JP4665444B2 - Production method of epoxy resin - Google Patents

Description

  The present invention is excellent in fluidity and curability during molding, and heat resistance of a cured product, has little mold contamination, and has a good hue, and can be suitably used as an electronic component sealing material, an optical material, and the like. The present invention relates to a method for producing an epoxy resin.

  Epoxy resins can be cured with various curing agents, resulting in cured products with excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc. It is used in a wide range of fields such as printed wiring boards, laminated board materials, resist inks, interlayer insulation materials, fiber reinforced composite materials, coating materials, molding materials, and adhesive materials.

  By the way, with the worldwide price reduction trend of electronic devices, various rationalization means are desired in the electronic component manufacturing process. For example, there is a demand for an epoxy resin excellent in continuous productivity and a composition using the epoxy resin that can increase the resin sealing productivity by transfer molding, that is, can be cured and molded in a short time and the molded product has no defects. ing.

  Also, with the development of information processing technology using light in recent years, resin sealing with an epoxy resin composition using an epoxy resin with excellent hue as a sealing material for optical semiconductor elements such as light emitting elements and light receiving elements Although it has become mainstream, in this field, as well as a rationalization means that is excellent in continuous productivity is desired, as well as contamination on the surface of a molded product resulting from mold contamination is a serious problem.

  Therefore, as an example of improving curability and heat resistance of the cured product compared to the composition using generally used ortho cresol novolac type epoxy resin, identification using dihydric phenol, aldehydes and epihalohydrin as raw materials An epoxy resin having a melt viscosity of 2 is proposed (for example, see Patent Document 1). The epoxy resin proposed in Patent Document 1 comprises a step of subjecting a dihydric phenol and an aldehyde to a condensation reaction in the presence of an acidic catalyst, followed by distillation at a high temperature in order to remove the solvent used and the generated water. After isolating polyphenols, the epoxy resin is obtained by reacting with epihalohydrin, but the cured product obtained by using this lacks the mechanical strength and thermal elastic modulus and has a releasability. Had a problem to worsen. In addition, since the resulting epoxy resin is easily colored pale yellow, there is a problem that the amount of use thereof is limited as a sealing material for an optical semiconductor element.

JP 2001-064358 (page 2-4)

  Therefore, the problem to be solved by the present invention is that the curability and heat resistance are drastically improved, the mold stain and the surface of the molded product are significantly less than the conventional one, and the hue is good. It is providing the manufacturing method of an epoxy resin.

As a result of intensive studies to solve the above-mentioned problems, the present inventors conducted a condensation reaction of dihydric phenols and aldehydes in the presence of an acidic catalyst, and then neutralized and / or washed with water, and then heated and distilled at 120 ° C. or higher. By continuing the glycidyl etherification reaction without carrying out the step, an epoxy resin having a good hue can be obtained in a high yield, and the curability of the composition using the obtained epoxy resin and the heat resistance of the cured product are improved. The present invention has been completed by finding that it is dramatically improved, that there is little mold contamination and contamination on the surface of the molded product, and excellent mass productivity.

That is, the present invention provides a polyhydric phenol (a) by subjecting a dihydric phenol (x1) and an aldehyde (x2) to a condensation reaction at 120 ° C. or lower in the presence of an acidic catalyst (I). Neutralization and / or washing with water, followed by addition of epihalohydrin (x3) without performing heating distillation at 120 ° C. or higher, and epoxidation reaction in the presence of basic catalyst (II) to obtain epoxy resin (A) The manufacturing method of the epoxy resin characterized by these is provided.

  The method for producing an epoxy resin of the present invention is excellent in production efficiency, and the resulting epoxy resin becomes a lustrous phase because free molecular weight compounds such as free phenols and bisphenol having an isopropylidene bond at the ortho position are suppressed. Moreover, the epoxy resin composition containing this has few mold stain | pollution | contamination and the stain | pollution | contamination of the molded article surface, and its heat resistance is also high. As described above, the epoxy resin composition containing the epoxy resin obtained by the production method of the present invention is used for sealing electronic parts, for optical materials, for laminated plates, for composite materials, resists, adhesives, paints, civil engineering, etc. It is extremely effective for a wide range of applications.

