TWI530511B - Phenol resin mixture, epoxy resin mixture, epoxy resin composition and cured product - Google Patents

Description

Phenolic resin mixture, epoxy resin mixture, epoxy resin composition and hardened material

The present invention relates to novel phenol resin mixtures, epoxy resin mixtures, epoxy resin compositions and cured products.

The epoxy resin composition is characterized by its excellent workability and heat resistance, heat resistance, chemical resistance, mechanical strength, adhesion, moisture resistance (water resistance), dimensional stability, and optical characteristics. Used in electric ‧ electronic parts materials, reinforced fiber composite materials, resist materials, optical materials, liquid crystal sealing materials, overcoat materials, prepregs, mold materials, adhesives , a wide range of areas such as adhesives and coatings.

For example, in the case of the electric ‧ electronic component material, for example, (1) a semiconductor sealing material, specifically, (a) a capacitor, a transistor, a diode, a light emitting diode, an IC (integrated circuit, that is, a product) An underfill used for potting immersion, transfer molding sealing, flip chip, etc., used in LSI (large-scale integration). (b) IC package types such as QFP (quad flat package), BGA (ball grid array), CSP (chip-scale package), etc. (B) a substrate material such as a printed wiring board, a build-up laminate, or an interlayer adhesive, a die bonding agent, and an underfill of a multilayer substrate; (3) BGA reinforcing underfill, an anisotropic conductive film, an anisotropic conductive paste, and the like, and an adhesive for assembly. In addition, the reinforcing fiber composite material may be, for example, a car body or a ship, a structural material of an airplane, a tennis racket or a golf club handle, and the like, and a fuel cell separator. A structural material represented by CFRP (carbon fiber reinforced plastic). The resist material may, for example, be a solder resist, a color resist, a black matrix or the like. Examples of the optical material include materials for lenses and the like.

In recent years, in the use of electric and electronic parts, the high-density of electric and electronic parts has been achieved, and the high-density and high-energy environments of electric and electronic parts have been used. The expansion of the use of the environment, the vicinity of the human body, and the transition to environmentally compatible technologies are progressing, and the required characteristics are more extensive and highly advanced.

In the field of, for example, a semiconductor sealing material and a substrate, in addition to heat resistance, water absorption, electrical insulation, low thermal expansion coefficient, and the like, flame resistance and solder fracture resistance are also required.

Regarding the flame resistance of the epoxy resin, the flame resistance of the resin such as a halogen epoxy resin or an epoxy resin containing a phosphorus atom, or the flame resistance of a flame retardant such as an antimony trioxide is also examined. technology. However, when such halogen or hydrazine is used, it is accused that improper disposal of the articles used may result in the production of toxic substances such as dioxin. Due to these reasons, the requirements for the flame-retardant technology of "halogen-free, 锑-free, and non-phosphorus" have been raised. For these requirements, proposals are for resin skeletons that exhibit flame resistance without the use of halogens or flame retardants. For example, a phenol-biphenyl aralkyl type epoxy resin is known as a resin which exhibits flame resistance without using a halogen or a flame retardant (see Patent Document 1 and Patent Document 2 to be described later).

In addition, changes in the assembly steps can affect the resistance to weld cracking. That is, in the semiconductor assembly method, the surface mounting method is common, and the semiconductor package is often directly exposed to high temperatures during solder reflow, and in recent years, with the awareness of environmental issues, The use of lead-free soldering when assembling semiconductors has increased. Compared to conventional soldering, the melting temperature of lead-free soldering is about 20 ° C (about 260 ° C), so the possibility of package cracking during soldering is much higher than in the past. In addition, in the printed wiring board on which electronic components such as LSI are mounted, the requirements for high density, high integration, and miniaturization are increasing. Therefore, it is necessary to reduce the wiring width, reduce the through hole diameter, or make plating. The thickness is thin. However, when the plating thickness is made thin, there is a flaw in the occurrence of cracking at the time of thermal shock, and a high resistance to solder cracking is required for the wiring substrate. For this reason, it is required that the epoxy resin composition used for the electric semiconductor material around the semiconductor such as a semiconductor sealing material or a printed wiring board is hard to be cured even in a lead-free solder having a higher temperature than conventional soldering. The performance of rupture. This crack is caused by stress on the hardened material due to thermal shock of lead-free soldering. One of the evaluation indicators can use the storage elastic modulus of the dynamic viscoelastic test. In general, when the storage elastic modulus at a high temperature is, for example, 100 MPa or more, the storage elastic modulus at 160 ° C is preferably as low as possible (see Patent Document 3 to be described later). On the other hand, it is known that the storage elastic modulus at high temperatures is preferably above a certain level above the glass transition temperature, in the thermal cycle test between 220 ° C and 260 ° C and from -50 ° C to 150 ° C. The highly reliable resin which does not rupture reveals an epoxy resin composition having a storage elastic modulus of from 0.5 GPa to 0.9 GPa at 220 ° C (see Patent Document 4 described later). Therefore, in order to suppress the occurrence of cracking under thermal shock, an appropriate storage elastic modulus at a high temperature is considered to be very important.

A phenol-biphenyl aralkyl type epoxy resin which is excellent in flame resistance is known, for example, an NC-3000 series manufactured by Nippon Kayaku Co., Ltd., and the like. The epoxy resin can be isolated from the bisphenol compound formed by reacting 4,4'-bis(hydroxymethyl)biphenyl with phenol, and then the isolated bisphenol compound is treated with epichlorohydrin. The epichlorohydrin is produced by epoxidation (see Patent Document 5 to be described later). Further, a method of using 4,4'-bis(chloromethyl)-biphenyl in place of the above 4,4'-bis(hydroxymethyl)biphenyl (see Patent Document 6 to be described later) is also known.

In the development of phenol-biphenyl aralkyl type epoxy resins in recent years, for example, a biphenyl derivative such as 4,4′-bis(chloromethyl)-biphenyl has been previously subjected to oligomerization treatment with phenol. A phenol resin obtained by condensation-like (refer to Patent Document 7 mentioned later).

Further, a generally known method is to synthesize the above-mentioned 4,4'-bis(chloromethyl)-biphenyl as a raw material by dichloromethylation of biphenyl, for example, in a cyclohexane solvent while vigorously stirring. Biphenyl, paraformaldehyde, and zinc chloride are introduced into a hydrogen chloride gas and reacted to obtain 4,4'-bis(chloromethyl)-biphenyl (see Patent Document No. 8 on page 10, paragraph 19, which will be described later). To 20 columns).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 11-140277

[Patent Document 2] Japanese Patent Laid-Open No. Hei 11-140166

[Patent Document 3] Japanese Patent No. 4023732

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2001-288244

[Patent Document 5] Japanese Patent No. 2952094

[Patent Document 6] Japanese Laid-Open Patent Publication No. 2002-338656

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2007-254685

[Patent Document 8] Japanese Patent Publication No. 54-929

An object of the present invention is to provide a flame retardancy equivalent to or higher than a cured product obtained by using a phenol-biphenyl aralkyl type epoxy resin excellent in flame resistance, and having a better storage elastic modulus. An epoxy resin cured product; an epoxy resin mixture used to obtain the cured epoxy resin; or/and an epoxy resin composition; and a phenol resin mixture for the epoxy resin.

The present inventors have intensively studied to solve the above problems, and as a result, it has been unexpectedly found that dihalomethylbiphenyl is used as a main component, and a certain amount of tris and tetrahalomethylbiphenyl is contained as a side reaction product, and contains The reaction product (mixture) obtained by halomethylation of a small amount of a monohalomethylbiphenyl and a bis(biphenyl)methane compound is obtained by directly reacting with a phenol without performing isolation purification. The phenol resin mixture is very suitable as a raw material for an epoxy resin mixture satisfying the above-mentioned desired properties, and thus the present invention has been completed.

That is, the present invention relates to the following:

(1) A phenol resin mixture obtained by subjecting a reaction product obtained by a halomethylation reaction of biphenyl to a methylene crosslinking reaction with a phenol, and the reaction product is relative to GC-MS (Gas Chromatograph-Mass Spectrometry, that is, gas chromatography-mass spectrometry), the ratio of the whole reaction product (GC area ratio), containing: 60% or more and less than 80% of dihalomethylbiphenyl, total 15% to 30% of tris(halomethyl)biphenyl and tetrakis(halomethyl)biphenyl, and other by-products of the remainder.

(2) The phenol resin mixture according to the above (1), which has a softening point of from 65 ° C to 85 ° C, and has a number average molecular weight of from 350 to 1200 as determined by GPC (gel permeation chromatography), and the weight average molecular weight is 400 to 2000, and OH equivalents from 160 g/eq to 250 g/eq.

(3) An epoxy resin mixture obtained by epoxidizing the phenol resin mixture described in the above (1) or (2).

(4) The epoxy resin mixture according to the above (3), which has a softening point of 50 ° C to 75 ° C and an ICI viscosity of 0.02 Pa ‧ s to 0.50 Pa s , which is obtained by GPC (gel permeation chromatography) The number average molecular weight is from 400 to 1200 and the weight average molecular weight is from 800 to 2,000, and the epoxy equivalent is from 200 g/eq to 360 g/eq.

