JP4747551B2 - Epoxy resin, epoxy resin composition, cured product thereof, and method for producing epoxy resin - Google Patents

Description

  The present invention is excellent in fluidity, water solubility, and the like, and is a high-purity epoxy resin substantially free of impurity chlorine, an epoxy resin composition containing the epoxy resin suitable for the electronics field and the high-performance paint field, The present invention relates to a production method and a cured product obtained by curing the epoxy resin composition.

  The epoxy resin is cured with various curing agents, and generally becomes a cured product excellent in low shrinkage (dimensional stability), electrical insulation, chemical resistance and the like at the time of curing. Most of the epoxy resins are glycidyl ether type, which is an epichlorohydrin derivative type, and among them, when classified by raw material intermediates, it can be divided into two types, polyhydric phenol base and polyhydric alcohol base. As the polyhydric phenol base, there are a bisphenol type, a phenol novolac type, and the like, but as a liquid epoxy resin, a bisphenol A type and a bisphenol F having a viscosity range (25 ° C.) of several thousand to several 10000 mPa · s are common. . As the polyhydric alcohol base, 1,6-hexanediol type, neopentyl glycol type, hydrogenated bisphenol A type and the like are common, and the viscosity thereof is in the range of several tens to several hundreds mPa · s (25 ° C.). Yes, the viscosity is much lower than that of the polyhydric phenol base, and the fluidity is excellent.

  By the way, due to recent technological innovations in the fields of electronics and high-performance paints, there is an increasing demand for a high-purity liquid epoxy resin having low viscosity, excellent fluidity, and substantially no impurity chlorine. For example, in the semiconductor field, bare chip mounting systems using an underfill material technology that can realize high-density mounting are rapidly spreading in the fields of mobile phones and PDAs. As the underfill material, a low-viscosity liquid epoxy resin is used, but in order to further improve the reliability, a high-purity epoxy resin having a lower viscosity and less impurities is strongly demanded. Due to the further low viscosity, the fluidity of the underfill material is excellent, the filling property into the ultra-narrow gap between the chip and the substrate is increased, and the defect occurrence rate can be reduced. In addition, instead of the current mainstream acid anhydride curing system, it becomes easy to switch to a phenol resin curing system with better moisture resistance reliability. In order to solve these problems, for example, a technique combining a bisphenol F type epoxy resin and an acid anhydride (for example, see Patent Document 1) or a technique using a bisphenol A type liquid resin (distilled product). (For example, refer to Patent Document 2).

  However, the technique described in Patent Document 1 has a problem that the amount of impurity chlorine in the epoxy resin used is large. If the amount of impurity chlorine is large, the fine wiring chip is exposed to free chloride ions after moisture absorption, and wiring corrosion failure tends to occur. In this case, it inevitably contains several hundred ppm to several thousand ppm of impurity chlorine. Moreover, in the technique of the said patent document 2, although the highly purified epoxy resin was used, there existed a difficulty that the viscosity of the epoxy resin to be used was high and the viscosity of a compound increased. Polyhydric alcohol-based epoxy resins are low in viscosity and excellent in fluidity, but on the other hand, they contain a large amount of impurity chlorine and have a great problem in terms of moisture resistance reliability. Alcoholic hydroxyl groups are much less reactive with epichlorohydrin than phenolic hydroxyl groups, so strong Lewis acid catalysts and onium salts must be used in epoxidation reactions, resulting in side reactions. Impurity chlorine on the order of several percent remains in the resin. Therefore, in the prior art, epoxy resins having both low viscosity and high purity are rare.

  Moreover, in the underfill material use etc., the outstanding joining reliability is requested | required, and the epoxy resin which is excellent in the softness | flexibility is desired as a means to solve it. Therefore, development of a liquid epoxy resin having low viscosity, high purity, and excellent flexibility is awaited.

  On the other hand, the demand for water-based epoxy resins is increasing more and more from the viewpoint of environmental response, which has recently become increasingly serious. However, conventional epoxy resins have poor water solubility and are often dealt with by emulsion technology using emulsifiers. However, the stability of emulsions is poor, and there are many problems such as quality deterioration due to emulsifiers. The demand for the development of highly water-soluble epoxy resins that can be improved in the future is increasing.

Japanese Patent Laid-Open No. 2002-17984 JP-A-9-176287

  Accordingly, an object of the present invention is to provide a novel liquid epoxy resin having a low viscosity and excellent fluidity, a cured product having excellent flexibility, and further imparting water solubility as required, and an epoxy resin containing the same It is an object of the present invention to provide a composition and a production method in which the liquid epoxy resin can be obtained with high purity with less impurity chlorine.

In order to solve the above-mentioned problems, the present inventors have obtained the following knowledge as a result of intensive studies.
(I) The epoxy resin (a) represented by the general formula (1) is a novel epoxy resin.

(In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X and Y are each independently an ethyleneoxyethyl group, a di (ethyleneoxy) ethyl group, a tri (ethyleneoxy) ethyl group, a tetra (Ethyleneoxy) ethyl group, propyleneoxypropyl group, di (propyleneoxy) propyl group, tri (propyleneoxy) propyl group, tetra (propyleneoxy) propyl group, butyleneoxybutyl group, di (butyleneoxy) butyl group, tri A (butyleneoxy) butyl group, a tetra (butyleneoxy) butyl group, an alkylene group having 2 to 15 carbon atoms, or an aliphatic hydrocarbon group having 6 to 17 carbon atoms having a cycloalkane skeleton, where n is a natural number. The average value is 0.01-20.)