In the production method of the present invention, a polyhydric phenol (a) is obtained by subjecting a dihydric phenol (x1) and an aldehyde (x2) to a condensation reaction at 120 ° C. or less in the presence of an acidic catalyst (I). Neutralization and / or washing with water, followed by addition of epihalohydrin (x3) without performing heating distillation at 120 ° C. or higher, and glycidyl etherification reaction in the presence of basic catalyst (II) to obtain epoxy resin (A) Features.

  Usually, a method for producing an epoxy resin using a polyhydric phenol obtained by a condensation reaction of a phenol and an aldehyde as a raw material reacts the phenol with an aldehyde in the presence of an acidic catalyst, and the catalyst is washed with water. After removal, after distillation and recovery of unreacted phenols and moisture under conditions of heating and decompression, a polyphenols production process (condensation reaction) in which it is once taken out in a molten state and cooled and solidified, and these polyphenols And an excess amount of epihalohydrin are divided into two steps, namely, a production process of epoxy resin (glycidyl etherification reaction) in which a base catalyst is reacted (hereinafter abbreviated as conventional method).

  In the condensation reaction, when bisphenol A is used as the phenol, the resulting polyphenols have an isopropylidene bond in addition to a methylene bond. This isopropylidene bond is decomposed and rearranged during distillation recovery (high temperature environment) due to the presence of a small amount of acidic catalyst remaining after washing with water, and low molecular weight such as bisphenol having isopropylidene bond in the free phenol or ortho position. A compound is easily formed. A cured product obtained from an epoxy resin using polyhydric phenols containing such a low molecular weight compound as a raw material has a non-uniform portion in the crosslink density, and particularly a low molecular weight compound having no hydroxyl group is epoxidized. Since this cannot be performed, the crosslink density is lowered, heat resistance, mechanical properties, etc. are insufficient, which may cause mold contamination and contamination of the molded product surface.

  In addition, when dihydric phenols are used, free phenols may be generated by a small amount of acidic catalyst during the distillation process as described above. It becomes a colored substance that is quinonated by oxidation (in general, even if the content of such a quinone is very small, the coloring effect on the whole resin is very high) In addition to aggravating, it causes quality degradation such as an increase in epoxy equivalent. The production method of the present invention solves these problems considered to be caused by the purification step after the condensation reaction.

  The dihydric phenols (x1) used in the present invention are not particularly limited. For example, bisphenol A, 4,4′-dihydroxybenzophenone, bis (4-hydroxyphenyl) ether, bis (4-hydroxy-) 3-methylphenyl) ether, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxy-3-methylphenyl) sulfide, bis (3,5- Dimethyl-4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy-3-methylphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 1,1 ′ -Bis (3-tert-butyl-6-methyl-4-hydroxyphenyl) but Bisphenols such as hydroquinone and resorcin; divalent naphthols such as dihydroxynaphthalene, bis (hydroxynaphthyl) methane and 1,1′-binaphthol; bis (4-hydroxyphenyl) dicyclopentane 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxy-3-methylphenyl) cyclohexane, 1,1-bis (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, etc. Alicyclic structure-containing dihydric phenols and other 4,4′-dihydroxybiphenyl-3,3 ′, 5,5′-tetramethylbiphenyl and the like. Among these, bisphenols, particularly bisphenol A can be obtained. Improvement of fluidity, curability and heat resistance of epoxy resin (A) From the viewpoint that becomes more pronounced.

  The aldehyde (x2) used in the present invention is not particularly limited as long as it is a compound having one or more aldehyde groups in one molecule. For example, formaldehyde, acetaldehyde, benzaldehyde, crotonaldehyde, etc. Among these, the fluidity and curability of the epoxy resin (A) from which formaldehyde is obtained, and the heat resistance improvement effect is particularly preferable,

  As a method for obtaining the polyhydric phenols (a) by reacting the phenols (x1) and the aldehydes (x2) in the presence of the acidic catalyst (I), the temperature condition may be 120 ° C. or less. There is no particular limitation. When the temperature condition exceeds 120 ° C., the aldehydes (x2) are liable to evaporate and the yield decreases, which is not preferable. A particularly preferred temperature is 50 to 120 ° C.

  The reaction ratio between the phenols (x1) and the aldehydes (x2) is not particularly limited, and is appropriately selected according to the molecular weight (number of nuclei), viscosity, etc. of the target epoxy resin (A). However, from the viewpoint of excellent reaction yield and melt viscosity of the resulting epoxy resin, it is possible to use 0.4 to 1.1 mol of aldehyde (x2) per mol of phenol (x1). preferable.