(5) An epoxy resin composition comprising the epoxy resin mixture of the above (3) and a curing agent.

(6) The epoxy resin composition according to (5) above, wherein the content of the hardener is 0.7 with respect to 1 equivalent of the epoxy group of the epoxy resin mixture. Equivalent to 1.2 equivalents.

(7) The epoxy resin composition according to the above (6), which contains 50% by weight to 90% by weight of a filler based on the total amount of the epoxy resin composition.

(8) A cured product obtained by curing an epoxy resin composition containing an epoxy obtained by epoxidizing the phenol resin mixture described in (1) above. The resin mixture, and 1 equivalent of the epoxy group relative to the epoxy group of the epoxy resin mixture, are 0.7 to 1.2 equivalents of a hardener.

(9) A cured product obtained by curing an epoxy resin composition containing an epoxy obtained by epoxidizing the phenol resin mixture described in (1) above. The resin mixture, the equivalent amount of 0.7 to 1.2 equivalents of the hardener with respect to the epoxy group of the epoxy resin mixture, and the inorganic filler of 50% by weight to 90% by weight based on the total amount of the epoxy resin composition.

(10) A method for producing a phenol resin mixture, wherein biphenyl, 2 to 8 equivalents of formaldehyde relative to 1 mol of biphenyl and hydrogen halide are reacted in the presence of excess hydrogen halide in the presence of a zinc halide The halomethylation of biphenyl is carried out to obtain a dihalomethylbiphenyl having a ratio of 60% or more and less than 80% of the total amount of the reaction product (GC area ratio) measured by GC-MS, and a total of 15 a reaction product of from about 30% to 30% of (halomethyl)biphenyl and tetrakis(halomethyl)biphenyl, and other by-products of the remainder, and directly reacting with the phenol without refining the reaction product A phenol resin mixture is produced.

(11) A method for producing an epoxy resin mixture by subjecting the phenol resin mixture obtained according to the above production method (10) to an equivalent amount of 0.8 to 12 equivalents of epihalohydrin relative to the hydroxyl group of the phenol resin mixture. reaction.

(12) An epoxy resin composition comprising the phenol resin mixture described in the above (1) or (2) as a curing agent.

The phenol resin mixture obtained by the present invention is used as a raw material for an epoxy resin mixture or an epoxy resin composition for providing a cured product having excellent flame resistance and a suitable storage modulus, and is easy to manufacture. Further, when the epoxy resin mixture or the epoxy resin composition of the present invention is cured, as described above, a cured product having excellent flame resistance and a suitable storage modulus can be obtained. Therefore, the epoxy resin mixture of the present invention or the epoxy resin composition of the present invention can be used for a wide range of applications including semiconductor sealing materials and printed wiring boards.

Hereinafter, the present invention will be described in detail.

First, a halomethylation reaction with respect to biphenyl used to obtain a phenol resin mixture of the present invention will be explained.

The halomethylation reaction of biphenyl is obtained by using a biphenyl, a formaldehyde or an equivalent thereof, an acetal (hereinafter collectively referred to as a carbon source), a hydrogen halide, a catalyst, and a solvent to obtain a biphenyl halide. The reaction of the methide. Depending on the reaction conditions, there are also cases where the halomethyl halide of biphenyl is further reacted to form diarylmethane. In general, for example, the chloromethylation reaction described in the 5th edition of Experimental Chemistry Lecture 13(2) p. 439 (2005) or SYNTHESIS, 1003 (1991) can be referred to.

For example, according to the aforementioned Patent Document 8 (Japanese Patent Publication No. Sho 54-929), 4, 4 can be produced by using a chloromethylation reaction of biphenyl, polyoxymethylene, hydrogen chloride gas, zinc chloride or cyclohexane. '-Bis(chloromethyl)-1,1'-biphenyl. In addition, the method described in Japanese Patent Laid-Open No. Hei 9-208506, JP-A No. 10-139699, and Japanese Patent No. 3784865 can be cited.

The halomethylation reaction of the present invention may be carried out as long as it contains the above composition, that is, it contains 60% to 80% of dihalomethylbiphenyl, and 15% to 30% of tris(halomethyl)biphenyl and tetra( The method of reacting the halomethyl)biphenyl and the other by-products of the remainder may be any of the above methods, or may be other methods.

In the following, the reaction example of Patent Document 8 of the most typical example will be described as an example of the halomethylation reaction of the present invention.

Preferable examples of the carbon source of the methyl group in the halomethylation include, for example, formalin, polyoxymethylene, methylal, and three. Formaldehydes such as trioxane are more preferably polyoxymethylene.

The feed equivalent of the carbon source (for example, formaldehyde in the reaction example of Patent Document 8) differs depending on the halomethylation rate (the number of halomethyl groups per molecule) relative to biphenyl, but is relative to The 1 molar biphenyl is preferably 1 equivalent to 15 equivalents, more preferably 1.5 equivalents to 10 equivalents, particularly preferably 2 equivalents to 8 equivalents. When it is 1 equivalent or less, the reaction point with biphenyl having a phenolic hydroxyl group is insufficient, and if it exceeds 15 equivalents, the reaction point and the crosslinking point are too large to be used. The amount of the substance becomes too large, or the concentration of the solid portion is increased to deteriorate the stirring state.

Any hydrogen halide may be used as the halogen source for halogenation, or any hydrogen halide may be used as the reaction. Hydrogen halide is most commonly used as the halogen source. Preferable examples of the hydrogen halide include hydrogen chloride, hydrogen bromide, and hydrogen iodide, and hydrogen chloride is preferred. These hydrogen halides can be utilized in the form of a gas. When a hydrogen halide is used in a gaseous form, the reaction can be carried out by directly blowing into a raw material mixture other than hydrogen halide.

Although hydrogen halide can also be used as a hydrogen halide solution in water or acetic acid or other organic solvents, the method of using hydrogen chloride in a gaseous form is preferred.

In the halomethylation reaction, in order to obtain a reaction product of the above composition, it is preferred to suppress the formation of a methylene-crosslinked diarylmethane which is observed as a by-product. It is known that when the concentration of hydrogen halide in the reaction system is low, diarylmethane is preferentially formed. In order to suppress the formation of the by-product, it is preferred to increase the concentration of the hydrogen halide. Therefore, it is preferred to introduce an excessive amount of hydrogen chloride gas into the reaction liquid. The method of introducing an excessive amount of hydrogen chloride gas may, for example, be a method of introducing hydrogen chloride gas under a pressurized condition or a low temperature condition.

In the reaction, preferred examples of the catalyst include sulfuric acid, thionyl chloride, orthophosphoric acid, zinc chloride, aluminum chloride, iron chloride, tin chloride, and the like. Friedel-Crafts type reaction catalyst; tetra-ammonium salt such as tetrabutylammonium bromide, trimethylbenzylammonium chloride, cetylpyridinium chloride. Among these, zinc chloride, aluminum chloride, ferric chloride, tin chloride, tetrabutylammonium bromide, trimethylbenzylammonium chloride, cetylpyridinium chloride are preferred. In particular, zinc chloride is particularly preferred because it is inexpensive and easy to handle.

The amount of the catalyst used is not particularly limited, but it is preferably in the range of 0.01 mol to 3 mol with respect to biphenyl. It is preferably in the range of 0.1 mol to 1 mol.

The solvent to be used in the reaction is not particularly limited as long as it is a non-reactive solvent. Preferred examples of the solvent include aliphatic hydrocarbon solvents (for example, a chain alkane such as hexane or heptane, a cyclic alkane such as cyclopentane or cyclohexane, and kerosene), and an aliphatic carboxylic acid solvent (for example, formic acid). , acetic acid, propionic acid, etc.), aromatic hydrocarbon solvents with low electron density of aromatic rings (such as chlorobenzene, nitrobenzene, o-dichlorobenzene, trichlorobenzene, etc.), aliphatic halogenated hydrocarbon solvents (such as chloroform, dichloro An organic solvent such as methane, dichloroethane or tetrachloroethane.

These solvents may be used alone or in combination of two or more. Preferable examples of the solvent include a C5-C6 cyclic alkane, and preferred examples thereof include cyclohexane which is inexpensive and which is easily removed by a low boiling point.

Further, when zinc chloride is used as a catalyst, an aliphatic alcohol such as 1-pentanol or 1-hexanol or water may be added depending on the degree of moiré such as a catalyst. It is known that such additions increase the solubility of the catalyst and enhance the reactivity depending on the situation (Bull. Chem. Soc. Jpn. 66, 3520 (1993)). It is also not particularly added in the present invention.

The amount of the solvent to be used is not particularly limited, but is preferably from about 1 part by weight to about 10 parts by weight, based on the solid part, more preferably not more than 8 parts by weight.

The reaction temperature is usually not particularly limited as long as it is an allowable temperature range in the solvent to be used. It is usually from 0 ° C to 100 ° C, preferably from about 15 ° C to 60 ° C. When the reaction is carried out near room temperature, it is preferably near room temperature.