(Ii) The epoxy resin composition containing the epoxy resin (a) represented by the general formula (1) and the curing agent (b) can solve the above problems.
(Iii) Divinyl ethers (c) containing at least one skeleton selected from the group consisting of a polyoxyalkylene skeleton, a cycloalkane skeleton and an alkylene skeleton , a glycidol (d) , a polyoxyalkylene skeleton and a cycloalkane A method of reacting a dialcohol (e) containing one or more skeletons selected from the group consisting of a skeleton and an alkylene skeleton is a novel method in which the epoxy resin (a) has a low impurity chlorine content and a high-purity epoxy resin can be obtained. It is a manufacturing method of an epoxy resin.

  The present invention is based on such knowledge. That is, this invention provides the epoxy resin represented by the said General formula (1).

  The present invention also provides an epoxy resin composition comprising the epoxy resin (a) represented by the general formula (1) and a curing agent (b).

The present invention also provides divinyl ethers (c) containing at least one skeleton selected from the group consisting of a polyoxyalkylene skeleton, a cycloalkane skeleton and an alkylene skeleton , glycidols (d), and a polyoxyalkylene skeleton. And a method for producing an epoxy resin represented by the general formula (1), comprising reacting a dialcohol (e) containing one or more skeletons selected from the group consisting of a cycloalkane skeleton and an alkylene skeleton. Also provide.

  According to the present invention, an epoxy resin composition capable of obtaining a highly flexible cured product extremely useful as a high-quality paint, semiconductor encapsulant, printed wiring board, composite material, etc., low viscosity and excellent fluidity In addition, it is possible to provide an epoxy resin which is substantially free of impurity chlorine and has high reliability as a result, and also has high water compatibility, and a method for producing these epoxy resins.

  Hereinafter, the present invention will be described in detail. The epoxy resin (a) of the present invention is represented by the general formula (1). These epoxy resins can be obtained from, for example, a method for producing an epoxy resin described later.

  Among these epoxy resins (a), the divalent organic groups X and Y in the general formula (1) are an ethyleneoxyethyl group, a di (ethyleneoxy) ethyl group, a tri (ethyleneoxy) ethyl group, a tetra (Ethyleneoxy) ethyl group, propyleneoxypropyl group, di (propyleneoxy) propyl group, tri (propyleneoxy) propyl group, tetra (propyleneoxy) propyl group, butyleneoxybutyl group, di (butyleneoxy) butyl group, tri What is a (butyleneoxy) butyl group, a tetra (butyleneoxy) butyl group, an alkylene group having 2 to 15 carbon atoms, or an aliphatic hydrocarbon group having 6 to 17 carbon atoms having a cycloalkane skeleton. Especially preferred.

  Among these, X and Y are preferably poly (alkyleneoxy) alkyl groups because of their low viscosity, excellent water solubility, and excellent flexibility of the cured product. Moreover, since the obtained hardened | cured material is excellent also in toughness in addition to a softness | flexibility, X and Y have a C6-C17 aliphatic hydrocarbon group which has a cycloalkane skeleton. Furthermore, X and Y are preferably alkylene groups having 2 to 15 carbon atoms because of low viscosity and excellent balance between flexibility and toughness of the cured product.

  In addition, the lower the epoxy equivalent of the epoxy resin (a), the lower the viscosity of the epoxy resin, but it is preferably 200 g / eq or more because the cured product has good flexibility. From the viewpoint of good properties, it is preferably 2000 g / eq or less. More preferably, it is 300-1000 g / eq.

  The number average molecular weight of the epoxy resin (a) is preferably 400 or more because the cured product has good flexibility, and 4000 or less because the viscosity is low and the fluidity and workability are good. It is preferable that it is 600, 2000 especially.

  In addition, the epoxy resin (a) preferably has a viscosity at 25 ° C. of 1000 mPa · s or less in many aspects such as fluidity, workability, and the degree of freedom in blending the composition. More preferably, the viscosity under the same conditions is 500 mPa · s or less.

  The epoxy resin (a) is preferable because the total chlorine content (after sodium metal treatment in butanol solution and silver nitrate titration method) is 50 ppm or less, which is excellent in moisture resistance reliability. More preferably, it is 10 ppm or less. Moreover, it is preferable that the said epoxy resin (a) is water-soluble, and specifically, it is preferable that the dilution value mentioned later is 1000 or more in 25 degreeC.

The epoxy resin (a) is, for example, a vinyl ether group or a glycidol of divinyl ethers (c) containing at least one skeleton selected from the group consisting of a polyoxyalkylene skeleton, a cycloalkane skeleton and an alkylene skeleton. hydroxyl group of d), and, a polyoxyalkylene backbone is obtained by a hydroxyl group of the di-alcohol containing one or more skeletons selected from the group consisting of cycloalkanes skeleton and alkylene backbone (e) is reacted acetalization.

  The divinyl ethers (c) are preferably compounds containing one or more skeletons selected from the group consisting of a polyoxyalkylene skeleton, a cycloalkane skeleton and an alkylene skeleton.

  The dialcohol (e) is preferably a compound containing at least one skeleton selected from the group consisting of a polyoxyalkylene skeleton, a cycloalkane skeleton and an alkylene skeleton.

