JPS60161973A - Preparation of novel epoxy resin - Google Patents

Abstract

NEW MATERIAL:An epoxy compound expressed by formula I {R1 is organic compound residue having l active H atoms; n1, n2...nl are integers 0-100, and the sum thereof is 1-100; l is an integer 1-100; B is expressed by formula II[X is expressed by formula III, IV or V (R2 is H, alkyl, alkylcarbonyl or arylcarbonyl)], and contains one or more groups expressed by formula III in the resin expressed by formula I }. EXAMPLE:The compound expressed by formula VI (n is 2 on the average). USE:An alicyclic epoxy resin compound, having rapidly curable terminal epoxy groups and improved heat resistance and electrical characteristics without containing chlorine, and applicable to preparation of large-scale integrated circuits (LSI) sealing materials, sealants for light emitting diodes (LED) and semiconductors and coating materials, etc. PREPARATION:An unsaturated compound expressed by formula VII (A is cyclohexane skeleton having vinyl group of formula VIII) is reacted with an epoxidizing agent, e.g. peracetic acid, if necessary in a solvent at -70-+200 deg.C to give the aimed compound expressed by formula I .

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a novel alicyclic epoxy resin having excellent heat resistance, water resistance, and weather resistance.

The epoxy resin currently widely used in industry is the shrimp-bis type epoxy resin, which is produced by the reaction of bisphenol A and epichlorohydrin. This resin can be used in a wide range of products ranging from liquids to solids, and has the advantage that the epoxy group has high reactivity and can be cured with polyamines at room temperature. However, although the cured product has excellent water resistance and is strong, it has drawbacks such as poor weather resistance, poor electrical properties such as tracking resistance, and low heat distortion temperature. In particular, recently, epoxy resins made by reacting phenol or novolak resin with epichlorohydrin have been used as sealing resins for VLSIs, etc., but the resin contains several 1,100 pp of chlorine, which deteriorates the electrical characteristics of electronic components. Problems such as this are occurring.

Alicyclic epoxy resins are examples of epoxy resins that do not contain chlorine and have excellent electrical properties and heat resistance. These are produced by epoxidation reaction of compounds having a 5-membered or 6-membered cycloalkenyl skeleton. The epoxy groups of these resins are so-called internal epoxy groups, and are usually cured by heating with acid anhydrides, but their reactivity is low.
Cannot be cured at room temperature with polyamine.

Therefore, the range of use of alicyclic epoxy resins is extremely narrow.

As alicyclic epoxy resins, those having the structures (m) and (EV) are industrially produced and used.

1 (m) is used as a heat-resistant epoxy diluent because of its very low viscosity, but it is highly toxic, and 2 it can cause damage to the skin of workers.
Skin: There are problems such as severe skin irritation and rash.

Although (IV) contains few impurities and has a low hue, and its cured product has a high heat distortion temperature, it suffers from poor water resistance due to ester bonds.

Furthermore, since both (III) and (IV) are low-viscosity liquid epoxy resins, solid epoxy resin molding systems such as transfer molding cannot be applied.

In view of this point, the present inventors have conducted unique research and found that when a polyether compound having a vinylcyclohexane skeleton is reacted with an epoxidizing agent, a fast-curing terminal epoxy group can be formed even though it has an alicyclic skeleton. Mochi, chlorine-free,
The inventors have discovered that it is possible to produce an epoxy resin with excellent heat resistance and electrical properties, leading to the present invention.

Specifically, the present invention relates to a method for producing an epoxy resin represented by the general formula (II), which comprises reacting an unsaturated compound represented by the general formula (I) with an epoxidizing agent.

However, R, ti is an organic compound residue having J active hydrogens.

”l * ”l * ”'”' nJ is 0 or l-1
It is an integer of 00 and the sum is 1 to 100.

l is an integer of l-100.

A is a cyclohexane skeleton having a vinyl group, and R
, is an organic compound residue having four active hydrogens.

