KR20110094278A - Phenolic resin mixture, epoxy resin mixture, epoxy resin composition, and cured article - Google Patents

Abstract

The present invention is a phenol resin mixture obtained by crosslinking a reaction product containing a by-product obtained by halomethylation of biphenyl with phenol, an epoxy resin mixture obtained by epoxidizing the phenol resin mixture, and an epoxy resin mixture thereof. The present invention relates to an epoxy resin composition comprising a cured product of the epoxy resin mixture of the present invention or an epoxy resin composition containing the same, which is not only excellent in flame retardancy, but also stored at 250 ° C. as compared to conventional flame retardant epoxy resin cured products. Since the elastic modulus is lowered within a certain range, the epoxy resin mixture or the epoxy resin composition containing the same is useful as a semiconductor sealing material requiring high flame retardancy and excellent lead-free solder resistance.

Description

Phenolic resin mixture, epoxy resin mixture, epoxy resin composition, and cured product {PHENOLIC RESIN MIXTURE, EPOXY RESIN MIXTURE, EPOXY RESIN COMPOSITION, AND CURED ARTICLE}

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

Epoxy resin composition utilizes excellent electrical properties, heat resistance, chemical resistance, mechanical strength, adhesion, moisture resistance (water resistance), dimensional stability, optical properties, and the like, which are excellent in workability and cured product thereof. , Reinforcing fiber composites, resist materials, optical materials, liquid crystal sealing materials, overcoating materials, prepregs, molding materials, adhesives, adhesives, paints and the like, and are used in a wide range of fields.

For example, the electrical and electronic component materials include (1) semiconductor sealing materials, specifically (a) for potting, dipping, transfer molding sealing, flip chip, etc., for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, and the like. Underfill, (b) Underfill for sealing and reinforcement when installing IC packages such as QFP, BGA, CSP, etc. (2) Substrate materials such as printed wiring boards and buildup laminates, and interlayer adhesives and die bonding agents for multilayer boards. Adhesives for semiconductors, such as underfill,

(3) Adhesive for installation, such as an underfill for BGA reinforcement, an anisotropic conductive film, and an anisotropic conductive paste, etc. are mentioned. As the reinforcing fiber composite material, structural materials such as CFRP which can be used for the vehicle body of a vehicle, a ship, an aircraft structural material, leisure sports equipment such as a tennis racket or a golf club shaft, and a fuel cell separator, etc. Can be mentioned. As a resist material, a soldering resist, a color resist, a black matrix, etc. are mentioned. Lens materials etc. are mentioned as an optical material.

In recent years, in the use of electrical and electronic component materials, high-density and high-density integration of electrical and electronic components has progressed along with high performance of electrical and electronic equipment, high-temperature environments such as the vicinity of engines of automobiles, outdoor environments, and human bodies. As the field of use in the vicinity and the like are being expanded, and the transition to environmentally compatible technology is in progress, the required characteristics are also being expanded.

For example, in the field of semiconductor sealing materials and substrates, flame retardancy and solder crack resistance are required for epoxy resins in addition to heat resistance, water absorption, electrical insulation, low thermal expansion coefficient, and the like.

In the flame retardancy of an epoxy resin, the flame retardant technique which uses flame retardation of resin itself, such as a halogen type epoxy resin and a person-containing epoxy resin, and a flame retardant, such as antimony trioxide, has been examined. However, when these halogens or antimony are used, it has been pointed out that contributing to the generation of toxic substances such as dioxins if the disposal of the used articles is not properly performed. In this context, the demand for flame retardant technology of "halogen free antimony free phosphorus free" is increasing. In response to this demand, a resin skeleton has been proposed in which flame retardancy is expressed without using a halogen or a flame retardant. For example, phenol biphenyl aralkyl type epoxy resins are known as resins that exhibit flame retardance without using halogens or flame retardants (Patent Documents 1 and 2).

In addition, the change of the mounting process is affecting solder crack resistance. That is, in the semiconductor mounting method, the surface mounting method is common, and semiconductor packages are also often exposed to high temperatures directly during solder reflow, and lead is used when mounting semiconductors in accordance with the recent improvement in awareness of environmental problems. The use of free solder is increasing. Since lead-free solder has a melting temperature of about 20 ° C. (about 260 ° C.) higher than that of conventional solder, the possibility of package cracking during solder reflow is much higher than in the prior art. In addition, in printed wiring boards on which electronic components such as LSIs are mounted, the demand for higher density, higher integration, and smaller size is increasing. Therefore, it is desirable to reduce the wiring width, reduce the through-hole diameter, and reduce the plating thickness. It is necessary. However, when the plating thickness is reduced, cracks may occur during thermal shock, and high solder crack resistance is required for the wiring board. From such a situation, cracks are generated in the cured product even in a lead-free solder having a higher temperature than conventional solders with respect to an epoxy resin composition that can be used for electrical and electronic materials around semiconductors such as semiconductor sealing materials and printed wiring boards. Difficult performance is required. This crack is caused by stress on the cured product when the lead-free solder is subjected to thermal shock. As one of the evaluation indexes, the storage modulus by dynamic viscoelasticity test can be used. Generally, it is known that low storage elastic modulus at high temperature is preferable, for example, when the storage elastic modulus at 160 degreeC is 100 Mpa or more (patent document 3). On the other hand, it is known that the storage modulus at high temperatures is higher or higher than the glass transition temperature to some extent, and is cracked at the time of solder reflow at 220 ° C to 260 ° C and in the heat cycle test at -50 ° C to 150 ° C. As a resin having high reliability that does not occur, an epoxy resin composition having a storage modulus at 220 ° C. of 0.5 GPa to 0.9 GPa is disclosed (Patent Document 4). Therefore, an appropriate storage modulus at high temperature is considered to be very important because it suppresses the occurrence of cracks in thermal shock.

As a phenol biphenyl aralkyl type epoxy resin excellent in flame retardancy, the NC-3000 series etc. of Nihon Kayaku Co., Ltd. are known as a commercial item, for example. This epoxy resin can be prepared by reacting 4,4'-dimethylolbiphenyl with phenol, isolating the resulting bisphenol compound, and then epoxidizing the isolated bisphenol compound with epichlorohydrin or the like (for example, , Patent Document 5). Moreover, the method of using 4,4'-bis (chloromethyl) -biphenyl is also known instead of said 4,4'- dimethylol biphenyl (patent document 6).

Recent developments on phenol-biphenyl aralkyl type epoxy resins include, for example, phenols that condensate with phenols those previously oligomerized by biphenyl derivatives such as 4,4'-bis (chloromethyl) -biphenyl. Resin is proposed (patent document 7).

Moreover, the method of synthesizing 4,4'-bis (chloromethyl) -biphenyl which is the said raw material by bischloromethylation of biphenyl is generally known, For example, in a cyclohexane solvent, biphenyl, paraform 4,4'-bis (chloromethyl) -biphenyl can be obtained by introducing and reacting hydrogen chloride gas with vigorous stirring of aldehyde and zinc chloride (Patent Documents 8, 10, p. 19-20). .

Japanese Laid-Open Patent Publication No. H11-140277 Japanese Laid-Open Patent Publication No. H11-140166 Japanese Patent No. 4027332 Japanese Laid-Open Patent Publication No. 2001-288244 Japanese Patent No. 2952094 Japanese Laid-Open Patent Publication No. 2002-338656 Japanese Laid-Open Patent Publication No. 2007-254685 Japanese Patent Publication S54-929.

An object of the present invention is an epoxy resin cured product having a flame retardancy equivalent to or greater than that of a cured product using a phenol-biphenyl aralkyl type epoxy resin having excellent flame retardancy and having a more optimal storage modulus, an epoxy resin mixture for obtaining the same, or And / or an epoxy resin composition, and a phenol resin mixture for the epoxy resin.

MEANS TO SOLVE THE PROBLEM As a result of earnestly researching in order to solve the said subject, as a result, bishalomethylbiphenyl is surprisingly contained as a main component, and it contains a fixed amount of tri and tetrahalomethyl biphenyl as a side reaction product, and a remainder and a small quantity Phenolic resin mixture obtained by reacting a reaction product (mixture) obtained by halomethylation of biphenyl, including monohalomethylbiphenyl and bisbiphenylylmethane compound of, with phenol without performing isolation purification. Was found to be very suitable as a raw material of the epoxy resin mixture that satisfies the required performance, and completed the present invention.

