JP2587739B2 - Epoxy resin, epoxy resin composition and cured product thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin and an epoxy resin composition having excellent heat resistance, toughness, and water resistance and a cured product thereof. Materials, composites, paints, adhesives,
It is extremely useful for a wide range of applications such as resists.

[0002]

2. Description of the Related Art Epoxy resins are generally cured with various curing agents to form cured products having excellent mechanical properties, water resistance, chemical resistance, heat resistance, and electrical properties. It is used in a wide range of fields, such as laminates, molding materials, and casting materials. Conventionally, there is a liquid and solid bisphenol A type epoxy resin obtained by reacting bisphenol A with epichlorohydrin as the epoxy resin most used industrially. In addition, a flame-retardant solid epoxy resin obtained by reacting tetrabromobisphenol A with a liquid bisphenol A-type epoxy resin is industrially used as a general-purpose epoxy resin.

Further, US Pat. No. 4,623,701 reports a polyfunctional epoxy resin in which the alcoholic hydroxyl group of the bisphenol A type epoxy resin is entirely epoxidized.

[0004]

However, as the molecular weight of the above-mentioned general-purpose epoxy resin increases, the toughness of a cured product obtained by using the same increases but the heat resistance decreases. On the other hand, a cured product obtained from a polyfunctional epoxy resin obtained by epoxidizing all of the alcoholic hydroxyl groups of this general-purpose epoxy resin has a drawback that the heat resistance is improved but it becomes brittle. On the other hand, with the remarkable development of the recent electronics industry, the heat resistance and toughness required for electrical insulating materials used in these are becoming increasingly severe, and the emergence of epoxy resins with excellent heat resistance and toughness Is eagerly awaited.

[0005]

Means for Solving the Problems In view of these circumstances, the present inventors have conducted intensive studies for an epoxy resin having excellent heat resistance and toughness.

[0006]

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Or the general formula (3)

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(Wherein R ₁ , R ₂ , R ₃ and m and n have the same meanings as in formula (1) described below) and a phenolic hydroxyl group and a specific proportion of alcohol The present inventors have found that an epoxy resin obtained by epoxidizing a hydrophilic hydroxyl group has both heat resistance and toughness, and completed the present invention.

That is, the present invention provides (1) a general formula (1)

[0010]

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Wherein R _1, R ₂ and R ₃ are the same or different;

[0012]

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(B)

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(C)

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(D)

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Or (e)

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A is alkylene; cycloalkylene; halogen; alkylene substituted with cycloalkyl or aryl;

[0018]

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Or

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Wherein X _{1 to} X ₄₂ are each independently hydrogen, an alkyl group or halogen. M and n each represent an integer of 1 or more. further

[0021]

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And

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Are arranged in an arbitrary order. Also, m
/(M+n)=0.10 to 0.80. (2) The epoxy resin according to (1), wherein the content of hydrolyzable chlorine is 0.15% or less. (3) An epoxy resin composition comprising an epoxy resin, a curing agent and, if necessary, a curing accelerator, wherein the epoxy resin described in the item (1) or (2) is contained as the epoxy resin component. Epoxy resin composition (4) The epoxy resin composition according to the item (3) is 80 to 2
A method for producing a cured product characterized by heating to 00 ° C. (5) An object of the present invention is to provide an epoxy resin composition for a laminate comprising the epoxy resin composition according to the item (3).

The epoxy resin of the present invention can be prepared by reacting a compound represented by the general formula (2) or (3) with a phenolic hydroxyl group or an alcoholic hydroxyl group and epichlorohydrin, for example, by using dimethyl sulfoxide or a quaternary ammonium salt. It can be obtained by carrying out in the coexistence of 3-dimethyl-2-imidazolidinone and alkali metal hydroxide and adjusting the amount of alkali metal hydroxide used. When the reaction between the alcoholic hydroxyl group of the compound represented by the general formula (2) and epichlorohydrin is carried out in the presence of a Lewis acid catalyst as in the reaction between general alcohols and epichlorohydrin, Since the reaction between the epoxy group and the alcoholic hydroxyl group of the compound represented by the formula (1) occurs simultaneously, it is difficult to obtain an epoxy resin in which only the alcoholic hydroxyl group of the compound represented by the general formula (2) of the present invention is epoxidized. is there. It should be noted that the reaction with the compound of the general formula (2) using an excess of epichlorohydrin only in the presence of a strong alkali does not react with the alcoholic hydroxyl group. The present inventors have conducted intensive studies and as a result of the general formula (2)
The alcoholic hydroxyl group of the epoxy resin represented by the formula (1) is more reactive than common alcohols, and for example, dimethyl sulfoxide or quaternary ammonium salt or 1,3-dithimer-2-imidazolidinone and alkali metal hydroxide coexist Surprisingly, the reaction between the alcoholic hydroxyl group and epichlorohydrin can be selectively performed, and further, by adjusting the amount of the alkali metal hydroxide, the alcoholic hydroxyl group of the epoxy resin represented by the general formula (2) can be formed. It has been found that epoxidation can be performed at a desired ratio, and the present invention has been completed. The reaction between the phenolic hydroxyl group and the alcoholic hydroxyl group of the compound represented by the general formula (3) and epichlorohydrin can be carried out by the above method or in the presence of a Lewis acid catalyst. The product in which epichlorohydrin reacts with the hydroxyl group of chlorohydrin in the product is formed in a large amount, and the content of hydrolyzable chlorine is very high and the content of epoxy group is low, which is not preferable.

