JP4969818B2 - Liquid epoxy resin, epoxy resin composition, and cured product - Google Patents

Description

  The present invention relates to an epoxy resin and an epoxy resin composition that give a cured product having high heat resistance and high mechanical strength.

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. In recent years, especially in the field of semiconductor-related materials, electronic devices such as mobile phones with cameras, ultra-thin liquid crystals, plasma TVs, and light-weight notebook computers have become key to light, thin, short, and small. Very high characteristics have been demanded for packaging materials represented by resins. In particular, the structure of the tip package is complicated, and there are an increasing number of things that are difficult to seal without liquid sealing. For example, a cavity down type structure such as Enhanced BGA needs to be partially sealed and cannot be handled by transfer molding. For these reasons, the development of highly functional liquid epoxy resins has been demanded.
Conventionally, as a liquid epoxy resin most used industrially, a compound obtained by reacting bisphenol A with epichlorohydrin is known. However, it has been pointed out that the bisphenol A type epoxy resin as described above is balanced in physical properties but has a high viscosity and is insufficient in heat resistance, mechanical strength and the like of the cured product.
As an epoxy resin that solves such a problem, Patent Document 1 discloses a prescription that a dimer of a resorcin-type epoxy resin is taken out by distillation, but its production method has a problem of extremely low yield. . However, the dimer of the resorcin type epoxy resin is not only excellent in cured product properties, but the aromatic epoxy resin having such an alcoholic hydroxyl group has extremely low contamination to liquid crystals as described in Patent Document 2. It is easy to use such a compound because it is excellent in application workability and bonding properties to a substrate, has a long pot life, has a long pot life, and is suitable for liquid crystal sealing agents that require strong adhesive strength. Synthetic methods are desired.

JP-A-2005-112896 JP 2004-244515 A

  An object of this invention is to provide the epoxy resin and epoxy resin composition which give the hardened | cured material with high heat resistance and mechanical strength.

  In view of the actual situation as described above, the present inventors have sought for an epoxy resin that gives a cured product having high heat resistance and high mechanical strength, and as a result, have completed the present invention.

（式中、ｎは０〜３の整数を、また、ｍは１〜３の整数をそれぞれ示す。複数存在するＲはそれぞれハロゲン原子、炭素数１〜８のアルキル基またはアリール基のいずれかを表し、それぞれ互いに同一であっても異なっていても良い。）
で表されるエポキシ化合物
（２）式（１）

で表される化合物及び式（２）

（式（１）及び（２）中、ｎ、ｍ及びＲは式（ａ）におけるのと同じ意味を表す。）
で表される化合物を主成分とするエポキシ樹脂、
（３）上記（１）に記載の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（３）に記載のエポキシ樹脂組成物を硬化してなる硬化物、
（５）下記式（ｂ）

（式中、ｎ、ｍ及びＲは式（ａ）におけるのと同じ意味を表す。）
で表されるメチロール基を有するフェノール類を、塩基性化合物の存在下、式（ｂ）の化合物のフェノール性水酸基１モルに対し、０．１〜１．０モルのエピハロヒドリンと反応させることを特徴とする上記（１）に記載のエポキシ化合物の製造方法、
（６）下記工程１〜３を含むことを特徴とする上記（２）に記載のエポキシ樹脂の製造方法、
工程１：上記（５）に記載の製造方法によりエポキシ化合物を得る工程
工程２：工程１で得られたエポキシ化合物のオキシグリシジル基を、式（ｂ）の化合物と反応させ、下記式（ｃ）の化合物を得る工程

工程３：工程２で得られた式（ｃ）の化合物のアルコール性水酸基をエポキシ化する工程
を提供するものである。 That is, the present invention provides (1) the following formula (a)

(In the formula, n represents an integer of 0 to 3, and m represents an integer of 1 to 3. Each of a plurality of R represents a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group. And each may be the same or different.)
An epoxy compound represented by formula (2): Formula (1)

And a compound represented by formula (2)

(In formulas (1) and (2), n, m and R represent the same meaning as in formula (a).)
An epoxy resin whose main component is a compound represented by
(3) An epoxy resin composition containing the epoxy resin and a curing agent according to (1) above,
(4) Hardened | cured material formed by hardening | curing the epoxy resin composition as described in said (3),
(5) The following formula (b)

