JP4915896B2 - Production method of epoxy resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for efficiently producing a crystalline epoxy resin powder which exhibits excellent heat resistance in its cured product and is useful in various composite materials, adhesives and the like. <P>SOLUTION: The method for producing the crystalline epoxy resin comprises three steps of step (1) of reacting a phenolic compound of a raw material with an epihalohydrin to effect glycidylation to obtain a reaction solution, step (2) of adding a solvent which is a poor solvent for a target epoxy resin and forms an azeotropic composition with the epihalohydrin to the obtained reaction solution and depositing a crystal of the epoxy resin to obtain a crystal dispersion solution, and step (3) of distilling the solvents from the obtained crystal dispersion solution. <P>COPYRIGHT: (C)2007,JPO&amp;INPIT

Description

  The present invention relates to a method for producing a crystalline epoxy resin having a high melting point.

  Epoxy resins are generally cured with various curing agents, resulting in cured products with excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc., adhesives, paints, laminates, moldings It is used in a wide range of fields such as materials and casting materials. Conventionally, as an epoxy resin most used industrially, a compound obtained by reacting bisphenol A with epichlorohydrin is known. In applications such as semiconductor encapsulants, cresol novolac epoxy resins are widely used because heat resistance is required. In addition, surface mounting methods are common, and semiconductor packages are often directly exposed to high temperatures during solder reflow, so high filler filling is effective to reduce the water absorption rate and linear expansion rate of the entire sealing material. Has been proposed. In order to enable high filler filling, a low melt viscosity of the epoxy resin is a necessary condition. Recently, epoxidized tetramethylbiphenol has been widely used in order to satisfy such requirements. This epoxy compound has a very low melt viscosity in the molten state because the molecule having crystallinity is a substantially monomolecular compound.

  Moreover, the storage stability is mentioned as a problem in using an epoxy resin. That is, the epoxy resin can be used separately in a two-part type that is stored separately from the curing agent and mixed at the time of use, and a one-part type that is stored in a state mixed with the curing agent from the beginning. The one-pack type is more advantageous in terms of workability, but the epoxy resin and the curing agent react gradually during storage, changing the viscosity in the case of a liquid composition and the fluidity in the case of a solid composition. It has been pointed out that the problem is.

  In recent years, a photosensitive resin composition has been frequently used because of its simple curing conditions and workability. However, simply curing with light cannot achieve the high reliability required for electrical / electronic materials due to its low moisture resistance and heat resistance, and in recent years, light / thermosetting resins have attracted particular attention. For example, in the fields of solder resist, hole-filling ink, overcoat agent, various adhesives, etc., an epoxy resin is added to the component, and after being first cured with light, it is further heated and secondarily cured. Has been. In such a field, the storage stability of the epoxy resin until secondary curing is important. From these reasons, crystalline epoxy resins are attracting attention.

  In recent years, a crystalline epoxy resin obtained by glycidylating a phenol compound having tetrakisphenolethane or a fluorene skeleton has been proposed as an epoxy resin having heat resistance and excellent storage stability (Patent Document 1). , 2, 3), it is desired to develop an industrially efficient method for producing the same. Specifically, Patent Document 1 describes a method for producing crystals of tetrakisphenolethane type epoxy resin, and Patent Document 2 describes a method for producing crystals of fluorene type epoxy resin, both of which are washed with water and excess epichlorohydrin from the oil layer. Then, after removing the reaction solvent and the like under heating and reduced pressure, the organic solvent is added and cooled to precipitate crystals. However, there are problems such as precipitation of crystals in the reaction kettle during the process of removing excess epichlorohydrin, reaction solvent, etc. under reduced pressure by heating. It is difficult to remove the solvent, and stirring is soon after the crystals are precipitated. It becomes impossible to cause damage to the device. Further, in the recrystallization method based on the temperature difference, the crystal is not completely precipitated, and the purity and yield of the crystal are difficult to stabilize due to the recrystallization time and the like, and the production efficiency is not good.

  When crystallization is directly performed from a reaction solution containing epihalohydrin, epihalohydrin is often taken into the crystal. In consideration of the environment, it is not preferable to mix epihalohydrin into a product. Furthermore, it itself becomes a halogen source, which may lead to a decrease in electrical reliability. Therefore, it is essential to reduce the remaining amount of epihalohydrin.