  The epoxy resin composition of the present invention is characterized by containing an epoxy resin (a) represented by the general formula (1) and a curing agent (b).

  In addition to the epoxy resin (a), other epoxy resins can be used in combination with the epoxy resin composition of the present invention. When used in combination, the proportion of the epoxy resin (a) in the total epoxy resin is preferably 10% by weight or more, and particularly preferably 30% by weight or more. The epoxy resin that can be used in combination with the epoxy resin is not particularly limited, and various epoxy resins can be used. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, resorcin type epoxy Bisphenol-type liquid epoxy resins such as resins, hydroquinone-type epoxy resins, catechol-type epoxy resins, dihydroxynaphthalene-type epoxy resins, allyl group-substituted bisphenol-type epoxy resins, alkyl group-substituted dihydroxybenzene-type epoxy resins, and 1,6- Hexanediol type epoxy resin, neopentyl glycol type epoxy resin, hydrogenated bisphenol A type epoxy resin, alcohol ether type epoxy resin such as butyl glycidyl ether, alkylphenol glycy Monofunctional reactive diluent type epoxy resin such as ruether, crystalline epoxy resin such as biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, tri Phenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolak type epoxy Resin, naphthol-cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resin, biphenyl modified novo Click type epoxy resin, tetrabromobisphenol A type epoxy resins, such as brominated phenol novolak type epoxy resins. Moreover, the said other epoxy resin may be used independently and may mix 2 or more types.

  Among these, in underfill materials and conductive paste applications, it is preferable to combine with a liquid epoxy resin, specifically, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, resorcin type epoxy resin. A combination with hydroquinone type epoxy resin, catechol type epoxy resin, dihydroxynaphthalene type epoxy resin and the like is preferable. A combination with a type obtained by purifying them by molecular distillation is more preferable.

  As the curing agent (b) used in the present invention, various ones can be used and are not particularly limited. For example, curing agents such as amine compounds, amide compounds, acid anhydride compounds, phenol compounds, and the like are used. Can be used. Examples of these amine compounds include ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, pentaethylenehexamine, and other aliphatic polyamines, metaxylylenediamine, diaminodiphenylmethane, and phenylene. Aromatic polyamines such as diamine, alicyclic polyamines such as 1,3-bis (aminomethyl) cyclohexane, isophorone diamine, norbornane diamine and the like can be mentioned. Also, dicyandiamides, polyamide resins synthesized from dimer of linolenic acid and ethylenediamine, polyamide resins obtained by reaction of the amine compound with various acids, and the like can be mentioned.

  Examples of acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride. And methyl hexahydrophthalic anhydride.

The phenolic compounds include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylol methane resin, tetraphenylol. Examples include ethane resins, naphthol novolak resins, naphthol-phenol co-condensed novolak resins, naphthol-cresol co-condensed novolak resins, biphenyl-modified phenol resins, aminotriazine-modified phenol resins, and modified products thereof. Examples of the latent catalyst include imidazole, BF ₃ -amine complex, and guanidine derivative.

  In addition, curing agents such as amine compounds, amide compounds, acid anhydride compounds, and phenol compounds may be used alone or in combination of two or more. In the epoxy resin composition of the present invention, the curing agent is used in an amount of active hydrogen groups in the curing agent with respect to 1 equivalent of the epoxy group of the epoxy resin because curing proceeds smoothly and good cured properties are obtained. Is preferably 0.7 to 1.5 equivalents.

  Moreover, a hardening accelerator can also be further used for the epoxy resin composition of this invention suitably. Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, and the like. Can be used in combination. For example, as a semiconductor sealing material, phosphorus-based triphenylphosphine and amine-based DBU are preferable because of excellent curability, heat resistance, electrical characteristics, moisture resistance reliability, and the like.

  An inorganic filler can be blended in the epoxy resin composition of the present invention. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. When particularly increasing the blending amount of the inorganic filler, it is preferable to use fused silica. The fused silica can be used in either a crushed shape or a spherical shape. However, in order to increase the blending amount of the fused silica and suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use a spherical shape. Furthermore, in order to increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling rate is preferably higher in consideration of flame retardancy, and particularly preferably 65% by weight or more with respect to the total amount of the epoxy resin composition. Moreover, when using for uses, such as an electrically conductive paste, electroconductive fillers, such as silver powder and copper powder, can be used.

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

  A flame retardant imparting agent can be added to the epoxy resin composition of the present invention as necessary. Various flame retardants can be used, for example, halogen compounds such as decabromodiphenyl ether and tetrabromobisphenol A, phosphorus atom-containing compounds such as red phosphorus and various phosphoric acid ester compounds, melamine or derivatives thereof, etc. Examples thereof include inorganic flame retardant compounds such as nitrogen atom-containing compounds, aluminum hydroxide, magnesium hydroxide, zinc borate, and calcium borate.

  The epoxy resin composition of this invention is obtained by mixing each component uniformly. The epoxy resin composition of the present invention, in which the epoxy resin of the present invention, a curing agent and, if necessary, a curing accelerator are blended, can be easily made into a cured product by a method similar to a conventionally known method.

  For example, in order to produce an epoxy resin composition prepared for paint, dispersion of a paint shaker or the like until an epoxy resin, a curing agent, and if necessary, an organic solvent, a filler, a pigment, and the like are uniformly mixed What is necessary is just to mix using a container and to obtain the composition for coating materials. For powder coatings, a mixture obtained by a production method similar to that of a semiconductor encapsulant described later is finally obtained by pulverizing with a pulverizer.