(In the formula, n, m and R represent the same meaning as in formula (a).)
A phenol having a methylol group represented by the formula (b) is reacted with 0.1 to 1.0 mol of epihalohydrin with respect to 1 mol of the phenolic hydroxyl group of the compound of the formula (b) in the presence of a basic compound. The method for producing an epoxy compound according to (1) above,
(6) The method for producing an epoxy resin according to the above (2), comprising the following steps 1 to 3,
Step 1: Step of obtaining an epoxy compound by the production method described in the above (5) Step 2: Reacting the oxyglycidyl group of the epoxy compound obtained in Step 1 with a compound of the formula (b), the following formula (c) To obtain a compound of

Step 3: A step of epoxidizing the alcoholic hydroxyl group of the compound of formula (c) obtained in Step 2 is provided.

  The epoxy resin of the present invention is a liquid having a relatively low viscosity, and the cured product has high heat resistance and excellent mechanical strength. The compound having an alcoholic hydroxyl group, which is one component of the epoxy resin of the present invention, can be added with a photopolymerizable functional group. Therefore, the epoxy resin composition 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, optical materials and the like.

（式中、ｎは０〜３の整数を、また、ｍは１〜３の整数をそれぞれ示す。複数存在するＲはそれぞれハロゲン原子、炭素数１〜８のアルキル基またはアリール基のいずれかを表し、それぞれ互いに同一であっても異なっていても良い。）
で表されるメチロール基を有するフェノール類（以下ＭＰと称す）出発原料とし、下記３工程を経て得ることができる。

（工程１）ＭＰを、塩基性化合物の存在下、そのフェノール性水酸基１モルに対し、０．１〜１．０のエピハロヒドリンと反応させるＭＰのフェノール性水酸基のみをエポキシ化する。（このエポキシ化物をＭＰＥと称す。）
ＭＰＥは、下記式（ａ）で表される化合物を主成分として含む混合物であり、ここから式（ａ）の化合物を単離することもできる。該混合物の他の成分としては、式（ａ）の化合物の二量体（式（ｃ）の化合物）等が含まれるが、工程（２）において、そのまま使用できる。

（式中、ｎ、ｍ及びＲは式（ｂ）におけるのと同じ意味を表す。）

（工程２）ＭＰＥのグリシジル基とＭＰとを反応させ、二量化を行う。（この二量体をＢ−ＭＰと称す。；下記式（ｃ））

（式中、ｎ、ｍ及びＲは式（ｂ）におけるのと同じ意味を表す。）

（工程３）Ｂ−ＭＰのアルコール性水酸基をエポキシ化し、エポキシ樹脂を得る。（得られたエポキシ樹脂をＢ−ＭＰＥと称す。） The epoxy resin of the present invention is usually represented by the following formula (b)

(In the formula, n represents an integer of 0 to 3, and m represents an integer of 1 to 3. Each of a plurality of R represents a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group. And each may be the same or different.)
And a phenol having a methylol group represented by (hereinafter referred to as MP) as a starting material, it can be obtained through the following three steps.

(Step 1) In the presence of a basic compound, MP is epoxidized only with the phenolic hydroxyl group of MP that reacts with 0.1 to 1.0 epihalohydrin with respect to 1 mol of the phenolic hydroxyl group. (This epoxidized product is referred to as MPE.)
MPE is a mixture containing a compound represented by the following formula (a) as a main component, from which the compound of the formula (a) can also be isolated. Other components of the mixture include dimers of the compound of the formula (a) (compound of the formula (c)) and the like, but can be used as they are in the step (2).

(In the formula, n, m and R have the same meaning as in formula (b).)

(Step 2) MPE is reacted with glycidyl group of MPE to perform dimerization. (This dimer is referred to as B-MP; the following formula (c))

(In the formula, n, m and R have the same meaning as in formula (b).)

(Step 3) Epoxy the alcoholic hydroxyl group of B-MP to obtain an epoxy resin. (The obtained epoxy resin is referred to as B-MPE.)