Hereinafter, the present invention will be described in detail. Examples of the epoxy resin represented by the general formula (1) of the present invention include, for example, R _1, R ₂ and R ₃ in the general formula (1) represented by the formula (a).

[0026]

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[0027]

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[0028]

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[0029]

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[0030]

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[0031]

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[0032]

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[0033]

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[0034]

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[0035]

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[0036]

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[0037]

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[0038]

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[0039]

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[0040]

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[0041]

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[0042]

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As the one represented by the above formula (b), for example,

[0044]

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[0045]

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As the formula (c), for example,

[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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[0054]

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[0055]

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[0056]

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[0057]

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[0058]

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[0059]

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[0060]

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[0061]

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[0062]

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[0063]

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[0064]

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[0065]

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[0066]

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As the one represented by the above formula (d), for example,

[0068]

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[0069]

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As the one represented by the above formula (e), for example,

[0071]

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[0072]

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The following are examples, but the present invention is not limited to these. Further, R _1, R ₂ and R _{3 in the} general formula (1) may include different ones.

The epoxy resin of the present invention is represented by the general formula (1), wherein m and n in the general formula (1) are each 1 or more, and m / (m + n) is 0.10 to 0.80, preferably Is 0.15 to 0.60, and m + n is preferably 2
To 13, particularly preferably 2 to 6. m / (m + n)
Is less than 0.10, the heat resistance of a cured product obtained using the same is insufficient, which is not preferred. Also, m / (m +
If n) exceeds 0.80, the cured product obtained using the same becomes brittle, which is not preferable. On the other hand, when m + n exceeds 13, the epoxy resin has a high softening point and a high melt viscosity, which makes the handling difficult, which is not preferable. R ₁ , R ₂ and R ₃ in the general formula (1) are the same as those in the above formula (c-3) or formula (c-
4) or a mixture of formulas (c-3) and (c-4) is particularly preferred. These epoxy resins are particularly preferable because both of the heat resistance and toughness of the cured product obtained by using them are very excellent. In the present invention, the content of hydrolyzable chlorine is determined by dissolving an epoxy resin in dioxane, adding an ethanol solution of 1N potassium hydroxide, and titrating chloride ion released when heated at reflux for 30 minutes with a silver nitrate solution. And a value represented by the weight percentage of chlorine atoms in the compound. When the content of the hydrolyzable chlorine exceeds 0.15%, the properties (especially, electrical properties) of the cured product are remarkably deteriorated, which may make the cured product unsuitable for use in electronic materials. Preferably, the content is 0.15% or less.

The reaction between the phenolic hydroxyl group and the alcoholic hydroxyl group of the compound represented by the general formula (2) or (3) and epichlorohydrin is performed by using dimethyl sulfoxide or a quaternary ammonium salt or 1,3-dimethyl-2.
-In the presence of imidazolidinone and alkali metal hydroxide,
It can be carried out by adjusting the amount of the alkali metal hydroxide used. At that time, alcohols, aromatic hydrocarbons, ketones, cyclic and ether compounds, etc. may be used in combination as a solvent. Further, dimethyl sulfoxide, quaternary ammonium salt, and 1,3-dimethyl-2-imidazolidinone may be used in combination.

The amount of dimethyl sulfoxide or 1,3-dimethyl-2-imidazolidinone used is represented by the general formula (2)
Or 5% by weight based on the compound represented by the general formula (3)
~ 300% by weight is preferred. When the content is 5% by weight or less based on the compound represented by the general formula (2) or (3), the reaction between the hydroxyl group of the compound represented by the general formula (2) or the general formula (3) and epichlorohydrin may occur. This is not preferable because it requires a long reaction time because it is slow. If the amount exceeds 300% by weight based on the compound represented by the general formula (2) or (3), the effect of increasing the amount is almost negligible, but the volumetric efficiency deteriorates, which is not preferable.

Examples of the quaternary ammonium salt include tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride and the like. The amount of the quaternary ammonium salt is the epoxy compound of the general formula (2) or (3). Hydroxyl group 1 to be converted
0.3 to 50 g is preferable to the equivalent weight. When the amount is less than 0.3 g per 1 equivalent of the hydroxyl group to be epoxidized, the reaction between the hydroxyl group of the compound represented by the general formula (2) or the general formula (3) and epichlorohydrin becomes slow, and a long-time reaction is required. Not preferred. If it exceeds 50 g with respect to 1 equivalent of the hydroxyl group to be epoxidized, the effect of increasing the amount is almost lost, but the cost increases, which is not preferable.

The amount of epichlorohydrin used may be at least one equivalent to one equivalent of the hydroxyl group to be epoxidized of the compound represented by the general formula (2) or (3). However, if it exceeds 15 equivalents with respect to 1 equivalent of the hydroxyl group to be epoxidized, the effect of increasing the amount is almost negligible, but the volumetric efficiency deteriorates, which is not preferable.

As the alkali metal hydroxide, caustic soda, caustic potash, lithium hydroxide, calcium hydroxide and the like can be used, but caustic soda is preferred. The amount of the alkali metal hydroxide used may be 1 to 1.3 times the equivalent of the hydroxyl group to be epoxidized of the compound represented by the general formula (2) or (3). The alkali metal hydroxide may be a solid or an aqueous solution. When an aqueous solution is used, the reaction can be carried out while distilling water out of the reaction system under normal pressure and reduced pressure during the reaction.