  In order to produce an epoxy resin composition prepared for a semiconductor encapsulant, an epoxy resin, a curing agent, a compounding agent such as a filler, and the like, if necessary, an extruder, a kneader, a roll, etc. It is sufficient to obtain a melt-mixed type epoxy resin composition by mixing well until it is uniform. At that time, silica is usually used as the filler, and the filling rate is preferably in the range of 30 to 95 parts by weight per 100 parts by weight of the epoxy resin composition. In order to improve moisture resistance and solder crack resistance, and to lower the linear expansion coefficient, the amount is particularly preferably 70 parts by weight or more, and in order to significantly improve these effects, 80 parts by weight or more is more preferable. When the epoxy resin or curing agent used in combination is liquid, the obtained sealing material becomes a liquid semiconductor sealing material, and becomes a final product form filled in a syringe container or the like. Moreover, when combined with a solid material, it becomes a solid sealing material for transfer molding, resulting in a tablet or powdery final product form.

  Further, in order to produce an epoxy resin composition prepared for printed wiring board materials or CFRP, the epoxy resin composition is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. It can be used as a composition. The solvent at this time is prepared so as to be 10 to 70 parts by weight, preferably 15 to 65 parts by weight, particularly preferably 15 to 65 parts by weight per 100 parts by weight of the mixture of the epoxy resin composition of the present invention and the solvent. It is preferable to do.

  Furthermore, a prepreg obtained by impregnating a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. with the above epoxy resin composition solution (varnish-like composition) and drying by heating is subjected to hot press molding. Thus, a laminated plate can be obtained.

  The cured product of the present invention can be obtained by thermally curing the epoxy resin composition of the present invention, and has forms such as a molded product, a laminate, a cast product, an adhesive, a coating film, and a film. For example, in the case of a melt-mixed type composition, the composition is cured by casting or molding using a transfer molding machine, an injection molding machine, etc., and further heating at 80 to 200 ° C. for 2 to 10 hours. A product can be obtained, and semiconductor package molding corresponds to this. In the case of a varnish-like composition, a coating film can be obtained by coating it on a substrate and drying it by heating, and the paint corresponds to this. In addition, it can be obtained by impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and drying by heating to obtain a prepreg, which can be obtained by hot press molding. This applies to the laminated material for CFRP and CFRP. The use of the underfill material, conductive paste, resist ink, and interlayer insulating material among these will be described.

  The method for using the epoxy resin composition of the present invention as an underfill material is not particularly limited. For example, Japanese Patent Application Laid-Open No. 9-266221 and “Plastics in the Electronics Field” (Industrial Research Council, pp. 27-34, 1999) Can be used. More specifically, the epoxy resin composition of the present invention is injected into the gap between the semiconductor element with electrodes and the printed wiring board with solder during flip-chip mounting by a capillary flow method using a capillary phenomenon. Examples thereof include a method of curing, a compression flow method in which the curable resin composition of the present invention is semi-cured on a substrate or a semiconductor element in advance, and then the semiconductor element and the substrate are adhered to each other by heating to be completely cured. In this case, the curable resin composition of the present invention is preferably used in the form of a liquid curable resin composition containing no organic solvent. In particular, when the capillary flow method is used, the viscosity needs to be low, and the viscosity is preferably 5000 mPa · s or less. If the said resin composition is a viscosity exceeding this, it can also inject | pour after heating to room temperature-100 degrees C or less.

  When using the epoxy resin composition of the present invention as a conductive paste, for example, fine conductive particles described in JP-A-3-46707 are dispersed in the resin composition, and the composition for anisotropic conductive film is used. And a paste resin composition for circuit connection which is liquid at room temperature as disclosed in JP-A-62-240183, JP-A-62-276215, JP-A-62-176139, etc. And an anisotropic conductive adhesive.

  When the epoxy resin composition of the present invention is used as a resist ink, for example, according to the method described in JP-A No. 5-186567, a resist ink composition is prepared and then printed on a printed circuit board by a screen printing method. The method of making it a resist ink hardened | cured material after apply | coating to is mentioned. Moreover, it can be used as a resist ink for a flexible wiring board, and can also be used as a coating type coverlay material.

  Although it does not specifically limit as a method of obtaining the interlayer insulation material for buildup boards from the epoxy resin composition of the present invention, for example, Japanese Patent Publication No. 4-6116, Unexamined-Japanese-Patent No. 7-304931, Unexamined-Japanese-Patent No. 8-64960, Various methods described in JP-A-9-71762, JP-A-9-298369 and the like can be employed. More specifically, the curable resin composition appropriately blended with rubber, filler, and the like is applied to a wiring board on which a circuit is formed using a spray coating method, a curtain coating method, or the like, and then cured. Then, after drilling a predetermined through-hole part etc. as needed, it treats with a roughening agent, forms the unevenness | corrugation by washing the surface with hot water, and metal-treats, such as copper. As the plating method, electroless plating or electrolytic plating treatment is preferable, and examples of the roughening agent include an oxidizing agent, an alkali, and an organic solvent. Such operations are sequentially repeated as desired, and a build-up base can be obtained by alternately building up and forming the resin insulating layer and the conductor layer having a predetermined circuit pattern. However, the through-hole portion is formed after the outermost resin insulating layer is formed. In addition, a resin-coated copper foil obtained by semi-curing the resin composition on the copper foil is thermocompression-bonded at 170 to 250 ° C. on a circuit board on which a circuit is formed, thereby forming a roughened surface and plating treatment. It is also possible to produce a build-up substrate by omitting the process.