All of these steps 1 to 3 may be performed in one pot, and the product may be taken out and purified for each step. When an asymmetric compound is to be obtained, the compound of the formula (a) taken out and purified in step 1 and MP different therefrom may be reacted in step 2.
The MP used in the epoxy resin of the present invention is not particularly limited as long as it is a phenol methylol. The methylol body of phenol can be synthesized by a known method (for example, formaldehyde Asakura Shoten p232-279). That is, it can be synthesized by reacting phenols with formaldehyde under basic conditions. The phenols referred to here are substituted phenols substituted with a halogen atom, a hydrocarbon group having 1 to 8 carbon atoms, or a trifluoromethyl group in addition to phenol. Specifically, the phenols o, m, and p It is a compound having a substituent described below at any one or two or three of five substitution positions.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Moreover, as a C1-C8 hydrocarbon group, a methyl group, an ethyl group, n-propyl group, isopropyl group, cyclopropyl group, n-butyl group, sec-butyl group, tert-butyl group, isobutyl group, cyclobutyl. Group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, cyclopentyl group, n-hexyl group, isohexyl group, cyclohexyl group, n-heptyl group, cycloheptyl group, n-octyl group, cyclooctyl group, etc. A chain alkyl group or a cyclic alkyl group, an allyl group or an aryl group. Examples of the aryl group include, but are not limited to, a phenyl group, a naphthyl group, and a toluyl group.

  In step 1, the above-described MP is reacted with only the phenolic hydroxyl group by utilizing the difference in reactivity between the phenolic hydroxyl group and the alcoholic hydroxyl group.

Hereinafter, the aspect which performs process 1-3 by one pot is demonstrated.
In step 1, the basic compound is preferably an alkali metal hydroxide, and specific examples include sodium hydroxide and potassium hydroxide. These may use a solid or an aqueous solution thereof. The usage-amount of a basic compound is 0.8-3.5 mol normally with respect to 1 mol of epoxy groups of the epihalohydrin to be used, Preferably it is 0.9-2.5 mol.

  The usage-amount of epihalohydrin is 0.1-1.0 mol normally with respect to 1 mol of phenolic hydroxyl groups of MP, Preferably it is 0.2-0.8 mol. The epihalohydrin used is epichlorohydrin, α-methylepichlorohydrin, β-methylepichlorohydrin, γ-methylepichlorohydrin, and other epichlorohydrin derivatives, epibulumhydrin, epiiohydrin. However, industrially, epichlorohydrin derivatives are easy to use, and epichlorohydrin is particularly easy to use. At this time, in order to increase the solubility of MP and to carry out the reaction under mild conditions, alcohols such as methanol, ethanol, isopropyl alcohol, butanol, t-butanol, dimethyl sulfoxide, dimethylformamide, dimethyl sulfone, tetrahydrofuran, dioxane , Aprotic polar solvents such as 1,3-dimethyl-2-imidazolidinone, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, esters such as ethyl acetate, butyl lactate, propylene glycol monomethyl ether acetate, toluene It is preferable to carry out the reaction by adding a solvent exemplified by aromatic compounds such as xylene. When a solvent is used, the amount used is usually 2 to 1000% by weight, preferably 5 to 500% by weight, based on the total weight.

  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.

  In step 2, the reaction between MP and MPE synthesized in step 1 is performed. In Step 1, some B-MP is already formed depending on the amount of the basic compound and the amount of epihalohydrin. In Step 2, the reaction is completely performed. As a reaction method, an alkali metal hydroxide may be further added, but a quaternary ammonium salt may be added as a catalyst. 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, based on 1 mol of the hydroxyl group of MP used in Step 2.

  In step 2, MP may be added separately. The amount used is generally 0.1 to 1.0, preferably 0.2 to 0.8, particularly preferably 0.5 as the total amount from step 1 (number of moles of epihalohydrin / number of moles of phenolic hydroxyl group of MP). It is a range that is in the vicinity.

  The reaction temperature is usually 30 to 180 ° C, preferably 35 to 120 ° C. The reaction time is usually 0.5 to 10 hours, preferably 1 to 8 hours.