JP 2004-10877 A JP 2004-35762 A JP 2004-43333 A

  An object of the present invention is to provide an efficient method for producing an epoxy resin which exhibits excellent heat resistance and storage stability in the cured product and is useful for various composite materials, adhesives, paints and the like.

で表される化合物を８０％（高速液体クロマトグラフィー（ＨＰＬＣ）による面積％）以上含有するフェノール化合物と他のフェノール化合物との混合物を除く）をエピハロヒドリンと反応させ、グリシジル化し、反応液を得る工程
工程ロ）得られた反応液に目的とするエポキシ樹脂の貧溶剤であって、エピハロヒドリンと共沸組成を組む溶剤を添加し、エポキシ樹脂の結晶を析出させ、結晶分散溶液を得る工程
工程ハ）得られた結晶分散溶液から溶剤類を留去する工程
の３工程を含むことを特徴とする結晶状エポキシ樹脂の製造法、
（２）フェノール化合物が式（１）

もしくは式（２）

（式（２）中Ｒはフェニル基またはハロゲン原子を示す）
で表される化合物を８０％（高速液体クロマトグラフィー（ＨＰＬＣ）による面積％）以上含有するフェノール化合物であることを特徴とする上記（１）に記載の結晶状エポキシ樹脂の製造方法、
（３）上記（１）または（２）に記載の製造法により得られる結晶状エポキシ樹脂及び硬化剤を含有するエポキシ樹脂組成物、
（４）上記（１）または（２）に記載の製造方法により得られる結晶状エポキシ樹脂及びエチレン性不飽和基を有する化合物を含有するエポキシ樹脂組成物
に関する。 That is, the present invention
(1)
Process a) Raw material phenol compound (however, the following formula (1)

A process of obtaining a reaction solution by reacting a compound represented by the above formula with 80% (excluding a mixture of a phenol compound and other phenol compound containing at least 80% by high performance liquid chromatography (HPLC)) with an epihalohydrin and glycidylating it. Step b) A step of the step of obtaining a crystal dispersion solution by adding a solvent which is a poor solvent of the target epoxy resin to the obtained reaction liquid and which forms an azeotropic composition with epihalohydrin, and depositing an epoxy resin crystal. A method for producing a crystalline epoxy resin, comprising three steps of distilling off solvents from the obtained crystal dispersion solution,
(2) The phenol compound is represented by the formula (1)

Or formula (2)

(In the formula (2), R represents a phenyl group or a halogen atom)
The method for producing a crystalline epoxy resin according to the above (1), which is a phenol compound containing 80% or more of the compound represented by formula (area% by high performance liquid chromatography (HPLC)),
(3) An epoxy resin composition containing a crystalline epoxy resin and a curing agent obtained by the production method described in (1) or (2) above,
(4) It is related with the epoxy resin composition containing the compound which has a crystalline epoxy resin obtained by the manufacturing method as described in said (1) or (2), and an ethylenically unsaturated group.

  The production method of the epoxy resin of the present invention is an industrially useful production method that has a higher yield than conventional methods and that allows the crystals to be taken out in a powder form safely and simply. The epoxy resin obtained by the production method of the present invention is extremely useful for a wide range of applications such as electric / electronic materials, molding materials, casting materials, laminated materials, paints, adhesives, resists, and optical materials.

  Examples of the crystalline epoxy resin obtained by the production method of the present invention include epoxidized products of tetrakisphenolethane type phenol compounds, epoxidized products of bisphenolfluorene type phenol compounds, epoxidized products of biphenols, and epoxidized products of hydroquinones. The melting point of these epoxy resins is usually 80 ° C. or higher, preferably 100 ° C. or higher.

The method for producing an epoxy resin of the present invention comprises the following three steps.
Step a) A step of reacting a raw material phenolic compound with epihalohydrin to glycidylate to obtain a reaction solution. Step b) A poor solvent for the target epoxy resin in the obtained reaction solution, and a solvent that forms an azeotropic composition with epihalohydrin. Step of adding and precipitating an epoxy resin crystal to obtain a crystal dispersion solution c) Step of distilling off solvents from the obtained crystal dispersion solution.

  In step a), the raw material phenol compound is reacted with epihalohydrin to carry out a glycidylation reaction. Biphenols, hydroquinones, tetrakisphenol ethanes, bisphenol fluorenes, and the like are used as the raw material phenol compound, and generally include phenol compounds having a melting point of 200 ° C. or higher.