The reaction temperature is preferably from 30 to 100 ° C. When the reaction temperature is lower than 30 ° C., the reaction becomes slow and a long-time reaction is required. If the reaction temperature exceeds 100 ° C., many side reactions occur, which is not preferable. After completion of the reaction, excess epichlorohydrin and solvents are distilled and recovered under reduced pressure, and then the resin is dissolved in an organic solvent, and a dehydrohalogenation reaction can be performed with an alkali metal hydroxide. After the reaction,
After washing and separation to separate by-product salts and solvents, excess epichlorohydrin and solvents are distilled and recovered from the oil layer under reduced pressure, and then the resin is dissolved in an organic solvent and dehydrohalogenated with an alkali metal hydroxide. May be. As the organic solvent, methyl isobutyl ketone, benzene, toluene, xylene and the like can be used, but methyl isobutyl ketone is preferable. They can be used alone or in a mixed system.

The epoxy resin of the present invention can be cured alone or in combination with other epoxy resins by adding a curing agent and, if necessary, a curing accelerator as in the case of ordinary epoxy resins. The curing agent that can be used in the present invention is an amine compound, an acid anhydride compound, an amide compound, a phenol compound, or the like. Specific examples include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, a polyamide resin synthesized from a dimer of linolenic acid and ethylenediamine, phthalic anhydride, trimellitic anhydride, and pyromethylene anhydride. Mellitic acid, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phenol novolak, and modified products thereof, imidazole, BF ₃ -amine Complexes and guanidine derivatives. These curing agents may be used alone or in combination of two or more.

The amount of the curing agent used is preferably 0.7 to 1.2 equivalents to the epoxy group. If the amount is less than 0.7 equivalents or more than 1.2 equivalents with respect to the epoxy group, curing may be incomplete and good cured physical properties may not be obtained.

When the above-mentioned curing agent is used, a curing accelerator may be used in combination. Examples of the curing accelerator include imidazoles, tertiary amines, phenols, and metal compounds. Furthermore, various compounding agents such as inorganic or organic fillers can be added as needed. The amount of these curing accelerators used is 100
0.1 to 5.0 parts by weight based on parts by weight is preferred.

The epoxy resin composition of the present invention containing the epoxy resin of the present invention, a curing agent and, if necessary, a curing accelerator can be easily prepared by a method similar to a conventionally known method. Obtainable. For example, an epoxy resin of the present invention and a curing agent, a filler and other additives are mixed as necessary using an extruder, a kneader, a roll, or the like, as needed, to obtain an epoxy resin composition,
After melting the epoxy resin composition, it is molded using a casting or transfer molding machine or the like.
A cured product can be obtained by heating to ° C. Further, the resin composition of the present invention is dissolved in a solvent, glass fiber,
A prepreg obtained by impregnating a substrate such as carbon fiber, polyester fiber, polyamide fiber, alumina fiber or paper and drying by heating may be subjected to hot press molding to obtain a cured product.

[0085]

EXAMPLES Next, the present invention will be described in detail with reference to Examples and Comparative Examples. Hereinafter, all parts are by weight unless otherwise specified. The hydrolyzable chlorine content is determined by dissolving an epoxy resin in dioxane, adding an ethanol solution of 1N-potassium hydroxide, and heating the solution at reflux for 30 minutes to titrate chloride ions released by titration with a silver nitrate solution. , The weight of chlorine atoms in the compound expressed as a percentage by weight.

Examples 1-2 and Comparative Examples 1-2 In the bisphenol A type epoxy resin wherein R _1, R ₂ and R ₃ in the general formula (2) are the aforementioned formula (c-3), the general formula (2) Is 3.3, epoxy equivalent is 650, and hydrolyzable chlorine content is 0.039.
%, Softening point 81.1 ° C, melt viscosity (150 ° C) 12.5
Poise epoxy resin (epoxy resin (15)) 394
Parts (1 equivalent of an alcoholic hydroxyl group) were mixed with 925 parts (10 moles) of epichlorohydrin and 462 parts of dimethyl sulfoxide.
After dissolving in 5 parts, 98.5% NaO
13.3 parts (0.33 mol) of H were added over 100 minutes. After the addition, the reaction was further performed at 70 ° C. for 3 hours. After the completion of the reaction, 250 parts of water was added and washed. After oil-water separation, most of the dimethyl sulfoxide and excess unreacted epichlorohydrin were recovered by distillation under reduced pressure from the oil layer, and the reaction product containing the by-product salt and dimethyl sulfoxide was dissolved in 750 parts of methyl isobutyl ketone.
Then, the mixture was reacted at 70 ° C. for 1 hour. After completion of the reaction, add water 2
Washing was performed twice with 00 parts. After oil-water separation, methyl isobutyl ketone is distilled and recovered from the oil layer, and the epoxy equivalent is 44.
4. Hydrolyzable chlorine content 0.054%, softening point
350 parts of an epoxy resin (1) at 5 ° C. and a melt viscosity (150 ° C.) of 11.5 poise was obtained. When the obtained epoxy resin (1) is calculated from the epoxy equivalent, about 1.1 of the 3.3 alcoholic hydroxyl groups in the general formula (2) are epoxidized.

In the same manner, an epoxy equivalent of 379, a hydrolyzable chlorine content of 0.067%, and a softening point of 78.5% NaOH with 24.3 parts (0.60 mol) of NaOH were used.
365 parts of an epoxy resin (2) having 6.8 ° C. and a melt viscosity (150 ° C.) of 11.0 poise was obtained. When the obtained epoxy resin (2) is described in terms of epoxy equivalent, about 1.7 of 3.3 alcoholic hydroxyl groups in the general formula (2) are epoxidized.