  In step 3, the alcoholic hydroxyl group remaining in the B-MPE obtained in step 2 is epoxidized. In step 3, 1.0 to 20 mol, preferably 1.5 to 10 mol of epihalohydrin is usually added to 1 mol of alcoholic hydroxyl group contained in the reaction solution obtained up to step 2, and the reaction is carried out. Do. The reaction is carried out at 20 to 120 ° C. over 0.5 to 10 hours while adding or adding an alkali metal hydroxide solid such as sodium hydroxide or potassium hydroxide. At this time, the alkali metal hydroxide may be used in the form of an aqueous solution. In this case, the alkali metal hydroxide is continuously added and water and epihalohydrin are continuously added from the reaction mixture under reduced pressure or normal pressure. Distillation, liquid separation, water removal, and epihalohydrin may be continuously returned to the reaction mixture. Examples of the epihalohydrin that can be used in Step 3 include the same compounds as described above. The usage-amount of an alkali metal hydroxide is 0.8-4.0 mol normally with respect to 1 mol of alcoholic hydroxyl groups in a phenol mixture, Preferably it is 0.8-2.0 mol. At this time, side reactions can be suppressed by adding an aprotic solvent such as dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, 1,3-dimethyl-2-imidazolidinone. The amount of the aprotic polar solvent used is 5 to 200% by weight, preferably 10 to 100% by weight, based on the weight of the epihalohydrin. In addition to the above-mentioned solvent, the reaction can easily proceed by adding alcohols such as methanol, ethanol, isopropyl alcohol, butanol, and t-butanol. Moreover, toluene, xylene, etc. can also be used.

  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 mol of the alcoholic hydroxyl group in the reaction solution.

  After completion of the reaction, the by-produced salt is removed by filtration, washing with water, and the like, and the epoxy resin (B-MPE) of the present invention can be obtained by distilling off excess epihalohydrin and the like under heating and reduced pressure. If it is necessary to epoxidize the remaining hydroxyl group in a trace amount, after the reaction is completed, the reaction product is washed with water, or after removing excess epihalohydrins and solvents under heating and reduced pressure without washing with water, and then again with toluene. Then, it is dissolved in a solvent such as methyl isobutyl ketone, methyl ethyl ketone, ethyl acetate, and an aqueous solution of alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to react again. In this case, the amount of the alkali metal hydroxide used is usually 0.01 to 0.2 mol, preferably 0.05 to 0.1 mol, relative to 1 mol of the hydroxyl group in the reaction product. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours. After completion of the reaction, the by-produced salt is removed by filtration, washing with water, etc., and the solvent and the like are distilled off under heating and reduced pressure to obtain the epoxy resin of the present invention.

  In the case of stepwise reaction, MP is reacted with epihalohydrin in step 1 and extracted as an epoxy compound, then reacted with another molecule of MP in step 2 to form B-MP, and this is reacted again with epihalohydrin. To obtain the epoxy compound (B-MPE) of the present invention.

  In Step 1, MP can be reacted with epihalohydrin in accordance with a conventionally known method. For example, a solid of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide or a methanol solution is added to a mixture of MP and epihalohydrin, or the methanol solution is added, or reacted at 20 to 120 ° C. for 0.5 to 10 hours. . At this time, the alkali metal hydroxide may be used in the form of an aqueous solution. In this case, the alkali metal hydroxide is continuously added and water and epihalohydrin are continuously added from the reaction mixture under reduced pressure or normal pressure. A method may be used in which the spilled liquid is further separated to remove water and the epihalohydrin is continuously returned to the reaction mixture. The epihalohydrin that can be used in this method is the same as described above.

  In said method, the usage-amount of epihalohydrin is 0.5-20 mol normally with respect to 1 equivalent of hydroxyl groups of a phenol mixture, Preferably it is 0.7-10 mol. The usage-amount of an alkali metal hydroxide is 0.5-1.5 mol normally with respect to 1 equivalent of hydroxyl groups in a phenol mixture, Preferably it is 0.7-1.2 mol. At this time, side reactions can be suppressed by adding an aprotic solvent such as dimethyl sulfone, dimethyl sulfoxide, dimethylformamide, 1,3-dimethyl-2-imidazolidinone. The amount of the aprotic polar solvent used is 5 to 200%, preferably 10 to 100%, based on the weight of the epihalohydrin. In addition to the above-mentioned solvent, the reaction can easily proceed by adding alcohols such as methanol, ethanol, isopropyl alcohol, butanol, and t-butanol. Moreover, toluene, xylene, etc. can also be used.