In general, since the methylene-crosslinked diarylmethane which is observed as a by-product in the chloromethylation reaction is preferentially formed when the reaction temperature is high, in order to suppress such by-products into a small amount It is preferred to lower the reaction temperature.

The reaction time is not particularly limited. It usually takes about 6 hours to 36 hours.

The feeding method is not particularly limited. Preferably, the raw material other than the hydrogen halide is initially fed, and then the hydrogen halide gas is blown into the system to maintain the state in which the hydrohalic acid in the system is excessive. Hydrogen halide is preferably hydrogen chloride.

In the present invention, the composition of the reaction product obtained as described above is a ratio of the total amount (total amount) of the reaction product measured by GC-MS (GC area ratio, the same as follows unless otherwise specified) Containing more than 60% and less than 80% of dihalomethylbiphenyl (preferably dichloromethylbiphenyl), a total content of 15% to 30% of tris(halomethyl)biphenyl (preferably three) a mixture of (chloromethyl)biphenyl) and tetrakis(halomethyl)biphenyl (preferably tetrakis(chloromethyl)biphenyl) and other by-products of the remainder (hereinafter, also referred to as the case It is a mixture of biphenyl compounds having a halomethyl group). Further, the total amount of dihalomethylbiphenyl, tris(halomethyl)biphenyl and tetrakis(halomethyl)biphenyl is preferably from 75% to 97%, more preferably from 80% to 95%. .

The main component of the dihalomethylbiphenyl is composed of 4,4'-dihalomethylbiphenyl and its positional isomers. In the dihalomethylbiphenyl, 4,4'-dihalomethyl linkage The benzene system accounts for about 50% to 98%, preferably about 60% to 95%, and the remainder is considered to be its isomer.

The main compound contained in the reaction product is represented by a compound in which a halomethyl group is a chloromethyl group, and is represented by a chemical formula as shown in Table A below. The "chloromethyl group" in Table A and the "chloromethyl group" in the following description are all interchangeably interpreted as "halomethyl" in the present invention.

The 4,4'-dichloromethyl-biphenyl group represented by Formula 1-3 is a main component of bischloromethylbiphenyl, and is considered to be 50% to 98% in bischloromethylbiphenyl, preferably. It is about 60% to 98%. In bischloromethylbiphenyl, the remainder other than 4,4'-dichloromethyl-biphenyl is considered to be 2,4'-dichloromethyl-biphenyl as shown in Formula 1-4. Positional isomer.

Tris(chloromethyl)biphenyl and tetrakis(chloromethyl)biphenyl are considered to be, for example, compounds of the formula 1-5 to formula 1-8 and the isomers (substituted positional isomers) Composition.

Examples of other by-products include monochloromethylbiphenyl (for example, a compound represented by Formula 1-1 and Formula 1-2), bisphenylmethane (Formula 1-9), and monochloromethyl group. - bisphenylmethane (a compound represented by Formula 1-10, etc.), bischloromethyl-diphenylmethane (a compound represented by Formula 1-11, etc.), etc.

The content of the bischloromethylbiphenyl is 60% or more and less than 80%, and preferably 65% to 75%, based on the total amount of the reaction product.

The total content of tris(chloromethyl)biphenyl and tetrakis(chloromethyl)biphenyl is from 15% to 30%, preferably from 15% to 25%, based on the total amount of the reaction product. The ratio of each of tris(chloromethyl)biphenyl and tetrakis(chloromethyl)biphenyl varies depending on the reaction conditions, so it cannot be generalized, but tris(chloromethyl)biphenyl relative to the total amount of the reaction product. The content is from 5% to 25%, preferably from 10% to 20%.

The content of tetrakis(chloromethyl)biphenyl is preferably from about 1% to about 15%, more preferably from 2% to 10%, based on the total amount of the reaction product.

Among the other by-products, monochloromethylenebiphenyl is usually the most, and the ratio (GC area ratio) of the entire reaction product measured by GC-MS (hereinafter, the same is true unless otherwise stated) is 1 % to about 10%.

Next, the reaction of the reaction product obtained above with phenol (also referred to as a methylene crosslinking reaction), and the phenol resin mixture of the present invention obtained by the reaction will be described.

The methylene crosslinking reaction is a condensation reaction in which a reaction product obtained as described above (a mixture of the above-described biphenyl compound having a halomethyl group) is condensed with a phenol. The methylene crosslinking reaction is preferably carried out under acidic conditions, for example, at a pH of about 1 to 4.

For example, the reaction can generally be referred to the 5th edition of Experimental Chemistry Lecture 26(2) P.142 (2005).

As described above, the halomethylation reaction product of biphenyl is a mixture, and in the present invention, the mixture is characterized by being directly used in a cross-linking reaction with a methylene group of a phenol. Therefore, the reaction liquid obtained by the halomethylation reaction can usually be used as it is.

Further, if necessary, the reaction solution may be subjected to concentration, dilution, degassing, water washing, neutralization, filtration, etc., and then used as a raw material for reaction with phenol. In this case, it is also preferable that it is substantially within the range of the composition of the reaction product.

It is generally preferred to use the reaction solution of the halomethylation reaction of biphenyl directly for subsequent methylene crosslinking reaction with phenol.

The methylene crosslinking reaction may be added with an acid catalyst as needed, and it is usually carried out in the presence of an acid catalyst. The acid catalyst can be used in various forms, and examples thereof include organic or inorganic acids such as sulfuric acid, p-toluenesulfonic acid, oxalic acid, methanesulfonic acid, and trifluoromethanesulfonic acid; zinc chloride, aluminum chloride, and ferric chloride; , a ferric acid such as tin chloride, such as a sulphate-Kraft type.

The amount of such acid catalyst used varies depending on the type of the catalyst, but it may be added in the range of 0.001 to 10 times the molar ratio with respect to the phenol. The amount is preferably from about 0.05 to about 3 moles.

In a preferred embodiment of the present invention, since the reaction liquid of the halomethylation reaction is directly used and the above condensation reaction is carried out, the acid catalyst used in the halomethylation reaction can be used as it is without re-adding. Acid catalyst.

The halomethylation reaction product of biphenyl and the phenol can be reacted in any ratio. In general, the halomethyl group 1 molar in the halomethylation reaction product of biphenyl is preferably from 1.5 moles to 40 moles, more preferably from 2 moles to 10 moles. In this case, if it is 1.5 mol or less, there is a high molecular weight, and if it exceeds 40 mol, the efficiency of the reactor may be deteriorated.

The amount of phenol added is approximately 0.3 times to 2 times (by weight), 0.5 times to 1.5 times, relative to the total amount of biphenyl, carbon source and acid catalyst added to achieve halomethylation of biphenyl. The amount is better.

Further, the reaction tracking of this reaction is preferably carried out by analyzing the residual amount of the halomethyl group to confirm the disappearance of the halomethyl group. Further, the total amount of saponifiable chlorine can be suitably used in accordance with, for example, the description of JIS K7246. In addition to this, it is also possible to perform the treatment before the reaction of the halomethyl group of the reactive mixture with the dye of the indicator, and the like.

The methylene crosslinking reaction (condensation reaction) can be carried out without a solvent or in the presence of a solvent. It is preferred to use a reaction liquid in which the above-mentioned halomethylation reaction is directly used, and the organic solvent exemplified in the above-mentioned halomethylation reaction can be used as it is. Therefore, a preferred solvent is, for example, a C5-C6 cyclic alkane, and a preferred example thereof is cyclohexane.

The solvent is usually used in an amount of from 5% by weight to 300% by weight, based on the total weight of the halomethylation reaction product of the biphenyl and the phenol, preferably from 10% by weight to 200% by weight. The reaction temperature of the methylene crosslinking reaction is usually from 0 ° C to 120 ° C, preferably from about 15 ° C to 100 ° C. The reaction time is usually from 1 hour to 10 hours.

The methylene crosslinking reaction is carried out by directly adding a phenol to a reaction liquid of a halomethylation reaction after carrying out a halomethylation reaction, and performing the reaction. The reaction solution of the halomethylation reaction may also be added to the phenol (and a mixture of the acid catalyst and the solvent as needed) as needed. Further, if necessary, it is also possible to carry out operations such as dilution, degassing, water washing, neutralization, etc., before and after the composition of the reaction product is not greatly changed.

After completion of the condensation reaction, the acid catalyst is removed by neutralization, water washing, or the like, and then the solvent to be used is removed by heating under reduced pressure to obtain the desired phenol resin mixture. It is preferred to remove the solvent to be used together with the unreacted phenol under heating and reduced pressure.

In the present invention, it is generally preferred that the recrystallization treatment is not carried out, and after the methylene crosslinking reaction is completed, the acid catalyst is removed by neutralization, water washing, etc., and then the solvent used and the unreacted phenol are removed. A phenol resin mixture is obtained, and this phenol resin mixture is used for the subsequent epoxidation reaction.

The reaction solution after the end of the methylene crosslinking reaction can be further used in the subsequent epoxidation step without removing the solvent and the unreacted phenol. At this time, in order to use the hydrogen halide or acid touch used in the reaction. The medium is neutralized, and it is necessary to carry out an operation of treating with a base such as an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. Further, since the unreacted phenol reacts with the epoxidized epichlorohydrin or the like, it cannot be said to be very good.