That is, the present invention relates to the following.

(1) Obtained by the halomethylation reaction of biphenyl, the ratio (GC area ratio) to the whole reaction product in GC-MS, bishalomethylbiphenyl is 60% or more, less than 80%, A phenol resin mixture obtained by a methylene crosslinking reaction with a reaction product comprising 15 to 30% of the total of halomethyl) biphenyl and tetra (halomethyl) biphenyl and other by-products as a residue.

(2) In (1), the softening point is 65 to 85 ° C, the number average molecular weight is 350 to 1200 by GPC (gel permeation chromatography), the weight average molecular weight is 400 to 2000, and the OH equivalent is 160 to 250 g / eq. Phenolic Resin Mixture.

(3) The epoxy resin mixture obtained by epoxidizing the phenol resin mixture as described in said (1) or (2).

(4) In (3), the softening point is 50 to 75 ° C, the ICI viscosity is 0.02 to 0.50 Pa.s, the number average molecular weight is 400 to 1200 and the weight average molecular weight is 800 to 2000 by GPC (gel permeation chromatography). And epoxy resin mixtures having an epoxy equivalent of 200 to 360 g / eq.

(5) The epoxy resin composition containing the epoxy resin mixture and hardening | curing agent as described in said (3).

(6) The epoxy resin composition as described in said (5) whose content of a hardening | curing agent is 0.7 equivalent-1.2 equivalent with respect to 1 equivalent of epoxy groups of an epoxy resin mixture.

(7) The epoxy resin composition as described in said (6) which contains 50 to 90 weight% of fillers with respect to the total amount of an epoxy resin composition further.

(8) To the epoxy resin mixture obtained by epoxidizing the phenol resin mixture as described in said (1), and the epoxy resin composition containing 0.7 equivalent-1.2 equivalent hardening | curing agent with respect to 1 equivalent of epoxy groups of this epoxy resin mixture, Cured product.

(9) 50 to 1.2 equivalents of the epoxy resin mixture obtained by epoxidizing the phenolic resin mixture according to the above (1) and 0.7 to 1.2 equivalents of the curing agent and the epoxy resin composition with respect to 1 equivalent of the epoxy group of the epoxy resin mixture. Hardened | cured material which hardened the epoxy resin composition containing 90 weight% of inorganic fillers.

(10) In the presence of zinc halide, 2 to 8 equivalents of formaldehyde and hydrogen halide are reacted with 1 mole of biphenyl and biphenyl in the presence of excess hydrogen halide, and halomethylation of biphenyl is carried out. And the ratio (GC area ratio) to the entire reaction product in GC-MS, wherein the bishalomethylbiphenyl is at least 60%, less than 80%, and the tri (halomethyl) biphenyl and tetra (halomethyl) ratios. A reaction product comprising 15 to 30% of phenyl in total and other by-products in a balance, and reacted with phenol without purification of the reaction product.

(11) An epoxy resin mixture characterized by reacting epihalohydrin with 0.8 to 12 equivalents of the phenol resin mixture obtained by the production method described in the above (10) with respect to 1 equivalent of the hydroxyl group of the phenol resin mixture. Manufacturing method.

(12) The epoxy resin composition containing the phenol resin mixture as described in said (1) or (2) as a hardening | curing agent.

The phenolic resin mixture obtained by the present invention is useful as a raw material for an epoxy resin mixture or an epoxy resin composition which provides a cured product having excellent flame retardancy and an appropriate storage modulus, and is also easy to manufacture. Moreover, when the epoxy resin mixture or epoxy resin composition of this invention is hardened | cured, it can be set as hardened | cured material which has flame retardance and a suitable storage modulus as mentioned above. Therefore, the epoxy resin mixture of this invention or the epoxy resin composition of this invention can be utilized for a wide range of uses, including a semiconductor sealing material and a printed wiring board board | substrate.

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

First, the halomethylation reaction of biphenyl for obtaining the phenol resin mixture of this invention is demonstrated.

The halomethylation reaction of biphenyl is a reaction of obtaining biphenyl halomethylate using biphenyl, formaldehyde or its equivalent acetals (hereinafter collectively referred to as “carbon source”), hydrogen halide, catalyst and solvent. . Depending on the reaction conditions, the biphenyl halomethylate may further react to produce diarylmethane. Generally, the chloromethylation reaction of 5th edition experimental chemical lecture 13 (2) p439 (2005) and SYNTHESIS, 1003 (1991) can be referred, for example.

For example, according to the said patent document 8 (Japanese Patent Publication No. S54-929), it is a 4,4'-bis by the chloromethylation reaction which used biphenyl, paraformaldehyde, hydrogen chloride gas, zinc chloride, and cyclohexane. (Chloromethyl) -1,1'-biphenyl can be prepared. Moreover, as another manufacturing method, the method of Unexamined-Japanese-Patent No. H09-208506, Unexamined-Japanese-Patent No. H10-139699, and Unexamined-Japanese-Patent No. 3784865 is mentioned, for example.

The halomethylation reaction in the present invention comprises the above composition, i.e., 60 to 80% by weight of bishalomethylbiphenyl, 15 to 30% in total of tri (halomethyl) biphenyl and tetra (halomethyl) biphenyl and As long as it is a method for obtaining a reaction product including other residues, any of the above methods may be used or other methods.

Hereinafter, the reaction example of patent document 8 which is the most typical example is demonstrated about the halomethylation reaction in this invention as an example.

As a preferable carbon source of the methyl group in halomethylation, formaldehyde, such as formalin, paraformaldehyde, methylral, and trioxane, is mentioned, Paraformaldehyde is preferable.

Although the input equivalent of a carbon source (for example, formaldehyde in the reaction example of patent document 8) changes with halomethylation rate (the number of halomethyl groups of 1 molecule) with respect to biphenyl, it is 1 equivalent with respect to 1 mol of biphenyls. -15 equivalents are preferable, 1.5 equivalents-10 equivalents are more preferable, and 2 equivalents-8 equivalents are more preferable. At 1 equivalent or less, the reaction point with biphenyl having a phenolic hydroxyl group may be insufficient, and if it exceeds 15 equivalent, the reaction point and crosslinking point may be too large, the molecular weight may be too large, or the solid content concentration may increase, causing the agitation to deteriorate. have.

As the halogen source for the halogenation, any one can be used, as long as hydrogen halide or hydrogen halide is generated by the reaction. It is most common to use hydrogen halide as the halogen source. Preferred hydrogen halides include hydrogen chloride, hydrogen bromide and hydrogen iodide, but hydrogen chloride is preferred. These hydrogen halides can be used in the form of a gas. When hydrogen halide is used in gaseous form, the reaction can be carried out directly by blowing to a raw material mixture other than hydrogen halide.

The hydrogen halide may be dissolved in water, acetic acid or other organic solvents and used as a hydrogen halide solution. However, hydrogen chloride is most preferably used in the gas phase.

In halomethylation reaction, in order to obtain the reaction product of the said composition, it is preferable to suppress production | generation of the methylene bridge | crosslinked diarylmethane observed as a by-product. When the concentration of hydrogen halide in a reaction system is low, it is known that diarylmethane produces | generates preferentially. In order to suppress the formation of the by-product, it is preferable to increase the concentration of hydrogen halide. For this purpose, it is preferable to introduce an excess amount of hydrogen chloride gas into the reaction liquid. As a method of introducing an excessive amount of hydrogen chloride gas, a method of introducing hydrogen chloride gas under a pressurized condition or a low temperature condition may be mentioned.

In the reaction, preferred catalysts include sulfuric acid, thionyl chloride, orthophosphoric acid, zinc chloride, Friedel-Crafts type reaction catalysts such as aluminum chloride, iron chloride and tin chloride, tetrabutylammonium bromide, trimethylbenzyl chloride and cetyl chloride. And quaternary ammonium salts such as pyridinium. Among these, zinc chloride, aluminum chloride, iron chloride, tin chloride, tetrabutylammonium bromide, trimethylbenzyl chloride and cetylpyridinium chloride are more preferable, and zinc chloride is particularly preferable in view of ease of handling.

These catalysts may be used alone, but may be used by mixing two or more kinds.