After completion of the reaction, by-product salts are removed by filtration, washing with water, etc., and MPE can be obtained by distilling off excess epihalohydrin and the like under heating and reduced pressure.
If higher purity MPE is required, after the reaction is completed, the reaction product is washed with water, or after removing excess epihalohydrins and solvents under heating and reduced pressure without washing with water, toluene, methyl isobutyl ketone, After dissolving in a solvent such as methyl ethyl ketone and ethyl acetate, an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to react again. In this case, the amount of alkali metal hydroxide used is usually 0.01 to 0.2 mol, preferably 0.05 to 0.1 mol, per 1 equivalent of the phenolic hydroxyl group of MP. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours. After the reaction is complete, MPE can be obtained by removing the by-produced salt by filtration, washing with water, etc., and further distilling off the solvent and the like under heating and reduced pressure.

  In step 2, B-MP is synthesized by reacting MPE obtained by the above-described method with MP. The usage-amount of MP is 0.5-1.5 mol normally with respect to 1 mol of MPE. This reaction is a technique commonly called fusion, and is non-catalytic or organic phosphines such as triphenylphosphine, tolylphenylphosphine, triphenylphosphine-hydroquinone complex, tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium The reaction can also be carried out using a catalyst such as a quaternary ammonium salt such as chloride, a solvent such as dimethylformamide or N-methylpyrrolidone, or an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide as a catalyst. Although the amount of the catalyst used depends on the catalyst, it is usually 0.0001 to 1.0 mol, preferably 0.0005 to 0.8 mol, per 1 equivalent of the hydroxyl group of MP used.

  The reaction may be solvent-free, but in order to carry out the reaction under mild conditions, it is also preferable to add a solvent separately. Specifically, aprotic polar solvents such as dimethyl sulfoxide, dimethylformamide, dimethyl sulfone, tetrahydrofuran, dioxane, 1,3-dimethyl-2-imidazolidinone, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetic acid Examples include, but are not limited to, esters such as ethyl, butyl lactate, and propylene glycol monomethyl ether acetate, and aromatic compounds such as toluene and xylene.

  The reaction temperature is usually 50 to 180 ° C., and the reaction time is usually 0.5 to 2 hours. After completion of the reaction, B-MP can be obtained by removing the catalyst by filtration, washing with water, and the like, if necessary, and further distilling off the solvent and the like under heating and reduced pressure as necessary.

  Step 3 is the same as that described above.

The epoxy resin of the present invention obtained as described above is an epoxy resin containing 50 mol% (area% by HPLC) or more of the compound of the formula (1) and the compound of (2) in the total epoxy resin. Here, the content ratio of the compound of formula (1) and the compound of formula (2) mainly depends on the amount of the alkali metal hydroxide used in step 3. That is, as the amount of the alkali metal hydroxide increases, the proportion of the compound of formula (2) increases and a highly heat-resistant epoxy resin can be obtained.
It can also be isolated by molecular distillation or introduction of a substituent to a hydroxyl group under heating and reduced pressure. The isolated compound of the formula (1) is useful in the field of high-performance electronic materials such as liquid crystal sealing materials. In addition, a functional group (for example, an isocyanate group-containing methacrylate such as Karenz MOI or Karenz AOI, an acrylate, , An isocyanate group-containing maleimide), or by connecting two molecules with a diisocyanate such as tolyl diisocyanate or bis (isocyanatophenyl) methane.

  The epoxy resin composition of the present invention contains the epoxy resin of the present invention and a curing agent as essential components. In the epoxy resin composition of the present invention, 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.

  Specific 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 dicyclopentadienephenol co-condensation type epoxy resins. , Triphenylmethane type epoxy resin, biphenyl novolac type epoxy resin and the like may be mentioned, but these may be used alone or in combination of two or more.

  In the epoxy resin composition of the present invention, 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 diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, polyamide resin synthesized from linolenic acid and ethylenediamine, phthalic anhydride, trimellitic anhydride Acid, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phenolic resin of the present invention, bisphenol A, bisphenol F Bisphenol S, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [1,1′-bi Enyl] -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 (methoxymethyl) -1,1′-biphenyl, 1,4′-bis (chlorome E) polycondensates with benzene, 1,4′-bis (methoxymethyl) benzene, etc. and their modified products, halogenated bisphenols such as tetrabromobisphenol A, imidazole, trifluoroborane-amine complexes, guanidine derivatives, Although the condensate of a terpene and phenols is mentioned, it is not limited to these. These may be used alone or in combination of two or more.