  The cured product of the present invention is obtained by subjecting the epoxy resin composition as described above to processing and molding according to the application using various apparatuses such as a press molding machine, transfer molding machine, coating apparatus, and printing apparatus. Alternatively, it is obtained after heating and sufficient time for curing. Curing conditions vary depending on the composition and application, but in the temperature range of room temperature to 200 ° C. when an aliphatic amine curing agent system is used, and in the temperature range of 60 to 250 ° C. when other curing agents are used. The curing may take 10 seconds to 10 hours. You may make it primary-cure in a shaping | molding apparatus, and after that, after removing from a shaping | molding apparatus, you may carry out secondary-curing in the oven etc. In substrate molding or the like, a vacuum press apparatus can be used to efficiently remove the solvent.

  The method for producing an epoxy resin (a) of the present invention is a reaction of divinyl ethers (c), glycidols (d) and dialcohols (e). More specifically, the vinyl ether group of the divinyl ether (c) and the hydroxyl group of the glycidol (d) are subjected to an acetalization reaction between the vinyl ether group of the divinyl ether (c) and the hydroxyl group of the dialcohol (e). It is the manufacturing method of the epoxy resin characterized. Since the production method of the present invention does not use a chlorine-containing compound such as epichlorohydrin as a method for introducing an epoxy group, it can be one that does not contain chlorine.

  The acetalization reaction is a reaction represented by the chemical reaction formula (1).

  Although it does not specifically limit with divinyl ether (c) used with the manufacturing method of the epoxy resin (a) of this invention, For example, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether, (Poly) oxy such as propylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, tetrapropylene glycol divinyl ether, dibutylene glycol divinyl ether, tributylene glycol divinyl ether, tetrabutylene glycol divinyl ether, etc. Divinyl ethers containing an alkylene group; 1,3-butanediol divinyl ether, 1,4-buta Alkylene groups such as didiol divinyl ether, 1,6-hexanediol divinyl ether, 1,9-nonanediol divinyl ether, 1,10-decanediol divinyl ether, neopentyl glycol divinyl ether, hydroxypivalic acid neopentyl glycol divinyl ether 1,4-cyclohexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, tricyclodecanediol divinyl ether, tricyclodecane dimethanol divinyl ether, pentacyclopentadecane dimethanol divinyl ether, pentacyclo Divinyl ethers containing a cycloalkane structure such as pentadecanediol divinyl ether; bisphenol A divinyl ether Le, ethylene oxide-modified bisphenol A divinyl ether, propylene oxide-modified bisphenol A divinyl ether, bisphenol F divinyl ether, ethylene oxide-modified bisphenol F divinyl ether, such as divinyl ethers, such as propylene oxide-modified bisphenol F divinyl ether.

  The divinyl ethers (c) may be selected appropriately considering the desired properties of the resulting epoxy resin. Among these, divinyl ethers containing a polyoxyalkylene skeleton, divinyl ethers containing an alkylene skeleton, and divinyl ethers containing a cycloalkane skeleton are preferable. Among these, divinyl ethers containing a polyoxyalkylene skeleton are preferred if excellent water solubility is desired in addition to low viscosity and flexibility of the cured product. If excellent toughness is desired in addition to flexibility in the resulting cured product, cycloalkane skeleton-containing divinyl ethers are preferred.

  Any glycidol (d) used in the method for producing an epoxy resin (a) of the present invention can be used as long as it is a three-carbon atom structure having an epoxy group and a hydroxyl group. Examples thereof include glycidol and β-position methyl group-substituted glycidol, and glycidol is preferred in view of industrial availability, economy, and curability.

  The dialcohols (e) used in the method for producing the epoxy resin (a) of the present invention are not particularly limited, and examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, and dipropylene glycol. , Dialcohols containing (poly) oxyalkylene groups such as tripropylene glycol, tetrapropylene glycol, dibutylene glycol, tributylene glycol, tetrabutylene glycol, etc .; 1,3-butanediol, 1,4-butanedidi Dialcohols having an alkylene group such as all, 1,6-hexanediol, 1,9-nonanediol, 1,10-decanediol, neopentyl glycol, and neopentyl glycol hydroxypivalate; -Dialcohols containing a cycloalkane structure such as cyclohexanediol, 1,4-cyclohexanedimethanol, tricyclodecane diol, tricyclodecane dimethanol, pentacyclopentadecane dimethanol, pentacyclopentadecanediol; ethylene oxide modified bisphenol A And dialcohols such as propylene oxide-modified bisphenol A, ethylene oxide-modified bisphenol F, and propylene oxide-modified bisphenol F.

  The said dialcohol (e) should just select an appropriate thing in consideration of the desired characteristic of the epoxy resin obtained. Among these, dialcohols containing a polyoxyalkylene skeleton, dialcohols containing an alkylene skeleton, and dialcohols containing a cycloalkane skeleton are preferred. Of these, dialcohols containing a polyoxyalkylene skeleton are preferred if excellent water solubility is desired in addition to low viscosity and flexibility of the cured product. If it is desired to have excellent toughness in addition to flexibility in the resulting cured product, cycloalkane skeleton-containing dialcohols are preferred.