  The acidic catalyst (I) used in this reaction is not particularly limited, and the epoxy resin (A) obtained in the present invention is compared with an epoxy resin obtained by a conventional method using the same catalyst regardless of which acidic catalyst is used. Although the hue becomes good, sulfuric acid, paratoluenesulfonic acid, oxalic acid, phosphoric acid, etc. may be used from the viewpoint that the reaction proceeds promptly and the treatment after the reaction (neutralization or washing with water) is easy. Particularly, when phosphoric acid is used, it is preferable because the hue is most favorable and the corrosiveness to stainless steel generally used as a reaction kettle is small.

  The amount of the acidic catalyst (I) used is preferably 0.01 to 2 parts by weight as an active ingredient with respect to 100 parts by weight of the phenols (x1). The form of the acidic catalyst (I) is not particularly limited, and may be an aqueous solution or a solid.

  As a specific method for this condensation reaction, acidic catalyst (I) is added to a mixture of phenols (x1) and aldehydes (x2) in a reaction vessel at once or gradually, but at a temperature of 50 to 120 ° C. The method of making it react for 0.5 to 10 hours under a normal pressure or pressure reduction is mentioned. In this case, an organic solvent may be used in combination for the purpose of increasing the reaction rate, and the solvent is not particularly limited. For example, methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol, tertiary Examples include alcohols such as butanol, cellosolves such as methyl cellosolve and ethyl cellosolve, benzene, toluene, xylene, methylene chloride, and the like, and these can be used alone or in combination. Of these, the glycidyl etherification reaction to be performed subsequently has an effect of increasing the reaction rate, and therefore it is preferable to use alcohols.

  Moreover, when the coloring of polyhydric phenol (a) obtained by the said condensation reaction is large, in order to suppress it, you may add antioxidant and a reducing agent. The antioxidant is not particularly limited, and examples thereof include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite compounds containing trivalent phosphorus atoms. be able to. The reducing agent is not particularly limited, and examples thereof include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, and salts thereof.

  After neutralizing and / or washing with water the polyhydric phenols (a) obtained by this reaction, epihalohydrin (x3) and basic catalyst (II) are subsequently added without performing heating distillation at 120 ° C. or higher, and glycidyl Perform etherification reaction. It is a conventional method to perform heating distillation at 120 ° C. or higher, which adversely affects the hue of the epoxy resin (A) obtained as described above, the heat resistance of the cured product, and the like.

  The basic compound that can be used for the neutralization is not particularly limited, but is preferably an inorganic compound from the viewpoint that a side reaction in the glycidyl etherification reaction hardly occurs. For example, potassium hydroxide Sodium hydroxide, calcium hydroxide, magnesium hydroxide, potassium carbonate, sodium carbonate, calcium hydrogen carbonate and the like. As the degree of neutralization, the pH of the aqueous phase of the reaction mixture is preferably 6 to 8, particularly preferably pH = 7 to 8.

  In the case of washing with water, there is a method in which ion-exchanged water or the like is added to the mixture and mixed, and then the aqueous phase is removed with vacuum or the like. At this time, it is preferable to measure the pH of the removed aqueous phase and repeat washing with water until pH = 6 to 8, preferably 7 to 8. Further, the acidic catalyst (I) may be removed by a plurality of steps such as washing with water after neutralization.

  The step of glycidyl etherification can be performed according to various methods and is not particularly limited. For example, 2 to 10 mol of epihalohydrin (x3) is added to 1 mol of the phenolic hydroxyl group of the polyhydric phenol (a) obtained above, and the phenolic hydroxyl group of the polyhydric phenol (a) is added to this mixture. The reaction is carried out at a temperature of 20 to 120 ° C. for 0.5 to 10 hours while 0.9 to 2.0 mol of basic catalyst (II) is added all at once or gradually. The basic catalyst (II) used at this time may be solid or an aqueous solution thereof. When an aqueous solution is used, it is continuously added and continuously added from the reaction mixture under reduced pressure or normal pressure. In this method, water and epihalohydrin (x3) are distilled off, and further separated to remove water, and epihalohydrin is continuously returned to the reaction mixture.

  Examples of the epihalohydrin (x3) that can be used here include epichlorohydrin, epibromohydrin, and the like. Of these, epichlorohydrin is preferable because it is easily available.