  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, 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 are added to the epoxy resin composition of the present invention. be able to.

  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 mixed thoroughly until uniform using an extruder, kneader, roll, etc. as necessary. An epoxy resin composition is obtained, and the epoxy resin composition is 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 the cured product of the present invention. be able to.

  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.

EXAMPLES Next, the present invention will be described in more detail with reference to examples. In the following, parts represent parts by weight unless otherwise specified. In addition, the measurement conditions of GPC (gel permeation chromatography) and HPLC (high performance liquid chromatography) in the examples are as follows.

GPC
Column: KF-804L + KF-803L (x2)
Linked eluent: THF (tetrahydrofuran); 1 ml / min. 40 ° C
Detector: UV (254 nm)
Calibration curve: Shodex standard polystyrene used

HPLC
Column: Intersil ODS-2, 5 μm, 2.1 × 250 mm 40 ° C.
Linked eluent: acetonitrile / water Time program: 0 min 50% / 50%, 20 min 90% / 10% gradient, 40 min 90% / 10%
Flow rate: 0.2 ml / min
Detector: UV (274 nm)

Example 1
A flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer was purged with nitrogen gas, and 92.5 parts of epichlorohydrin and 248 parts of tert-butyl alcohol were added to 248 parts of parahydroxybenzyl alcohol and dissolved under stirring. The temperature was raised to ° C. Next, 40 parts of flaky sodium hydroxide was added in portions over 90 minutes, and then post-reaction was performed at 70 ° C. for 1 hour. Furthermore, 10 parts of flaky sodium hydroxide was added and stirred at 90 ° C. for 2 hours. After confirming that epoxy groups could not be detected, the system was cooled to 50 ° C. Subsequently, 555 parts of epichlorohydrin and 5 parts of tetramethylammonium chloride were added, and the temperature was raised to 70 ° C. Next, 120 parts of flaky sodium hydroxide was added in portions over 90 minutes, and then post-reaction was performed at 70 ° C. for 1 hour. After completion of the reaction, 300 parts of water was added and washed with water. Excess epichlorohydrin and the like were distilled off from the oil layer under reduced pressure at 130 ° C. using a rotary evaporator. 700 parts of methyl isobutyl ketone was added to the residue and dissolved, and the temperature was raised to 70 ° C. Under stirring, 20 parts of a 30% by weight aqueous sodium hydroxide solution was added and the reaction was carried out for 1 hour, followed by washing with water three times. Distilling off methyl isobutyl ketone under reduced pressure at 180 ° C. using a rotary evaporator. Formula (3)

で表される化合物及び式（４）

And a compound represented by formula (4)

で表される化合物を主成分とするエポキシ樹脂が得られた。（ＧＰＣ純度 ８３ａｒｅａ％）２９０部を得た。得られたエポキシ樹脂は液状であり、エポキシ当量は２０９ｇ／ｅｑであった。ＨＰＬＣで確認したところ、式（３）と式（４）の化合物は１：１の割合（モル比；以下同様）で生成していることがわかった。

The epoxy resin which has as a main component the compound represented by this was obtained. (GPC purity 83 area%) 290 parts were obtained. The obtained epoxy resin was liquid, and the epoxy equivalent was 209 g / eq. When confirmed by HPLC, it was found that the compounds of formula (3) and formula (4) were produced at a ratio of 1: 1 (molar ratio; the same applies hereinafter).

