaldehyde is preferably 40/60 to 97/3.

  In carrying out the second stage reaction, water or an organic solvent can be used as necessary. Specific examples of the organic solvent that can be used include, but are not limited to, methyl cellosolve, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone. The amount of the organic solvent used is usually 10 to 500% by mass, preferably 30 to 250% by mass, based on the total mass of the charged raw materials. The reaction temperature of the first-stage methylolation reaction is usually 20 to 150 ° C., more preferably 30 to 100 ° C., and the reaction time is usually 1 to 10 hours. Subsequently, the reaction temperature in the second stage is usually from 40 to 250 ° C, and more preferably from 100 to 200 ° C. The reaction time is usually 1 to 10 hours.

  Further, when the resulting polyvalent hydroxy compound is highly colored, an antioxidant or a reducing agent may be added to suppress it. The antioxidant is not particularly limited, and examples thereof include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite compounds containing trivalent phosphorus atoms. be able to. Although it does not specifically limit as said reducing agent, For example, hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, these salts, zinc, etc. are mentioned.

  After completion of the reaction, the reaction mixture is neutralized or washed with water until the pH value of the reaction mixture becomes 3 to 7, preferably 4 to 7. What is necessary is just to perform a neutralization process and a water washing process in accordance with a conventional method. For example, when an acid catalyst is used, basic substances such as sodium hydroxide, potassium hydroxide, sodium carbonate, ammonia, triethylenetetramine, and aniline can be used as the neutralizing agent. At the time of neutralization, a buffer such as phosphoric acid may be added in advance, or the pH may be adjusted to 3 to 7 with oxalic acid after the base side is once used. After the neutralization or water washing treatment, an unreacted raw material or organic solvent mainly containing a hydroxy group-containing aromatic compound (x1) and an alkoxy group-containing condensed polycyclic aromatic compound (x2) under reduced pressure heating, By-products are distilled off and the product is concentrated to obtain the target polyvalent hydroxy compound. The unreacted raw material recovered here can be reused. It is preferable to introduce a microfiltration step in the processing operation after the completion of the reaction because inorganic salts and foreign substances can be purified and removed.

  Next, the third stage is a process for producing the target epoxy resin by reacting the phenol resin obtained in the second stage with epihalohydrin. Specifically, for example, 2 to 10 mol of epihalohydrin is added to 1 mol of phenolic hydroxyl group in the phenol resin, and 0.9 to 2.0 mol of basic catalyst is collectively added to 1 mol of phenolic hydroxyl group. The method of making it react for 0.5 to 10 hours at the temperature of 20-120 degreeC, adding or adding gradually is mentioned. The basic catalyst may be solid or an aqueous solution thereof. When an aqueous solution is used, it is continuously added and water and epihalohydrins are continuously distilled from the reaction mixture under reduced pressure or normal pressure. Alternatively, the solution may be separated and further separated to remove water and the epihalohydrin is continuously returned to the reaction mixture.

  In the first batch of epoxy resin production, all of the epihalohydrins used for preparation are new in industrial production, but the subsequent batches are consumed by the reaction with epihalohydrins recovered from the crude reaction product. It is preferable to use in combination with new epihalohydrins corresponding to the amount disappeared. At this time, the epihalohydrin used is not particularly limited, and examples thereof include epichlorohydrin, epibromohydrin, β-methylepichlorohydrin, and the like. Of these, epichlorohydrin is preferred because it is easily available industrially.

  Specific examples of the basic catalyst include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. In particular, alkali metal hydroxides are preferable from the viewpoint of excellent catalytic activity of the epoxy resin synthesis reaction, and examples thereof include sodium hydroxide and potassium hydroxide. In use, these basic catalysts may be used in the form of an aqueous solution of about 10 to 55% by mass, or in the form of a solid. Moreover, the reaction rate in the synthesis | combination of an epoxy resin can be raised by using an organic solvent together. Examples of such organic solvents include, but are not limited to, ketones such as acetone and methyl ethyl ketone, alcohols such as methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol, and tertiary butanol, methyl Examples include cellosolves such as cellosolve and ethyl cellosolve, ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethoxyethane, and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide and dimethylformamide. These organic solvents may be used alone or in combination of two or more as appropriate in order to adjust the polarity.