On the other hand, for comparison, 98.5%
The amount of NaOH used was 60.9 parts (1.5 mol), and the epoxy equivalent was 280 and the hydrolyzable chlorine content was 0.070.
%, A softening point of 64.2 ° C and a melt viscosity (150 ° C) of 7.1 poise (370 parts) of an epoxy resin (27) were obtained. When the obtained epoxy resin (27) is calculated from the epoxy equivalent, the total amount of 3.3 alcoholic hydroxyl groups in the general formula (2) is epoxidized.

The obtained epoxy resins (1) to
(2) For comparison, epoxy resins (15) and (2)
7) Kayahard MCD (Nippon Kayaku Co., Ltd.)
, Methylendmethylenetetrahydrophthalic anhydride), 2E4MZ (2-ethyl-4-
Using methylimidazole), the composition shown in Table 1 (numerical values indicate parts by weight) is such that the number of acid anhydride groups is 0.9 per epoxy group of the epoxy resin. 2 hours at 120 ° C., then 2 hours at 120 ° C., then 20
Hardened at 0 ° C for 5 hours to obtain test specimens, JIS
The heat deformation temperature, bending strength, breaking energy, and water absorption were measured according to K-6911. Table 1 shows the results.

[0090] * Fracture energy is obtained by calculating the chart area up to the fracture in the stress-strain curve in the bending test and expressing the area per fracture area.

Example 3, Comparative Examples 3 and 4 Instead of the epoxy resin (15), R _1, R ₂ and R ₃ in the general formula (2) are the same as those of the formulas (c-3) and (c).
-4), wherein the average m + n in the general formula (2) is 2.5, the epoxy equivalent is 725, the hydrolyzable chlorine content is 0.106%, the softening point is 86.1 ° C., and the melt viscosity (1
Using 580 parts (1 equivalent of an alcoholic hydroxyl group) of an epoxy resin (16) having 13.5 poises and a bromine content of 27.7%, 13.3 parts of 98.5% NaOH was used.
An epoxy equivalent of 474 and a hydrolyzable chlorine content of 0.0 were prepared in the same manner as in Example 2 except that 3 parts (0.5 mol) were used.
52%, softening point 80.0 ° C, melt viscosity (150 ° C) 1
562 parts of an epoxy resin (3) having 2.1 poise and a bromine content of 26.5% were obtained. When the obtained epoxy resin (3) is calculated from the epoxy equivalent, 1.2 out of 2.5 alcoholic hydroxyl groups in the general formula (2) are epoxidized.

On the other hand, for comparison, 98.5%
The amount of NaOH used was changed to 60.9 parts (1.5 mol), and the epoxy equivalent was 353 and the hydrolyzable chlorine content was 0.052.
%, Softening point 75.2 ° C, melt viscosity (150 ° C) 10.1
Poise, epoxy resin with bromine content of 25.2% (28)
565 g were obtained. When the obtained epoxy resin (28) is calculated from the epoxy equivalent, the total amount of 2.5 alcoholic hydroxyl groups in the general formula (2) is epoxidized.

The obtained epoxy resin (3) and, for comparison, epoxy resins (16) and (28) were dissolved in methyl ethyl ketone to prepare a solution having a resin concentration of 80% by weight. These epoxy resin solutions were blended with dicyandiamide as a curing agent, 2MZ (2-methylimidazole) as a curing accelerator, methyl cellosolve and dimethylformamide as a solvent in the composition shown in Table 2 (numerical values indicate parts by weight) to form a varnish. An epoxy resin composition was prepared. This composition was mixed with a glass cloth (WE-1 manufactured by Nitto Boseki Co., Ltd.).
8K-BZ2) and heated at 110 ° C. for 30 minutes to obtain B
A staged prepreg was obtained, and this prepreg was 9
A glass cloth laminate having a thickness of 1.5 mm is formed under ply stacking, 170 ° C., 40 kgf / cm ² , and molding conditions for 45 minutes, and has a glass transition temperature, anti-mesling properties, and copper foil in accordance with JISC-6481. The peel strength was measured. Table 2 shows the results.

[0094] * Abnormal appearance after boiling for 1 hour and immersion in 260 ° C solder for 20 seconds

Examples 4 to 5, Comparative Examples 5 to 8 Instead of the epoxy resin (15), R _1, R ₂ and R ₃ in the general formula (2) are the above formulas (c-3), and the average m + n is 5.2, epoxy equivalent 910, softening point 100.
Bisphenol A type epoxy resin (17) 350 at 5 ° C
Part (1 equivalent of an alcoholic hydroxyl group), and 98.5%
340 parts of an epoxy resin (4) having an epoxy equivalent of 625 and a softening point of 95.1 ° C was obtained in the same manner as in Example 1 except that 13.3 parts of NaOH was changed to 8.6 parts (0.21 mol). When the obtained epoxy resin (4) is calculated from the epoxy equivalent, about 1.0 of 5.2 alcoholic hydroxyl groups in the general formula (2) are epoxidized. In the same manner, the amount of 98.5% NaOH used was changed to 25.7 parts (0.63%).
Mol), to obtain 350 parts of an epoxy resin (5) having an epoxy equivalent of 429, a hydrolyzable chlorine content of 0.037%, and a softening point of 90.1 ° C. When the obtained epoxy resin (5) is calculated from the epoxy equivalent, about 2.6 of the 5.2 alcoholic hydroxyl groups in the general formula (2) are epoxidized.