  When industrial production is performed, the first batch of epoxy resin production uses all of the prepared epihalohydrin, but after the next batch, the epihalohydrin recovered from the crude reaction product and the amount consumed in the reaction. It is preferable to use a new epihalohydrin corresponding to

  The basic catalyst (II) is not particularly limited, and examples thereof include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. In particular, alkali metal hydroxides are preferable from the viewpoint of excellent catalytic activity of the glycidyl etherification reaction, and examples thereof include sodium hydroxide and potassium hydroxide. In use, these alkali metal hydroxides may be used in the form of an aqueous solution of about 10 to 55% by weight or in the form of a solid. Moreover, it may be the same as or different from the basic compound used in the neutralization.

  In the reaction, the reaction rate can be increased by using an organic solvent in combination. Although it does not specifically limit as an organic solvent which can be used, For example, alcohols, such as ketones, such as acetone and methyl ethyl ketone, methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, secondary butanol, tertiary butanol, methyl cellosolve And cellosolves such as ethyl cellosolve, ethers such as tetrahydrofuran, 1,4-dioxane, 1,3-dioxane and diethoxyethane, and aprotic polar solvents such as acetonitrile, dimethyl sulfoxide and dimethylformamide. These organic solvents may be used alone or in combination of two or more as appropriate in order to adjust the polarity.

  After washing the reaction product obtained in the above reaction with water, unreacted epihalohydrin and the organic solvent to be used in combination are distilled off by distillation under heating and reduced pressure. At this time, the organic solvent and other impurities used for obtaining the polyhydric phenols (a) can be distilled off at the same time. Further, in order to obtain an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is again dissolved in an organic solvent such as toluene, methyl isobutyl ketone, methyl ethyl ketone, and alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. Further reaction can be carried out by adding an aqueous solution of the product. The synthesis process (condensation reaction) of polyhydric phenols (a) and the epoxidation process (glycidyl etherification reaction) may be performed continuously in one reaction kettle or in two or more independent reaction kettles. May be.

  The epoxy resin (A) obtained according to the above-mentioned method has a theoretical quantity obtained from the raw material charge quantity because the polyphenols (a) are not required to be taken out from the conventional process. It is a production method that can be obtained with a high yield of 95% by weight or more, and in some cases 98% by weight or more, and can be suitably used for industrial production.

  Also, the hue of the resulting epoxy resin (A) is good. For example, when bisphenol A is used as a raw material, the conventional method uses a Hazen color (resin solution in which an equal weight of epoxy resin and acetone is used). When the number of colors obtained according to the method described in JIS K6901 is only 180 or more, when synthesized according to the production method of the present invention, the Hazen color is 160 or less, In particular, about 30 to 100 are easily obtained.

  The usage method and application of the epoxy resin (A) obtained by the production method of the present invention are not limited at all, and an electronic component sealing material, an optical material, a printed wiring board, and a laminate that normally use an epoxy resin. Can be widely used in the fields of plate materials, resist inks, interlayer insulation materials, fiber reinforced composite materials, coating materials, molding materials, adhesive materials, etc., especially the heat resistance and mechanical properties of the resulting cured products are good Therefore, it can be suitably used as an optical material from the viewpoint of a sealing material for continuous production using a mold and a good hue.

  The epoxy resin (A) of this invention can be used as an epoxy resin composition by using together with a hardening | curing agent and another epoxy resin. When used in combination with other epoxy resins, the proportion of the epoxy resin (A) in the total epoxy resin by the production method of the present invention is preferably 30% by weight or more, particularly preferably 40% by weight or more.

  Other epoxy resins that can be used in combination are not particularly limited. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AD type epoxy resin, resorcin type epoxy resin, hydroquinone type epoxy resin, catechol Type epoxy resin, dihydroxynaphthalene type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin etc. liquidity epoxy resin, phenol novolac type epoxy resin, cresol novolak type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane Type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolac type epoxy Fatty, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resin, biphenyl modified novolac type epoxy resin, tetrabromo Examples thereof include bisphenol A type epoxy resins and brominated phenol novolac type epoxy resins. Also included are reactive diluent type epoxy resins such as butyl glycidyl ether, alkylphenol glycidyl ether, and aliphatic chain carboxylic acid glycidyl ester, and liquid epoxy resins such as alicyclic epoxy resins. Moreover, the said other epoxy resin may be used independently and may mix 2 or more types.