  After the reaction product of the epoxidation reaction is washed with water, unreacted epihalohydrin and the organic solvent to be used in combination are distilled off by distillation under heating and reduced pressure. Further, in order to obtain an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is again dissolved in an organic solvent such as toluene, methyl isobutyl ketone, methyl ethyl ketone, and alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. Further reaction can be carried out by adding an aqueous solution of the product. At this time, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present for the purpose of improving the reaction rate. When the phase transfer catalyst is used, the amount used is preferably in the range of 0.1 to 3.0% by mass with respect to the epoxy resin used. After completion of the reaction, the generated salt is removed by filtration, washing with water, and a high-purity epoxy resin can be obtained by distilling off a solvent such as toluene and methyl isobutyl ketone under heating and reduced pressure.

  In the epoxy resin composition of the present invention, in addition to the epoxy resin (A) detailed above, other epoxy resins may be used in combination as long as the effects of the present invention are not impaired. When using together, it is preferable that the ratio of the epoxy resin (A) of this invention which occupies for the whole epoxy resin is a ratio used as 30 mass% or more, and especially the ratio used as 40 mass% or more is preferable.

  As the other epoxy resin that can be used in combination with the epoxy resin (A), various epoxy resins can be used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl Type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl Type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed Novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resin, a biphenyl novolak type epoxy resins. Among these, phenol aralkyl type epoxy resins, biphenyl novolac type epoxy resins, naphthol novolak type epoxy resins containing a naphthalene skeleton, naphthol aralkyl type epoxy resins, naphthol-phenol co-condensed novolac type epoxy resins, naphthol-cresol co-condensed novolacs. Type epoxy resin, crystalline biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, and xanthene type epoxy resin are particularly preferable because a cured product having excellent flame retardancy can be obtained.

Next, the acid group-containing radical polymerizable monomer (B) used in the present invention reacts with the epoxy resin (A) and at the same time causes polymerization of acryloyl groups by radical polymerization. In this invention, the heat resistance of hardened | cured material can be improved greatly by making it harden | cure by such an in-situ reaction. Such an acid group-containing radically polymerizable monomer (B) specifically includes acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid and anhydrides thereof; or
Structural formula I

（式中、Ｒ^１は炭素原子数２〜１０の脂肪族炭化水素基又は芳香族炭化水素基、Ｘはエステル結合又はカーボネート結合、Ｒ^２は炭素原子数２〜１０の脂肪族炭化水素基又は芳香族炭化水素基を表し、ｎは１〜５の整数を示す。）で表される化合物が挙げられる。

(Wherein R ¹ is an aliphatic hydrocarbon group or aromatic hydrocarbon group having 2 to 10 carbon atoms, X is an ester bond or carbonate bond, R ² is an aliphatic hydrocarbon group having 2 to 10 carbon atoms, or Represents an aromatic hydrocarbon group, and n represents an integer of 1 to 5.).

Here, in the structural formula I, as X having an ester bond,
A compound obtained by reacting a hydroxyalkyl (meth) acrylate with an aliphatic dicarboxylic acid having 2 to 10 carbon atoms; a compound obtained by reacting a hydroxyalkyl (meth) acrylate with an aromatic dicarboxylic acid; A compound obtained by reacting a (meth) acrylate, an aliphatic diol having 2 to 10 carbon atoms, and an aliphatic dicarboxylic acid having 2 to 10 carbon atoms; a hydroxyalkyl (meth) acrylate, and 2 to 2 carbon atoms A compound obtained by reacting 10 aliphatic diols with an aromatic dicarboxylic acid;
Is mentioned.

  Here, examples of the hydroxyalkyl (meth) acrylate include β-hydroxyethyl methacrylate and β-hydroxyethyl acrylate. Examples of the aliphatic dicarboxylic acid having 2 to 10 carbon atoms include succinic anhydride, adipic acid, maleic anhydride, tetrahydrophthalic acid, and cyclohexanedicarboxylic acid. Examples of the aromatic dicarboxylic acid include phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid and the like.

  Furthermore, as the aliphatic diol having 2 to 10 carbon atoms, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propane Diol, 3-methyl-1,5-pentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanediethanol, 1,3-cyclohexanedie Nord, 1,4-cyclohexane diethanol, and the like. Of these, butanediol, pentanediol, hexanediol, cyclohexanediol, and cyclohexanedimethanol having 4 to 8 carbon atoms are preferred from the viewpoint of excellent compatibility with the epoxy resin (A).

  Moreover, as what has a carbonate bond as said X in the said structural formula I, after obtaining a polycarbonate diol by transesterification of C2-C10 aliphatic diol and dialkyl carbonate, for example, (meth) acrylic acid or The compound obtained by making it react with the derivative is mentioned.