  In the method for producing the epoxy resin (a) of the present invention, the reaction usually proceeds even in a catalyst-free system, but the reaction rate is increased or the reaction proceeds under a low temperature condition that prevents the self-polymerization of divinyl ether or glycidol. For this, it is preferable to use an acidic catalyst (f). The type of the acidic catalyst (f) is not particularly limited. For example, inorganic acids such as sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid, acidic phosphoric acid esters, toluenesulfonic acid, methanesulfonic acid, xylenesulfonic acid, trifluoromethane Organic acids such as sulfonic acid, oxalic acid, formic acid, trichloroacetic acid, trifluoroacetic acid, aluminum chloride, iron chloride, tin chloride, gallium chloride, titanium chloride, aluminum bromide, gallium bromide, boron trifluoride ether complex, trifluoride Lewis acids such as borohydride phenol complex. The amount of the catalyst added may be in the range of 10 ppm to 5% by weight with respect to the total weight of the raw material. Among these, acidic phosphates and oxalic acid are particularly preferable from the viewpoints of good reaction rate and few side reactions.

  The production operation conditions for the epoxy resin (a) of the present invention include divinyl ethers (c), glycidols (d), dialcohols (e) and an acidic catalyst (f), and 0 to 150 ° C., preferably An epoxy resin can be obtained by heating and stirring at a temperature of 0 to 100 ° C. for about 0.5 to 30 hours. The progress of the reaction can be traced by measuring the residual amount of the raw material using gas chromatography, liquid chromatography, GPC or the like. In this case, an organic solvent can be used as needed. The organic solvent that can be used is not particularly limited, and examples thereof include aromatic organic solvents such as benzene, toluene, and xylene, and ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. It can be selected as appropriate in consideration of properties such as the raw materials used and the solubility of the product, reaction conditions, economics, and the like. The amount of the organic solvent is preferably 5 to 500% by weight based on the raw material weight. When an organic solvent is used, it is removed by distillation or the like. When a catalyst is used, it is deactivated with a deactivator if necessary, and then removed by washing with water or filtering.

  The reaction ratio of the divinyl ethers (c), glycidols (d) and dialcohols (e) in the above reaction is not particularly limited and may be prepared according to desired properties, but the cured product properties are given priority. Then, the number of moles of vinyl ether groups (c ′) of divinyl ethers (c), the number of moles of hydroxyl groups (d ′) of glycidols (d), and the number of moles of hydroxyl groups of dialcohols (e) (e ′ ) At a ratio of ““ (c ′) <[(d ′) + (e ′)] ”so that the vinyl ether group does not remain. Excess glycidols and dialcohols remaining after the reaction may be removed by washing with alkaline water, distillation or the like, if necessary. If low viscosity is prioritized even if the physical properties of the cured product are sacrificed, the vinyl ether group may be left by charging at a ratio of [(c ′)> [(d ′) + (e ′)]]. The resulting epoxy resin can be applied to a light and thermal cationic polymerization system utilizing residual vinyl ether groups. Therefore, the reaction may be carried out under the charging conditions of [(c ′) / [(d ′) + (e ′)]] = (100) / 25 to 100/500 according to the desired characteristics. In addition, as a charging ratio of the glycidols (d) and the dialcohols (e), it is preferable to excessively add the glycidols (d) if the molecular weight is reduced and low viscosity is given priority, and the molecular weight is increased. If priority is given to flexibility, the dialcohol (e) is preferably charged excessively.

  Next, the present invention will be specifically described with reference to examples and comparative examples. In the examples, “parts” represent parts by weight.

Example 1
A flask equipped with a thermometer and a stirrer was charged with 303 g of triethylene glycol divinyl ether (manufactured by ISP: trade name Rapi-Cure DVE-3), 74 g of glycidol (2,3-epoxy-1-propanol), and 62 g of ethylene glycol. 2 g of oxalic acid was added at room temperature, the temperature was raised to 70 ° C., and stirring was continued for 8 hours. After confirming the substantial disappearance of the raw material by GPC, the contents were taken out to obtain 441 g of a colorless and transparent liquid. The resin obtained from the NMR spectrum ( ¹³ C) shown in FIG. 1 and from the mass spectrum, peaks of M ⁺ = 614 and M ⁺ = 878 corresponding to the theoretical structure of n = 1 and n = 2 were obtained. It confirmed that it was the target epoxy resin (E1) represented by following Structural formula (2). The epoxy equivalent of the resin is 489 g / eq, the viscosity at 25 ° C. (E-type viscometer) is 207 mPa · s, and total chlorine (silver nitrate titration method after metal sodium treatment in butanol solution) is below the limit of quantification ( The limit of quantification was 10 ppm). Moreover, the average value of n in the following structural formula (2) calculated from the epoxy equivalent was 2.38. Further, water-soluble evaluation (dilution value: 5 g of epoxy resin was put into a 100 ml Erlenmeyer flask, distilled water was added dropwise with stirring with a magnetic stirrer at 25 ° C., and the volume of distilled water required for cloudiness was obtained. The dilution value was 1000 or more.