  Although it does not specifically limit as said hardening | curing agent, For example, an amine compound, an acid anhydride type compound, a phenol type compound etc. are mentioned, Especially for electronic component sealing materials, a phenol type compound is sclerosing | hardenable and heat-resistant. From the viewpoint of excellent properties, an acid anhydride compound having a good balance between hue and heat resistance is preferred as an optical material application.

  Examples of amine compounds include aliphatic polyamines such as ethylenediamine, propylenediamine, butylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, and pentaethylenehexamine, and aromatic polyamines such as metaxylylenediamine, diaminodiphenylmethane, and phenylenediamine. Examples thereof include alicyclic polyamines such as 1,3-bis (aminomethyl) cyclohexane, isophoronediamine and norbornanediamine, and polyamide resins synthesized from dimer of dicyandiamide and linolenic acid and ethylenediamine.

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

Examples of phenolic compounds include phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenol resins, dicyclopentadiene phenol addition resins, phenol aralkyl resins, naphthol aralkyl resins, trimethylol methane resins, tetraphenylols. 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 latent catalysts include imidazole, BF ₃ -amine complexes, guanidine derivatives, and the like.

  Further, these amine compounds, acid anhydride compounds, phenol compounds and the like curing agents may be used alone or in combination of two or more.

  As the usage-amount of the said hardening | curing agent, since hardening progresses smoothly and favorable hardened | cured material physical property is obtained, 0.7-1.2 equivalent is preferable with respect to 1 equivalent of epoxy groups of the epoxy resin to be used.

  A curing accelerator may be used. Specific examples of curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza- And tertiary amines such as bicyclo (5,4,0) undecene-7, phosphines such as triphenylphosphine, and metal compounds such as tin octylate. The use amount of the curing accelerator is 0.1 to 5.0 parts by weight with respect to 100 parts by weight of the epoxy resin, and is appropriately selected as necessary.

  Moreover, an inorganic filler can be mix | blended with the said epoxy resin composition. 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. In order to further 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.

  If necessary, the epoxy resin composition may contain various compounding agents such as a silane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate and calcium stearate, a pigment and an emulsifier. it can.

  A flame retardant imparting agent can be added to the epoxy resin composition 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 can be used in the form of a varnish diluted with an organic solvent as necessary. The organic solvent is used to lower the viscosity and improve the fluidity and moldability, and the type is not particularly limited. Illustrative examples include methanol, toluene, xylene, diethyl ether, acetone, methyl ethyl ketone, dimethylformamide and the like. As the amount used, it is preferable that the solid content value of the epoxy resin composition is in the range of 20 to 95% by weight.

  The said epoxy resin composition uses the stirring method according to the viscosity of the composition obtained, the epoxy resin (A), the other epoxy resin used together as needed, a hardening | curing agent, a hardening accelerator, an organic solvent, etc. Can be obtained by mixing uniformly. The shape of the epoxy resin composition is not limited at all, and the shape of the composition may be appropriately selected depending on the intended use, desired performance, and the like.

  The use application of the epoxy resin composition is not particularly limited. For example, for printed circuit boards, electronic component sealing materials, resist inks, conductive pastes, resin casting materials, adhesives, insulating paints, etc. Coating materials and the like.

  As the printed circuit board, it can be suitably used particularly for prepregs, copper-clad laminates, and interlayer insulation materials for build-up printed circuit boards.

  In order to make an epoxy resin composition into a resin composition for a prepreg for a printed circuit board, it can be used without a solvent depending on the viscosity of the resin composition, but a resin composition for a prepreg can be made into a varnish using an organic solvent. It is preferable that Examples of the organic solvent include alcoholic solvents such as methanol, ethanol, isopropyl alcohol, methyl cellosolve, and ethyl cellosolve, aromatic hydrocarbon solvents such as toluene and xylene, non-alcohols such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and dimethylformamide. Examples thereof include solvents having a boiling point of 160 ° C. or lower, such as a polar solvent, and can be appropriately used as a mixed solvent of two or more. The obtained varnish is impregnated into various reinforcing substrates such as paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth, and the heating temperature according to the solvent type used, preferably 50 By heating at ˜170 ° C., a prepreg that is a cured product can be obtained. The weight ratio of the resin composition and the reinforcing substrate used at this time is not particularly limited, but it is usually preferable that the resin content in the prepreg is adjusted to 20 to 60% by weight.