Although the usage-amount of a catalyst is not specifically limited, The range of 0.01 mol-3 mol with respect to biphenyl is preferable. 0.1 mol-1 mol are more preferable.

The solvent used for the reaction is not particularly limited as long as it is a non-reactive solvent. Preferred solvents include aliphatic hydrocarbon solvents (e.g., chain alkanes such as hexane and heptane, cyclic alkanes such as cyclopentane, cyclohexane, and kerosene), aliphatic carboxylic acid solvents (e.g. formic acid, acetic acid, propionic acid, etc.); Aromatic hydrocarbon solvents having low electron density of aromatic rings (for example, chlorobenzene, nitrobenzene, orthodichlorobenzene, trichlorobenzene, etc.) and aliphatic halogenated hydrocarbon solvents (for example, chloroform, dichloromethane, dichloroethane, tetrachloroethane, etc.) Organic solvents can be mentioned.

These solvents may be individual or two or more types of mixed solvents may be sufficient as them. Preferable examples of the solvent include C5-C6 cyclic alkanes, and most preferred examples include cyclohexane which is inexpensive and easy to remove because of its low boiling point.

When zinc chloride is used as a catalyst, aliphatic alcohols such as 1-pentanol, 1-hexanol, and water can be added in equimolar amounts to the catalyst. These additions are known to improve the solubility of a catalyst and to improve reaction activity in some cases (Bull. Chem. Soc. Jpn. 66, 3520 (1993)). In this invention, it does not need to add in particular.

Although the usage-amount of a solvent is not specifically limited, About 1/2 to 10 times weight part of solid content is preferable, and 8 weight part or less is more preferable.

The reaction temperature is not particularly limited as long as it is an acceptable temperature range in the solvent usually used. Usually, it is 0 degreeC-100 degreeC, Preferably it is about 15-60 degreeC. In the case where the reaction proceeds near room temperature, near room temperature is preferable.

In general, methylene-crosslinked diarylmethane observed as a by-product in the chloromethylation reaction is known to be preferentially produced when the reaction temperature is high. Therefore, in order to suppress such by-products, it is necessary to lower the reaction temperature. desirable.

The reaction time is not particularly limited. Usually, it can carry out about 6 to 36 hours.

The feeding method is not particularly limited. As a preferable method, it is preferable to initially input raw materials other than hydrogen halide, and to blow hydrogen halide gas in the system so as to maintain a state in which excessive hydrogen halide in the system is present during the reaction. Hydrogen chloride is preferable as the hydrogen halide.

In the present invention, the composition of the reaction product obtained above is a ratio (GC area ratio: the same unless otherwise specified) to the total (total amount) of the reaction product in GC-MS (Gas Chromatograph / Mass Spectrometry), Halomethylbiphenyl (preferably bischloromethylbiphenyl) content of at least 60%, less than 80%, tri (halomethyl) biphenyl (preferably tri (chloromethyl) biphenyl) and tetra (halo A mixture of methyl) biphenyl (preferably tetra (chloromethyl) biphenyl) of 15% to 30% and other byproducts (hereinafter, optionally, of the biphenyl compound having a halomethyl group) Also referred to as a mixture). Moreover, 75%-97% are preferable and, as for the sum total of the three characters of bishalomethyl biphenyl, tri (halomethyl) biphenyl, and tetra (halomethyl) biphenyl, 80%-95% are more preferable.

Bishalomethylbiphenyl which is a main component consists of 4,4'-bishalomethylbiphenyl and its positional isomer, and 4,4'-bishalomethylbiphenyl is 50- among bishalomethylbiphenyl. It is about 98%, Preferably it is about 60 to 95%, and remainder is considered that the isomer.

The main compound contained in the reaction product is condensed with a compound in the case where the halomethyl group is a chloromethyl group, and is represented by Table A as described later. In the present invention, the "chloromethyl" group in Table A and "chloromethyl" in the following description can be shared as "halomethyl" in the present invention.

4,4'-bischloromethyl-biphenyl of Formula 1-3 is a main component in bischloromethylbiphenyl, and occupies about 50 to 98%, preferably about 60 to 98% of bischloromethylbiphenyl. I think. In bischloromethyl biphenyl, remainder other than 4,4'-bischloromethyl biphenyl is considered to be positional isomers, such as 2,4'-bischloromethyl biphenyl of Formula 1-4.

As tri (chloromethyl) biphenyl and tetra (chloromethyl) biphenyl, it is thought that it consists of a compound of Formula 1-5-Formula 1-8, and these isomers (substituted position isomers), for example.

As other by-products, for example, monochloromethylbiphenyl (for example, a compound of formulas 1-1 and 1-2), bisbiphenylylmethane (formula 1-9), monochloromethyl-bisbi Phenyl yl methane (the compound of Formula 1-10), bischloromethyl bisbiphenylyl methane (the compound of Formula 1-11, etc.) etc. are mentioned.

The content of bischloromethylbiphenyl relative to the total amount of reaction product is at least 60%, less than 80%, more preferably 65 to 75%.

The total content of tri (chloromethyl) biphenyl and tetra (chloromethyl) biphenyl relative to the total amount of the reaction product is about 15 to 30%, preferably about 15 to 25%. Although the ratio of each of tri (chloromethyl) biphenyl and tetra (chloromethyl) biphenyl varies depending on the reaction conditions, it cannot be said uniformly, but the content of trichloromethylbiphenyl relative to the total amount of the reaction product is 5% to 25%. It is about% and 10%-20% are preferable.

The content of tetra (chloromethyl) biphenyl relative to the total amount of the reaction product is preferably 1% to 15%, more preferably 2% to 10%.

Among the other by-products, monochloromethylbiphenyl is usually the most, and the ratio (GC area ratio) to the entire reaction product in GC-MS (hereinafter, unless otherwise specified) is about 1% to 10%. to be.

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

For example, the reaction can generally be referred to the fifth edition of Experimental Chemistry Lecture 26 (2) p142 (2005).

As described above, the halomethylation reaction product of biphenyl is a mixture, and in the present invention, the mixture is used as it is for the methylene crosslinking reaction with phenol. Therefore, normally, the reaction liquid obtained by the halomethylation reaction can be used as it is.

Moreover, if necessary, the reaction liquid may be used as a reaction raw material with phenol after performing treatment such as concentration, dilution, degassing, washing with water, neutralization, and filtration. Also in that case, it is preferable to exist in the range of the composition of the said reaction product substantially.

Usually, it is preferable to use the reaction liquid of the halomethylation reaction of biphenyl as it is for the methylene crosslinking reaction with the next phenol.

The methylene crosslinking reaction can be added with an acid catalyst, if necessary, and is usually preferably carried out in the presence of an acid catalyst. Various kinds of acid catalysts can be used, but for example, organic or inorganic acids such as sulfuric acid, p-toluenesulfonic acid, oxalic acid, methanesulfonic acid and trifluoromethanesulfonic acid, zinc chloride, aluminum chloride, iron chloride, and tin chloride Friedel-Crafts type Lewis acid catalyst etc. are mentioned.

Although the usage-amount of these acid catalysts changes with kinds of catalyst, they can be added in 0.001-10 times molar ratio with respect to phenol. Preferably the amount is about 0.05-3 mol.

In a preferable embodiment of the present invention, since the reaction solution of the halomethylation reaction is used as it is and the condensation reaction is subsequently performed, the acid catalyst used in the halomethylation reaction can be used as it is, and it is not necessary to add an acid catalyst newly.

The halomethylation reaction product of biphenyl and phenol can be reacted at any ratio. Usually, it is preferable to use 1.5 mol-40 mol of phenols with respect to 1 mol of halomethyl groups in the halomethylation reaction product of biphenyl, More preferably, they are 2 mol-10 mol. It is because there exists a possibility of making high molecular weight into it when it is 1.5 mol or less, and when it exceeds 40 mol, kettle efficiency may worsen.

The addition amount of phenol is about 0.3 to 2 times (weight ratio) with respect to the total amount of the biphenyl, the carbon source, and the acid catalyst added for the halomethylation of biphenyl, Preferably it is 0.5 to 1.5 times.