"+ +"t #......nJ is 0 or 1~Zo
o is an integer whose sum is 1-Zoo.

l is an integer from 1 to 100.

B is a cyclohexane skeleton having a substituent, and is represented by the following formula.

Contains one or more.

In the production of the novel epoxy resin of the formula (n) of the present invention, Ro in the formula (ff) is an organic residue having active hydrogen. .

Examples include phenols, carboxylic acids, amines, and thiols.

The alcohol may be a monohydric alcohol or a polyhydric alcohol.

Examples, t hametanol, ethanol, zolopanol.

Aliphatic alcohols such as butanol, pentanol, hexanol, octatool, etc., aromatic alcohols such as benzyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, fluoropylene glycol, dipropylene glycol, 1.3゛Butanediol, 1,4-butanediol, bentanediol, 1.6-hexanediol, neopentyl glycol, neobentylgutcol ester of oxypivalic acid. Examples include cyclohexane dimetatool, glycerin, diglycerin, polyglycerin, trimethylolpropane, trimethylolethane, pentaerythritol, dipentaerythritol, and the like.

Phenols include phenol, cresol, catechol, pyrogallol, and hydroquinone.

Hydroquinone monomethyl ether, bisphenol A
, bisphenol F, 4.4'-dihydroxybenzophenone, bisphenol S, phenol resin, cresol novolak resin, etc.

Carboxylic acids include formic acid, acetic acid, zolobionic acid, butyric acid, fatty acids from animal and vegetable oils, fumaric acid, maleic acid, adipic acid, dodecanoic acid, trimellitic acid, pyromellitic acid,
Examples include polyacrylic acid, phthalic acid, inphthalic acid, and terephthalic acid. Also included are compounds having both a hydroxyl group and a carboxylic acid, such as lactic acid, citric acid, and oxycaproic acid.

Amines include methylamine and ethylamine.

Propylamine, butylamine, pentylamine.

Examples include hexylamine, cyclohexylamine, octylamine, dodecylamine, 4,4'-diaminodiphenylmethane, inphoronediamine, toluenediamine, hexamethylenediamine, xylenediamine, diethylenetriamine, triethylenetetramine, ethanol, and amines.

Examples of thiols include mercapto compounds such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, and phenyl mercaptan, mercaptopropionic acid or polyhydric alcohols of mercaptopropionic acid,
Examples include ethylene glycol dimercabutopropionic acid ester, trimethylolpropane trimercabutopropionic acid ester, pentaerythritol benthamercaptopropionic acid ester, and the like.

In addition, other active hydrogen-containing compounds include polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, cellulose, cellulose acetate, cellulose acetate butyrate, hydroxyethyl cellulose, acrylic polyol resin, styrene allyl alcohol copolymer resin, styrene-arein. Acid copolymer resin, alkyd resin.

Polyester polyol resin, polyester carboxylic acid resin, poly-licapro, urinated polyol resin,
Examples include polypropylene polyol, polyetramethylene glycol, etc.

In addition, compounds with active hydrogen have unsaturated 2 atoms in their skeleton.
It may have a double bond, and specific examples include allyl alcohol, acrylic acid, methacrylic acid, 3-cyclohexenemethanol, and tetrahydrophthalic acid.

In this case, in the general formula (IF) of the epoxy resin, all or some of the unsaturated double bonds are epoxidized.

n in general formula (n), , n2. . . . n7 is 0 or an integer from 1 to 100, and the sum thereof is from 1 to 100, but if it is 3100 or more, the resin will have a high melting point and will be difficult to handle, and will not be usable in practice.

l is an integer from 1 to 100t.

Among the substituents X of B in formula (I[), in other words, in the present invention, the substituent A polyether resin obtained by ring-opening polymerization of 4-vinylcyclohexene-1-oxide, that is, a polycyclohexene oxide polymer having a vinyl group side chain, is epoxidized with an oxidizing agent such as a peracid, that is, an epoxidizing agent. This can be done by

4-vinylcyclohexene-1-oxide is obtained by partially epoxidizing vinylcyclohexene obtained by a dimerization reaction of butadiene with peracetic acid.