Here, as the aliphatic diol having 2 to 10 carbon atoms, for example, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- Hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1, 3-propanediol, 3-methyl-1,5-pentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexane Dimethanol, 1,4-cyclohexanedimethanol, 1,2-cyclohexanediethanol, 1,3-cyclohexane Sanji ethanol, those having 3 to 10 carbon atoms such as 1,4-cyclohexane diethanol, and the like. Of these, butanediol, pentanediol, hexanediol, cyclohexanediol, and cyclohexanedimethanol having 4 to 8 carbon atoms are preferred from the viewpoint of excellent compatibility with the epoxy resin (A).
On the other hand, examples of the dialkyl carbonate include dimethyl carbonate from the viewpoint of reactivity.

  Among these, particularly selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid and their anhydrides from the viewpoint of the effect of reducing the viscosity and the heat resistance of the cured product. Of these, acrylic acid and methacrylic acid are preferable, and methacrylic acid is particularly preferable.

  The blending ratio of the epoxy resin (A) and the acid group-containing radical polymerizable monomer (B) detailed above is 100 parts by mass in total of the epoxy resin (A) and the acid group-containing radical polymerizable monomer (B). With respect to the flowability of the composition, the epoxy resin (A) is 40 to 90 parts by mass and the acid group-containing radical polymerizable monomer (B) is 10 to 60 parts by mass. It is preferable from the point that the balance of heat resistance of the cured product is good.

  The radical polymerization initiator (C) used in the present invention is not particularly limited as long as it is used as a thermal radical polymerization initiator. For example, methyl ethyl ketone peroxide, methylcyclohexanone peroxide, methyl acetoacetate peroxide, acetylacetone peroxide, 1, 1-bis (t-butylperoxy) 3,3,5-trimethylcyclohexane, 1,1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-hexylperoxy) 3,3,5 -Trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) ) Cyclododecane, n-butyl 4,4-bis (t-butyl pero) B) Valerate, 2,2-bis (t-butylperoxy) butane, 1,1-bis (t-butylperoxy) -2-methylcyclohexane, t-butyl hydroperoxide, P-menthane hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, t-hexyl hydroperoxide, dicumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, α, α '-Bis (t-butylperoxy) diisopropylbenzene, t-butylcumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, Isobutyryl peroxide, 3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide Id, lauroyl peroxide, cinnamic acid peroxide, m-toluoyl peroxide, benzoyl peroxide, diisopropyl peroxydicarbonate, bis (4-t-butylcyclohexyl) peroxydicarbonate, di-3-methoxybutylperoxy Dicarbonate, di-2-ethylhexylperoxydicarbonate, di-sec-butylperoxydicarbonate, di (3-methyl-3-methoxybutyl) peroxydicarbonate, di (4-t-butylcyclohexyl) peroxy Dicarbonate, α, α′-bis (neodecanoylperoxy) diisopropylbenzene, cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, 1-cyclohexyl- 1-methyl Ethyl peroxyneodecanoate, t-hexylperoxyneodecanoate, t-butylperoxyneodecanoate, t-hexylperoxypivalate, t-butylperoxypivalate, 2,5-dimethyl- 2,5-bis (2-ethylhexanoylperoxy) hexane, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexanoate, 1-cyclohexyl-1-methylethylperoxy-2-ethyl Hexanoate, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-butylperoxyisobutyrate, t-butylperoxymaleic acid, t- Butyl peroxylaurate, t-butyl peroxy-3,5,5-trimethylhexanoate, t-butylperoxyisopropyl monocarbonate, t-butylperoxy-2-ethylhexyl monocarbonate, 2,5-dimethyl-2,5-bis (benzoylperoxy) hexane, t-butylperoxyacetate, t-hexylper Oxybenzoate, t-butylperoxy-m-toluoylbenzoate, t-butylperoxybenzoate, bis (t-butylperoxy) isophthalate, t-butylperoxyallyl monocarbonate, 3,3 ′, 4,4 Examples include '-tetra (t-butylperoxycarbonyl) benzophenone. The radical polymerization initiator (C) is used in an amount of 0.001% by mass to 5% by mass with respect to the total mass of the radical polymerizable component and the total mass of the radical polymerization initiator (C). Preferably it is done.

  In the curable resin composition of the present invention, a reaction catalyst for reacting the bisphenol-type epoxy resin (A) with the acid group-containing radical polymerizable monomer (B) can be used in combination as appropriate. Examples of the reaction catalyst include tertiary amines such as triethylamine, N, N-benzyldimethylamine, N, N-dimethylphenylamine, N, N-dimethylaniline or diazabicyclooctane; trimethylbenzylammonium chloride, triethylbenzyl Quaternary ammonium salts such as ammonium chloride and methyltriethylammonium chloride; phosphines such as triphenylphosphine and tributylphosphine; imidazoles such as 2-methylimidazole, 1,2-dimethylimidazole and 2-ethyl-4-methylimidazole; Examples include triphenyl stibine and anion exchange resin. The amount of the catalyst used is preferably in the range of 0.01 to 5% by mass, particularly 0.05 to 0.5% by mass in the resin composition that is a varnish from the viewpoint of excellent reactivity.