The phenol resin mixture of the present invention obtained as described above is a phenol resin mixture in which a phenol and a biphenyl are linked by a methylene crosslinking group (part of which is a biphenyl group which is linked by a methylene crosslinking group). Further, it also includes a phenol resin in which a phenol and a biphenyl are crosslinked by a methylene group, and is used as a raw material of the epoxy resin mixture of the present invention, and can be used as an epoxy resin mixture through a subsequent epoxidation reaction.

The phenol resin mixture of the present invention obtained as described above has a softening point of 65 ° C to 85 ° C, and the number average molecular weight determined by GPC (gel permeation chromatography) is about 350 to 1200, and is about 400 to 1000. Preferably, it is preferably from about 450 to 950, preferably from about 500 to 900, and the weight average molecular weight is from about 400 to about 2,000, preferably from about 500 to about 1,700, preferably from about 550 to about 1600, and most preferably from about 600 to about 1600. To about 1000. The OH equivalent is from about 160 g/eq to about 250 g/eq, preferably from about 170 g/eq to about 240 g/eq, most preferably from about 180 g/eq to about 230 g/eq.

The chemical structure of a representative compound of the phenol resin mixture of the present invention is based on the analysis results of the reaction product of the halomethylation reaction, etc., and is exemplified by F2-1 to F2-6 exemplified below. Where n is from about 1 to about 10.

The phenol resin mixture of the present invention is a mixture of a linear molecule or a branched molecule as exemplified below.

(F2-1 to F2-3)

(F2-4 to F2-6)

Next, the epoxidation reaction for obtaining the epoxy resin mixture of the present invention will be explained.

The epoxy resin mixture of the present invention is an epoxide of the phenol resin mixture of the present invention obtained as described above. The phenol resin mixture can be obtained by epoxidation by reaction with epihalohydrin according to a usual method. More specifically, the following methods are listed.

A preferred method of epoxidation may be, for example, a method in which the phenol resin mixture of the present invention is reacted with an epihalohydrin in the presence or absence of a solvent in the presence of an alkali metal hydroxide, and the glycidyl ether is etherified. . In this method, the reaction temperature is usually from about 10 ° C to about 100 ° C, preferably from about 30 ° C to about 90 ° C.

The epoxidation reaction using the epihalohydrin is exemplified by the epoxidation reaction described in Japanese Patent No. 3934829, the one-stage method described in JP-A-2007-308642, and the fusion method.

In the reaction for obtaining the epoxy resin of the present invention, an alkali metal hydroxide may also be used in an aqueous solution thereof. In this case, the method may be as follows: continuously adding an aqueous solution of an alkali metal hydroxide to the reaction system while continuously distilling off water and epihalohydrin under reduced pressure or normal pressure, and then A method in which the epihalohydrin is continuously returned to the reaction system by separating and removing water. Further, in the present invention, the catalyst which has been used up to the previous step is used without any special operation, that is, it is left without being removed, and therefore, it is carried out by feeding an excessive amount of an alkali metal hydroxide which is usually more than usual. Neutralization operation allows the reaction to proceed smoothly.

Further, it may be a method of adding vaporized tetramethylammonium, tetramethylammonium bromide, trimethylbenzylammonium chloride, etc. to the mixture of the phenol resin mixture of the present invention and an epihalohydrin. The quaternary ammonium salt is used as a catalyst and reacted at 50 ° C to 150 ° C for 0.5 hour to 8 hours to obtain a haloalcohol ether compound of a phenol resin, and then a solid or aqueous solution of an alkali metal hydroxide is added, at 20 ° C to 120 ° C A method of dehydrohalogenating (closed loop) by reacting for 1 hour to 10 hours.

Preferred examples of the epihalohydrin include epichlorohydrin, epibromohydrin, epiiodohydrin, β-methylepichlorohydrin, α-methylepichlorohydrin, and γ-methylepichlorohydrin. Chlorohydrin is preferred.

The epihalohydrin used in the above epoxy reaction is usually used in an amount of from 0.8 to 12 equivalents, preferably from 0.9 to 11 equivalents, per equivalent of the hydroxyl group of the phenol resin of the present invention. In this case, in order to allow the reaction to proceed smoothly, a polar solvent is preferably added, preferably an alcohol (for example, a C1-C4 alcohol such as methanol or ethanol) or an aprotic polar solvent (for example, dimethylsulfone or dimethylene). It is preferred to carry out the reaction by dimethylsulfoxide or the like. The amount of the polar solvent to be used may be appropriately selected and used depending on the type of the solvent or the like, etc., in an amount of from 2% by weight to 150% by weight, based on the amount of the epihalohydrin. For example, when an alcohol is used, it is usually used in an amount of 2% by weight to 20% by weight, preferably 4% by weight to 15% by weight based on the amount of the epihalohydrin. Further, when an aprotic polar solvent is used, it is usually from 5% by weight to 150% by weight, preferably from 10% by weight to 140% by weight, based on the amount of the epihalohydrin.

The alkali metal hydroxide may, for example, be lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide or barium hydroxide, preferably sodium hydroxide or potassium hydroxide.

The epoxy resin mixture of the present invention can be obtained by subjecting the reaction product of the epoxidation reaction to washing with water or without washing with water, removing epihalohydrin, a solvent, and the like under heating and reduced pressure.

Further, in order to further prepare an epoxy resin mixture having less hydrolyzable halogen, it is preferred to dissolve the recovered epoxy resin mixture in a solvent such as toluene, methyl isobutyl ketone or the like, and add sodium hydroxide thereto. An aqueous solution of an alkali metal hydroxide such as potassium hydroxide is reacted with a hydrolyzable halogen contained in the reaction product to remove a hydrolyzable halogen. With this post-treatment, the epoxy ring can also be made more reliable. The post-treated alkali metal hydroxide is usually used in an amount of from 0.01 to 0.3 equivalents, preferably from 0.05 to 0.2 equivalents, per equivalent of the epoxy group in the reaction product. The post-treatment temperature is usually from 50 ° C to 120 ° C, and the reaction time is usually from 0.5 hour to 2 hours.

After the post-treatment, the resulting salt is removed by filtration, water washing or the like, and the solvent is further distilled off under heating and reduced pressure to obtain an epoxy resin mixture of the present invention.

The epoxy resin mixture of the present invention obtained by the above operation has a softening point of 50 ° C to 75 ° C, preferably 52 ° C to 65 ° C, more preferably 54 ° C to 60 ° C, and an ICI viscosity of 0.02 Pa ‧ s to 0.50Pa‧s, preferably 0.04Pa‧s to 0.40Pa‧s, more preferably 0.06Pa‧s to 0.20Pa‧s, and the number average molecular weight determined by GPC (gel permeation chromatography) is 400 to 1200 or so, preferably 500 to 1000 or so, preferably 600 to 900 or so, preferably 600 to 850 or so, and the weight average molecular weight is about 800 to 2000, preferably about 900 to 1800, and 1000 to 1600 or so is better, and the best is about 1000 to 1500. The epoxy equivalent is from about 200 g/eq to about 360 g/eq, preferably from 230 g/eq to 340 g/eq, most preferably from 250 g/eq to 310 g/eq.

The chemical structures of representative compounds of the epoxy resin mixture of the present invention are exemplified by the following F3-1 to F3-6 and the like. The epoxy resin mixture of the present invention is a reaction product of the phenol resin mixture of the present invention and an epihalohydrin, and is a mixture of a linear molecule or a branched molecule as exemplified below.

Further, n in the formula is the same as in the above F2-1 to F2-6.

(F3-1 to F3-3)

(F3-4 to F3-6)

Next, the epoxy resin composition of the present invention will be described.

The epoxy resin composition of the present invention is not particularly limited as long as it contains the epoxy resin mixture and the curing agent of the present invention.

For example, in the epoxy resin composition of the present invention, in addition to the epoxy resin mixture of the present invention, other epoxy resins may be used in combination as one of the components of any of the additive components. When used in combination, the ratio of the epoxy resin mixture of the present invention to the total epoxy resin is preferably 30% by weight or more and 100% by weight or less, more preferably 40% by weight or more and 100% by weight or less or less. 50% by weight or more and 100% by weight or less are particularly preferable. The epoxy resin mixture of the invention is preferably 60% by weight or more, and 70% by weight, from the viewpoint of sufficiently achieving the characteristics of the epoxy resin mixture of the invention, particularly the excellent flame resistance of the cured product and the proper storage modulus of elasticity. The above is preferable, and it is particularly preferably 80% by weight or more, and more preferably 90% by weight or more. The upper limit is 100% by weight.

Other epoxy resins which can be used in combination with the epoxy resin mixture of the present invention include, for example, a novolac type epoxy resin, a bisphenol A type epoxy resin, a triphenylmethane type epoxy resin, and the like.