Example 3
A flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer was purged with nitrogen gas, and 92.5 parts of epichlorohydrin and 248 parts of tert-butyl alcohol were added to 248 parts of parahydroxybenzyl alcohol and dissolved under stirring. The temperature was raised to ° C. Next, 40 parts of flaky sodium hydroxide was added in portions over 90 minutes, and then post-reaction was performed at 70 ° C. for 1 hour. Furthermore, 10 parts of flaky sodium hydroxide was added and stirred at 90 ° C. for 2 hours. After confirming that epoxy groups could not be detected, the system was cooled to 50 ° C. Subsequently, 555 parts of epichlorohydrin and 5 parts of tetramethylammonium chloride were added, and the temperature was raised to 70 ° C. Next, 100 parts of flaky sodium hydroxide was added in portions over 90 minutes, and then post-reaction was performed at 70 ° C. for 1 hour. After completion of the reaction, 300 parts of water was added and washed with water. Excess epichlorohydrin and the like were distilled off from the oil layer under reduced pressure at 130 ° C. using a rotary evaporator. 700 parts of methyl isobutyl ketone was added to the residue and dissolved, and the temperature was raised to 70 ° C. Under stirring, 20 parts of a 30% by weight aqueous sodium hydroxide solution was added and the reaction was carried out for 1 hour, followed by washing with water three times. Distilling off methyl isobutyl ketone under reduced pressure at 180 ° C. using a rotary evaporator. The epoxy resin which has as a main component the compound represented by the said Formula (3) and Formula (4) was obtained. (GPC purity: 76 area%) 281 parts were obtained. The obtained epoxy resin was liquid and the epoxy equivalent was 216 g / eq. When confirmed by HPLC, it was found that the compounds of formula (3) and formula (4) were produced at a ratio of 5: 3.

Example 4
While purging a flask equipped with a thermometer, dropping funnel, condenser, and stirrer with nitrogen gas purge, add 555 parts of epichlorohydrin and 275 parts of isopropyl alcohol to 124 parts of parahydroxybenzyl alcohol, dissolve under stirring, and rise to 50 ° C. Warm up. Next, 40 parts of sodium hydroxide was dissolved in 360 parts of methanol and added dropwise over 60 minutes, and then the reaction was further carried out at 50 ° C. for 7 hours. After completion of the reaction, excess epichlorohydrin and the like were distilled off under reduced pressure at 90 ° C. using a rotary evaporator. To the residue, 300 parts of methyl ethyl ketone was added and dissolved, and 200 parts of water was added and washed with water. The obtained oil layer was heated to 70 ° C., 10 parts of a 30 wt% sodium hydroxide aqueous solution was added with stirring, and the reaction was performed for 1 hour, followed by washing with water three times, and using a rotary evaporator at 100 ° C. By distilling off methyl ethyl ketone under reduced pressure at the formula (5)

で表される化合物が主成分であるエポキシ化物を１７１部得た。（ＧＰＣ純度 ９３ａｒｅａ％）室温で放置すると程なく結晶化した。得られた結晶のポキシ当量は１９０ｇ／ｅｑ．であった。

As a result, 171 parts of an epoxidized product containing as a main component a compound represented by the formula: (GPC purity: 93 area%) Crystallization occurred soon after standing at room temperature. The obtained crystals have a poxy equivalent of 190 g / eq. Met.

Example 5
In the same manner as in Example 4 except that orthohydroxybenzyl alcohol was used instead of parahydroxybenzyl alcohol in Example 4, the compound of formula (6)

で表される化合物が主成分であるエポキシ化物を１６３部得た。（ＧＰＣ純度 ９０ａｒｅａ％）得られたエポキシ化物は、結晶化しなかった。また、そのエポキシ当量は１９９ｇ／ｅｑ．であった。

As a result, 163 parts of an epoxidized product containing as a main component a compound represented by the formula: (GPC purity 90 area%) The resulting epoxidized product did not crystallize. Moreover, the epoxy equivalent is 199 g / eq. Met.

Example 6
95 parts of the epoxy resin obtained in Example 4 and 99.5 parts of the epoxy resin obtained in Example 5 while performing nitrogen gas purging on a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer, parahydroxybenzyl 124 parts of alcohol, 150 parts of methyl ethyl ketone and 150 parts of tert-butyl alcohol were mixed, and the temperature was raised to 70 ° C. (Step 2). Further, 5 parts of flaky sodium hydroxide was added and reacted at 70 ° C. for 2 hours and at 90 ° C. for 3 hours, and then the system was cooled to 50 ° C. Subsequently, 555 parts of epichlorohydrin and 5 parts of tetramethylammonium chloride were added, and the temperature was raised to 70 ° C. Next, 160 parts of flaky sodium hydroxide was added in portions over 90 minutes, and then post-reaction was performed at 70 ° C. for 1 hour. After completion of the reaction, 300 parts of water was added and washed with water. Excess epichlorohydrin and the like were distilled off from the oil layer under reduced pressure at 130 ° C. using a rotary evaporator. 700 parts of methyl isobutyl ketone was added to the residue and dissolved, and the temperature was raised to 70 ° C. Under stirring, 20 parts of a 30% by weight aqueous sodium hydroxide solution was added and the reaction was carried out for 1 hour, followed by washing with water three times. Distilling off methyl isobutyl ketone under reduced pressure at 180 ° C. using a rotary evaporator. Formula (7)