  In the present invention, a curing reaction with a normal curing agent for epoxy resin is caused at a ratio of less than 80%, preferably less than 50%, particularly preferably less than 30% of the epoxy group of the epoxy resin (A). Also good.

Examples of epoxy resin curing agents that can be used here include amine compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complexes, guanidine derivatives; Amide compounds such as polyamide resin synthesized from dimer of linolenic acid and ethylenediamine; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride Acid anhydride compounds such as methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride; phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin Polyhydric phenol compounds such as phenol resin, dicyclopentadiene phenol addition resin, triphenylol methane resin, tetraphenylol ethane resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin; Examples thereof include benzaldehyde resin, naphthol benzaldehyde resin, phenol naphthaldehyde resin, naphthol naphthaldehyde resin, aminotriazine-modified phenol resin (polyhydric phenol compound in which phenol nuclei are linked by melamine, benzoguanamine, or the like). When using these epoxy resin curing agents, the active hydrogen in the curing agent is less than 0.8 equivalent, preferably 0.5, based on the epoxy group of the bisphenol type epoxy resin (A). The range is less than equivalent, particularly preferably less than 0.3 equivalent.

  The curable resin composition of the present invention is described above in terms of being able to impart functionalities such as appropriate flexibility and strength to the cured product according to the application, and further reducing the viscosity of the varnish. It is preferable to use other radically polymerizable monomer (D) in combination with component B). Examples of the radical polymerizable monomer that can be used here include styrene, methylstyrene, halogenated styrene, divinylbenzene, and (meth) acrylic acid esters represented by the following.

  Examples of the monofunctional (meth) acrylate that can be used in the present invention include methyl, ethyl, propyl, butyl, 3-methoxybutyl, amyl, isoamyl, 2-ethylhexyl, octyl, isooctyl, nonyl, isononyl, decyl, isodecyl, dodecyl, Tridecyl, hexadecyl, octadecyl, stearyl, isostearyl, cyclohexyl, benzyl, methoxyethyl, butoxyethyl, phenoxyethyl, nonylphenoxyethyl, glycidyl, dimethylaminoethyl, diethylaminoethyl, isobornyl, dicyclopentanyl, dicyclopentenyl, dicyclo (Meth) acrylate etc. which have substituents, such as pentenyloxyethyl, are mentioned.

  Examples of the polyfunctional (meth) acrylate include 1,3-butylene glycol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1,6-hexanediol. Di (meth) such as neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, tricyclodecane dimethanol, ethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol Di (meth) acrylate of diol obtained by adding 2 mol or more of ethylene oxide or propylene oxide to 1 mol of 1,6-hexanediol, acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate , Di (meth) acrylate of diol obtained by adding 4 mol or more of ethylene oxide or propylene oxide to 1 mol of neopentyl glycol, diol obtained by adding 2 mol of ethylene oxide or propylene oxide to 1 mol of bisphenol A Di (meth) acrylate, 3 mol or more of ethylene oxide or propylene oxide added to 1 mol of trimethylolpropane, diol or tri (meth) acrylate of triol, 4 mol or more of ethylene oxide or propylene per 1 mol of bisphenol A Di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra of diol obtained by adding oxide Meth) acrylate, dipentaerythritol poly (meth) acrylate, ethylene oxide-modified phosphoric acid (meth) acrylate, ethylene oxide-modified alkylated phosphoric acid (meth) acrylate.

  In addition to the above (meth) acrylates, functional oligomers containing ethylenic double bonds such as urethane (meth) acryl oligomers and epoxy (meth) acryl oligomers may be added as necessary. These can be used alone or in combination of two or more at any ratio.

  Here, the use amount of the radical polymerizable monomer (D) is 100 parts by mass of the total mass total amount of the acid group-containing radical polymerizable monomer (B) and the radical polymerizable monomer (D). On the other hand, the ratio is preferably 5 to 40 parts by mass. In the range of 5 parts by weight or more, the impregnation property to the fiber base material is good, while in the range of 40 parts by weight or less, the dimensional stability and high heat resistance of the molded product which is a cured product are excellent.