Specifically, examples thereof include glycidyl ether compounds of an aromatic compound having 2 to 4 hydroxyl groups (for example, bisphenol A, bisphenol F, bisphenol S, decylene diphenol, terpene diphenol, 4,4'-biphenol (4,4'-biphenol), 2,2'-biphenol, 3,3'-5,5'-tetramethyl-[1,1'-biphenyl]-4, 4'-diol, hydroquinone, resorcinol, naphthalenediol, tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane Or a phenol (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and an aldehyde or a ketone, or a reactive derivative thereof (eg, formaldehyde, Acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone or o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-double ( Chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 1,4-bis(chloromethyl)benzene, 1,4 a glycidyl etherate of a polycondensate of bis(methoxymethyl)benzene or the like; a glycidyl etherate of the polycondensate modified product; a shrinkage derived from a halogenated bisphenol or an alcohol such as tetrabromobisphenol A Glycerol ether Thereof; alicyclic epoxy resins; glycidyl amine-based epoxy resins; glycidyl ester epoxy resin; a solid or liquid epoxy resin and the like. These may be used alone or in combination of two or more. In addition, epoxy resins other than these may be used in combination.

In the epoxy resin composition of the present invention, the phenol resin mixture of the present invention can be used alone or in combination with other hardeners as a hardener. When used in combination, the proportion of the phenol resin mixture of the present invention in the total hardener is preferably 30% by weight or more, more preferably 40% by weight or more. The upper limit is 100% by weight.

Examples of the curing agent used in the epoxy resin composition of the present invention include an amine compound, an acid anhydride compound, a guanamine compound, and a phenol compound. Specific examples include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylphosphonium, isophoronediamine, trifluoroborane-amine. An amine compound such as a complex compound; a guanamine compound such as a polyamine compound synthesized from a dimer of dicyandiamide or linolenic acid; and a phthalic anhydride or a trimellitic anhydride; An acid anhydride compound such as pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride or methyl hexahydrophthalic anhydride; Phenols to 4 hydroxyl groups {bisphenol A, bisphenol F, bisphenol S, sub-digodiol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 '-5,5'-Tetramethyl-[1,1'-biphenyl]-4,4'-diol, hydroquinone, resorcinol, naphthalenediol, tris-(4-hydroxyphenyl) Methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane}, phenols (phenols, alkyl-substituted phenols, naphthols, alkyl-substituted naphthols, dihydroxybenzenes, dihydroxynaphthalenes, etc.) 1 to 2 hydroxy benzene or naphthalene, and may be substituted by an alkyl group which is a C1-C4 alkyl group And a condensate of aldehydes or ketones {formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone}, or Reactive derivatives of phenols with aldehydes or ketones {dicyclopentadiene, furfural, 4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis (a) a polycondensate of oxymethyl)-1,1'-biphenyl, 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, etc., and the polycondensate A modified substance, a phenol compound such as tetrabromobisphenol A; an imidazole; a guanidine derivative or the like. However, it is not limited to this.

These may be used alone or in combination of two or more.

Among these hardeners, a phenol compound or an amine compound is preferred, and a phenol compound, especially a phenol aralkyl resin or a phenol resin mixture of the present invention is preferred. The most preferred is a phenol aralkyl resin.

The amount of the hardener used in the epoxy resin composition of the present invention is equivalent to 1 equivalent of the epoxy group of the epoxy resin, and is equivalent to the hydroxyl group equivalent of the epoxy group of the hardener. The amine compound is preferably an amine equivalent weight based on 0.7 equivalents to 1.2 equivalents. With respect to 1 equivalent of the epoxy group, when the active group equivalent of the hardener is less than 0.7 equivalent or more than 1. 2 equivalents, the hardening is incomplete and the good hardenability is not obtained.

In the epoxy resin composition of the present invention, there is no problem even if a hardening accelerator is used. Specific examples of the hardening accelerator which can be used include, for example, imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole; 2-(dimethylaminomethyl)phenol And tertiary amines such as 1,8-diazabicyclo(5,4,0)undecene-7; phosphines such as triphenylphosphine; and metal compounds such as tin octylate. Although it is not necessary to use a hardening accelerator, when it is used, 0.1 parts by weight to 5.0 parts by weight may be appropriately used depending on 100 parts by weight of the epoxy resin.

In the epoxy resin composition of the present invention, an inorganic filler (also referred to as a filler) may be added as needed. Examples of the inorganic filler include crystalline cerium oxide, molten cerium oxide, alumina, zircon, calcium silicate, calcium carbonate, cerium carbide, cerium nitride, boron nitride, and zirconia. ), forsterite, steatite, spinel, titania, talc, or other spheroidal beads (beads) Etc., but not limited to this. These may be used alone or in combination of two or more. The content of such inorganic fillers is from 0% by weight to 95% by weight, preferably from 20% by weight to 95% by weight, more preferably from 50% by weight to 95% by weight, based on the total amount of the epoxy resin composition. It is particularly preferably from about 70% by weight to about 95% by weight, more preferably from 70% by weight to 90% by weight.

In the epoxy resin composition of the present invention, it may be further added as needed: a decane coupling agent; a release agent such as stearic acid, palmitic acid, zinc stearate, calcium stearate; carbon black, phthalocyanine blue (phthalocyanine blue), phthalocyanine green and other colorants; polybutadiene and its modified materials, modified acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimine, fluororesin, Malay An additive such as a quinone imine compound, a cyanate resin (or a prepolymer thereof), a polymer such as a silicone gel or a polyoxygenated oil; or the like.

The more preferred epoxy resin composition of the present invention is as follows.

(1) An epoxy resin composition comprising the epoxy resin mixture of the present invention and a hardener, wherein the epoxy group reacts with an epoxy group of the hardener in an amount of 1 equivalent with respect to the epoxy group of the epoxy resin The base equivalent is from 0.7 equivalents to 1.2 equivalents of the hardener, and the epoxy resin mixture of the present invention is contained in an amount of from 4% by weight to 80% by weight based on the total amount of the epoxy resin composition, and the remainder is any optional component .

(2) The epoxy resin composition according to the above (1), wherein the optional additive component is an inorganic filler, and the content thereof is 50% by weight to 95% by weight based on the total amount of the epoxy resin composition. It is 70% by weight to 90% by weight.

(3) The epoxy resin composition according to the above (2), wherein the epoxy resin mixture of the present invention is 5% by weight to 30% by weight based on the total of the epoxy resin mixture and the inorganic filler of the present invention. And the remainder is an inorganic filler.

(4) The epoxy resin composition according to any one of (1) to (3) above, wherein the optional component is either or both of a release agent or a coupling agent, and the content thereof is relative to The total amount of the epoxy resin composition is from 0.05% by weight to 1% by weight.

(5) The epoxy resin composition according to any one of the above (1) to (4) wherein the epoxy resin mixture of the present invention has a softening point of 52 ° C to 65 ° C and an ICI viscosity of 0.04 Pa ‧ s The number average molecular weight determined by GPC (gel permeation chromatography) was from 400 to 1200 and the weight average molecular weight was from 800 to 2,000, and the epoxy equivalent was from 200 g/eq to 360 g/eq to 0.40 Pa s.

(6) The epoxy resin composition according to any one of (1) to (5) above, wherein the epoxy resin mixture of the present invention is obtained by epoxidizing a phenol resin mixture, the phenol The resin mixture is obtained by subjecting a reaction product obtained by a halomethylation reaction of biphenyl to a methylene crosslinking reaction with a phenol, and wherein the ratio of the reaction product as a whole is measured with respect to GC-MS ( GC area ratio), containing: 60% or more and less than 80% of dihalomethylbiphenyl, a total of 15% to 30% of tris(halomethyl)biphenyl and tetrakis(halomethyl)biphenyl, and Other by-products of the remainder.

(7) The epoxy resin composition according to the above (6), wherein the phenol resin mixture has a softening point of from 65 ° C to 85 ° C, and the number average molecular weight determined by GPC (gel permeation chromatography) is 350 to 1200, the weight average molecular weight is from 400 to 2,000, and the OH equivalent is from 160 g/eq to 250 g/eq.

(8) The epoxy resin composition according to any one of the above (1), wherein the curing agent is a phenol compound.

The epoxy resin composition of the present invention is obtained by uniformly mixing the epoxy resin mixture, the curing agent, and any optional components of the present invention. The epoxy resin composition of the present invention can be easily produced into a cured product by the same method as the conventionally known method.

More specifically, first, the epoxy resin mixture of the present invention and a hardener, and any optional components as needed, for example, using an extruder, a kneader, a roll, etc. (for example, selected from a hardening accelerator) The components of the inorganic filler, the coupling agent, and the release agent are thoroughly mixed until they become uniform, and the epoxy resin composition of the present invention is prepared. Next, the obtained epoxy resin composition is melted, and then molded by a casting or transfer molding machine, an injection molding machine, a casting machine, or the like, and more preferably heated at 80 ° C to 200 ° C for 2 hours to 16 hours. As a post cure, a cured product of the epoxy resin composition of the present invention can be obtained.