It is preferable to use a catalyst when polymerizing 4-vinylcyclohexene-1-oxide in the presence of active hydrogen.

Examples of catalysts include amines such as methylamine, ethylamine, propylamine and bibenzine, organic bases such as pyridines and imidazoles, and formic acid.

Organic acids such as acetic acid and propionic acid, inorganic acids such as sulfuric acid and hydrochloric acid, alkali metal alcolades such as sodium methylate, alkalis such as KOH and NaOH, BF3
．． Examples include Lewis acids such as ZnC4 and AlCll5*5nC14 or their complexes, and organometallic compounds such as triethylaluminum and diethylzinc.

These catalysts are used in an amount of 0.01 to 10%, preferably 0.1 to 5%, based on the reactants. The reaction temperature is -70 to 200°C, preferably -30°C to 100°C.
It is ℃.

The reaction can also be carried out using a solvent. A solvent containing active hydrogen cannot be used.

In other words, ketones such as acetone, methyl ethyl ketone, and methyl imbutyl ketone, benzene, toluene,
Aromatic solvents such as xylene and other ethers2. Aliphatic hydrocarbons, esters, etc. can be used.

Now, in the present invention, the polycyclohexene oxide polymer having a vinyl group side chain synthesized in this way is epoxidized with an epoxidizing agent to obtain the formula (
The method is characterized by producing the novel epoxy resin of n).

As the epoxidizing agent, either peracids or hydroperoxides can be used.

Peracids include performic acid, peracetic acid, and perbenzoic acid.

Trifluoroperacetic acid and the like can be used.

Among these, peracetic acid is a particularly preferred epoxidizing agent because it is industrially available at low cost and has high stability.

Hydrogen peroxide is a hydroperoxide.

Tertiary butyl hydroperoxide, rimer oxide, etc. can be used.

A catalyst can be used during epoxidation if necessary. For example, in the case of a peracid, an alkali such as soda carbonate or an acid such as sulfuric acid may be used as a catalyst. In the case of hydroperoxides, the catalytic effect is obtained by using a mixture of tungstic acid and caustic nose with hydrogen peroxide, or an organic acid with hydrogen peroxide, or molybdenum hexacarbonyl with ternarybutylhydroborohonside. be able to.

The epoxidation reaction is carried out by adjusting the presence or absence of a solvent and the reaction temperature depending on the equipment and physical properties of the raw materials.

The usable reaction temperature range is determined by the reactivity of the epoxidizing agent used.

Regarding peracetic acid, which is the preferred epoxidizing agent, 0
~70°C is preferred. The reaction is slow below 0°C, and at 70°C
Above this level, peracetic acid decomposes.

In addition, in the case of turnyabutyl hydroperoxide/molybdenum dioxide diacetylacetonate, which is an example of hydroperoxide, for the same reason, 20 to 150
°C is preferred.

The solvent can be used for purposes such as lowering the viscosity of the raw material and stabilizing the epoxidizing agent by diluting it.

In the case of excessive vinegar use, aromatic compounds, ether compounds, ester compounds, ketone compounds, etc. can be used as the solvent.

The molar ratio of the epoxidizing agent to the unsaturated bonds can be changed depending on the purpose, such as how many unsaturated bonds are desired to remain. When the objective is to obtain a compound with a large number of epoxy groups, it is preferable to add the epoxidizing agent in an amount equal to or more than the same mole relative to the unsaturated groups.

However, it is usually disadvantageous to exceed 2 times the molar amount due to economic considerations and the problem of side reactions described below, and in the case of peracetic acid, 1-
1.5 times the molar amount is preferable.