  Among these phenol compounds, tetrakisphenol ethanes or bisphenol fluorenes are preferable, and among them, the purity of the compound represented by the following formula (1) or (2) is 80% (250 to 300 nm by high performance liquid chromatography (HPLC)). Of these, a phenol compound containing at least (% by area as measured at any wavelength) is preferred.

（式（２）中Ｒはフェニル基またはハロゲン原子を示す）

(In the formula (2), R represents a phenyl group or a halogen atom)

  As a method for producing such a phenol compound, it is generally produced by a condensation reaction of ketones or aldehydes with phenols. As a specific production method, Patent Document 4 describes a method for synthesizing high-purity tetrakisphenol ethane, and Patent Document 5 describes a method for synthesizing a high-purity bisphenol-type fluorene. Patent Documents 6 and 7 describe a synthesis method of biphenols, and Patent Document 8 describes a synthesis method of hydroquinones. Specific products include tetrakisphenolethanes; TEP-DF series, TEOC-DF, TE25X-DF, TE26X-DF, TE3M6B-DF (Asahi Organic Materials Co., Ltd.), Tek-P, TekP-E, TekOC- E, Tek26X-E (Honshu Chemical Industry Co., Ltd.) and other bisphenol fluorenes; BPFL (JFE Chemical Co., Ltd.), BisP-FL, BisOC-FL, Bis25X-FL, Bis26X-FL, BisOPP-FL, BisFP-FL ( Honshu Chemical Co., Ltd.), biphenols; DOQ-O (Sanko Co., Ltd.), 3,3 ′, 5,5′-tetramethylbiphenol, hydroquinones; 3,5-di-t-butylhydroquinone, etc. Can be mentioned.

Japanese Patent No. 3381819 JP 2003-221352 A JP 2003-327554 A JP-A-11-236343 JP 2003-104926 A

In the glycidylation reaction in step a), the reaction between the phenol compound and epihalohydrin is performed in the presence of an alkali metal hydroxide.
In this reaction, the alkali metal hydroxide may use a solid substance or an aqueous solution thereof. When an aqueous solution is used, the alkali metal hydroxide aqueous solution is continuously added to the reaction system, and water and epihalohydrin are continuously distilled off under reduced pressure or normal pressure, and the solution is further separated to remove the water. Epihalohydrin may be continuously returned to the reaction system. The usage-amount of an alkali metal hydroxide is 0.9-2.5 mol normally with respect to 1 equivalent of hydroxyl groups of the phenol compound to be used, Preferably it is 0.95-2.0 mol.

  In this reaction, a quaternary ammonium salt may be added as a catalyst as necessary to facilitate the reaction. Examples of quaternary ammonium salts that can be used include tetramethylammonium chloride, tetramethylammonium bromide, and trimethylbenzylammonium chloride. The amount of the quaternary ammonium salt used is usually 0.1 to 15 parts by weight, preferably 0.2 to 10 parts by weight with respect to 1 equivalent of the hydroxyl group of the phenol compound.

  Epihalohydrins that can be used include epichlorohydrin, epibromohydrin, epiiodohydrin, β-methylepichlorohydrin, α-methylepichlorohydrin, γ-methylepichlorohydrin. The usage-amount of epihalohydrin is 0.8-12 mol normally with respect to 1 equivalent of hydroxyl groups of a phenolic compound, Preferably it is 0.9-11 mol. As an epihalohydrin, an epichlorohydrin derivative is industrially easy to use. At this time, in order to increase the solubility of the phenol compound, aprotic properties such as alcohols such as methanol, ethanol, isopropyl alcohol and butanol, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, sulfolane, dimethylimidazolidinone and N-methylpyrrolidone It is preferable to carry out the reaction by adding a polar solvent or the like.

  When alcohols and aprotic polar solvents are used, the amount used is usually 2 to 150% by weight, preferably 4 to 100% by weight, based on the amount of epihalohydrin.

  The reaction temperature is usually 30 to 90 ° C, preferably 35 to 80 ° C. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours.

  The reaction solution of these glycidylation reactions can be purified by washing with water to obtain an epoxy resin reaction solution. Next, step b) is performed on the reaction solution.