In addition, it is preferable to analyze the amount of halomethyl group remaining and to confirm the loss of the halomethyl group in the reaction trace of this reaction. For example, the total amount of chlorine which can be saponified can be applied according to the description of JIS K7246. In addition, it can also track | require by carrying out and analyzing pretreatment which makes the halomethyl group of a reactive mixture react with the pigment etc. which become a marker.

The methylene crosslinking reaction (condensation reaction) can be carried out even in the absence of a solvent and in the presence of a solvent. Usually, it is preferable to use the reaction liquid of the said halomethylation reaction as it is, and the organic solvent mentioned by the said halomethylation reaction can be used as it is. Therefore, a preferable solvent can also mention C5-C6 cyclic alkane similarly, and cyclohexane is mentioned as the most preferable thing.

As the usage-amount of a solvent, it is 5-300 weight% normally with respect to the total weight of the halomethylation reaction product of biphenyl and a phenol, Preferably it is 10-200 weight%. The reaction temperature of methylene crosslinking reaction is 0-120 degreeC normally, Preferably it is about 15-100 degreeC. The reaction time is usually 1 to 10 hours.

In the methylene crosslinking reaction, after the halomethylation reaction is carried out, it is most simple to add phenol to the reaction solution of the halomethylation reaction and to react. If necessary, the reaction solution of the halomethylation reaction may be added to phenol (and a mixture of an acid catalyst and a solvent, if necessary). Moreover, as needed, in the range which the composition of a reaction product does not change significantly, operations, such as dilution, degassing, water washing, neutralization, etc., can be performed before and after them.

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

In the present invention, the phenol resin mixture obtained by removing the acid catalyst by neutralization, washing with water, etc. after completion of the methylene crosslinking reaction without the recrystallization treatment is usually carried out in the next epoxidation reaction. It is desirable to go.

The reaction solution after the completion of the methylene crosslinking reaction may be continuously carried out to the next epoxidation step without removing the solvent and the unreacted phenol, but in this case sodium hydroxide and hydroxide to neutralize the hydrogen halide or acid catalyst used in the reaction. An operation of treating alkali metal hydroxides such as potassium with a base is necessary. Moreover, since unreacted phenol reacts with epichlorohydrin etc. of epoxidation, it cannot say that it is very preferable.

The phenol resin mixture of the present invention obtained as described above is a phenol resin mixture in which phenol and biphenyl are linked by a methylene crosslinking group (partially linked by biphenyl mutual methylene crosslinking, and further, phenol is biphenyl and methylene crosslinking). And phenol resins linked thereto), are useful as raw materials for the epoxy resin mixture of the present invention, and can be used as epoxy resin mixtures through the following epoxidation reaction.

The phenol resin mixture of the present invention obtained as described above has a softening point of 65 to 85 DEG C, a number average molecular weight of 350 to 1200 by GPC (gel permeation chromatography), preferably about 400 to 1000, more preferably It is about 450-950, most preferably about 500-900, the weight average molecular weight is about 400-2000, Preferably it is about 500-1700, More preferably, it is about 550-1600, Most preferably, it is about 600-1000 . The OH equivalent is about 160 to 250 g / eq, preferably about 170 to 240 g / eq, and most preferably about 180 to 230 g / eq.

The chemical structure of the typical compound of the phenol resin mixture of the present invention is considered to be F2-1 to F2-6 and the like, which are exemplified below from the analysis results of the reaction product of the halomethylation reaction. N in the said formula is about 1-10.

The phenol resin mixture of the present invention is a mixture of linear molecules or branched molecules, for example, as is apparent from the following examples.

(F2-1 ~ F2-3)

(F2-4 ~ F2-6)

Next, the epoxidation reaction for obtaining the epoxy resin mixture of this invention is demonstrated.

The epoxy resin mixture of the present invention is an epoxide of the phenol resin mixture of the present invention obtained above, and is obtained by epoxidation of the phenol resin mixture by a reaction with epihalohydrin by a conventional method. Can be. More specifically, the following method is mentioned.

As a preferable method of epoxidation, the method of reacting phenol resin mixture of this invention with epihalohydrin in presence of an alkali metal hydroxide in presence or absence of a solvent, and glycidyl etherification is mentioned. . In this method, reaction temperature is about 10-100 degreeC normally, Preferably it is about 30-90 degreeC. Examples of the epoxidation reaction using the epihalohydrin include the epoxidation reaction described in Japanese Patent No. 3934829, the one-step method described in Japanese Unexamined Patent Publication No. 2007-308642, and the fusion method.

In the reaction for obtaining the epoxy resin of the present invention, the aqueous solution may be used for the alkali metal hydroxide. In this case, an aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and water and epihalohydrin are continuously distilled off under reduced pressure or normal pressure, followed by further separation to remove water, and epihalohydrin. May be a method of returning continuously in the reaction system. In addition, in the present invention, since the catalyst used up to the previous step remains without being removed unless a special operation is performed, the reaction is smoothly advanced by adding an alkali metal hydroxide in excess and neutralizing it. Can be.

Moreover, quaternary ammonium salts, such as tetramethylammonium chloride, tetramethylammonium bromide, and trimethylbenzyl ammonium chloride, are added as a catalyst to the mixture of the phenol resin mixture and epihalohydrin of this invention, and are 0.5 to 50 degreeC-150 degreeC. A solid or aqueous solution of an alkali metal hydroxide is further added to the halo hydrin etherate of the phenol resin obtained by reacting for 8 hours, and reacted at 20 ° C. to 120 ° C. for 1 hour to 10 hours to dehydrohalide (close ring). It may be a method.

Preferable examples of epihalohydrin include epichlorohydrin, epibromohydrin, epiiodhydrin, β-methyl epichlorohydrin, α-methyl epichlorohydrin and γ-methyl epichlorohydrin. Epichlorohydrin is preferable.

The amount of epihalohydrin used in the epoxidation reaction is usually 0.8 equivalents to 12 equivalents, preferably 0.9 equivalents to 11 equivalents to 1 equivalent of the hydroxyl group of the phenol resin of the present invention. At this time, in order to make the reaction proceed smoothly, a polar solvent, preferably alcohols (for example, C1-C4 alcohols such as methanol and ethanol) or aprotic polar solvents (for example, dimethyl sulfone and dimethyl sulfoxide) It is preferable to add, etc., and to perform reaction. The amount of the polar solvent used can be appropriately selected depending on the kind of solvent or the like, usually between 2% by weight and 150% by weight with respect to the amount of epihalohydrin. For example, when alcohols are used, the amount thereof is usually 2% by weight to 20% by weight, preferably 4% by weight to 15% by weight relative to the amount of epihalohydrin. Moreover, when using an aprotic polar solvent, it is 5 weight%-150 weight% normally with respect to the quantity of epihalohydrin, Preferably they are 10 weight%-140 weight%.

Examples of alkali metal hydroxides include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide, and sodium hydroxide and potassium hydroxide are preferable.

The epoxy resin mixture of this invention can be obtained by removing epihalohydrin, a solvent, etc. after the reaction product of an epoxidation reaction is washed with water or without water washing under reduced pressure.

In addition, in order to obtain an epoxy resin mixture containing less hydrolyzable halogen, the recovered epoxy resin mixture is dissolved in a solvent, for example, toluene, methyl isobutyl ketone or the like, and therein alkali metal hydroxides such as sodium hydroxide and potassium hydroxide. It is preferable to add an aqueous solution, to react with the hydrolyzable halogen contained in the reaction product, and to remove the hydrolyzable halogen. By this post-treatment, it is also possible to make an epoxy ring certain. The use amount of alkali metal hydroxide in the post-treatment is usually 0.01 to 0.3 equivalents, preferably 0.05 to 0.2 equivalents, relative to 1 equivalent of the epoxy group in the reaction product. The temperature of this post-treatment is usually 50 ° C to 120 ° C, and the reaction time is usually 0.5 hours to 2 hours.

After this post-treatment, the produced salt is removed by filtration, washing with water or the like, and the epoxy resin mixture of the present invention is obtained by further distilling the solvent under heating and reduced pressure.

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

Representative chemical structures of the epoxy resin mixture in the present invention are illustrated in the following F3-1 to F3-6. Since the epoxy resin mixture of the present invention is a reactant of the phenol resin mixture of the present invention and epihalohydrin, it is a mixture of linear molecules or branched molecules, as is apparent from the following examples.