  The curable resin composition of the present invention described in detail above can further use a flame retardant from the viewpoint of imparting flame retardancy to the cured product. Examples of the flame retardant used here include halogen-based flame retardants such as polybrominated diphenyl ether, polybrominated biphenyl, tetrabromobisphenol A, and tetrabromobisphenol A type epoxy resin, and phosphorus-based flame retardants, nitrogen-based flame retardants, and silicones. Non-halogen flame retardants such as flame retardants, inorganic flame retardants, and organic metal salt flame retardants. Of these, non-halogen flame retardants are preferred because of the recent high demand for non-halogens.

  Various compounding agents, such as a silane coupling agent, a mold release agent, an ion trap agent, a pigment, can be added to the curable resin composition of this invention as needed.

  The curable resin composition of the present invention can be easily obtained as a liquid composition by uniformly stirring the above-described components.

  As described above, the curable resin composition of the present invention is a liquid composition at room temperature, and can be varnished without using an organic solvent or by using a very small amount. Here, acetone, methyl ethyl ketone, toluene, xylene, methyl isobutyl ketone, ethyl acetate, ethylene glycol monomethyl ether, N, N-dimethylformamide, methanol, ethanol and the like can be mentioned. The amount of the organic solvent used is preferably 10% by mass or less in the composition, and it is particularly preferable that the organic solvent is not substantially used.

  The curable resin composition of this invention can be manufactured by mixing each above-mentioned component uniformly. The curable resin composition thus obtained, that is, the varnish, is liquid at room temperature (25 ° C.), has excellent fluidity, and has characteristics of exhibiting extremely high heat resistance after curing. Become. Specifically, the varnish obtained by uniformly mixing the above-mentioned components has a viscosity measured at 25 ° C. using an E-type viscometer (“TV-20 type” cone plate type manufactured by Toki Sangyo Co., Ltd.). It is preferably 5 to 500 mPa · S, specifically 5 to 350 mPa · S.

  As described above, the cured product of the curable resin composition of the present invention is obtained by in-situ polymerization reaction of a composition obtained by uniformly mixing the above-described components in a use state corresponding to various uses. is there. Here, as described above, the in-situ reaction is performed simultaneously or continuously without distinguishing the reaction between the epoxy group and the acid group and the polymerization reaction of the radical polymerizable group as reaction steps. Is.

  Specifically, the curing temperature at the time of performing the in-situ reaction is preferably in the temperature range of 50 to 250 ° C., and in particular, after curing at 50 to 100 ° C. to obtain a tack-free cured product. Furthermore, it is preferable to perform the treatment under a temperature condition of 120 to 200 ° C.

  The curable resin composition described in detail above is a laminate for printed wiring boards, an interlayer insulating material for build-up boards, an adhesive film for build-ups, a die attach agent, an underfill material for flip chip mounting, a grab top material, and for TCP. Liquid sealing materials, conductive adhesives, liquid crystal sealing materials, flexible circuit board cover lays, resin materials for electronic circuit boards such as resist inks, semiconductor sealing materials, optical materials such as optical waveguides and optical films, resin casting Coating materials such as materials, adhesives and insulating paints; Various optical semiconductor devices such as LEDs, phototransistors, photodiodes, photocouplers, CCDs, EPROMs, photosensors; Various uses such as CFRP and other fiber reinforced resin molded products Can be applied to. Among these, from the viewpoints of particularly high heat resistance, low dielectric constant, and low dielectric loss tangent, electronic component materials such as electronic circuit board resin materials and semiconductor sealing materials are preferable. In particular, in the present invention, it is a liquid composition at room temperature and has excellent heat resistance and reflow resistance after curing, and a material having a low dielectric constant and a low dielectric loss tangent. It is particularly useful in various applications such as an adhesive film for up, a liquid sealing material, and an underfill material for flip chip mounting.

  When the curable resin composition of the present invention is used for a laminated board for a printed wiring board, specifically, a varnish obtained by blending the above-described components is made of paper, glass cloth, glass nonwoven fabric, aramid paper, aramid By impregnating various fiber base materials such as cloth, glass mat, and glass roving cloth, and heating at a heating temperature corresponding to the solvent type used, preferably 50 to 170 ° C., a laminate as a cured product can be obtained. it can. In the present invention, it is possible to adjust a varnish excellent in fluidity, so that a fiber base necessary for laminate production is laminated in advance without impregnating and curing the prepreg, and impregnated with the varnish. It can be produced by curing by an in situ polymerization reaction. Under the present circumstances, it is preferable to prepare so that the resin part in a laminated board may be 20-60 mass%.