  Step (b) is a step in which a crystal dispersion solution is obtained by precipitating an epoxy resin crystal from the obtained reaction solution. Crystals are precipitated by adding a solvent that is an poor solvent for the target epoxy resin and has an azeotropic composition with epihalohydrin. At this time, by partially distilling off excess epihalohydrin or the like from the reaction solution in advance, the concentration of the target product can be increased to promote the precipitation of crystals, or the crystals can be precipitated or dispersed. It doesn't matter. The concentration is preferably adjusted under reduced pressure, and heating may be used in combination as necessary. The conditions at this time are not particularly specified, but the degree of reduced pressure is preferably -0.01 MPa to -0.1 MPa, and the temperature at that time is preferably 140 ° C. or lower, particularly preferably 100 ° C. or lower. Thereby, the epoxy resin concentration of the reaction liquid to be adjusted is preferably 40 to 90% by weight, particularly preferably 50 to 80% by weight.

  The poor solvent used is a solvent in which the crystalline epoxy resin is difficult to dissolve, and is not particularly limited. For example, alcohols such as methanol, ethanol, isopropanol, n-butanol, t-butanol, ethylene glycol, propylene glycol, propylene glycol monomethyl ether, etc. Depending on the resin and the epoxy resin resin skeleton, ester organic solvents such as ethyl acetate, butyl acetate, and butyl lactate, and ketone organic solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone are also included. Can be mentioned. These may be used alone or in combination.

In addition, the crystallization in the step (b) can be used in combination with a solvent other than the above. Although the solvent which can be used together is shown below, since the solubility to a solvent changes with epoxy resin frame | skeletons, the solvent which overlaps with the said poor solvent in part is also mentioned as an example.
Aprotic polar solvent; dimethyl sulfoxide, N, N′-dimethylformamide, tetrahydrofuran, N-methylpyrrolidone, diglyme, triglyme, etc.
Examples include ester organic solvents; ketone organic solvents such as ethyl acetate, butyl acetate, and butyl lactate; aromatic organic solvents such as methyl isobutyl ketone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; and toluene and xylene. The amount of these solvents used is usually 20 to 500% by weight, preferably 50 to 300% by weight, based on the theoretical yield.

  Moreover, the poor solvent mentioned above and the solvent which can be used together need to be a solvent which can form an azeotropic composition with epihalohydrin. Such a solvent can be known, for example, by referring to Solvent Pocketbook, edited by the Society of Synthetic Organic Chemistry, Ohm Co., pages 346-347. As such a solvent, use of water is particularly preferable.

  Step c) is a step of distilling off the solvents from the crystal dispersion obtained in step b). Solvent recovery conditions are preferably carried out under reduced pressure by heating, and the temperature is preferably [(melting point of epoxy resin) −200] ° C. to [(melting point of epoxy resin) −10] ° C. The degree of reduced pressure is preferably -0.01 MPa to -0.1 MPa.

  When the distillation of 90 to 99.99% by weight of the solvent is completed, the drying process is started. In the drying step, [(melting point of epoxy resin obtained) −100] ° C. to [(melting point of epoxy resin) −10] ° C. is preferable, and drying is preferably performed at a vacuum degree of −0.07 MPa or more. The drying time is usually preferably 1 hour to 36 hours, more preferably 2 to 24 hours.

  The crystalline epoxy resin thus obtained has a small amount of residual epihalohydrin, is excellent in environment and electrical reliability, is a semiconductor sealing material that requires heat resistance, and light-heat that requires high storage stability of the epoxy resin. It can be used for a curable epoxy resin composition.

Hereinafter, the epoxy resin composition of the present invention will be described.
In the epoxy resin composition of the present invention, the epoxy resin obtained as described above (hereinafter referred to as the epoxy resin of the present invention) can be used alone or in combination with other epoxy resins. When used in combination, the proportion of the epoxy resin of the present invention in the total epoxy resin is preferably 30% by weight or more, particularly preferably 40% by weight or more.

  Examples of other epoxy resins that can be used in combination with the epoxy resin of the present invention include novolac type epoxy resins, bisphenol A type epoxy resins, bisphenol F type epoxy resins, biphenyl type epoxy resins, and triphenylmethane type epoxy resins. Specifically, bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [1 , 1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetofu Non, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1,1′-biphenyl, 1, Glycidyl ethers derived from polycondensates with 4-bis (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene and the like, modified products thereof, halogenated bisphenols such as tetrabromobisphenol A, and alcohols Solid or liquid epoxy resins such as chemical compounds, alicyclic epoxy resins, glycidyl amine epoxy resins, glycidyl ester epoxy resins and the like are not limited thereto. These may be used alone or in combination of two or more.