In addition, n in the said formula is the same as that of said F2-1-F2-6.

(F3-1 ~ F3-3)

(F3-4 ~ F3-6)

Next, the epoxy resin composition of this invention is demonstrated.

If the epoxy resin composition of this invention contains the epoxy resin mixture and hardening | curing agent of this invention, there will be no restriction | limiting in particular in other arbitrary addition components.

For example, in the epoxy resin composition of this invention, other epoxy resin can be used together as one of arbitrary additives other than the epoxy resin mixture of this invention. When using together, the ratio which occupies in the whole epoxy resin of the epoxy resin mixture of this invention is 30 weight% or more and 100 weight% or less, More preferably, it is 40 weight% or more and 100 weight% or less, More preferably, It is 50 weight% or more and 100 weight% or less. In terms of sufficiently achieving the properties of the epoxy resin mixture of the invention, in particular, excellent flame retardancy and appropriate storage modulus in the cured product, the epoxy resin mixture of the invention is preferably at least 60% by weight, more preferably at least 70% by weight More preferably, it is 80 weight% or more, Most preferably, it is 90 weight% or more. The upper limit is up to 100% by weight.

As another epoxy resin which can be used together with the epoxy resin mixture of this invention, a novolak-type epoxy resin, a bisphenol-A epoxy resin, a triphenylmethane type epoxy resin, etc. are mentioned.

Specifically, glycidyl ether compounds of aromatic compounds having 2 to 4 hydroxyl groups (for example, bisphenol A, bisphenol F, bisphenol S, fluorenylidenediphenol, terpenediphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3'-5,5'-tetramethyl- [1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- ( 4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxy) ethane}; Or phenols (phenol, alkyl substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and aldehydes or ketones, or reactive derivatives thereof (e.g. formaldehyde, acetaldehyde, benzaldehyde, p Hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone or o-hydroxyacetophenone, dicyclopentadiene, frfural, 4,4'-bis (chloromethyl) -1,1'-r Polycondensation with phenyl, 4,4'-bis (methoxymethyl) -1,1'-biphenyl, 1,4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene, etc. Glycidyl ethers of water and glycidyl ethers of modified polycondensates thereof; Glycidyl ether derivatives derived from halogenated bisphenols or alcohols such as tetrabromobisphenol A; Alicyclic epoxy resins; Glycidyl amine epoxy resins; Glycidyl ester epoxy resins; Solid or liquid epoxy resins, such as these, are mentioned. These can be used independently and can be used together 2 or more types. Moreover, epoxy resins other than these can also be used together.

In the epoxy resin composition of this invention, the phenol resin mixture of this invention can be used individually or in combination with another hardening | curing agent, as a hardening | curing agent. When using together, 30 weight% or more is preferable and, as for the ratio to the total hardening | curing agent of the phenol resin mixture of this invention, 40 weight% or more is especially preferable. The upper limit is 100 weight%.

As a hardening | curing agent used by the epoxy resin composition of this invention, an amine compound, an acid anhydride compound, an amide compound, a phenol compound etc. are mentioned, for example. Specific examples include amine compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, and trifluoroborane-amine complexes; Amide compounds such as dicyandiamide, polyamide resin synthesized from dimer of linolenic acid and ethylenediamine; Acid anhydride compounds such as phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride and methylhexahydrophthalic anhydride; Phenols having 2 to 4 hydroxyl groups {bisphenol A, bisphenol F, bisphenol S, fluorenylidenediphenol, terpenediphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3'-5 , 5'-tetramethyl- [1,1'-biphenyl] -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2, 2-tetrakis (4-hydroxyphenyl) ethane} and phenols (benzene, naphthalene having 1 to 2 hydroxyl groups such as phenol, alkyl substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene and dihydroxy naphthalene). Alkyl may be substituted, and C 1 -C 4 alkyl is preferable) and aldehyde or ketone (formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o Polycondensate with hydroxyacetophenone} or the reaction of the phenols with aldehydes or ketones Derivatives {dicyclopentadiene, frfural, 4,4'-bis (chloromethyl) -1,1'-biphenyl, 4,4'-bis (methoxymethyl) -1,1'-biphenyl, 1 Phenol compounds, such as polycondensates with, 4-bis (chloromethyl) benzene, 1, 4-bis (methoxymethyl) benzene, etc., modified products of these polycondensates, and tetrabromobisphenol A; Imidazole; Guanidine derivatives; Although these etc. are mentioned, it is not limited to these.

These can be used independently and can also use 2 or more types.

Among these curing agents, a phenol compound or an amine compound is preferable, and a phenol compound, a phenol aralkyl resin, or a phenol resin mixture of the present invention is preferable. Most preferably phenolaralkyl resin.

In the epoxy resin composition of this invention, the usage-amount of a hardening | curing agent is 0.7 equivalent-1.2 in active group equivalent (hydroxyl equivalent in a phenol compound, amino group equivalent in an amine compound) reacting with the epoxy of a hardening | curing agent with respect to 1 equivalent of epoxy groups of an epoxy resin. Equivalent weight is preferred. With respect to 1 equivalent of epoxy group, when the active group equivalent of the curing agent is less than 0.7 equivalent or exceeds 1.2 equivalent, in all cases, the curing becomes incomplete and there is a fear that good cured product properties cannot be obtained.

In the epoxy resin composition of this invention, even if it uses a hardening accelerator, it does not interfere. Specific examples of the curing accelerator that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole; Tertiary amines such as 2- (dimethylaminomethyl) phenol and 1,8-diaza-bicyclo (5,4,0) undecene-7; Phosphines, such as triphenylphosphine; Metal compounds, such as tin octylate, etc. are mentioned. Although the hardening accelerator does not need to be used, 0.1 weight part-5.0 weight part can be suitably used as needed with respect to 100 weight part of epoxy resins when using.

An inorganic filler (also referred to as a filler) can be added to the epoxy resin composition of the present invention as needed. As the inorganic filler, powders such as crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc or spherical particles thereof Although a bead etc. are mentioned, It is not limited to these. These can be used independently and can also use 2 or more types. Content of these inorganic fillers is 0 to 95 weight% with respect to the total amount of an epoxy resin composition, Preferably it is 20 to 95 weight%, More preferably, it is 50 to 95 weight%, More preferably, it is 70 weight%- About 95% by weight, most preferably 70% to 90% by weight.

Further, the epoxy resin composition of the present invention may include, if necessary, release agents such as silane coupling agents, stearic acid, palmitic acid, zinc stearate, calcium stearate and the like; Coloring agents such as carbon black, phthalocyanine blue and phthalocyanine green; Polybutadiene and this modified product, modified product of acrylonitrile copolymer, polyphenylene ether, polystyrene, polyethylene, polyimide, fluororesin, maleimide compound, cyanate resin (or its prepolymer), silicone gel, silicone Resins such as oils; Additives such as these may be added.

Preferred epoxy resin compositions of the present invention are as follows.

(1) The epoxy resin mixture of this invention and a hardening | curing agent are included, The epoxy resin mixture of this invention contains 0.7-1.2 equivalents of hardening agent with respect to the active group equivalent reacting with the epoxy group of the hardening | curing agent with respect to 1 equivalent of epoxy groups of the epoxy resin. The epoxy resin composition which contains 4 weight%-80 weight% with respect to the total amount of an epoxy resin composition, and remainder is an optional component.

(2) The epoxy resin composition as described in said (1) in which optional component is an inorganic filler and contains 50 weight%-95 weight%, Preferably it is 70 weight%-90 weight% with respect to the epoxy resin composition whole quantity.

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

(4) The epoxy resin in any one of said (1)-(3) which arbitrary additives are either or both of a mold release agent or a coupling agent, and contain 0.05 weight%-1 weight% with respect to the epoxy resin composition whole quantity. Composition.

(5) In any one of said (1)-(4), the epoxy resin mixture of this invention has a softening point of 52-65 degreeC, an ICI viscosity of 0.04-0.40 Pa.s, and GPC (gel permeation chromatography). The epoxy resin composition whose average molecular weights are 400-1200, the weight average molecular weights are 800-2000, and epoxy equivalents are 200-360 g / eq.