On the other hand, for comparison, 98.5%
The amount of NaOH used was 60.9 parts (1.5 mol), and the epoxy equivalent was 293 and the hydrolyzable chlorine content was 0.076.
%, And 350 parts of an epoxy resin (29) having a softening point of 81.3 ° C. were obtained. When the obtained epoxy resin (29) is calculated from the epoxy equivalent, the total amount of 5.2 alcoholic hydroxyl groups in the general formula (2) is epoxidized.

The obtained epoxy resins (4) to
(5) For comparison, epoxy resins (17) and (2)
9), phenol novolak (softening point 80
° C), and using TPP (triphenylphosphine) as a curing accelerator, so that the number of hydroxyl groups of phenol novolak is 1.0 per epoxy group of epoxy resin.
At a temperature of 70 ° C.
At 150 ° C. for 180 seconds, and then transfer molding at 160 ° C. for 2 hours.
Test specimens were prepared by post-curing at 80 ° C for 8 hours.
The heat deformation temperature, bending strength, breaking energy, and water absorption were measured in accordance with K-6911. Table 3 shows the results.

Example 6, Comparative Examples 7 and 8 Instead of the epoxy weight (15), R _1, R ₂ and R ₃ in the general formula (2) are the above formulas (c-4), and the general formula (2) Is 2.3, epoxy equivalent is 1018, softening point is 132.6 ° C., and bromine content is 51.9%.
885 parts (1 equivalent of alcoholic hydroxyl group) of epoxy resin (18) was used, and 13.3 parts of 98.5% NaOH was added to 2 parts.
An epoxy equivalent of 657 and a hydrolyzable chlorine content of 0.2 were obtained in the same manner as in Example 1 except that 2.3 parts (0.55 mol) were used.
070%, softening point 125.3 ° C, bromine content 50.2%
870 parts of epoxy resin (6) was obtained. When the obtained epoxy resin (6) was calculated from the epoxy equivalent, 1.2 of 2.3 alcoholic hydroxyl groups in the general formula (2) were obtained.
The pieces are epoxidized.

On the other hand, for comparison, 98.5%
Epoxy equivalent of 503 and hydrolyzable chlorine content of 0.061 using 60.9 parts (1.5 mol) of NaOH.
%, A softening point of 110.7 ° C. and a bromine content of 48.8%, giving 872 parts of an epoxy resin (30). When the obtained epoxy resin (30) is calculated from the epoxy equivalent, the general formula (2)
The total amount of 2.3 alcoholic hydroxyl groups in is epoxidized.

The obtained epoxy resin (6) and, for comparison, epoxy resins (18) and (30) were cured in the same manner as in Example 4, and the physical properties of the cured product were measured. Table 3 shows the results.

[0101]

[0102]

Example 7, Comparative Examples 9 to 10 In the general formula (2), R _1, R ₂ and R ₃ are the above formulas (a-1), and the average m + n in the general formula (2)
2.1, epoxy equivalent 284, hydrolyzable chlorine content 0.129%, softening point 56.0 ° C, melt viscosity (150
℃) 1.9 parts of 1.9 poise epoxy resin (19) (1 equivalent of alcoholic hydroxyl group) was added to epichlorohydrin 925.
(10 mol), 5 parts of tetramethylammonium chloride was added at 70 ° C. with stirring, and then 9 parts
26.4 parts (0.65 mol) of 8.5% NaOH
Added over minutes. After the addition, the reaction was further performed at 70 ° C. for 3 hours. After the completion of the reaction, 250 parts of water was added and washed. After oil-water separation, excess unreacted epichlorohydrin was recovered by distillation from the oil layer, and the reaction product was treated with methyl isobutyl ketone 75
0%, and 10 parts of 30% NaOH (0.0 part).
75 mol) and reacted at 70 ° C. for 1 hour. After the completion of the reaction, the resultant was washed twice with 200 parts of water. After oil-water separation, methyl isobutyl ketone was distilled and recovered from the oil layer to obtain 250 parts of a semi-solid epoxy resin (7) having an epoxy equivalent of 206, a melt viscosity (150 ° C.) of 1.8 poise and a semi-solid. When the obtained epoxy resin (7) is calculated from the epoxy equivalent, about 1.1 of the 2.1 alcoholic hydroxyl groups in the general formula (2) is obtained.
One is epoxidized.

On the other hand, for comparison, an epoxy equivalent of 167, a hydrolyzable chlorine content of 0.024%, and a melt viscosity (150 ° C.) of 60.9 parts (1.5 mol) of NaOH were used in the same manner. This gave 255 parts of a 1.7 poise, semi-solid epoxy resin (31). In the obtained epoxy resin, the total amount of 2.1 alcoholic hydroxyl groups in the general formula (2) is epoxidized.

The obtained epoxy resin (7) and, for comparison, epoxy resins (19) and (31) were blended in the same manner as in Example 1 with the composition shown in Table 4 (the numerical values indicate parts by weight). A resin composition was obtained, cured in the same manner as in Example 1, and the physical properties of the cured product were measured. Table 4 shows the results
Shown in

[0106]

Example 8, Comparative Examples 11 to 12 Instead of the epoxy resin (19), R _1, R ₂ and R ₃ in the general formula (2) are the above formulas (c-5), and the average m + n is 2 6, epoxy equivalent 496, hydrolyzable chlorine content 0.104%, softening point 65 ° C, melt viscosity (15
0 ° C.) Except that 382 parts of 2.2 poise epoxy resin (20) (1 equivalent of alcoholic hydroxyl group) was used, the same procedure as in Example 7 was carried out, and the epoxy equivalent was 320, the hydrolyzable chlorine content was 0.069%, and Point 60 ° C, melt viscosity (150
C) 380 parts of a 2.0 poise epoxy resin (8). The obtained epoxy resin (8), when calculated from the epoxy equivalent, has an alcoholic hydroxyl group of 1. in general formula (2).
About 1.3 of the six are epoxidized.