Depending on the conditions of the epoxidation reaction, the substituents in the raw materials undergo a side reaction with the epoxidizing agent and the like at the same time as the olefin bond is epoxidized, resulting in modified substituents that are included in the target compound. The ratio of the three substituents formed as substituents in the target compound is determined by the type of epoxidizing agent, the molar ratio of the epoxidizing agent to the olefin bond, and the reaction conditions.

For example, when the epoxidizing agent is peracetic acid, the modified substituent mainly has the structure shown below, and is generated from the produced epoxy group and the by-produced acetic acid.

The target compound can be removed from the reaction crude solution by conventional chemical engineering means such as concentration.

The novel epoxidizing agent obtained according to the present invention is generally obtained as a mixture in many cases.

By crosslinking with phenolic novolac resins and other curing agents, the novel epoxy compounds obtained in this way have excellent L.
It can be used as an SI sealing material.

It also has the advantage that it can be used as an alternative to conventional uses of epoxides, such as impregnating coils, and its performance can be adjusted by freely adjusting the degree of polymerization. Furthermore, LED
It can be used in a wide range of applications, including as a semiconductor encapsulant and paint.

The present invention will be further explained in detail with reference to Examples below.

Example-1 Allyl alcohol 16 g (2 mol), 4-vinylcyclohexene-1-oxide 4969 (4 mol) and BF, etherate 3.19 were mixed at 60°C,
The reaction was continued until the conversion of 4-vinylcyclohexene-1-oxide reached 98% or more as determined by gas chromatography. Ethyl acetate was added to the obtained reaction crude liquid and washed with water, and then the ethyl acetate layer was concentrated to obtain a viscous liquid.

In the infrared absorption spectrum of the product, the absorption by the epoxy group of 810.850cIrL-t, which was observed in the raw material, disappeared, 1oso, ils.

The presence of absorption due to m-”K ether bonds.

Gas chromatography analysis showed that the amount of allyl alcohol in the product was only traces, but the infrared absorption spectrum showed 34.
It was confirmed that this compound had the structure shown by the following formula from the absorption of the iCOH group at 50 cm-''.

434 g of the compound was dissolved in ethyl acetate and charged into a reactor, and 388 g of peracetic acid was added as an ethyl acetate solution to the reactor.
dripped over time. During this time, the reaction temperature was maintained at 40°C. After the addition of peracetic acid, the mixture was further aged at 40°C for 6 hours.

Ethyl acetate was added to the reaction crude solution, and the mixture was washed with alkaline water containing sodium carbonate 4169, and then thoroughly washed with distilled water.

The ethyl acetate layer was concentrated to obtain a viscous clear liquid.

This compound had an oxirane oxygen content of 9.97%, and a characteristic absorption due to the epoxy group was observed at 1260CILL-' in the infrared absorption spectrum. Furthermore, 16406rI
Absorption due to residual vinyl groups is observed in L-', 34
OH group in 50 cIrL-', 173 ocIIL-'
It was confirmed that the product had the structure of general formula (I) (R, nigericidyl group or allyl group, n=average 2, including a part of the group in which acetic acid was added to the epoxy group).

Example-2 In the same manner as in Example-1, 58 g of allyl alcohol,
4-vinycinchlorohexene-1-,t-kifide 868
4.7 g of BF3 etherate was reacted to obtain a viscous liquid product.

In the infrared absorption spectrum of the product, 810,850% was found in the raw material. Absorption due to the epoxy group of -1 is eliminated, 1080, 11. +50am-”K
Gas chromatography analysis revealed that there was absorption due to ether bonds, and although there was only a trace amount of allyl alcohol in the product, the infrared absorption spectrum showed that it was 3450 cIL.
It was confirmed that this compound has the structure shown by the following formula since there is an absorption of OH group at -'.

Furthermore, 492 g of this compound was reacted with 395 g of peracetic acid in the same manner as in Example 1 to obtain a viscous transparent liquid.

This compound has an oxirane oxygen content of 9.27%,
In the infrared absorption spectrum, characteristic absorption due to epoxy groups was observed at 1260 an-''.Furthermore.