  When the curable resin composition of the present invention is used as a die attach agent or a conductive paste, for example, a method of dispersing fine conductive particles in the curable resin composition to obtain a composition for an anisotropic conductive film. And a paste resin composition for circuit connection and an anisotropic conductive adhesive which are liquid at room temperature.

  Further, in order to produce a buildup substrate using the curable resin composition of the present invention as an interlayer insulating material for a buildup substrate, for example, a circuit is formed by using a curable resin composition appropriately blended with rubber, filler, etc. The coated wiring board is applied using a spray coating method, a curtain coating method, or the like, and then cured. Then, after drilling a predetermined through-hole part etc. as needed, it treats with a roughening agent, forms the unevenness | corrugation by washing the surface with hot water, and metal-treats, such as copper. Such operations are sequentially repeated as desired, and a build-up substrate can be obtained by alternately building up and forming a resin insulating layer and a conductor layer having a predetermined circuit pattern.

  The method for producing an adhesive film for buildup from the curable resin composition of the present invention is, for example, a multilayer printed wiring board in which the curable resin composition of the present invention is applied on a support film to form a resin composition layer. And an adhesive film for use.

  When the curable resin composition of the present invention is used for an adhesive film for build-up, the adhesive film is applied to the circuit board at the same time as the circuit board is laminated under the temperature condition of lamination in the vacuum laminating method (usually 70 ° C to 140 ° C). It is important to exhibit fluidity (resin flow) that allows resin filling in existing via holes or through holes, and it is preferable to blend the above-described components so as to exhibit such characteristics.

  Here, the diameter of the through hole of the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm. It is usually preferable to allow resin filling in this range. When laminating both surfaces of the circuit board, it is desirable to fill about 1/2 of the through hole.

  Specifically, the method for producing the adhesive film described above is, after preparing the varnish-like curable resin composition of the present invention, coating the varnish-like composition on the surface of the support film, further heating, Or it can manufacture by drying an organic solvent by hot air spraying etc. and forming the layer ((alpha)) of a curable resin composition.

  The thickness of the formed layer (α) is usually not less than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm.

  In addition, the said layer ((alpha)) may be protected with the protective film mentioned later. By protecting with a protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches.

  The above-mentioned support film and protective film are made of polyolefin such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester such as polyethylene naphthalate, polycarbonate, polyimide, and further. Examples thereof include metal foil such as pattern paper, copper foil, and aluminum foil. In addition, the support film and the protective film may be subjected to a release treatment in addition to the mud treatment and the corona treatment.

  Although the thickness of a support film is not specifically limited, Usually, it is 10-150 micrometers, Preferably it is used in 25-50 micrometers. Moreover, it is preferable that the thickness of a protective film shall be 1-40 micrometers.

  The above support film is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film is peeled after the adhesive film is heat-cured, adhesion of dust and the like in the curing process can be prevented. In the case of peeling after curing, the support film is usually subjected to a release treatment in advance.

  Next, the method for producing a multilayer printed wiring board using the adhesive film obtained as described above is, for example, when the layer (α) is protected with a protective film, (α) is laminated on one side or both sides of the circuit board so as to be in direct contact with the circuit board, for example, by a vacuum laminating method. The laminating method may be a batch method or a continuous method using a roll. Further, the adhesive film and the circuit board may be heated (preheated) as necessary before lamination.

Lamination conditions are preferably a pressure bonding temperature (laminating temperature) of 70 to 140 ° C., a pressure bonding pressure of preferably 1 to 11 kgf / cm 2 (9.8 × 10 ^{4 to} 107.9 × 10 ⁴ N / m 2), and air pressure. Lamination is preferably performed under a reduced pressure of 20 mmHg (26.7 hPa) or less.

  When the curable resin composition of the present invention is used for a semiconductor sealing material, it can be prepared by blending a filler with the curable resin composition. As the filler, silica is usually used, and the filling ratio is preferably in the range of 30 to 95% by mass per 100 parts by mass of the curable resin composition. Among them, flame retardancy and moisture resistance are preferred. In order to improve solder crack resistance and decrease the linear expansion coefficient, it is particularly preferably 70 parts by mass or more, and in order to significantly increase these effects, 80 parts by mass or more can further enhance the effect. it can.

  Next, when the curable resin composition of the present invention is used in a fiber reinforced resin molded product, each component constituting the curable resin composition of the present invention is uniformly mixed to prepare a varnish, and then this is reinforced fiber It can be produced by impregnating a reinforced substrate made of the above, followed by in situ polymerization reaction.