Further, the epoxy resin composition of the present invention may be low-viscosity by heating and melting, or may be low-viscosity by mixing a solvent into the epoxy resin composition, and then impregnated into the glass fiber. A substrate such as carbon fiber, polyester fiber, polyamide fiber, alumina fiber or paper is heated to be semi-dried to obtain a prepreg, and the prepreg is subjected to hot press molding to obtain a cured product. Examples of the solvent include aromatic solvents such as toluene and xylene; ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; N,N-dimethylformamide and N,N- A guanamine solvent such as dimethylacetamide or N,N-dimethylimidazolidinone; an oxime solvent such as dimethyl hydrazine or cyclobutyl hydrazine; N-methylpyrrolidine An internal amide solvent such as ketone (N-methylpyrrolidone); a lactone solvent such as γ-butyrolactone; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether single B A solvent such as an ether solvent such as an acid ester or propylene glycol monobutyl ether.

The solvent to be used may be used singly or in combination of two or more. Further, when the above solvent is mixed, the solvent is usually used in an amount of from 10% by weight to 70% by weight, preferably from 15% by weight to 70% by weight based on the total amount of the mixture of the epoxy resin composition of the present invention and the solvent. %.

The prepreg is cut into a desired shape, and if necessary, laminated with a copper foil or the like, and then applied by a press molding method, an autoclave molding method, a sheet winding molding method, or the like. By heat-hardening under pressure, a cured product of a prepreg or a laminated board having the cured product can be obtained. Moreover, the circuit may be formed by laminating a laminate of copper foil on the surface and stacking the prepreg and the copper foil thereon, or stacking a copper foil having the above prepreg, and forming a circuit, and if necessary, This operation is repeated to obtain a multilayer circuit substrate.

A semiconductor device manufactured by sealing a semiconductor element (semiconductor wafer) with the epoxy resin composition of the present invention includes, for example, a DIP (dual in-line package), QFP (quartz) Flat package), BGA (Ball Grid Array), CSP (Chip Size Package), SOP (small outline package), TSOP (thin small outline package), TQFP (TQFP) Thin quad flat package, that is, thin quad flat package). In addition, in the field of optical semiconductors, for example, a light-emitting diode (LED), a photoelectric crystal, a CCD (charge-coupled device), a UV-EPROM (UV-erasable programmable read only memory, That is, an optical semiconductor element (semiconductor wafer) such as an EPROM, such as an ultraviolet ray erasable programmable read only memory, is sealed.

The epoxy resin composition of the present invention may be used as a photo-thermosetting resin composition by mixing with a compound having an ethylenically unsaturated group. This composition is a compound having an ethylenically unsaturated group as an optional component added to the epoxy resin composition of the present invention, and preferably contains a crosslinking agent in addition to the alkaline aqueous solution-soluble resin (A). B) Photopolymerization initiator (C).

In such a photocurable resin composition, the content of the epoxy resin mixture of the present invention is usually from 1% by weight to 50% by weight, preferably from 2% by weight to 30% by weight, based on the internal ratio.

The respective components of the photocurable resin composition containing the epoxy resin mixture of the present invention will be more specifically described below.

Alkaline aqueous solution-soluble resin (A): for example, an epoxy carboxylic acid ester compound obtained by reacting an epoxy compound having two epoxy groups in the molecule with a monocarboxylic acid compound having an ethylenically unsaturated group in the molecule Specific examples of the reaction product of the carboxylic anhydride include, for example, KAYARAD CCR-1159H, KAYARAD PCR-1169H, KAYARAD TCR-1310H, KAYARAD ZFR-1401H, and KAYARAD ZAR-1395H (all manufactured by Nippon Kayaku Co., Ltd.).

Crosslinking agent (B): a compound having an ethylenically unsaturated group, and examples thereof include an acrylate, a methacrylate compound, and the like, and specifically, for example, KAYARAD HX-220, KAYARAD HX-620, KAYARAD DPHA, KAYARAD DPCA- 60 (all manufactured by Nippon Kayaku Co., Ltd.) and the like.

Photopolymerization initiator (C): benzoin, acetophenone, anthraquinone, thioxanthone, ketal, benzophenone, phosphine oxide Specifically, for example, KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.), IRGACURE 907 (manufactured by Ciba Specialty Chemicals Co., Ltd.), and the like can be mentioned.

Various additives may be further added for the purpose of improving the properties of the composition, for example: talc, barium sulfate, aluminum hydroxide, aluminum oxide, cerium oxide, clay, etc.; gas phase cerium oxide (AEROSIL) Such as thixotropy-imparting agent; coloring agent such as phthalocyanine blue, phthalocyanine green, titanium oxide; polyfluorene-oxygen, fluorine-based leveling agent or defoaming agent; hydroquinone, hydroquinone monomethyl ether Such as polymerization inhibitors and the like.

The photocurable resin composition may contain a solvent as needed. Solvent series which can be used are: ketones such as acetone, methyl ethyl ketone and cyclohexanone; aromatic hydrocarbons such as benzene, toluene, xylene and tetramethylbenzene; ethylene glycol dimethyl ether and ethylene glycol Diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether and other glycol ethers; ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate (methyl cellosolve acetate), ethylene glycol ethyl ether acetate, ethylene glycol butyl ether acetate, carbitol acetate, propylene glycol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate And esters such as dialkyl adipate; cyclic esters such as γ-butyrolactone; petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum brain, solvent naphtha, and the like. These may be used alone or in combination of two or more.

The photocurable resin composition containing the epoxy resin mixture of the present invention is used as an interlayer insulating material for electronic components, a solder resist for connecting optical components, a solder resist for a printed circuit board, a coverlay, and the like. In addition to the material, it can also be used as a color filter, a printing ink, a sealant, a coating, a coating agent, and an adhesive.

The photocurable resin composition containing the epoxy resin mixture of the present invention can be cured by irradiation with an energy ray such as ultraviolet rays. The hardening by energy rays such as ultraviolet rays can be carried out according to a conventional method. For example, when irradiating ultraviolet rays, a device that generates ultraviolet rays, such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, an ultraviolet light-emitting laser (excimer laser), or the like, may be used.

The photocurable resin composition containing the epoxy resin mixture of the present invention is used as a resist film, an interlayer insulating material for an additive process, or an optical waveguide for use in a printed circuit board, an optoelectronic substrate, or an optical substrate. ‧Electronic ‧ light substrate Specific items such as computers, home electric appliances, and portable machines can be cited. Specifically, for example, when a liquid resin composition is used in the production of a printed wiring board constituting a printed circuit board, first, according to a screen printing method, a spray method, a roll coating method, an electrostatic coating method, By a method such as a curtain coating method, a photocurable resin composition containing the epoxy resin of the present invention is applied to a printed wiring board at a film thickness of 5 μm to 160 μm, and the coating film is usually at 50 ° C to 110 ° C (preferably 60). Drying at ° C to 100 ° C) to form a coating film. Then, a mask having an exposure pattern is formed through a negative film or the like, and the coating film is directly or indirectly irradiated with a high-energy line such as ultraviolet rays at an intensity of about 10 mJ/cm ² to 2000 mJ/cm ² , and an unexposed portion. The developing solution described later is used for development by spraying, shaking, scouring, brushing, scrubbing, or the like. Thereafter, ultraviolet rays are further irradiated as needed, and secondly, heat treatment is usually performed at a temperature of from 100 ° C to 200 ° C (preferably from 140 ° C to 180 ° C), thereby obtaining excellent gold plating properties and satisfying heat resistance and resistance. A printed wiring board of a permanent protective film having properties such as solvent resistance, acid resistance, adhesion, and flexibility.

The above developing solution can be an inorganic alkaline aqueous solution such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium phosphate or potassium phosphate, or tetramethylammonium hydroxide or hydroxide. An organic alkaline aqueous solution such as tetraethylammonium, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine or triethanolamine.

(Example)

Hereinafter, the present invention will be described in more detail based on examples.

Further, in the following, the resin properties were measured by the following methods.

‧ Determination of softening point: determined according to the method of JIS K-7234

‧GC-MS (gas chromatography-mass spectrometry) determination

Model: 5975 inert MSD (Agilent)

Column: HP-5MS 15m-0.25mm-0.25μm

Carrier gas: helium gas 1.0mL / min (Constant flow mode)

Oven: 50 ° C (2 minutes) -10 ° C / min - 300 ° C (23 minutes)

Injection: 1 μL, Split (30:1), 300 ° C

Ion source: EI

Measured by SEM-EDS (Scanning electron microscopy-Energy dispersive spectroscopy, ie, scanning electron microscope-energy dispersive spectrometer)

Model: JED-2140 (made by JEOL)

Acceleration voltage: 20kV

Working distance: 10mm

‧ Determination of number average molecular weight and weight average molecular weight determined by GPC (gel permeation chromatography)

Pipe column: Showa Denko Co., Ltd. Shodex KF-801, KF-802, KF-802.5, KF-803

Column temperature: 40 ° C

Injection amount: 0.02mL

Liquid volume: 1.0mL/min

Detector: RI

Solvent: tetrahydrofuran

‧ Measurement of viscosity: measured at 150 ° C using an ICI viscosity meter (manufactured by CODIX Co., Ltd.)