(6) In any one of (1) to (5), the epoxy resin mixture of the present invention is obtained by a halomethylation reaction of biphenyl, in a ratio (GC area ratio) to the entire reaction product in GC-MS. A reaction product containing at least 60% of bishalomethylbiphenyl, less than 80%, and containing 15 to 30% of tri (halomethyl) biphenyl and tetra (halomethyl) biphenyl in total and the balance of other by-products And an epoxy resin mixture obtained by further epoxidizing a phenol resin mixture obtained by a methylene crosslinking reaction of phenol.

(7) In (6), the phenol resin mixture has a softening point of 65 to 85 ° C, a number average molecular weight of 350 to 1200 by GPC (gel permeation chromatography), a weight average molecular weight of 400 to 2000, and an OH equivalent of 160 to Epoxy resin composition which is 250 g / eq.

(8) The epoxy resin composition as described in any one of said (1)-(7) whose hardening | curing agent is a phenolic compound.

The epoxy resin composition of this invention is obtained by mixing the epoxy resin mixture of this invention, a hardening | curing agent, and arbitrary addition components uniformly. The epoxy resin composition of this invention can be easily made into the hardened | cured material by the method similar to the method known conventionally.

More specifically, first, for example, the epoxy resin mixture and the curing agent of the present invention and, if necessary, optional additive components (for example, a component selected from the group consisting of a curing accelerator, an inorganic filler, a coupling agent and a release agent). Etc.) is sufficiently mixed until it becomes uniform using an extruder, a kneader, a roll, etc., for example, to make the epoxy resin composition of this invention. Subsequently, the obtained epoxy resin composition is melted and then molded using a mold or transfer molding machine, an injection molding machine, a molding machine, or the like, and more preferably 2 to 16 hours at 80 to 200 ° C as a post-cure. By heating, the hardened | cured material of the epoxy resin composition of this invention can be obtained.

Moreover, the epoxy resin composition of this invention is made low-viscosity by heat melting, or it is made low viscosity by mixing a solvent with this epoxy resin composition, and it is glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber. The prepreg obtained by impregnating a substrate, such as paper or the like, by heating and semi-drying, may be hot press molded to obtain a cured product. As said solvent, Aromatic solvents, such as toluene and xylene; Ketone solvents such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Amide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide and N, N-dimethyl imidazolidinone; Sulfone solvents such as dimethyl sulfoxide and tetramethylene sulfone; Lactam solvents such as N-methylpyrrolidone; lactone solvents such as γ-butyrolactone; And solvents such as ether solvents such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether monoacetate, and propylene glycol monobutyl ether.

The solvent used above may be single or 2 or more types of mixed solvents may be sufficient as it. Moreover, when mixing a solvent in the above, the amount which occupies 10 weight%-70 weight% normally, Preferably it is 15 weight%-70 weight% with respect to the total amount of the mixture of the epoxy resin composition of this invention and this solvent, is used. .

The prepreg is cut into a desired shape and, if necessary, laminated with copper foil or the like, and then pressurized by a method such as a press molding method, an autoclave molding method, a sheet winding molding method, or the like to heat-cure the cured product of the prepreg, or its It can be set as the laminated board which has hardened | cured material. Moreover, a circuit is formed in the laminated board formed by superimposing copper foil on the surface, the prepreg and copper foil are superimposed on it, or the copper foil etc. which have the said prepreg are superposed, and a circuit is formed as needed, The operation can be repeated to obtain a multilayer circuit board.

As a semiconductor device which can be manufactured by sealing a semiconductor element (semiconductor tip) in the epoxy resin composition of this invention, For example, DIP (Dual Inlina Package), QFP (Quad Flat Package), BGA (Ball Grid Array), Thin Size Package (CSP), Small Outline Package (SOP), Thin Small Outline Package (TSOP), Thin Quad Flat Package (TQFP), and the like. Moreover, in the optical semiconductor field, what sealed the optical semiconductor element (semiconductor tip), such as EPROM, such as a light emitting diode (LED), a photo transistor, a CCD (charge-coupled element), and UV-EPROM, is mentioned.

The epoxy resin composition of this invention can be mixed with the compound which has an ethylenically unsaturated group, and can also be used as a photo-thermosetting resin composition. In the epoxy resin composition of the present invention, the composition further contains a crosslinking agent (B) and a photopolymerization initiator (C) in addition to the compound having an ethylenically unsaturated group, preferably an aqueous alkali solution soluble resin (A), as an optional additive component. do.

In such a photocurable resin composition, content of the epoxy resin mixture of this invention is 1 weight%-50 weight% normally as an internal ratio, Preferably they are 2 weight%-30 weight%.

Each component etc. of the photocurable resin composition containing the epoxy resin mixture of this invention are demonstrated below more concretely.

Alkali aqueous solution soluble resin (A); For example, an epoxy carboxylate compound obtained by reacting an epoxy compound having two or more epoxy groups in a molecule with a monocarboxylic acid compound having an ethylenically unsaturated group in a molecule, and a polybasic acid anhydride, and the like, specifically, KAYARAD CCR -1159H, KAYARAD PCR-1169H, KAYARAD TCR-1310H, KAYARAD ZFR-1401H, KAYARAD ZAR-1395H (all, Nihon Kayaku Co., Ltd.), etc. are mentioned.

Crosslinking agent (B); The compound which has ethylenically unsaturated group, for example, an acrylate, a methacrylate compound, etc. are mentioned, Specifically, KAYARAD HX-220, KAYARAD HX-620, KAYARAD DPHA, KAYARAD DPCA-60 (all, Nihon Kayaku) Co., Ltd.) etc. are mentioned.

Photopolymerization initiator (C); For example, benzoin, acetophenone, anthraquinone, thioxanthone, ketal, benzophenone, phosphine oxide, etc. are mentioned, Specifically, KAYACURE DETX-S (Nihon Kayaku Co., Ltd.), IRGACURE 907 (Ciba specialty chemical company) etc. are mentioned.

Furthermore, if necessary, various additives such as fillers such as talc, barium sulfate, aluminum hydroxide, aluminum oxide, silica, clay and the like; Thixotropic imparting agents such as aerosil; Coloring agents such as phthalocyanine blue, phthalocyanine green and titanium oxide; Silicone and fluorine leveling agents and antifoaming agents; Polymerization inhibitors, such as hydroquinone and hydroquinone monomethyl ether, etc. can be added for the purpose of improving the various performance of a composition.

The photocurable resin composition can contain a solvent as needed. As a solvent which can be used, For example, ketones, such as acetone, methyl ethyl ketone, cyclohexanone; Aromatic hydrocarbons such as benzene, toluene, xylene and tetramethylbenzene; Glycol ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether and triethylene glycol diethyl ether; Ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, dialkyl diadipic acid Esters; cyclic esters such as γ-butyrolactone; Petroleum solvents, such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha, etc. are mentioned, These can be used independently and can also be used together 2 or more types.

The photocurable resin composition containing the epoxy resin mixture of the present invention is useful as an insulating material between layers of electronic components, as a resist material such as an optical waveguide for connecting optical components, solder resists for printed boards, coverlays, etc. It can also be used as a printing ink, sealant, paint, coating agent and adhesive.

The photocurable resin composition containing the epoxy resin mixture of this invention can be hardened by energy-beam irradiation, such as an ultraviolet-ray. Hardening by energy-beam irradiation, such as an ultraviolet-ray, can be performed by a conventional method. For example, when irradiating an ultraviolet-ray, ultraviolet-ray generators, such as a low pressure mercury lamp, a high pressure mercury lamp, an ultra high pressure mercury lamp, xenon, and an ultraviolet luminescence laser (excimer laser etc.) can be used.