Absorption due to residual vinyl groups is observed in 1640cIIL-1% OH group + 173 in 3450cIIL-1
Since absorption by the 1-C〇- group is observed in ``00rlL-'', this compound has the structure of general formula (I) (R, nigericidyl group or R allyl group, n-average 7. (including some of them).

Example-3 Methanol 649.4-
Vinylcyclohexene-1-oxide 74411B
F3 Nieteller 1-4.1. iil was reacted to obtain a viscous liquid product.

In the infrared absorption spectrum of the product, 810,850. The absorption by the epoxy group at -' is increasing, the absorption by the ether bond is present at 1080.1150cm-', and gas chromatography analysis shows that the allyl alcohol in the product is only a trace amount, but it is infrared rays. It was confirmed that this compound had the structure shown by the following formula since there was an absorption of OH group at 3450cIIL-'' in the absorption spectrum.

Furthermore, in the same manner as in Example 5, 573 g of this compound and 9 peracid were added.
The reaction of 3879 was carried out to obtain a viscous transparent liquid.

This compound has an oxirane oxygen content of 9.03%,
In the infrared absorption spectrum, characteristic absorption due to epoxy groups was observed at 1260 cm-''.Furthermore.

1640cIIL-"K Absorption due to residual vinyl group is observed, OH group at 3450 an-', 1730c
Since absorption by 1100-group is observed in "pn-", this compound has a structure of general formula (I) (R,: methyl group, n=3 on average, 1 part of a group in which acetic acid is added to an epoxy group). (including).

Reference Example The total amount of chlorine in the epoxy resins synthesized in Examples 1 and 2.3 was measured.

The measurement was carried out by weighing sample 211 and decomposing and burning it in a % oxygen cylinder, and the results shown in Table 1 were obtained. If we consider that ordinary epoxy resins using shrimp μ-cruhydrin as a starting material usually contain about several hundred ppm of total chlorine, it can be seen that the total chlorine content of the resin of the present invention is extremely small.

Table 1 Total amount of chlorine in epoxy resin Application example 1 A curing agent was added to the product of Example 1.2.3, gel time was measured, and the curability of the epoxy resin was investigated. Novolak type phenolic resin CPSF-43 as hardening agent
00 Gunei Chemical Industry C Co., Ltd.)), and 2-
Undecylimidazole (Curezole C11z, Shikoku Kasei Kogyo C Co., Ltd.) was used. In addition, as a comparative resin, 3,4-epoxycyclohexylmethyl-37,4/-epoxycyclohexanecarboxylate (Celoxide 2021, Daicel Chemical Industries, Ltd. 0)), which is a typical alicyclic epoxy resin, was used, and the following The mixture was blended according to the formulation, melt-mixed at 120° C. for about 1 minute, and then cooled to obtain a blend. The gel time of the obtained formulation at 120°C was measured according to JIS-02104-7 (hot plate method), and the results shown in Table 2 were obtained. It can be seen that the resin of the present invention has higher curability than conventional alicyclic epoxy resins.

Compounding recipe Epoxy resin i, o equivalent PSF-43001, t1 equivalent Curazole C,, Z 0.7% by weight (based on the formulation) Table 2 Gel time application example 2 of the formulation Compounds of Examples 1 and 2.3 The physical properties of the cured product were measured using the same method.

The same curing agent and curing catalyst as in Application Example 1 were used, and the following formulation was mixed in the same manner as in Application Example 1 to obtain a blend. The resulting mixture was pulverized and press molded to obtain a test piece.

Molding is carried out at 60°C under pressure of 90 to 100 kgf/cIi.
The temperature was raised to 170℃ in about 30 minutes, and then heated to 170℃ under pressure.
After leaving it at ℃ for 10 minutes, put it in the oven set at 180℃ for 2 minutes.
Curing was carried out after an hour. The obtained cured product was cut into a test piece, and its physical properties were measured according to JIS-6911, and the results shown in Table 3 were obtained.