‧ Determination of OH equivalent: The equivalent is the average mass of the compound per OH group, determined according to the acetonitrile method of JIS K-0070

‧ Determination of epoxy equivalent: The equivalent is the average mass of each epoxy compound, measured according to JIS K-7236

DMA (Dynamic Viscoelasticity Measurement) Analysis: The storage elastic modulus at Tg and 250 ° C was measured using a DMA 2980 (Dynamic Viscoelasticity Tester) manufactured by TA Instruments Co., Ltd. at a frequency of 10 Hz.

Example 1

(1) Chloromethylation of biphenyl

In a 300 mL flask made of a stirrer, a thermometer, and a cooler, 200 mL of cyclohexane, 77.05 g of biphenyl, 33.55 g of polyacetal, and 46.38 g of zinc chloride were fed. While stirring vigorously, hydrogen chloride gas was strongly blown into the mixture to carry out a reaction until it became a homogeneous solution. During this time, the liquid temperature was maintained at 50 °C. Further, the liquid temperature was lowered by 30 ° C, hydrogen chloride gas was blown thereinto for 24 hours, and the reaction was continued to obtain a reaction liquid.

A small amount of the obtained reaction solution was taken to prepare a dichloromethane solution for GC-MS measurement. As a result, it was found to be 2.5% of mono(chloromethyl)biphenyl, 72.0% of bischloromethylbiphenyl, 14.9% of tris(chloromethyl)biphenyl, and 5.8% of tetrakis(chloromethyl)biphenyl. Further, regarding the by-products other than the above mono(chloromethyl)biphenyl, it was detected as penta(chloromethyl)biphenyl 0.3%, bisphenylmethane 0.5%, and monochloromethyl-diphenylmethane 1.1. %, dichloromethyl-bisbiphenylmethane 0.6%. Further, a component in which no compound was specified was also contained, and as another by-product, it was found to be 2.3% (full GC area%).

Further, from the insoluble component generated when the reaction liquid was made into a dichloromethane solution for GC-MS measurement, zinc element (Zn) was detected by elemental analysis using SEM-EDS.

(2) Reaction of chloromethylation reaction product with phenol

Next, 157.77 g of phenol was added to the reaction liquid obtained in the above (1), and the mixture was stirred at room temperature for 2 hours. After deaeration of the reaction vessel, the temperature was raised to 180 ° C under reduced pressure for 10 hours, and the solvent cyclohexane and the unreacted phenol were distilled off.

As a result, 181.5 g of the phenol resin mixture of the present invention was obtained. The resin mixture had a softening point of 74.9 ° C, and the number average molecular weight determined by GPC (gel permeation chromatography) was 513, the weight average molecular weight was 639, and the OH equivalent was 215 g/eq.

The composition of the phenol resin mixture is based on the composition of the chloromethylation reaction product of biphenyl obtained in the above (1), and it is estimated that the component derived from bischloromethylbiphenyl (the aforementioned F2-1) is 72%. The component of trichloromethylbiphenyl (the above F2-2) is 15%, the component derived from tetrachloromethylbiphenyl (the aforementioned F2-3) is 6%, and the other components (the aforementioned F2-4, F2-5, F2-6, etc.) is 7%.

Example 2

Synthesis of epoxy resin mixture

In a 300 mL flask made of a glass equipped with a stirrer, a thermometer, and a cooler, 26.3 g of the phenol resin mixture of the present invention obtained in Example 1, 52.0 g of epichlorohydrin, 8.6 g of dimethylarsine, and 30% by weight of hydroxide were fed. 12.3 g of an aqueous sodium solution was stirred and mixed at 45 ° C for 1 hour. Next, 3.95 g of flake-like sodium hydroxide was added thereto, and the mixture was stirred at 45 ° C for 2 hours and then at 70 ° C for 1 hour. Methyl isobutyl ketone was added to the obtained reaction liquid and diluted, and water was added thereto, and the mixture was washed with water/liquid. 0.93 g of a 30% by weight aqueous sodium hydroxide solution was added to the obtained organic layer, and the mixture was stirred at 70 ° C for 1 hour. The water washing was again carried out by liquid/liquid separation in the same manner as above. The resulting reaction liquid was concentrated to obtain 20.5 g of the epoxy resin mixture of the present invention.

The obtained resin mixture had a softening point of 57.6 ° C, an ICI viscosity of 0.11 Pa·s, an epoxy equivalent of 292 g/eq, and a number average molecular weight of 668 and a weight average molecular weight determined by GPC (gel permeation chromatography). For 1187.

The composition of the epoxy resin mixture is based on the composition of the chloromethylation reaction product of biphenyl obtained in the above (1), and it is estimated that the component derived from bischloromethylbiphenyl (the aforementioned F3-1) is 72%. The composition of trichloromethylbiphenyl (the above F3-2) is 15%, the component derived from tetrachloromethylbiphenyl (the aforementioned F3-3) is 6%, and other components (the aforementioned F3-4, F3-5) , F3-6, etc.) is 7%.

Example 3 and Comparative Example 1

Modification of flame resistant resin composition and evaluation of its cured product

The epoxy resin mixture of the present invention obtained in Example 2 or the phenol-biphenyl aralkyl type epoxy resin NC-3000 manufactured by Nippon Kayaku Co., Ltd. as a comparative example (softening point 57.4 ° C, ICI viscosity) 0.08 Pa·s, an epoxy equivalent of 277 g/eq, a number average molecular weight of 793 obtained by GPC, and a weight average molecular weight of 1229), and a flame resistant resin composition having the composition shown in Table 1 below was prepared to transfer a molding machine. Molding was carried out at 175 ° C to obtain a cured product.

(Note)

XLC-3L: phenol aralkyl resin, manufactured by Mitsui Chemicals, Inc.

TPP: triphenylphosphine

MSR-2212: Kyklos MSR-2212, manufactured by Longsen Co., Ltd.

Brazilian Palm No. 1: Brazilian Palm Wax No. 1, manufactured by CERARICA Noda Co., Ltd.

KBM-303: decane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd.

With respect to the hardened material thus obtained, the flame resistance and the storage elastic modulus at 250 ° C were evaluated according to the methods shown below, and the results are shown in Table 2.

‧ Determination of flame resistance: The flame resistance test is based on UL-94, and the total burning time (time until self-extinguishing) is measured on a test piece (hardened material) having a thickness of 0.8 mm.

Measurement of storage modulus at 225 ° C: The storage elastic modulus at Tg and 250 ° C was measured using a DMA 2980 (Dynamic Viscoelasticity Tester) manufactured by TA Instruments Co., Ltd. at a frequency of 10 Hz.

Compared with NC-3000 which is widely used as an excellent flame-retardant resin, the epoxy resin composition containing the epoxy resin mixture of the present invention is equivalent or more excellent in flame resistance, and is at a specific glass transition point. The storage elastic modulus at a higher temperature of 250 ° C is higher than the value of 2000 MPa or more compared with NC-3000, and the epoxy resin composition containing the epoxy resin mixture of the present invention is considered to be resistant to weld cracking. The aspect is preferably in the range of 500 to 1000 MPa. From this feature, it is understood that the epoxy resin composition containing the epoxy resin mixture of the present invention has excellent properties.

The epoxy resin mixture of the present invention has excellent properties as described above, and can be produced consistently from biphenyl, which is also easy to manufacture.

Example 4

(1) Chloromethylation of biphenyl

In a 1000 mL flask made of a stirrer, a thermometer, and a cooler, 200 mL of cyclohexane, 154 g of biphenyl, 66 g of polyoxymethylene, and 93 g of zinc chloride were fed. While stirring vigorously, hydrogen chloride gas was strongly blown into the mixture to carry out a reaction until it became a homogeneous solution. During this time, the temperature was maintained at 30 °C. Then, hydrogen chloride gas was blown at 50 ° C for 10 hours, and the reaction was continued to obtain a reaction liquid.

A part of the reaction solution was taken to prepare an N,N'-dimethylformamide solution for LC measurement. As a result, it was found to be 8.1% monochloromethylbiphenyl, 68.2% bischloromethylbiphenyl, and three (three) The total of chloromethyl)biphenyl and tetrakis(chloromethyl)biphenyl was 18.2% (LC area%).

(2) Reaction of chloromethylation reaction product with phenol

Next, 301 g of phenol was added to the reaction liquid obtained in the above (1), and the mixture was stirred at 70 ° C for 2 hours. While raising the temperature to 180 ° C under reduced pressure, the solvent of cyclohexane and unreacted phenol were distilled off.

As a result, 329 g of the phenol resin mixture of the present invention was obtained.

The resin mixture had a softening point of 79.6 ° C, and the number average molecular weight determined by GPC (gel permeation chromatography) was 855, the weight average molecular weight was 1,332, and the OH equivalent was 196 g/eq.

The composition of the phenol resin mixture is based on the composition of the chloromethylation reaction product obtained in the above (1), and is presumed to contain: 8% of monochloromethylbiphenyl, a component derived from bischloromethylbiphenyl (F2- 1) is 68%, and the component derived from tris(chloromethyl)biphenyl (F2-2) and the component derived from tetrakis(chloromethyl)biphenyl (F2-3, etc.) are 18% in total.