The photocurable resin composition containing the epoxy resin mixture of the present invention is used for electrical, electronic and optical materials such as printed circuit boards, optoelectronic substrates and optical substrates, for example, as resist films, interlayer insulating materials for build-up methods or optical waveguides. . As a specific article using these, a computer, a home appliance, a portable device, etc. are mentioned, for example. Specifically, for example, in the case of manufacturing a printed wiring board constituting a printed board, when using a liquid resin composition, first, methods such as screen printing, spraying, roll coating, electrostatic coating, curtain coating, etc. By coating the photocurable resin composition containing the epoxy resin of the present invention at a film thickness of 5 to 160 µm and drying the coating film at 50 to 110 ° C, preferably at 60 to 100 ° C. do. Thereafter, a high-energy ray such as ultraviolet rays is irradiated directly or indirectly to the coating film with an intensity of about 10 to 2000 mJ / cm 2 through a photomask in which an exposure pattern such as a negative film is formed, and a developing solution to describe the unexposed portion described later. It develops by spraying, rocking dipping, brushing, scrubbing etc., for example. Then, if necessary, by further irradiating with ultraviolet rays, and then performing heat treatment at a temperature of usually 100 to 200 ° C, preferably 140 to 180 ° C, the plating properties are excellent, and heat resistance, solvent resistance, acid resistance, and adhesiveness are excellent. The printed wiring board which has a permanent protective film which satisfy | fills various characteristics, such as flexibility, is obtained.

Examples of the developer include inorganic alkali aqueous solutions such as potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium phosphate and potassium phosphate, tetramethylammonium hydroxide, tetraethylammonium hydrooxide and tetrabutylammonium. An organic alkali aqueous solution, such as hydrooxide, monoethanolamine, diethanolamine, and triethanolamine, can be used.

Example

Hereinafter, the present invention will be described in more detail with reference to Examples.

In addition, in the following, resin physical property was measured by the following method.

ㆍ Measuring softening point: measured by the method according to JIS K-7234

ㆍ Measurement of GC-MS (Gas Chromatography-Maspetrometry)

Model: 5975 inert MSD (Agilent)

Column: HP-5MS 15m-0.25mm-0.25μm

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

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

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

Ion Source: EI

ㆍ Measurement of SEM-EDS (Scanning Electron Microsopy-Energy Disperse Spectroscopy)

Model: JED-2140 (JEOL Corporation)

Acceleration voltage: 20 kV

Working distance: 10 mm

ㆍ Measurement of number average molecular weight and weight average molecular weight by GPC (gel permeation chromatography)

Column: Shodex KF-801, KF-802, KF-802.5, KF-803

Column temperature: 40 ℃

Dosage: 0.02ml

Feeding amount: 1.0ml / min

Detector: RI

Solvent: Tetrahydrofuran

ㆍ Measurement of viscosity: measured at 150 ° C using ICI Viscometer (Cordix Co., Ltd.)

Measurement of OH equivalent: Average mass number of compounds per OH group, measured by acetylation method according to JIS K-0070

Measurement of epoxy equivalent: Average mass number of compounds per epoxy group, measured according to JIS K-7236.

-DMA (dynamic viscoelasticity measurement) analysis: The storage elastic modulus in Tg and 250 degreeC was measured using TA Instruments DMA2980 (dynamic viscoelasticity meter) using the frequency of 10 Hz.

Example  One

1) Chloromethylation of Biphenyl

200 ml of cyclohexane, 77.05 g of biphenyl, 33.55 g of paraformaldehyde, and 46.38 g of zinc chloride were charged into a 300 ml flask made of glass equipped with a stirrer, a thermometer, and a cooler. While stirring them vigorously, hydrogen chloride gas was blown strongly in it, and it reacted until it became a uniform solution. Meanwhile, the liquid temperature was maintained at 50 ° C. Moreover, liquid temperature was lowered to 30 degreeC, the hydrogen chloride gas was blown for 24 hours, and reaction was continued and the reaction liquid was obtained.

A small amount of the obtained reaction solution was taken and subjected to GC-MS measurement as a dichloromethane solution. As a result, 2.5% mono (chloromethyl) biphenyl, 72.0% bischloromethylbiphenyl, 14.9% tri (chloromethyl) biphenyl and 5.8% tetra (chloromethyl) biphenyl were detected. As other by-products other than the mono (chloromethyl) biphenyl, penta (chloromethyl) biphenyl 0.3%, bisbiphenylylmethane 0.5%, monochloromethyl-bisbiphenylylmethane 1.1%, bischloromethyl- 0.6% of bisbiphenylylmethane was detected. In addition, 2.3% (all GC area%) were detected as other by-products, including the component which cannot specify a compound.

Moreover, zinc element (Zn) was detected by elemental analysis using SEM-EDS (Scanning Electron Microscopy / Energy Dispersive Spectroscopy) from the insoluble matter which generate | occur | produced when the reaction liquid was made into the dichloromethane solution for GC-MS measurement.

(2) Reaction of Chloromethylation Reaction Product with Phenol

Subsequently, 157.77 g of phenol was added to the reaction solution obtained in the above (1), followed by stirring at room temperature for 2 hours. After degassing the reaction vessel, the mixture was heated up to 180 ° C. over 10 hours under reduced pressure, and the solvent cyclohexane and unreacted phenol were distilled off.

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

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

Example  2

Synthesis of Epoxy Resin Mixture

In a glass 300 ml flask 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 dimethyl sulfoxide, 12.3 aqueous solution of 30% by weight sodium hydroxide g was added and stirred and mixed at 45 ° C for 1 hour. Subsequently, 3.95 g of flake shaped sodium hydroxide was added thereinto, and stirred at 45 ° C. for 2 hours and at 70 ° C. for 1 hour. Methyl isobutyl ketone was added to the obtained reaction solution, after dilution, water was added, and water washing was performed by liquid / liquid separation. 0.93 g of 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. Again, washing with water / liquid separation was performed in the same manner as above. The obtained reaction solution was concentrated to give 20.5 g of the epoxy resin mixture of the present invention.

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

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

Example  3, and Comparative example  One

Preparation of flame-retardant resin composition and evaluation of the hardened | cured material

Epoxy resin mixture of the present invention obtained in Example 2 or phenol-biphenyl aralkyl type epoxy resin NC-3000 of Nihon Kayaku Co., Ltd. (softening point 57.4 ° C, ICI viscosity 0.08 Pa.s, epoxy equivalent 277 g / eq) , The flame-retardant resin composition of the composition shown in following Table 1 was prepared using the number average molecular weight 793 by GPC, and the weight average molecular weight 1229), It shape | molded at 175 degreeC with the transfer molding machine, and hardened | cured material was obtained.

(week)

XLC-3L: phenol aralkyl resin, Mitsui Chemicals

TPP: Triphenylphosphine

MSR-2212: KYKLOS MSR-2212, Tatsumori Co., Ltd.

Carnauba 1: Carnauba wax 1, ceraricanoda

KBM-303: Silane Coupling Agent, Shin-Etsu Chemical Co., Ltd.

About the hardened | cured material obtained in this way, Table 2 shows the result which evaluated the flame retardance and the storage elastic modulus in 250 degreeC based on the method shown below.

Measurement of flame retardance: The flame retardance test measured total combustion time (time until self-extinguishing) about the test piece (hardened material) of thickness 0.8mm based on UL-94.

Measurement of storage modulus at 250 ° C .: Storage modulus at Tg and 250 ° C. was measured using a TA instrument DMA2980 (dynamic viscoelasticity meter) using a frequency of 10 Hz.

The epoxy resin composition comprising the epoxy resin mixture of the present invention is equal to or higher in flame retardancy than NC-3000, which is widely used as an excellent flame retardant resin, and is excellent in flame retardancy, and further, 250 ° C. higher than the glass transition point. In storage modulus at high temperature, compared with the value of 2000 MPa or more of NC-3000, the solder crack resistance falls within the range of 500-1000 MPa which is considered to be preferable, and it turns out that it has the outstanding characteristic also in that point. have.

The epoxy resin mixture of the present invention has excellent properties as described above, and can be manufactured consistently from biphenyls, and is therefore easy to manufacture.

Example  4

(1) chloromethylation of biphenyl

200 ml of cyclohexane, 154 g of biphenyl, 66 g of paraformaldehyde, and 93 g of zinc chloride were put into a glass 1000 ml flask equipped with a stirrer, a thermometer, and a cooler. While stirring them, hydrogen chloride gas was blown vigorously therein and reacted until a uniform solution was formed. In the meantime, it kept at 30 degreeC. Thereafter, hydrogen chloride gas was further blown at 50 ° C for 10 hours, and the reaction was continued to obtain a reaction solution.

A part of the reaction solution was taken and LC was measured as N, N'-dimethylformamide solution. As a result, 8.1% monochloromethylbiphenyl, 68.2% bischloromethylbiphenyl, tri (chloromethyl) biphenyl and tetra (chloro Methyl) biphenyl was combined to detect 18.2% (LC area%).