  Specifically, the curing temperature at the time of performing the in-situ reaction is preferably in the temperature range of 50 to 250 ° C., and in particular, after curing at 50 to 100 ° C. to obtain a tack-free cured product. Furthermore, it is preferable to perform the treatment under a temperature condition of 120 to 200 ° C.

  In the present invention, the varnish viscosity is significantly lower than that of the conventional CFRP varnish, so that the heating temperature when impregnating the varnish into the fiber reinforcement is kept low, or in the normal temperature range of 5 to 40 ° C. Impregnation is possible. On the other hand, the molded product obtained by impregnating the fiber reinforcement and in-situ curing in spite of such a low viscosity varnish is not inferior to the conventional CFRP molded product in strength, but rather has a drastic heat resistance. improves.

  Here, the reinforcing fiber may be any of a twisted yarn, an untwisted yarn, or a non-twisted yarn, but the untwisted yarn or the untwisted yarn has both the moldability and mechanical strength of the fiber-reinforced plastic member, preferable. Furthermore, the form of a reinforced fiber can use what the fiber direction arranged in one direction, and a textile fabric. The woven fabric can be freely selected from plain weaving, satin weaving, and the like according to the site and use. Specifically, since it is excellent in mechanical strength and durability, carbon fiber, glass fiber, aramid fiber, boron fiber, alumina fiber, silicon carbide fiber and the like can be mentioned, and two or more of these can be used in combination. Among these, carbon fiber is preferable from the viewpoint that the strength of the molded product is particularly good. As the carbon fiber, various types such as polyacrylonitrile-based, pitch-based, and rayon-based can be used. Among these, a polyacrylonitrile-based one that can easily obtain a high-strength carbon fiber is preferable. Here, the use amount of the reinforcing fiber when the varnish is impregnated into a reinforcing base material made of reinforcing fiber to form a fiber-reinforced composite material is such that the volume content of the reinforcing fiber in the fiber-reinforced composite material is 40 to 85%. The amount is preferably in the range.

  The fiber-reinforced resin molded product of the present invention is a molded product having a cured product of a resin composition for fiber-reinforced composite material and reinforcing fibers, specifically, the amount of reinforcing fibers in the fiber-reinforced resin molded product is: It is in the range of 40 to 70% by mass, and particularly preferably in the range of 50 to 70% by mass from the viewpoint of strength.

  As a method for producing such a fiber reinforced resin molded article, a fiber aggregate is laid on a mold, and a hand layup method or a spray-up method in which the varnish is laminated in multiple layers, either a male type or a female type, Vacuum bag method in which a base made of reinforcing fibers is stacked and impregnated while impregnating varnish, covered with a flexible mold that allows pressure to act on the molded product, and hermetically sealed is vacuum (reduced pressure) molding, reinforcing fibers in advance SMC press method in which a varnish containing varnish is formed into a sheet is compression-molded with a mold, RTM method in which the varnish is injected into a mating die laid with fibers, and a prepreg is produced by impregnating the varnish into a reinforcing fiber, There are methods such as baking this with a large autoclave. Among these methods, the RTM method is particularly preferred because of its excellent varnish fluidity. Preferred.

Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, “parts” and “%” are based on weight unless otherwise specified. In addition, each physical property evaluation was measured on condition of the following.
1) Varnish viscosity: Measured at 25 ° C. using an E-type viscometer (“TV-20 type” cone plate type manufactured by Toki Sangyo Co., Ltd.).
2) Glass transition point (dynamic viscoelasticity measurement (DMA method)): The cured product was cut into a width of 5 mm and a length of 50 mm with a diamond cutter, and measured using “DMS6100” manufactured by SII Nanotechnology, Inc. Room temperature to 260 ° C., temperature rising rate: 3 ° C./min, frequency: 1 Hz (sine wave), strain amplitude: 10 μm, dynamic viscoelasticity due to double-end bending of the cured product was measured. The temperature at the maximum value of tan δ was defined as Tg.
3) Thermomechanical analysis (TMA): When measured with a temperature rise rate of 3 ° C./min using a thermomechanical analyzer “TMA / SS6100” manufactured by Seiko Denshi Kogyo Co., Ltd. and changed to 40-60 ° C. The linear expansion coefficient (α1: linear expansion coefficient in the glass region) and the linear expansion coefficient (α2: linear expansion coefficient in the high temperature (rubber) region) when changed to 220 to 240 ° C. were measured.
4) Dielectric constant, dielectric loss tangent: In accordance with JIS-C-6481, after the test piece was dried with an impedance material analyzer “HP4291B” manufactured by Agilent Technologies, it was placed in a room at 23 ° C. and 50% humidity. The dielectric constant and dielectric loss tangent at 100 MHz and 1 GHz of the cured product after storage for 24 hours were measured (test piece size 75 × 25 × 2 mm).
5) Differential scanning calorimetry (DSC): The peak of the melting peak in the DSC curve measured under the following conditions was defined as the melting peak temperature.
Equipment: DSC1 manufactured by METTLER TOLEDO
Sample amount; about 5mg
Temperature condition: 10 ° C./min.