  In order to obtain a resin composition for a copper-clad laminate from an epoxy resin composition, the method is the same as the above-described resin composition for prepreg, and the obtained prepreg is described in, for example, JP-A-7-41543. Then, a copper-clad laminate can be obtained by stacking copper foils as appropriate and heating and press-bonding them at 170 to 250 ° C. for 10 minutes to 3 hours under a pressure of 1 to 10 MPa.

  A method for obtaining an interlayer insulating material for a build-up substrate from an epoxy resin composition is not particularly limited. For example, JP-B-4-6116, JP-A-7-304931, JP-A-8-64960, JP-A-9 Various methods described in JP-A-771762 and JP-A-9-298369 can be employed. More specifically, the 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 substrate 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.

  As the electronic component sealing material, it can be suitably used for a semiconductor chip sealing material, underfill, and semiconductor interlayer insulating film.

  In order to adjust the epoxy resin composition for a semiconductor sealing material, an epoxy resin (A), other epoxy resins used in combination as necessary, a curing agent, a coupling agent, an additive such as a release agent, An example is a method in which an inorganic filler or the like is premixed and then sufficiently mixed until uniform using an extruder, kneader, roll, or the like. In the case of a melt mixed type (solvent-free) composition, the composition is cast or molded using a transfer molding machine, an injection molding machine, etc., and further heated at 50 to 200 ° C. for 2 to 10 hours. Thus, a cured product can be obtained, and semiconductor package molding corresponds to this.

  Moreover, when using as a tape-shaped sealing agent, after heating the resin composition obtained by the above-mentioned method and producing a semi-hardened sheet and using it as a sealing agent tape, this sealing agent tape is used as a semiconductor chip. Examples of the method include placing it on top, heating to 100 to 150 ° C, softening and molding, and completely curing at 170 to 250 ° C.

  Furthermore, when using as a potting type liquid sealing agent, the resin composition obtained by the above-mentioned method may be applied on a semiconductor chip or an electronic component and directly cured.

  The method of using the epoxy resin composition as an underfill resin is not particularly limited, but is described in Japanese Patent Application Laid-Open No. 9-266221 and “Plastics in the Electronics Field” (Industry Research Council, 1999, pages 27 to 34). 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 and cured. And a compression flow method in which the epoxy 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 brought into close contact with each other to be completely cured. In this case, the epoxy resin composition of the present invention is preferably used in the form of a liquid epoxy 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 the epoxy resin composition is used as a semiconductor interlayer insulating material, for example, the method described in JP-A-6-85091 can be employed. When used as an interlayer insulating film, it will be in direct contact with the semiconductor, so it is required that the linear expansion coefficient of the insulating material be close to the linear expansion coefficient of the semiconductor so that cracks due to the difference in linear expansion coefficient do not occur in a high temperature environment. The In addition, in order to deal with the problem of signal delay due to miniaturization, multilayering, and high density of semiconductors, there is a demand for technology for reducing the capacity of insulating materials, and this problem can be solved by reducing the dielectric of insulating materials. be able to. The resin composition is preferable because it has characteristics satisfying these requirements.

  When the epoxy resin composition is used as a resist ink, for example, according to the method described in JP-A-5-186567, a resist ink composition is applied to a printed circuit board by a screen printing method. Then, the method of setting it as a resist ink hardened | cured material is mentioned.

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

  When using an epoxy resin composition as a resin composition for paints, for example, an epoxy resin (A), other epoxy resins used in combination as needed, pigments, colorants, additives, etc. are blended and necessary. Depending on the condition, add an organic solvent, mix thoroughly using a device such as a paint shaker, mixing mixer, ball mill, etc., and disperse it uniformly. The viscosity can be prepared with an organic solvent or the like.

  The resin composition prepared for the paint obtained by the above technique can be applied to various substrates by various coating methods, and the technique is not particularly limited. For example, a gravure coater, a knife Examples of the coating method include a coater, a roll coater, a comma coater, a spin coater, a bar coater, brush coating, dipping coating, spray coating, and electrostatic coating. Further, the curing method after coating the resin composition prepared for the paint is not particularly limited.

  When the epoxy resin composition is used as a resin composition for an adhesive, for example, the epoxy resin (A), other epoxy resin used in combination as necessary, a curing agent, a curing accelerator, an additive, and the like are used at room temperature. Or it can obtain by mixing uniformly using a mixing mixer etc. under a heating, and after apply | coating to various base materials, a base material can be adhere | attached by leaving it to stand under a heating.