で表される化合物及び式（８）

And a compound represented by formula (8)

で表される化合物が主成分であるエポキシ樹脂を液状の樹脂として２７５部得た。（ＧＰＣ純度 ７６ａｒｅａ％）エポキシ当量は１７５ｇ／ｅｑ．であった。

As a liquid resin, 275 parts of an epoxy resin whose main component is a compound represented by the formula: (GPC purity 76 area%) Epoxy equivalent was 175 g / eq. Met.

Example 7, Comparative Example 1, Comparative Example 2
To 105 parts of the epoxy resin obtained in Example 1, 33 parts of Kayahard A-A (bis-3-ethyl 4-aminophenyl) methane Nippon Kayaku Co., Ltd. amine-based curing agent) was uniformly mixed. An epoxy resin composition was obtained. This was cast into a mold and cured at 120 ° C. for 2 hours, 150 ° C. for 3 hours, and 180 ° C. for 2 hours to obtain a cured test piece. Similarly, 98 parts of epoxy resin (epoxy equivalent 198 g / eq.) Synthesized by the method described in Patent Document 1 (Comparative Example 1), bisphenol A type epoxy resin (RE-310S Nippon Kayaku Epoxy resin, epoxy equivalent 190 g) / Eq.) 95 parts (Comparative Example 2) were used, and all were mixed with 33 parts Kayahard A-A to obtain a composition, which was cured in the same manner. The glass transition temperature of the test piece of the cured product thus obtained was measured using TMA (TM-7000, temperature rise rate: 2 ° C./min, manufactured by Vacuum Mechanical Engineering Co., Ltd.), and IZOD was measured according to JIS as an impact test. Measured based on K6911. The results are shown in Table 1 below.

Example 7
Comparative Example 1 2
Epoxy resin Example 1 Patent Document 1 RE-310S
Viscosity (25 ° C./mPa·s) 9620 8120 15240
TMA (° C.) 127 129 130
IZOD (kJm) 18.0 14.1 7.8

  As described above, the epoxy resin of the present invention is a liquid having a low viscosity as compared with the liquid epoxy resins generally used conventionally, and the cured product is excellent in heat resistance and mechanical strength.

Claims (4)

Following formula (1)

And a compound represented by formula (2)

(In the formulas (1) and (2), n represents an integer of 0 to 3, and m represents an integer of 1 to 3. Multiple Rs are each a halogen atom or an alkyl group having 1 to 8 carbon atoms. Or any of aryl groups, which may be the same or different from each other.
The epoxy resin which has as a main component the compound represented by these. An epoxy resin composition comprising the epoxy resin according to claim 1 and a curing agent. A cured product obtained by curing the epoxy resin composition according to claim 2. The manufacturing method of the epoxy resin of Claim 1 including the following processes 1-3.
Step 1: the following formula (b)

(In the formula, n, m and R represent the same meaning as in formula (a).)
In the presence of a basic compound, phenols having a methylol group represented by the formula (b) are reacted with 0.1 to 1.0 mol of epihalohydrin with respect to 1 mol of the phenolic hydroxyl group of the compound of formula (b), The following formula (a)

(In the formula, n represents an integer of 0 to 3, and m represents an integer of 1 to 3. Each of a plurality of R represents a halogen atom, an alkyl group having 1 to 8 carbon atoms, or an aryl group. And each may be the same or different.)
Step 2 for obtaining an epoxy compound represented by formula: Step for reacting the oxyglycidyl group of the epoxy compound obtained in Step 1 with a compound of the formula (b) to obtain a compound of the following formula (c)

(In the formula, n, m and R represent the same meaning as in formula (a).)
Step 3: Epoxidizing the alcoholic hydroxyl group of the compound of formula (c) obtained in Step 2