On the other hand, for comparison, 98.5%
The amount of NaOH used was 60.9 parts (1.5 mol), and the epoxy equivalent was 247 and the hydrolyzable chlorine content was 0.035.
%, A softening point of 55.0 ° C., and a melt viscosity (150 ° C.) of 1.8 poise, giving 385 parts of an epoxy resin (32). When the obtained epoxy resin (32) is calculated from the epoxy equivalent, the total amount of 2.6 alcoholic hydroxyl groups in the general formula (2) is epoxidized.

The obtained epoxy resin (8) and, for comparison, epoxy resins (20) and (32) were mixed in the same manner as in Example 1 with the composition shown in Table 5 (numerical values indicate parts by weight). A resin composition was obtained, cured in the same manner as in Example 1, and the physical properties of the cured product were measured. Table 5 shows the results
Shown in

Example 9, Comparative Examples 13 and 14 Instead of the epoxy resin (19), R _1, R ₂ and R ₃ in the general formula (2) are (c-19), and the average m + n is 2. 1, epoxy equivalent (636), hydrolyzable chlorine content 0.085%, softening point 91.0 ° C, melt viscosity (150 ° C) 6.2 poise epoxy resin (21) 60
Epoxy equivalent 436, hydrolyzable chlorine content 0.070%, softening point 80.5 ° C, melt viscosity (150 ° C) in the same manner as in Example 7, except that 6 parts (1 equivalent of alcoholic hydroxyl group) are used. 4.8 poise epoxy resin (9) 595
Got a part. When the obtained epoxy resin (9) is calculated from the epoxy equivalent, about 1.1 of the 2.1 alcoholic hydroxyl groups in the general formula (2) are epoxidized.

On the other hand, for comparison, 98.5%
The amount of NaOH used was changed to 60.9 parts (1.5 mol), and the epoxy equivalent was 339 and the hydrolyzable chlorine content was 0.092.
%, A softening point of 75.1 ° C. and a melt viscosity (150 ° C.) of 4.0 poise, giving 600 parts of an epoxy resin (33). When the obtained epoxy resin (33) is calculated from the epoxy equivalent, the total of 2.1 alcoholic hydroxyl groups in the general formula (2) has been epoxidized.

The obtained epoxy resin (9) and, for comparison, epoxy resins (21) and (33) were mixed in the same manner as in Example 1 with the composition shown in Table 5 (numerical values indicate parts by weight). A composition was obtained and cured in the same manner as in Example 1, and the physical properties of the cured product were measured. Table 5 shows the results.

[0113]

[0114]

Example 10, Comparative Examples 15 to 16 Instead of the epoxy resin (19), R _1, R ₂ and R ₃ in the general formula (2) are the above formulas (c-20), and the average m + n is 2 9.9, epoxy equivalent 531, hydrolyzable chlorine content 0.105%, softening point 161 ° C. Epoxy resin (22) 366 parts (1 equivalent of alcoholic hydroxyl group) was used in the same manner as in Example 7, Epoxy equivalent 32
7. Hydrolyzable chlorine content 0.065%, softening point 65.
370 parts of an epoxy resin (10) having 0 ° C. and a melt viscosity (150 ° C.) of 7.8 poise were obtained. The obtained epoxy resin (1
When 0) is calculated from the epoxy equivalent, about 1.5 out of 2.9 alcoholic hydroxyl groups in the general formula (2) are epoxidized.

On the other hand, for comparison, 98.5%
The amount of NaOH used was 60.9 parts (1.5 mol),
Epoxy equivalent 250, hydrolyzable chlorine content 0.085
%, A melt viscosity (150 ° C.) of 6.8 poise, and 365 parts of a semi-solid epoxy resin (34) were obtained. When the obtained epoxy resin (34) is calculated from the epoxy equivalent, the general formula (2)
Are epoxidized in 2.9 total alcoholic hydroxyl groups.

The obtained epoxy resin (10) and, for comparison, epoxy resins (22) and (34) were mixed in the same manner as in Example 1 with the composition shown in Table 6 (the numerical values indicate parts by weight). A resin composition was obtained, cured in the same manner as in Example 1, and the physical properties of the cured product were measured. Table 6 shows the results.

Example 11, Comparative Examples 17 to 18 Instead of the epoxy resin (19), R _1, R ₂ and R ₃ in the general formula (2) are the above formulas (c-13), and the average m + n is 2 Epoxy resin (23) 42 having an epoxy equivalent of 466, a hydrolyzable chlorine content of 0.090%, a softening point of 55.0 ° C. and a melt viscosity (150 ° C.) of 3.8 poise
Epoxy equivalent 321, hydrolyzable chlorine content 0.053%, melt viscosity (150 ° C.) 3.3 except that 4 parts (1 equivalent of alcoholic hydroxyl group) were used.
380 parts of a poise and semi-solid epoxy resin (11) were obtained. When the obtained epoxy resin (11) is calculated from the epoxy equivalent, about 1.1 of 2.2 alcoholic hydroxyl groups in the general formula (2) are epoxidized.