  Examples of the curing agent that can be contained in the epoxy resin composition of the present invention include amine compounds, acid anhydride compounds, amide compounds, and phenol compounds. Specific examples of the curing agent that can be used include amine compounds such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, trifluoroborane-amine complex; Amide compounds such as polyamide resin; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methyl Acid anhydride compounds such as hexahydrophthalic anhydride; bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4'-biphenol, 2,2 ' Biphenol, 3,3 ′, 5,5′-tetramethyl- [1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1, 1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o -Hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1'-biphenyl, 4,4'-bis ( Toximethyl) -1,1′-biphenyl, 1,4′-bis (chloromethyl) benzene, polycondensates with 1,4′-bis (methoxymethyl) benzene, and their modified products, tetrabromobisphenol A, etc. Non-limiting examples include phenolic compounds such as halogenated bisphenols, condensates of terpenes and phenols; imidazoles, guanidine derivatives, and the like. These may be used alone or in combination of two or more, but phenolic compounds or amine compounds are preferred, and phenolic compounds are particularly preferred.

  In the epoxy resin composition of the present invention, the amount of the curing agent used is preferably 0.7 to 1.2 equivalents relative to 1 equivalent of the epoxy group of the epoxy resin. When less than 0.7 equivalent or more than 1.2 equivalent with respect to 1 equivalent of epoxy group, curing may be incomplete and good cured properties may not be obtained.

  In the epoxy resin composition of the present invention, 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. When using a hardening accelerator, 0.1-5.0 weight part is used as needed with respect to 100 weight part of epoxy resins.

  If necessary, an inorganic filler can be added to the epoxy resin composition of the present invention. Examples of inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like. However, the present invention is not limited to these. These may be used alone or in combination of two or more. The content of these inorganic fillers is 0 to 95% by weight in the epoxy resin composition of the present invention. Furthermore, the epoxy resin composition of the present invention includes a silane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate and calcium stearate, various compounding agents such as pigments, and various thermosetting resins. can do.

  The epoxy resin composition of this invention is obtained by mixing each component uniformly. The epoxy resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, the epoxy resin of the present invention, a curing agent and, if necessary, a curing accelerator, an inorganic filler, and a compounding agent are sufficiently mixed until uniform using an extruder, kneader, roll, etc. as necessary. An epoxy resin composition can be obtained, and the epoxy resin composition can be melted and then molded using a casting or transfer molding machine, and further heated at 80 to 200 ° C. for 2 to 10 hours to obtain a cured product. .

  Further, the epoxy resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like, and glass fiber, carbon fiber, polyester fiber, polyamide It is also possible to obtain a cured product by hot press molding a prepreg obtained by impregnating a substrate such as fiber, alumina fiber or paper and heating and semi-drying. The solvent used here is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the epoxy resin composition of the present invention and the solvent.

  As a semiconductor device that can be manufactured by sealing a semiconductor element (semiconductor chip) with the epoxy resin composition of the present invention, for example, DIP (dual inline package), QFP (quad flat package), BGA (ball grid array) ), CSP (chip size package), SOP (small outline package), TSOP (thin small outline package), TQFP (think quad flat package), and the like. In the field of optical semiconductors, there are encapsulated optical semiconductor elements (semiconductor chips) such as light emitting diodes (LEDs), phototransistors, CCDs (charge coupled devices), and EPROMs such as UV-EPROMs.

Next, the photocurable resin composition containing the epoxy resin of the present invention will be described.
The epoxy resin of this invention can be used as a hardening | curing agent for improving the reliability in a photo-thermosetting resin composition.

The photocurable resin composition containing the epoxy resin of the present invention contains the epoxy resin of the present invention and a compound having an ethylenically unsaturated group, preferably an aqueous alkali-soluble resin (A), a crosslinking agent (B), It prepares by adding the epoxy resin of this invention to the photosensitive resin composition containing a photoinitiator (C).
In the photocurable resin composition containing the epoxy resin of the present invention, the content of the epoxy resin of the present invention is usually 1 to 50% by weight, and preferably 2 to 30% by weight.