Example 2
Example except that triethylene glycol divinyl ether was changed to 213 g of 1,4-butanedidiol divinyl ether (ISP: trade name Rapi-Cure DVB1D) and ethylene glycol was changed to 90 g of 1,4-butanedidiol In the same manner as in Example 1, 379 g of a colorless and transparent liquid was obtained. From the NMR spectrum ( ¹³ C) shown in FIG. 2, the resin obtained peaks of M ⁺ = 522 and M ⁺ = 754 corresponding to the theoretical structure of n = 1 and n = 2 in the mass spectrum. It confirmed that it was the target epoxy resin (E2) represented by following Structural formula (3). The epoxy equivalent of the resin was 431 g / eq, the viscosity at 25 ° C. (E-type viscometer) was 205 mPa · s, and the total chlorine was below the limit of quantification. Moreover, the average value of n in the following structural formula (3) calculated from the epoxy equivalent was 2.46.

Example 3
Change triethylene glycol divinyl ether to 245 g of 1,4-cyclohexanedimethanol divinyl ether (Nippon Carbide Industries Co., Ltd .: trade name CHDVE), change ethylene glycol to 72 g of 1,4-cyclohexanedimethanol, and change 74 g of glycidol to 111 g. 430 g of a colorless and transparent liquid was obtained in the same manner as in Example 1 except that. From the NMR spectrum ( ¹³ C) shown in FIG. 3, the resin obtained peaks of M + = 684 and M + = 1024 corresponding to the theoretical structure of n = 1 and n = 2 in the mass spectrum. It confirmed that it was the target epoxy resin (E3) represented by Formula (4) . The epoxy equivalent of the resin was 329 g / eq, the viscosity at 25 ° C. (E-type viscometer) was 800 mPa · s, and the total chlorine was below the limit of quantification. Moreover, the average value of n in the following structural formula (4) calculated from the epoxy equivalent was 0.92.

Examples 4-6 and Comparative Examples 1-2
Comparison of the three types of epoxy resins (E1), (E2), and (E3) synthesized in this way with general liquid epoxy resins was evaluated for the following items. The epoxy resin used for comparison is a commercially available bisphenol F type liquid epoxy resin (abbreviated as E4. Epoxy equivalent: 171 g / eq, viscosity at 25 ° C .: 3800 mPa · s, total chlorine: 1500 ppm), commercially available bisphenol A type liquid epoxy. There are two types of resin, high-purity molecular distilled products (abbreviated as E5, epoxy equivalent: 173 g / eq, viscosity at 25 ° C .: 4300 mPa · s, total chlorine: 620 ppm).

(1) Moisture resistance reliability test In a container made of polytetrafluoroethylene, 5 g of epoxy resin (E1), (E2), (E3), (E4) and (E5) and 50 g of distilled water are placed, and made of pressure-resistant metal. It was installed in a container and a PCT (pressure cooker) test at 160 ° C./4 atm / 20 hours was performed. The extracted water after the test was measured for chloride ion concentration with an ion chromatography measuring device (detection limit = 0.1 ppm), and the obtained results are shown in Table 1.

(2) Evaluation of physical properties of cured product (flexibility evaluation)
Epoxy resins (E1), (E2), (E3), (E4) and (E5) and an aliphatic amine curing agent (triethylenetetramine, active hydrogen equivalent 24 g / eq) in an equivalent amount of epoxy group and active hydrogen group The mixture was uniformly mixed at such a ratio and poured into an iron petri dish (diameter 65 mm, height 12 mm) and heated at 80 ° C. for 3 hours and 150 ° C. for 2 hours to obtain a cured product having a thickness of 2 mm. Flexibility was evaluated by conducting a bending test using the cured product. In the bending test, the cured product was judged as ◯ when the cured product was bent at about 180 degrees, and x when not bent. Further, a phenol novolac resin curing agent (softening point 80 ° C., hydroxyl group equivalent 104 g / eq) was uniformly mixed at a ratio such that the epoxy group and the hydroxyl group were equivalent, and 0.8 part of benzyldimethylamine was added as an accelerator, The mixture was uniformly mixed, poured into an iron petri dish, and heated at 120 ° C. for 1 hour and further at 175 ° C. for 5 hours to obtain a cured product having a thickness of 2 mm. A bending test was similarly performed using the cured product. The obtained results are shown in Table 1.

From the results of Examples and Comparative Examples, it was found that (1) The epoxy resin of the present invention has a high epoxy equivalent, but the bisphenol F type epoxy resin and the high purity molecular distillation type bisphenol A type epoxy Compared with resin, it has much lower viscosity and excellent fluidity.

  (2) The epoxy resin of the present invention not only has a very low total chlorine in the resin, but also the epoxy resin composition obtained therefrom is a bisphenol F type epoxy resin or a high purity molecular distillation type bisphenol A type epoxy resin. Compared to the above, it was confirmed that the moisture reliability in practice was excellent in reliability.

  (3) In the epoxy resin of this invention, it confirmed that the epoxy resin which has poly (alkyleneoxy) alkyl frame | skeleton like E-1 had high water solubility.

  (4) The hardened | cured material of the epoxy resin composition of this invention has confirmed that it was excellent in the softness | flexibility compared with the bisphenol F type epoxy resin and the high purity molecular distillation type bisphenol A type epoxy resin.

1 is a ¹³ C NMR spectrum of the epoxy resin (E1) obtained in Example 1. FIG. FIG. 2 is a ¹³ C NMR spectrum of the epoxy resin (E2) obtained in Example 2. FIG. 3 is a ¹³ C NMR spectrum of the epoxy resin (E3) obtained in Example 3.