Compounding recipe Epoxy resin 1.0 equivalent PSF -43000, g equivalent Curesol G,, Z (based on the compound) 0.7% by weight Table 3 Physical property procedure correction band for cured product (voluntary) March 1985 1y Japan Patent Office Commissioner Manabu Shiga 1, Indication of the case: Patent Application No. 14860 of 1982, 2 Title of the invention: Novel method for manufacturing epoxy resin 3, Person making the amendment Relationship to the case Patent applicant postal code: 590 Address: 1 Teppocho, Sakai City, Osaka Name (290) "Detailed Description of the Invention" column of Daicel Chemical Industries, Ltd. Specification.

5. Next to Table 3 on page 27 of the Statement of Contents of Amendment, the following "Example-4" Example-4 Trimethylolpropa/134,9 5 degrees 1, 8, 6; 8
1 part 5 mol] was reacted with J' in the same manner as in Example-1 to obtain a product.

When the obtained product was analyzed by elemental analysis, IR, and NMR, it was confirmed that it had a structure represented by formula 0v).

n,, (1,, (1,4%75 IR analysis shows 810,850 and 1 as in Example-1)
The absorption of the epoxy group at 850 am-,' disappears, and at 10
A new absorption of ether bond at 80 cm-" was generated.Furthermore, 910 cm-" and 1640 cm-"
Absorption of vinyl groups remains.

In NMR, peaks similar to those in Example 1 were confirmed. The elemental analysis values are shown below.

CH Analysis value 76.05 9.65 Theoretical value ? 5.82 9.73 From the above results, the structure of formula (g) was confirmed.

Further, in the same manner as in Example-1, 573 g of this compound and 71 g of peracetic acid 3B! A viscous transparent liquid was obtained.

This compound had an oxirane oxygen content of 9.03%, and a characteristic absorption due to the epoxy group was observed at 1260a-1 in the infrared absorption spectrum. Furthermore, 1640 crn-'
Absorption due to residual vinyl groups is observed in 3450
Since absorption is observed by an OH group at am-' and a 1100- group at 1730 cra-', this compound has the general formula (Structure 11 (R, nido IJ methylolpropane residue!=3, n, , It was confirmed that n, , n = 5 on average, including one part of a group in which acetic acid was added to an epoxy group).

Procedural amendment (spontaneous) March 1tF, 19851, Indication of the case, 1982 Patent Application No. 148602, Name of the invention, New method for manufacturing epoxy resin 3, Person making the amendment Relationship with the case Patent application Postal code: 590 Address: 1 Teppocho, Sakai City, Osaka Name: (290) Daicel Chemical Industries, Ltd. 1 Column "Claims J" in the specification.

Stop.

(1) General formula (1) on page 6 of the specification I am corrected.

(2) General formula (n) on page 7 of the same I am corrected.

(3) On page 7, lines 5 and 6 from the bottom, "case alkyl group, car 2 aryl group" is corrected to ``1 alkyl carzenyl group, aryl car 1 group''.

(4) 2nd line from the bottom of page 8, “Oxypinoceric acid”
Delete "," after.

(5) On page 9, lines 8-9, "phenol resin" is corrected to "phenol tumerac resin."

(6) "Phthalic acid" in the 8th line from the bottom of page 9 is corrected to "phthalic acid."

(7) On page 10, line 7, "Mercapto" is corrected to "Mercaptan."

(8) On page 10, lines 9-10, [ethylene glycol dimercaptopropionic acid ester] is corrected to "ethylene glycol bismercaptopropionic acid ester."

(9) On page 10, lines 10 to 12, "trimethylolpro/etrimercaptopropionic acid ester" is corrected to "trimethylolpronocentrismercaptopropionic acid ester."

From No. 10, lines 9 to 8, "pentaerythritol pentamercazotopropionic acid ester" is corrected to "pentaerythritol tetrakis mercaptopropionic acid ester."