On the other hand, for comparison, 98.5%
The amount of NaOH used was 60.9 parts (1.5 mol),
Epoxy equivalent 251, Hydrolyzable chlorine content 0.055
%, A melt viscosity (150 ° C.) of 3.0 poise, and 380 parts of a semi-solid epoxy resin (35) were obtained. When the obtained epoxy resin (35) is calculated from the epoxy equivalent, the general formula (2)
The total amount of 2.2 alcoholic hydroxyl groups in is epoxidized.

The obtained epoxy resin (11) and, for comparison, epoxy resins (23) and (35) were blended in the same manner as in Example 1 with the composition shown in Table 6 (numerical values indicate parts by weight). A resin composition was obtained, cured in the same manner as in Example 1, and the physical properties of the cured product were measured. Table 6 shows the results.

[0121]

[0122]

Example 12, Comparative Rows 19 to 20 Instead of the epoxy resin (19), R _1, R ₂ and R ₃ in the general formula (2) are the above formulas (d-1), and the average m + n is 2 Epoxy resin (24) 33 having an epoxy equivalent of 384, a hydrolyzable chlorine content of 0.093%, a softening point of 76.0 ° C, and a melt viscosity (150 ° C) of 6.5 poise.
Epoxy equivalent 261, hydrolyzable chlorine content 0.085%, softening point 71.0 ° C, melt viscosity (150 ° C) in the same manner as in Example 7 except that 4 parts (1 equivalent of alcoholic hydroxyl group) are used. 5.8 poise epoxy resin (12) 30
5 parts were obtained. When the obtained epoxy resin (12) is calculated from the epoxy equivalent, about 1.2 of the 2.3 alcoholic hydroxyl groups in the general formula (2) are epoxidized.

On the other hand, for comparison, 98.5%
The amount of NaOH used was 60.9 parts (1.5 mol),
Epoxy equivalent 209, hydrolyzable chlorine content 0.082
%, A softening point of 65.0 ° C., and a melt viscosity (150 ° C.) of 5.0 poise (320 parts) were obtained. When the obtained epoxy resin (36) is calculated from the epoxy equivalent, the total amount of 2.3 alcoholic hydroxyl groups in the general formula (2) is epoxidized. The obtained epoxy resin (12) and epoxy resins (24) and (3)
6) was blended with the composition shown in Table 7 in the same manner as in Example 1 to obtain an epoxy resin composition, and cured in the same manner as in Example 1 to measure the physical properties of the cured product. Table 7 shows the results.

[0125]

Example 13, Comparative Examples 21 to 224 242 parts (1 mol) of 4,4'-bishydroxy-3,3 ', 5,5'-tetramethylbiphenyl were mixed with 61 parts (0.066 mol) of epichlorohydrin. After dissolving in 370 parts of dimethylsulfoxide, 98.5% at 70 ° C. under stirring.
29.5 parts (0.73 mol) of NaOH were added over 30 minutes. After the addition, the reaction was carried out at 70 ° C. for 1 hour and further at 90 ° C. for 5 hours. After completion of the reaction, methyl isobutyl ketone 800
Was washed with water. After oil-water separation, methyl isobutyl ketone and dimethyl sulfoxide were distilled and recovered from the oil layer under reduced pressure to obtain R ₁ in the general formula (3).
And R ₂ and R ₃ are the formula (b-2), and the average m
278 parts of compound (1) having + n of 2.2 was obtained. 224 parts of the obtained compound (1) (phenolic hydroxyl group 0.5
Equivalent, alcoholic hydroxyl group 0.55 equivalent)
An epoxy equivalent of 350, a hydrolyzable chlorine content of 0.101%, and a softening point of 8 were obtained in the same manner as in Example 7 except that 24.9 parts of 8.5% NaOH was changed to 34.9 parts (0.86 mol).
250 parts of an epoxy resin (13) having 9.1 ° C. and a melt viscosity (150 ° C.) of 72 poise was obtained. When the obtained epoxy resin (13) is calculated from the epoxy equivalent, about 1.1 of the two phenolic hydroxyl groups and 2.2 of the alcoholic hydroxyl groups in the general formula (3) are epoxidized.

On the other hand, for comparison, 98.5%
20.3 parts (0.5 mol) of NaOH was used,
Epoxy equivalent 512, hydrolyzable chlorine content 0.098
%, Epoxy resin (25) 245 having a softening point of 137.7 ° C.
Got a part. In the obtained epoxy resin (25), only the phenolic hydroxyl group in the general formula (3) is epoxidized. In the same manner, the amount of 98.5% NaOH was changed to 54.0 parts (1.33 mol), the epoxy equivalent was 273, the hydrolyzable chlorine content was 0.095%, and the softening point was 8
452 parts of an epoxy resin (37) having 0.1 ° C. and a melt viscosity (150 ° C.) of 6.8 poise were obtained. When the obtained epoxy resin (37) is calculated from the epoxy equivalent, the total amount of two phenolic hydroxyl groups and 2.2 alcoholic hydroxyl groups in the general formula (3) is epoxidized.

The obtained epoxy resin (13) and, for comparison, epoxy resins (25) and (37) were blended in the same manner as in Example 1 with the composition shown in Table 8 (the numerical values indicate parts by weight). A resin composition was obtained, cured in the same manner as in Example 1, and the physical properties of the cured product were measured. Table 8 shows the results.