Examples 1-2
1. Epoxy resin composition formulation According to the formulation shown in Table 1 below, an epoxy resin and a carboxylic acid, a polymerizable compound, a radical polymerization initiator, a curing accelerator and the like were blended using a stirrer to obtain an epoxy resin composition. . Varnish viscosity was evaluated using this epoxy resin composition.
2. Preparation of cured resin plate of epoxy resin An epoxy resin composition was poured into a mold gap in which a spacer (silicone tube) having a thickness of 2 mm was sandwiched between glass plates, and cured in an oven at 100 ° C. for 1 hour. After confirming that it was tack-free, it was further subjected to after-curing at 170 ° C. for 1 hour to obtain a cured resin plate having a thickness of 2 mm. Using this as a test piece, various evaluation tests were performed. The results are shown in Table 1.

Comparative Example 1
According to the composition shown in Table 1 below, each component was mixed, then press molded at 150 ° C. for 20 minutes, and then cured (aftercured) at 175 ° C. for another 5 hours. A plate-like cured product was obtained. Using this as a test piece, various evaluation tests were performed. The results are shown in Table 1.

In addition, each component used for the epoxy resin composition of an Example and a comparative example is as follows.
"Epoxy resin (A-2)": Epoxy resin obtained in Synthesis Example 1 "HP-5000": Polyglycidyl ether of phenol resin which is a polycondensate of methoxynaphthalene, phenol and formaldehyde (manufactured by DIC Corporation) “EPICLON HP-5000” manufactured by DIC Corporation, epoxy equivalent 250 g / eq, melt viscosity at 150 ° C. 0.7 dPa · s)
“Perhexa HC”: 1,1-di (t-hexylperoxy) cyclohexane, trade name “Perhexa HC” manufactured by NOF Corporation “2E4MZ”: 2-ethyl-4-methylimidazole “XLC-LL” : Phenol aralkyl resin (“XLC-LL” manufactured by Mitsui Chemicals, hydroxyl equivalent 176 g / eq)

Claims (8)

A curable resin composition comprising an epoxy resin (A), an acid group-containing radical polymerizable monomer (B), and a radical polymerization initiator (C) as essential components, wherein the epoxy resin (A) is:
Glycidyloxy group-containing aromatic hydrocarbon group (E),
An alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X), and
Divalent hydrocarbon group (Y) selected from a methylene group, an alkylidene group, and an methylene group containing an aromatic hydrocarbon structure
And the glycidyloxy group-containing aromatic hydrocarbon group (E) and the alkoxy group-containing condensed polycyclic aromatic hydrocarbon group (X) are the methylene group and the alkylidene group. And a molecular structure having a structure bonded via a divalent hydrocarbon group (Y) selected from methylene groups containing an aromatic hydrocarbon structure. 2. The acid group-containing radically polymerizable monomer (B) is selected from the group consisting of acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid and anhydrides thereof. Curable resin composition. The blending ratio of the components (A) to (C) is equivalent ratio of the epoxy group in the epoxy resin (A) and the acid group in the acid group-containing radical polymerizable monomer (B) [ Epoxy group / acid group] is a ratio of 1/1 to 1 / 0.1, and the ratio of the radical polymerization initiator (C) is 0.1 to 3 parts by mass per 100 parts by mass of the composition. The curable resin composition according to claim 1 or 2. The total mass of the acid group-containing radical polymerizable monomer (B) and the radical polymerizable monomer (D) is in the range of 5 to 50% by mass of the synthetic mass of the components (A) to (D). The curable resin composition according to claim 1. The curability according to claim 4, wherein the mass ratio of the acid group-containing radical polymerizable monomer (B) and the radical polymerizable monomer (D) is in the range of the former / the latter = 20/80 to 80/20. Resin composition. The curable resin composition according to any one of claims 1 to 5, further comprising an epoxy resin curing agent in addition to the components described above. Hardened | cured material obtained by carrying out in situ polymerization reaction of the curable resin composition as described in any one of Claims 1-6. The resin material for electronic components which consists of a curable resin composition as described in any one of Claims 1-6.