  Depending on the viscosity, it is possible to use a solvent-free system to obtain a composite material from the epoxy resin composition. However, when it is difficult to handle in a solvent-free system, it is varnished with an organic solvent, and the varnish is used. A method of impregnating a reinforcing base material and heating it to obtain a prepreg, then laminating it so that the direction of the fiber is changed little by little, giving it pseudo-isotropic properties, and then heating to form a prepreg Is mentioned. Examples of the organic solvent include alcoholic solvents such as methanol, ethanol, isopropyl alcohol, methyl cellosolve, and ethyl cellosolve, aromatic hydrocarbon solvents such as toluene and xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, and the like. Non-alcoholic polar solvents and the like have a boiling point of 160 ° C. or lower, and can be used as a mixed solvent of two or more as appropriate. The heating temperature is determined in consideration of the type of solvent used, and is preferably 50 to 150 ° C. The type of the reinforcing substrate is not particularly limited, and examples thereof include carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. The ratio of the resin component and the reinforcing substrate is not particularly limited, but it is usually preferable that the resin component in the prepreg is adjusted to 20 to 60% by weight.

  A cured product obtained using the epoxy resin composition can be obtained by molding and curing the resin composition, and has a form 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 cast or molded using a transfer molding machine, an injection molding machine, etc., and further heated at 80 to 250 ° C. for 2 to 10 hours. A cured 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 method for obtaining the cured product may be based on a general method for curing an epoxy resin composition. For example, the heating temperature condition may be appropriately selected depending on the type and use of the curing agent to be combined. What is necessary is just to heat the composition obtained by this in the temperature range of about room temperature-250 degreeC. As a molding method, a general method of an epoxy resin composition is used, and in particular, conditions specific to the epoxy resin (A) obtained in the present invention are unnecessary.

EXAMPLES Hereinafter, although the manufacturing method of this invention is demonstrated in detail, giving an Example and a comparative example, this invention is not limited only to these Examples. The measurement conditions for the property values in the table and the meanings of the abbreviations are as follows.
[1] Number of colors: After dissolving 5.0 g of epoxy resin in 5.0 g of acetone, it conformed to the Hazen color number measuring method described in JIS K6901.
[2] Epoxy equivalent: Measured by a method according to JIS K-7236.
[3] Yield:% by weight of the actual yield based on the theoretical yield calculated from the amount of dihydric phenol (x1) used.
[4] Glass transition temperature: measured by DMA method.

Examples 1-2
Synthesis of polyhydric phenols (a) While flowing nitrogen gas through a heating device, a stirrer, a condenser, a thermometer, and a reactor equipped with a separator cock at the bottom, the amounts of bisphenol A and bisphenol A 1 mol shown in Table 1 0.62 mol of 41 wt% formaldehyde aqueous solution and 5 parts by weight of isopropyl alcohol were added to 100 parts by weight of bisphenol A.

  Next, 0.2 parts by weight of the acidic catalyst (I) shown in Table 1 was added at 90 ° C. with respect to 100 parts by weight of bisphenol A. After the addition, the temperature was raised to a reflux state (about 100 ° C.) over 30 minutes, and the mixture was further stirred for 6 hours while maintaining the reflux state. Then neutralized with potassium carbonate. The degree of neutralization was confirmed by the following work. First, after neutralizing agent (potassium carbonate) was added to the reaction solution and mixed uniformly, 1 part by weight of the reaction solution was taken out, and 2 parts by weight of toluene was added thereto and stirred. Furthermore, 1 part by weight of distilled water was added, and after stirring, the mixture was allowed to stand, and the pH of the aqueous phase was measured with a pH test paper to confirm that pH = 7.

Synthesis of Epoxy Resin (A) After the synthesis of polyhydric phenols (a), the reaction apparatus was subsequently charged with 3.5 moles of epichlorohydrin and 100 parts by weight of epichlorohydrin per mole of hydroxyl groups of polyhydric phenols (a). A part by weight of isopropyl alcohol was added and the temperature was lowered to 40 ° C. while dissolving.

  Next, a 35 wt% aqueous potassium hydroxide solution in the amount shown in Table 1 was added in two steps as the basic catalyst (II). First, 10% by weight of the total amount was added at 40 ° C., and the mixture was stirred for 4 hours while maintaining 40 ° C. Next, the temperature was raised to 50 ° C., and the remaining 90% by weight was added dropwise over 3 hours while maintaining 50 ° C. Further, after stirring at 50 ° C. for 30 minutes, an amount of water such that the produced salt has a saturated concentration was added to dissolve the salt, stirring was stopped, and the aqueous layer was discarded. Next, unreacted epichlorohydrin was distilled off to obtain a crude resin.