[0129]

Example 14, Comparative Examples 23 to 24 Instead of the epoxy resin (19), R _1, R ₂ and R ₃ in the general formula (2) are the above formulas (e-1), and the average m + n is 2 1. Epoxy equivalent 658, hydrolyzable chlorine content 0.099%, 627 parts of epoxy resin (26) having a softening point of 165 ° C. (1 equivalent of alcoholic hydroxyl group), and instead of 5 parts of tetramethylalmonium chloride 1,3-dimethyl-2-imidazolidinone 462.5
630 parts of an epoxy resin (14) having an epoxy equivalent of 444, a hydrolyzable chlorine content of 0.109%, and a softening point of 151.2 ° C. was obtained in the same manner as in Example 7 except for using parts.
When the obtained epoxy resin (14) was calculated from the epoxy equivalent, the alcoholic hydroxyl group 2.1 in the general formula (2) was obtained.
About 1.1 of them are epoxidized.

On the other hand, for comparison, 98.5%
The amount of NaOH used was 60.9 parts (1.5 mol),
Epoxy equivalent 349, hydrolyzable chlorine content 0.093
%, Epoxy resin (38) 635 having a softening point of 148.0 ° C.
Got a part. When the obtained epoxy resin (38) is calculated from the epoxy equivalent, the total amount of 2.1 alcoholic hydroxyl groups in the general formula (2) is epoxidized.

The obtained epoxy resin (14) and, for comparison, epoxy resins (26) and (38) were blended in the same manner as in Example 1 with the composition shown in Table 9 (the numerical values indicate parts by weight). A resin composition was obtained, cured in the same manner as in Example 1, and the physical properties of the cured product were measured. Table 9 shows the results.

[0133]

Example 15 222 parts (1 mol) of resorcinol diglycidyl ether and 550 parts (5 mol) of resorcinol were dissolved in 780 parts of methyl isobutyl ketone, and the mixture was stirred at 70 ° C. and 30% N 2.
13.4 parts (0.1 mol) of aOH were added. After the addition,
The reaction was performed at 70 ° C. for 1 hour and further at 85 ° C. for 8 hours.
After the completion of the reaction, the resultant was washed twice with 400 parts of water. After oil-water separation, methyl isobutyl ketone and resorcinol are distilled and recovered from the oil layer, and R _1, R ₂ and R ₃ in the general formula (3) are the above-mentioned formulas (a-1), and the average m + n is 2.6.
444 parts of compound (2) was obtained. 135 parts of the obtained compound (2) (0.5 equivalent of phenolic hydroxyl group, 0.65 equivalent of alcoholic hydroxyl group) was added to epichlorohydrin 9
25 parts (10 moles) and dimethyl sulfoxide 462.5
And 98.5% NaOH at 70 ° C. with stirring.
36.5 parts (0.9 mol) were added over 70 minutes. After the addition, the reaction was further performed at 70 ° C. for 3 hours. Next, most of the dimethyl sulfoxide and excess unreacted epichlorohydrin were distilled and recovered under reduced pressure, and the reaction product containing the by-product salt and dimethyl sulfoxide was purified with methyl isobutyl ketone 75%.
0%, and then 10 parts of 30% NaOH (0.1 part).
0 mol) and reacted at 70 ° C. for 1 hour. After the completion of the reaction, the resultant was washed twice with 200 parts of water. After oil-water separation, methyl isobutyl ketone was distilled and recovered from the oil layer to obtain 185 parts of an epoxy resin (39) having an epoxy equivalent of 211 and a hydrolyzable chlorine content of 0.095%. When the obtained epoxy resin (39) is calculated from the epoxy equivalent, the general formula (3)
About 1.5 out of 2 phenolic hydroxyl groups and 2.6 alcoholic hydroxyl groups in the above are epoxidized. The epoxy resin (39) was subjected to liquid chromatography to fractionate each component, and after concentration, subjected to NMR and mass spectrometry to confirm the structure. The epoxy resin (39) contains 52.3% of the epoxy resin of the present invention. Table 10 shows the results.

[0135]

The epoxy resin of the present invention is compared with the epoxy resin represented by the general formula (2) and the epoxy resin represented by the general formula (2) in which all of the alcoholic hydroxyl groups are epoxidized. As is clearer, the laminates obtained using them are heat-resistant,
Has excellent adhesive properties. Also, as is clear from Table 1 and Tables 3 to 9, it does not become brittle like a cured product obtained by using an epoxy resin which is entirely epoxidized,
It has excellent properties of heat resistance, toughness and water resistance.

[0137]

The epoxy resin of the present invention can give a cured product having excellent properties of heat resistance, toughness, adhesiveness and water resistance, and can be used as a molding material, a casting material, a laminating material, a paint, and an adhesive. It is extremely useful for a wide range of applications such as agents and resists.

Claims (5)

(57) [Claims] 1. A compound of the general formula (1) Embedded image Embedded image Embedded image Embedded image Embedded image A is alkylene; cycloalkylene; halogen; alkylene substituted with cycloalkyl or aryl; Or And X _{1 to} X ₄₂ are each independently a hydrogen atom, an alkyl group or a halogen. M and n are integers of 1 or more. Further, And And are arranged in any order. Also, m / (m + n)
= 0.10 to 0.80. Epoxy resin represented by). 2. The epoxy resin according to claim 1, wherein the content of hydrolyzed chlorine is 0.15% or less. 3. An epoxy resin composition comprising an epoxy resin, a curing agent and, if necessary, a curing accelerator, wherein the epoxy resin according to claim 1 or 2 is contained as the epoxy resin component. Epoxy resin composition. 4. The epoxy resin composition according to claim 3,
A method for producing a cured product, wherein the cured product is heated to 0 to 200 ° C. 5. An epoxy resin composition for a laminate comprising the epoxy resin composition according to claim 3.