Example 5

Synthesis of epoxy resin mixture

Into a 1000 mL flask made of a stirrer, a thermometer, and a cooler, 196 g of the phenol resin mixture of the present invention obtained in Example 4, 555 g of epichlorohydrin, and 29.6 g of methanol were fed and mixed. While stirring the mixture at 70 ° C, 42 g of sodium hydroxide in the form of a sheet was divided and added thereto. It was then stirred at 70 ° C for 1 hour. After 150 g of water was added to the obtained reaction liquid and mixed, the mixture was allowed to stand, and the aqueous layer separated into two layers was removed. Unreacted epichlorohydrin was distilled off from the washed reaction solution. Methyl isobutyl ketone was added thereto and diluted, and then 13.3 g of a 30% by weight aqueous sodium hydroxide solution was added, and the mixture was stirred at 70 ° C for 1 hour. Water was added thereto, and the liquid/liquid separation was washed with water. The water-washed reaction liquid was concentrated to obtain 215 g of the epoxy resin mixture of the present invention.

The epoxy resin mixture has a softening point of 56.5 ° C, an ICI viscosity of 0.11 Pa·s, an epoxy equivalent of 264 g/eq, and a number average molecular weight of 803 and a weight average obtained by GPC (gel permeation chromatography). The molecular weight is 1419.

The composition of the epoxy resin mixture is based on the composition of the chloromethylation reaction product obtained in the above Example 4 (1), and it is presumed to contain: 8% derived from monochloromethylbiphenyl, derived from dichloromethyl The composition of the phenyl group (structural formula: F3--1, etc.) is 68%, derived from the constituents of tris(chloromethyl)biphenyl (structural formula: F3-2, etc.) and derived from tetra(chloromethyl) linkage The total composition of benzene (structural formula: F3-3, etc.) is 18% in total.

Example 6

Using the epoxy resin mixture of the present invention obtained in Example 5, a flame-retardant resin composition having the composition shown in the following Table 3 was prepared in the same manner as in Example 3, and molded by a transfer molding machine to obtain a cured product.

With respect to the cured product thus obtained, the flame resistance and the storage elastic modulus were measured in the same manner as in Example 3. The results are shown in Table 4.

Example 7

500 g of the phenol resin mixture of the present invention obtained in the same manner as in Example 4 was dissolved in 1000 mL of methyl isobutyl ketone, and the insoluble components were filtered, and water was added thereto, followed by washing with water/liquid. As a result, a phenol resin mixture (referred to as EX7PhnolMix) having a hydroxyl group (OH) equivalent of 204 g/eq was obtained.

The obtained phenol resin mixture was used as a hardener, and the phenol-biphenyl aralkyl type epoxy resin NC-3000 manufactured by Nippon Kayaku Co., Ltd. was used as an epoxy resin, and the composition shown in Table 5 below was prepared. The epoxy resin composition of the invention is molded by a transfer molding machine to obtain a cured product.

With respect to the cured product thus obtained, the flame resistance and the storage elastic modulus were measured in the same manner as in Example 3. The results are shown in Table 6 below.

Example 8 and Comparative Example 2

The phenol resin mixture (EX7PhnolMix) of the present invention obtained in Example 7 was used as a hardener, and the phenol-biphenyl aralkyl type epoxy resin NC-3000 manufactured by Nippon Kayaku Co., Ltd. was used as an epoxy resin. The epoxy resin composition of the present invention (EX8 EPOXY COM) having the composition shown in Table 7 below.

On the other hand, in Comparative Example 2, a phenol-biphenyl aralkyl type phenol resin GPH-65 (OH equivalent: 199 g/eq, softening point 65.1 ° C) manufactured by Nippon Kayaku Co., Ltd. was used instead of the phenol resin mixture of the present invention ( EX7PhnolMix) As a curing agent, a comparative epoxy resin composition (Comparative Example 2) (CPA2 EPOXY COM) shown in Table 7 below was prepared.

The epoxy resin composition prepared above was kneaded by a roll to prepare an epoxy resin composition for evaluation.

The maximum value of the torque was measured using a Curelastometer manufactured by JSR Co., Ltd. to evaluate the hardenability of the epoxy resin composition obtained above.

Further, in terms of evaluation of fluidity, a spiral flow was measured at 175 ° C under a molding pressure of 70 kg/cm ² (according to ASTM F 3133). The results are shown in Table 8.

The larger the Curelastometer torque system of the hardening property index, the stronger the hardening property, the epoxy resin composition of Example 8 showed more excellent hardenability than the epoxy resin composition of Comparative Example 2.

Further, in the epoxy resin composition having the same gel time, the longer the swirling flow as the fluidity index, the higher the fluidity, so that compared with the epoxy resin composition of Comparative Example 2, The epoxy resin composition of Example 8 showed more excellent fluidity.

(industrial availability)

The cured product of the epoxy resin composition containing the epoxy resin mixture of the present invention is excellent not only in flame resistance, but also has a storage elastic modulus at a temperature of 250 ° C in a certain range compared with the conventional flame retardant epoxy resin cured product. When it is lowered, the weld fracture resistance is also excellent. The epoxy resin mixture of the present invention and the epoxy resin composition containing the epoxy resin mixture are suitable as a semiconductor sealing material or a semiconductor peripheral material such as a printed wiring board.

Further, the phenol resin mixture of the present invention is an intermediate material for the epoxy resin mixture of the present invention having the above-described excellent properties, and can be produced because the halomethylbiphenyl of the intermediate is not isolated and purified, so that it is easy to manufacture. It is highly useful in the industry.

Claims (12)

A phenol resin mixture obtained by reacting a halomethylation reaction of biphenyl to a halomethyl 1 mol in a halomethylation reaction product of biphenyl, using 1.5 mol The result is obtained by performing a methylene crosslinking reaction to 40 mol of the phenol, and the reaction product contains 60% or more of the ratio of the reaction product (GC area ratio) measured by GC-MS. 80% of dihalomethylbiphenyl, a total of 15% to 30% of tris(halomethyl)biphenyl and tetrakis(halomethyl)biphenyl, and other by-products of the remainder. The phenol resin mixture as claimed in claim 1 has a softening point of 65 ° C to 85 ° C, and the number average molecular weight determined by GPC (gel permeation chromatography) is 350 to 1200, and the weight average molecular weight is 400 to 2000, and those having an OH equivalent of from 160 g/eq to 250 g/eq. An epoxy resin mixture obtained by epoxidizing a phenol resin mixture of the first or second aspect of the patent application. The epoxy resin mixture according to claim 3 of the patent application has a softening point of 50 ° C to 75 ° C and an ICI viscosity of 0.02 Pa ‧ s to 0.50 Pa s , which is obtained by GPC (gel permeation chromatography). The number average molecular weight is from 400 to 1200 and the weight average molecular weight is from 800 to 2,000, and the epoxy equivalent is from 200 g/eq to 360 g/eq. An epoxy resin composition comprising an epoxy resin mixture and a hardener according to item 3 of the patent application. An epoxy resin composition according to claim 5, wherein the content of the hardener is 1 equivalent to the epoxy group of the epoxy resin mixture. From 0.7 equivalents to 1.2 equivalents. The epoxy resin composition of claim 6, wherein the filler is further contained in an amount of 50% by weight to 90% by weight based on the total amount of the epoxy resin composition. A cured product obtained by curing an epoxy resin composition comprising: an epoxy resin mixture obtained by epoxidizing a phenol resin mixture of the first application of the patent scope; One equivalent of 0.7 to 1.2 equivalents of the hardener per 100 equivalents of the epoxy group of the epoxy resin mixture. A cured product obtained by hardening an epoxy resin composition comprising: an epoxy resin mixture obtained by epoxidizing a phenol resin mixture of the first application of the patent scope; The epoxy group of the epoxy resin mixture has an epoxy group equivalent of 0.7 to 1.2 equivalents of the hardener, and an inorganic filler of 50% by weight to 90% by weight based on the total amount of the epoxy resin composition. A method for producing a phenol resin mixture by reacting biphenyl, 2 to 8 equivalents of formaldehyde with respect to 1 mol of biphenyl, and hydrogen halide in the presence of excess hydrogen halide in the presence of a zinc halide The methylation of benzene is carried out to obtain a dihalomethylbiphenyl having a ratio of 60% or more and less than 80% of the total amount of the reaction product (GC area ratio) measured by GC-MS, and a total of 15% to a reaction product of 30% tris(halomethyl)biphenyl and tetrakis(halomethyl)biphenyl, and other by-products of the remainder, and the reaction product is not refined, ie, relative to the biphenyl Halomethyl 1 molar in the base reaction product, using 1.5 to 40 moles The phenol is reacted to produce a phenol resin mixture. A method for producing an epoxy resin mixture by reacting a phenol resin mixture obtained according to the production method of claim 10 with an equivalent amount of 0.8 to 12 equivalents of epihalohydrin relative to a hydroxyl group of the phenol resin mixture. . An epoxy resin composition comprising a phenol resin mixture of the first or second aspect of the patent application as a hardener.