  Although it demonstrates concretely about each component of the resin composition containing the said component (A)-(C) component which is a preferable aspect of the photocurable resin composition containing an epoxy resin, each is described in detail below, respectively. It is as follows. Although described in the specific examples, each component in the photocurable resin composition containing the epoxy resin of the present invention includes the following each of the epoxy resin and the compound having an ethylenically unsaturated group. It is not limited to ingredients.

Alkaline aqueous solution-soluble resin (A);
For example, an epoxy carboxylate compound obtained by reacting an epoxy compound (a) having two or more epoxy groups in the molecule with a monocarboxylic acid compound (b) having an ethylenically unsaturated group in the molecule, and a polybasic Reaction products with acid anhydride (c), etc., specifically, KAYARAD CCR-1159H, KAYARAD PCR-1169H, KAYARAD TCR-1310H, KAYARAD ZFR-1401H, KAYARAD ZFR-1395H (all Nippon Kayaku Stock Co., Ltd.) Company-made).

Cross-linking agent (B);
Examples include compounds having an ethylenically unsaturated group, such as acrylates and methacrylate compounds. Specifically, KAYARAD HX-220, KAYARAD HX-620, KAYARAD DPHA, KAYARAD DPCA-60 (all manufactured by Nippon Kayaku Co., Ltd.) ) And the like.

Photopolymerization initiator (C);
Examples include benzoins, acetophenones, anthraquinones, thioxanthones, ketals, benzophenones, phosphine oxides, and more specifically, KAYACURE DETX-S (manufactured by Nippon Kayaku Co., Ltd.), Irgacure 907 (Ciba Specialty) Chemical) and the like.

  Furthermore, various additives as necessary, for example, fillers such as talc, barium sulfate, aluminum hydroxide, aluminum oxide, silica, clay, thixotropic agents such as aerosil; coloring of phthalocyanine blue, phthalocyanine green, titanium oxide, etc. An agent, silicone, fluorine-based leveling agent or defoaming agent; a polymerization inhibitor such as hydroquinone or hydroquinone monomethyl ether can be added for the purpose of enhancing various performances of the composition.

  The photocurable resin composition containing the epoxy resin of this invention can contain a solvent as needed. Usable solvents include, for example, ketones such as acetone, ethyl methyl ketone and cyclohexanone, aromatic hydrocarbons such as benzene, toluene, xylene and tetramethylbenzene, ethylene glycol dimethyl ether, ethylene glycol diethyl ether and dipropylene glycol. Glycol ethers such as dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate , Dialkyl glutarate, dialkyl succinate, dialkyl adipate, etc. Examples include esters, cyclic esters such as γ-butyrolactone, petroleum solvents such as petroleum ether, petroleum naphtha, hydrogenated petroleum naphtha, and solvent naphtha. These may be used alone or in combination of two or more. May be.

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

  The photocurable resin composition containing the epoxy resin of the present invention can be cured by irradiation with energy rays such as ultraviolet rays. Curing can be performed by conventional methods by irradiation with energy rays such as ultraviolet rays. For example, in the case of irradiating ultraviolet rays, an ultraviolet generator such as a low-pressure mercury lamp, a high-pressure mercury lamp, an ultrahigh-pressure mercury lamp, a xenon lamp, or an ultraviolet light emitting laser (such as an excimer laser) may be used.

  The cured product of the photocurable resin composition containing the epoxy resin of the present invention is, for example, a resist film, an interlayer insulating material for a build-up method, or an optical waveguide as a printed board, an electrical / electronic / Used for optical substrates. Specific articles using these include, for example, computers, home appliances, portable devices, and the like.

Specifically, for example, when manufacturing a printed wiring board constituting a printed circuit board, when using a liquid resin composition, first, a screen printing method, a spray method, a roll coating method, electrostatic coating is applied to the printed wiring board. A coating film is formed by applying the composition of the present invention with a film thickness of 5 to 160 μm by a method such as a method of coating or curtain coating, and drying the coating film at 50 to 110 ° C., preferably 60 to 100 ° C. Let Thereafter, the coating film is directly or indirectly irradiated with high energy rays such as ultraviolet rays with an intensity of about 10 to 2000 mJ / cm ² through a photomask having an exposure pattern such as a negative film, and the unexposed portion is described later. Using the liquid, development is performed, for example, by spraying, rocking dipping, brushing, scrubbing, or the like. Thereafter, if necessary, further ultraviolet irradiation is performed, and then heat treatment is usually performed at a temperature of 100 to 200 ° C., preferably 140 to 180 ° C., so that the gold plating property is excellent, and heat resistance, solvent resistance, acid resistance, A printed wiring board having a permanent protective film that satisfies various properties such as adhesion and flexibility can be obtained.