(2) Reaction of Chloromethylation Reaction Product with Phenol

Subsequently, 301 g of phenol was added to the reaction solution obtained in the above (1), followed by stirring at 70 ° C. for 2 hours. Under reduced pressure, cyclohexane which was a solvent and unreacted phenol were distilled off, heating up to 180 degreeC.

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

This resin mixture was 79.6 degreeC of softening point, the number average molecular weight 855 by GPC (gel permeation chromatography), the weight average molecular weight 1332, and OH equivalent 196 g / eq.

The composition of the phenol resin mixture is 8% monochloromethylbiphenyl, 68% bischloromethylbiphenyl-derived component (F2-1) and tri (chloro) from the composition of the chloromethylation reaction product obtained in the above (1). It is estimated to contain 18% of the methyl) biphenyl derived component (F2-2) and the tetra (chloromethyl) biphenyl derived component (F2-3 etc.) in total.

Example  5

Synthesis of Epoxy Resin Mixture

Into a glass 1000 ml flask equipped with 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 added and mixed. While stirring the mixture at 70 ° C, 42 g of flake sodium hydroxide was added in portions. It stirred at 70 degreeC after that for further 1 hour. 150 g of water was added and mixed with the obtained reaction liquid, and it was left still to remove the lower aqueous layer separated into two layers. Unreacted epichlorohydrin was distilled off from the reaction liquid after water washing. Methyl isobutyl ketone was added and diluted there, and then 13.3 g of 30 weight% sodium hydroxide aqueous solution was added, and it stirred at 70 degreeC for 1 hour. Water was added there, and water washing by liquid / liquid separation was performed. The reaction solution after washing with water was concentrated to obtain 215 g of the epoxy resin mixture of the present invention.

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

The composition of the epoxy resin mixture was 8% monochloromethylbiphenyl-derived component and bischloromethylbiphenyl-derived component (structural formula: F3-1, etc.) from the composition of the chloromethylation reaction product obtained in Example 4 (1). It is estimated that 68% and 18% of tri (chloromethyl) biphenyl-derived components (structure: F3-2, etc.) and tetra (chloromethyl) biphenyl-derived components (structure: F3-3, etc.) are included in total.

Example  6

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

About the obtained hardened | cured material, flame retardance and storage modulus were measured by the method similar to what was shown in Example 3. The results are shown in Table 4.

Example  7

After dissolving 500 g of the phenol resin mixture of the present invention obtained in the same manner as in Example 4 in 1000 ml of methyl isobutyl ketone, filtering insoluble content, water was added thereto, followed by water washing by liquid / liquid separation. Was carried out. As a result, a phenol resin mixture (called EX7PhnolMix) having a hydroxyl group (OH) equivalent of 204 g / eq was obtained.

The obtained phenol resin mixture is used as a hardening | curing agent, the phenol- biphenyl aralkyl type epoxy resin NC-3000 of the said Nihon Kayaku Co., Ltd. is used as an epoxy resin, and this invention epoxy resin composition of the composition shown in following Table 5 is prepared. And the hardened | cured material was obtained by shape | molding with the transfer molding machine.

About the obtained hardened | cured material, it carried out similarly to what was shown in Example 3, and flame retardance and storage modulus were measured. 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 curing agent, and the phenol-biphenyl aralkyl type epoxy resin NC-3000 of Nihon Kayaku Co., Ltd. was used as an epoxy resin. The present invention epoxy resin composition (EX8 EPOXY COM) of the composition shown was prepared.

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

The epoxy resin composition prepared above was roll-kneaded and it was set as the epoxy resin composition for evaluation.

As evaluation of the hardenability of the epoxy resin composition obtained above, the maximum value of torque was measured with the Curelastometer of JSR Corporation.

Moreover, as an evaluation of fluidity | liquidity, spiral flow was measured on condition of 175 degreeC and the molding pressure of 70 kg / cm <2> (based on ASTM F3133). The results are shown in Table 8.

Since Curelasto torque which is an index of sclerosis | hardenability is large, it shows that it is hardening hardly, The epoxy resin composition of Example 8 is showing that it is excellent in sclerosis | hardenability than the epoxy resin composition of the comparative example 2.

In the epoxy resin composition having the same gel time, the longer the spiral flow, which is an index of fluidity, the higher the fluidity. Thus, the epoxy resin composition of Example 8 is superior in flowability to the epoxy resin composition of Comparative Example 2. It is shown.

(Industrial availability)

Since the hardened | cured material of the epoxy resin composition containing the epoxy resin mixture of this invention is not only excellent in flame retardancy, but also the storage elastic modulus in 250 degreeC falls in a fixed range compared with the conventional hardened | cured flame retardant epoxy resin, Also excellent in solder crack resistance, the epoxy resin mixture of the present invention and the epoxy resin composition containing the same are suitable as electric and electronic materials around semiconductors such as semiconductor sealing materials and printed wiring boards.

Moreover, since the phenol resin mixture of this invention is an intermediate raw material for the epoxy resin mixture of this invention which has the said outstanding characteristic, and can be manufactured without isolating and refine | purifying the halomethyl biphenyl of an intermediate, it is also easy to manufacture, The utility of the jacket is high.

Claims (12)

Obtained by halomethylation of biphenyl, the ratio (GC area ratio) to the entire reaction product in GC-MS is at least 60%, less than 80%, tri (halomethyl) biphenyl And a phenol resin mixture obtained by a methylene crosslinking reaction of a phenol with a reaction product containing 15 to 30% of tetra (halomethyl) biphenyl in total and other byproducts. The phenol according to claim 1, having a softening point of 65 to 85 ° C, a number average molecular weight of 350 to 1200 by GPC (gel permeation chromatography), a weight average molecular weight of 400 to 2000, and an OH equivalent of 160 to 250 g / eq. Resin mixture. The epoxy resin mixture obtained by epoxidizing the phenol resin mixture of Claim 1 or 2. The softening point is 50-75 degreeC, ICI viscosity is 0.02-0.50 Pa.s, the number average molecular weight is 400-1200 by GPC (gel permeation chromatography), and the weight average molecular weight is 800-2000. And an epoxy resin mixture having an epoxy equivalent of 200 to 360 g / eq. The epoxy resin composition containing the epoxy resin mixture of Claim 3, and a hardening | curing agent. The epoxy resin composition according to claim 5, wherein the content of the curing agent is 0.7 equivalents to 1.2 equivalents based on 1 equivalent of the epoxy group in the epoxy resin mixture. The epoxy resin composition according to claim 6, further comprising 50 to 90% by weight of a filler based on the total amount of the epoxy resin composition. The hardened | cured material which hardened | cured the epoxy resin composition obtained by epoxidizing the phenol resin mixture of Claim 1, and the epoxy resin composition containing 0.7 equivalent-1.2 equivalent hardening | curing agent with respect to 1 equivalent of epoxy groups of this epoxy resin mixture. The epoxy resin mixture obtained by epoxidizing the phenol resin mixture of Claim 1, and 50-90 weight% of inorganics with respect to the total amount of the hardening | curing agent and epoxy resin composition of 0.7 equivalent-1.2 equivalent with respect to 1 equivalent of epoxy groups of this epoxy resin mixture. Hardened | cured material which hardened the epoxy resin composition containing a filler. In the presence of zinc halide, 2 to 8 equivalents of formaldehyde and hydrogen halide are reacted with 1 mole of biphenyl and biphenyl in the presence of an excess of hydrogen halide, followed by halomethylation of biphenyl, and GC-MS. The ratio (GC area ratio) with respect to the whole reaction product in 15-30 total of bishalomethyl biphenyl more than 60%, less than 80%, tri (halomethyl) biphenyl, and tetra (halomethyl) biphenyl in total. A process for producing a phenolic resin mixture, wherein the reaction product comprising% and other by-products is obtained and reacted with phenol without purifying the reaction product. The phenol resin mixture obtained by the manufacturing method of Claim 10 is made to react with 0.8-12 equivalent of epihalohydrin with respect to 1 equivalent of hydroxyl groups of this phenol resin mixture, The manufacturing method of the epoxy resin mixture characterized by the above-mentioned. The epoxy resin composition containing the phenol resin mixture of Claim 1 or 2 as a hardening | curing agent.