Qll "Aleic acid" in the first line from the bottom of page 10 [
Aleic acid,” he corrected.

a3 Correct "preferably, especially" in the first line of page 12 of the same statement to "preferably, on the contrary."

a3 Correct “Oxide” in the 9th line from the bottom of page 12 to “Oxide”.

α4 Correct "Oxide" in the 6th line from the bottom of page 12 to "Oxide".

09 "Oxide" in the second line of page 13 is corrected to "oxide".

θe 10th line from the bottom of page 13, "after rBF6J"
,'' is deleted and rAIcA'5J on the 10th line from the bottom is corrected to 1llcllsJ.

Alpha power Correct "hydroperoxides" in lines 9 and 10 at the bottom of page 14 to "hydroperoxides."

θυ On the 4th line from the bottom of page 15, "decomposition occurs." is corrected to "decomposition occurs."

a9 Correct "Oxide" in the fourth line from the bottom of page 18 to "Oxide".

(b) "Oxide" in the first line from the bottom of page 18 is corrected to "Oxide".

12υ Correct "General formula (I)" in the 7th line from the bottom of page 20 to "General formula (p)".

(2) Change the “glycidyl group” in the 7th line from the bottom of page 20 to “
Correct it to glycidyl ether group J.

(To) "Allyl group" in the 6th line from the bottom of page 20 is corrected to "allyloxy group."

Q4 Correct "Oxide" in the 2nd to 1st lines from the bottom of page 20 to "Oxide".

(c) "1 general formula (I)" on page 22, line 4 of the same document is corrected to "general formula (1)."

(c) "Glycidyl group" on page 22, line 4 is corrected to "glycidyl ether group."

@ On page 22, line 5, "allyl group" is corrected to "allyloxy group."

(To) "Oxide" on page 22, line 9 is corrected to "oxide."

(2) "Allyl alcohol" in lines 4 to 6 from the bottom of page 22 is corrected to "1 methanol."

(To) "General formula (I)" in the 5th line from the bottom of page 23 of the same page is changed to "
general formula (■)” and the “methyl group” in the fifth line from the bottom as “
methoxy group" respectively.

69. On page 24, line 1 of the same page, replace "I went." with "I did it."

” he corrected.

(To) Correct "few things" in line 7 of page 24 to "few things."

(To) Correct "I went." in the fourth line from the bottom of page 26 to "I did it."

(Incorporated Foundation), page 27, line 6, [Curezol G,,ZJ is corrected to [Curezol C11ZJ].

Claims: A novel method for producing an epoxy resin represented by the general formula (1), which comprises reacting an unsaturated compound represented by the general formula (1) with an epoxidizing agent. An organic compound residue containing hydrogen.

n1*12g...nL is 0 or an integer from 1 to 100, and the sum thereof is from 1 to 100.

l is an integer from 1 to 100.

A is a cyclohexane skeleton having a vinyl group, and is represented by the following formula.

However, R1 is an organic compound residue having one active hydrogen.

n l Hn21...The town is 0 or an integer from 1 to 100, and the sum thereof is 1 to 100.

l is an integer from 1 to 100.

B is a cyclohexane skeleton having a substituent.

It is expressed by the following formula.

Contains one or more.

Claims (1)

[Claims] A novel method for producing an epoxy resin represented by the general formula (n), which comprises reacting an unsaturated compound represented by the general formula (I) with an epoxidizing agent, where R is no. An organic compound residue with active hydrogen. n, I n, #... nl is 0 or 1 to 10
It is an integer of 0 and its sum is 1 to ZOO.゛l is an integer of 1=100. A is a cyclohexane skeleton having a vinyl group and is represented by a linear formula. However, R1 is an organic compound residue having one active hydrogen. "l s nt m...nj is an integer of 0 or 100, and the sum thereof is 1-1oo. l is an integer of 1-100. B is a cyclohexane skeleton having a substituent, It is expressed by the following formula: υ Contains one or more in fat.