  Examples of the alkaline aqueous solution used for development include potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, sodium phosphate, potassium phosphate, and other inorganic alkaline solutions and tetramethylammonium. Organic alkaline aqueous solutions such as hydroxide, tetraethylammonium hydroxide, tetrabutylammonium hydroxide, monoethanolamine, diethanolamine, and triethanolamine can be used.

  EXAMPLES Next, the present invention will be described more specifically with reference to examples. In the following, parts are parts by weight unless otherwise specified.

Example 1
A condensate of glyoxal and phenol {within 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane content of 98 area while purging nitrogen gas purge to a flask equipped with a thermometer, dropping funnel, condenser and stirrer % (Detected by HPLC UV 274 nm) 99.5 parts of TEP-DF} manufactured by Asahi Organic Materials Co., Ltd., 740 parts of epichlorohydrin and 148 parts of methanol were charged and heated to reflux temperature with stirring, and dissolved. Next, 40 parts of flaky sodium hydroxide was added in portions over 100 minutes, and then further reacted at reflux temperature for 1 hour. After completion of the reaction, 250 parts of water was added and washed with water to remove the generated salt and the like to obtain an epoxy resin reaction liquid (A1) (Step A). Gradually the temperature and the degree of vacuum were raised, finally about 70 ° C. and about −0.08 MPa, and epichlorohydrin and the like were distilled off until the resin concentration was about 60% by weight. To the obtained suspension, 310 parts of methanol was added, and 155 parts of ion-exchanged water at 25 ° C. was further added to obtain a crystal dispersion solution (Step B). Further, the temperature and the degree of pressure reduction were gradually increased and finally adjusted to about 80 ° C. and about −0.09 MPa, and the solvent was distilled off until no distillation of the solvent was observed. The amount of solvent contained in the crystals at this time was 12000 ppm. Furthermore, conditions were severed to about 120 ° C. and about −0.095 MPa, and a drying process was performed for 24 hours (process c). In this way, 152 parts of the desired crystalline epoxy resin was obtained. The epoxy equivalent of the obtained epoxy resin is 167 g / eq. And its melting point was 169 ° C. The remaining epichlorohydrin was 100 ppm or less.

Reference example 1
The same procedure was carried out except that 300 parts of methyl isobutyl ketone was used as a solvent instead of 310 parts of methanol and 155 parts of ion-exchanged water in Example 1, step b). In this way, 153 parts of the desired crystalline epoxy resin was obtained. The epoxy equivalent of the obtained epoxy resin is 169 g / eq. And its melting point was 169 ° C. The remaining epichlorohydrin was 100 ppm or less.

Example 3
The same procedure was performed except that the purity of the condensate of glyoxal and phenol in Example 1 was changed from 98% to 94%. In this way, 153 parts of the desired crystalline epoxy resin was obtained. The epoxy equivalent of the obtained epoxy resin was 166 g / eq. The melting points were 153 ° C. and 172 ° C. The remaining epichlorohydrin was 100 ppm or less.

Example 4
175 parts of bisphenolfluorene {including 9,9'-bis (4-hydroxyphenyl) fluorene content 99 area% (detected by HPLC UV 274 nm) while purging nitrogen gas purge to a flask equipped with a thermometer, dropping funnel, condenser and stirrer )}, 740 parts of epichlorohydrin and 148 parts of methanol were charged, and the mixture was heated to reflux temperature with stirring and dissolved. Next, 40 parts of flaky sodium hydroxide was added in portions over 100 minutes, and then further reacted at reflux temperature for 1 hour. After completion of the reaction, 250 parts of water was added and washed with water to remove the generated salt and the like, and an epoxy resin reaction liquid (A2) was obtained (Step A). Gradually the temperature and degree of vacuum were increased to about 70 ° C. and about −0.08 MPa, and epichlorohydrin and the like were distilled off until the resin concentration was about 60% by weight. 100 parts of acetone was added to the obtained suspension, and 200 parts of methanol was further added. Further, 200 parts of ion-exchanged water at 25 ° C. was added to obtain a crystal-dispersed aqueous solution (Step B). Further, the temperature and the degree of pressure reduction were gradually increased, and finally the temperature was adjusted to about 80 ° C. and about −0.09 MPa, and the solvent was distilled off until no outflow of the solvent was observed. The amount of solvent contained in the crystals at this time was 12000 ppm. Furthermore, conditions were severed to about 120 ° C. and about −0.095 MPa, and a drying process was performed for 24 hours (process c). In this way, 229 parts of the desired crystalline epoxy resin was obtained. The epoxy equivalent of the obtained epoxy resin was 233 g / eq. The melting point was 147 ° C. The remaining epichlorohydrin was 100 ppm or less.