  Next, after adding 150 parts by weight of methyl isobutyl ketone to 100 parts by weight of the crude resin, 50 parts by weight of n-butanol and 12 parts by weight of 10% by weight sodium hydroxide aqueous solution are added to 100 parts by weight of methyl isobutyl ketone. Was added and stirred at 80 ° C. for 2 hours for liquid separation. After neutralizing with sodium phosphate, it was dehydrated by azeotropic distillation, and after passing through microfiltration, methyl isobutyl ketone was distilled off by distillation to obtain an epoxy equivalent epoxy resin (A) shown in Table 1.

Comparative Examples 1-2
Synthesis of polyhydric phenols (a ′) Using the amount of bisphenol A shown in Table 2, after synthesizing polyhydric phenols in the same manner as in Examples 1-2, the temperature was raised to 170 ° C. and methanol or water was added. Distilled off by distillation, extracted from the lower separation cock in the molten state, then cooled and solidified at room temperature to obtain polyhydric phenols (a ′).

Synthesis of Epoxy Resin (A ′) While flowing nitrogen gas through a heating device, a stirring device, a condenser, a thermometer, and a reactor equipped with a separator cock at the bottom, the amount of polyhydric phenols (a ′ ) And epichlorohydrin and 100 parts by weight of epichlorohydrin, the temperature was lowered to 40 ° C. while adding 30 parts by weight of isopropyl alcohol. Subsequently, the epoxy resin (A ') was obtained in the same operation as Examples 1-2.

Test Examples 1-2 and Comparative Test Examples 1-2
According to the composition described in Tables 3 and 4, after mixing the epoxy resin, curing agent, curing accelerator, inorganic filler and release agent, the mixture was kneaded at 85 ° C. for 5 minutes using a heating roll, and then cooled. . Then, it grind | pulverized and obtained sealing resin. As a curing agent, a phenol resin [Dainippon Ink Chemicals, Phenolite TD-2131] is used, as a curing accelerator is triphenylphosphine [made by Hokuko Chemical Co., Ltd.], and as an inorganic filler is crystalline silica [ Natural carnauba wax was used as a mold release agent.

  Using the sealing resins obtained in each test example and each comparative test example, an evaluation sample was prepared by the following method, and the heat resistance and mold stain resistance of the cured product were measured by the following method. As an evaluation index of heat resistance, glass transition temperature (DMA method) was measured. The test piece was molded and post-cured using a transfer molding machine after molding at 170 ° C. for 90 seconds, and then taken out and post-cured at 175 ° C. for 6 hours. The mold dirtiness was evaluated by continuously molding a TO220 type evaluation sample and visually observing the dirt state of the mold. In addition, the case where mold contamination occurred after molding 250 times or less was marked as x, the case where mold contamination did not occur even after molding 500 times or more was marked as ◎, and the middle case was marked as ◯. As a molding method, molding was performed at 170 ° C. for 90 seconds using a transfer molding machine.

  As shown in Tables 3 to 4, it was confirmed that each test example was superior in heat resistance and mold stain resistance as compared with the comparative test example.

Claims (6)

Dihydric phenols (x1) and aldehydes (x2) are subjected to a condensation reaction at 120 ° C. or lower in the presence of acidic catalyst (I) to obtain polyhydric phenols (a), and then neutralized and / or washed with water. Production of an epoxy resin characterized by obtaining an epoxy resin (A) by adding epihalohydrin (x3) and subjecting it to glycidyl etherification in the presence of a basic catalyst (II) without performing distillation at 120 ° C. or higher. Method. The method for producing an epoxy resin according to claim 1, wherein the acidic catalyst (I) is phosphoric acid. The method for producing an epoxy resin according to claim 1, wherein the basic catalyst (II) is an alkali metal hydroxide. The method for producing an epoxy resin according to claim 1, wherein the dihydric phenol (x1) is a bisphenol. The method for producing an epoxy resin according to claim 4 , wherein the bisphenol is bisphenol A. The method for producing an epoxy resin according to any one of claims 1 to 5 , wherein the aldehyde (x2) is formaldehyde.