Claims (19)

General formula (1)

(In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X and Y are each independently an ethyleneoxyethyl group, a di (ethyleneoxy) ethyl group, a tri (ethyleneoxy) ethyl group, a tetra (Ethyleneoxy) ethyl group, propyleneoxypropyl group, di (propyleneoxy) propyl group, tri (propyleneoxy) propyl group, tetra (propyleneoxy) propyl group, butyleneoxybutyl group, di (butyleneoxy) butyl group, tri A (butyleneoxy) butyl group, a tetra (butyleneoxy) butyl group, an alkylene group having 2 to 15 carbon atoms, or an aliphatic hydrocarbon group having 6 to 17 carbon atoms having a cycloalkane skeleton, where n is a natural number. And the average value is 0.01 to 20.) An epoxy resin (a) and a curing agent (b Epoxy resin composition characterized by containing. The epoxy resin (a) is a divinyl ether (c) containing at least one skeleton selected from the group consisting of a polyoxyalkylene skeleton, a cycloalkane skeleton and an alkylene skeleton , a glycidol (d), and a polyoxyalkylene The epoxy resin composition according to claim 1, which is an epoxy resin obtained by reacting a dialcohol (e) containing one or more skeletons selected from the group consisting of a skeleton, a cycloalkane skeleton and an alkylene skeleton . The epoxy resin composition according to claim 1 or 2 , wherein an epoxy equivalent of the epoxy resin (a) is 200 to 2000 g / eq. The epoxy resin composition according to claim 1 or 2, wherein the epoxy resin (a) has a viscosity (E-type viscometer ) at 25 ° C of 1000 mPa · s or less. The epoxy resin composition as described in any one of Claims 1-4 prepared for the resin composition for printed circuit boards. The epoxy resin composition as described in any one of Claims 1-4 prepared for semiconductor sealing materials. The epoxy resin composition according to any one of claims 1 to 4 , which is prepared for a liquid sealing material (underfill material). The epoxy resin composition according to any one of claims 1 to 4 , prepared for a conductive paste. The epoxy resin composition according to any one of claims 1 to 4 , which is prepared for resist ink. The epoxy resin composition according to any one of claims 1 to 4 , which is prepared for an interlayer insulating material. Hardened | cured material obtained by hardening | curing the epoxy resin composition as described in any one of Claims 1-4 . General formula (1)

(In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X and Y are each independently an ethyleneoxyethyl group, a di (ethyleneoxy) ethyl group, a tri (ethyleneoxy) ethyl group, a tetra (Ethyleneoxy) ethyl group, propyleneoxypropyl group, di (propyleneoxy) propyl group, tri (propyleneoxy) propyl group, tetra (propyleneoxy) propyl group, butyleneoxybutyl group, di (butyleneoxy) butyl group, tri A (butyleneoxy) butyl group, a tetra (butyleneoxy) butyl group, an alkylene group having 2 to 15 carbon atoms, or an aliphatic hydrocarbon group having 6 to 17 carbon atoms having a cycloalkane skeleton, where n is a natural number. An average value of which is 0.01 to 20). ). Divinyl ethers (c) containing at least one skeleton selected from the group consisting of polyoxyalkylene skeleton, cycloalkane skeleton and alkylene skeleton, glycidols (d), polyoxyalkylene skeleton, cycloalkane skeleton and alkylene The epoxy resin (a) according to claim 12, obtained by reacting a dialcohol (e) containing one or more skeletons selected from the group consisting of skeletons. The epoxy resin (a) according to claim 12 , which has an epoxy equivalent of 200 to 2000 g / eq. The epoxy resin (a) according to claim 12 , which has a viscosity (E-type viscometer) at 25 ° C of 1000 mPa · s or less. The epoxy resin (a) according to claim 12 , wherein the total chlorine is 10 ppm or less. The epoxy resin (a) according to claim 12 , wherein a dilution value with respect to water at 25 ° C is 1000 or more. Divinyl ethers (c) containing at least one skeleton selected from the group consisting of polyoxyalkylene skeleton, cycloalkane skeleton and alkylene skeleton , glycidols (d) , polyoxyalkylene skeleton, cycloalkane skeleton and alkylene A process for producing an epoxy resin represented by the general formula (1), comprising reacting a dialcohol (e) containing one or more skeletons selected from the group consisting of skeletons .

(In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. X and Y are each independently an ethyleneoxyethyl group, a di (ethyleneoxy) ethyl group, a tri (ethyleneoxy) ethyl group, a tetra (Ethyleneoxy) ethyl group, propyleneoxypropyl group, di (propyleneoxy) propyl group, tri (propyleneoxy) propyl group, tetra (propyleneoxy) propyl group, butyleneoxybutyl group, di (butyleneoxy) butyl group, tri A (butyleneoxy) butyl group, a tetra (butyleneoxy) butyl group, an alkylene group having 2 to 15 carbon atoms, or an aliphatic hydrocarbon group having 6 to 17 carbon atoms having a cycloalkane skeleton, where n is a natural number. The average value is 0.01-20.) Manufacturing method of the divinyl ethers (c) and the glycidol compound (d) and the dialcohols (e) and using an acidic catalyst (f) as a catalyst in the reaction of claim 18 of the epoxy resin.

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