Example 5
The same procedure was followed except that 175 parts of bisphenolfluorene in Example 7 were changed to 193 parts of 9,9′-bis (3-fluoro-4-hydroxyphenyl) fluorene. The obtained epoxy resin was 245 parts. Its epoxy equivalent is 257 g / eq. The melting point was 153 ° C. The remaining epichlorohydrin was 100 ppm or less.

Comparative Example 1
A condensate of glyoxal and phenol {within 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane content of 98 area while purging nitrogen gas purge to a flask equipped with a thermometer, dropping funnel, condenser and stirrer % (Detected by HPLC UV 274 nm) 99.5 parts of TEP-DF} manufactured by Asahi Organic Materials Co., Ltd., 740 parts of epichlorohydrin and 148 parts of methanol were charged and heated to reflux temperature with stirring, and dissolved. Next, 40 parts of flaky sodium hydroxide was added in portions over 100 minutes, and then further reacted at reflux temperature for 1 hour. After completion of the reaction, 250 parts of water was added and washed to remove the generated salt and the like, and then the temperature and the degree of vacuum were gradually increased to about 70 ° C. and about −0.08 MPa, and the resin concentration was about 50% by weight. Epichlorohydrin and the like were distilled off until The mixture was allowed to stand at room temperature for 20 hours and in a refrigerator (4 ° C.) for 24 hours, and it was confirmed that crystals were sufficiently deposited, followed by filtration and drying at 100 ° C. for 48 hours. As a result, 97 parts of the desired epoxy resin crystal powder was obtained (yield 63%). The epoxy equivalent of the obtained epoxy resin was 166 g / eq. And its melting point was 173 ° C. The remaining epichlorohydrin was 6900 ppm.

Comparative Example 2
Condensation product of glyoxal and phenol according to the method described in Patent Document 2 (including 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane content of 98 area% (detected by HPLC UV 274 nm) Asahi Organic Materials Co., Ltd. An epoxy resin was manufactured using 99.5 parts of TEP-DF} manufactured by Co., Ltd. As a result, 84 parts of the desired epoxy resin crystal powder was obtained (54% yield). The epoxy equivalent of the obtained epoxy resin is 168 g / eq. And its melting point was 154,175 ° C. The remaining epichlorohydrin was 100 ppm or less.

  From the above results, it can be said that the production method of the present invention is an efficient method that can be produced easily and stably in a high yield, and that a crystalline powder epoxy resin with little epihalohydrin can be obtained.

Claims (2)

Process a) Biphenols, hydroquinones, tetrakisphenolethanes or bisphenolfluorenes (however, the following formula (1))

(Excluding mixtures of phenolic compounds containing more than 80% (area% by high performance liquid chromatography (HPLC)) and other phenolic compounds)
B) Step of obtaining glycidyl by reacting with epihalohydrin to obtain a reaction solution. B) Concentrating the obtained reaction solution so that the epoxy resin concentration becomes 40 to 90% by weight, and the reaction solution after concentration is the target epoxy resin In the step of distilling the solvents from the crystal dispersion solution obtained by adding the water, which is a poor solvent, and precipitating the crystals of the epoxy resin to obtain the crystal dispersion solution, and the crystal dispersion solution obtained in step b). A process for producing a crystalline epoxy resin comprising three steps. The phenol compound is represented by the formula (1)

Or formula (2)

(In the formula (2), R represents a phenyl group or a halogen atom)
The method for producing a crystalline epoxy resin according to claim 1, wherein the compound is represented by 80% or more (area% by high performance liquid chromatography (HPLC)).