JPS60166675A - Novel epoxy resin - Google Patents

Abstract

PURPOSE:To obtain an alicyclic epoxy resin having improved heat resistance, water resistance, and weather resistance, by polymerizing 4-vinylcyclohexene-1- oxide through ring opening to give a polyether resin, epoxidizing the prepared polyether resin with an oxidizing agent such as a peracid, etc. CONSTITUTION:4-Vinylcyclohexene-1-oxide is polymerized through ring opening by the use of an active hydrogen-containing organic compound in the presence of a catalyst (e.g., amine, organic base, etc.) at -70-200 deg.C, preferably at -30- 100 deg.C to give a polycyclohexene oxide polymer containing a vinyl group side chain, which is epoxidized with a peracid, or hydroperoxide to give an epoxy resin shown by the formula I [R1 is organic compound residue containing l active hydrogens; n1, n2...nl are 1-100 integer and total of them is 1-100; l is 1- 100; A is group shwon by the formula II; X is group shown by the formula III, formula IV, or formula V (R2 is H, alkyl, alkylcarbonyl, or arylcarbonyl), with the proviso that containing at least one of the group shown by the formula III].

Description

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

The epoxy resin currently most widely used in industry is the disadvantageous 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.2 Moreover, the epoxy group has a high reactivity, and it has the advantage of being able to 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 reciprocating and knocking properties, and low heat distortion temperature. In particular, recently, epoxy resins made by reacting phenol, novola resin, and epichlorohydrin have been used as sealing resins for VLSIs, etc., but the resin contains several 1,100 pp of chlorine, which affects the electrical properties of electronic components. This may cause problems such as worsening the condition.

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 the epoxidation reaction of compounds having a 5- or 6-membered cycloalkyl skeleton. The epoxy groups of these resins are so-called internal epoxy groups, and are usually cured by heating with acid anhydrides, but because of their low reactivity,
Cannot be cured at room temperature with polyamine.

Therefore, the usage limit for alicyclic epoxy resin is extremely limited.

As alicyclic epoxy resins, those having the structures of (IT) and (ITJ) are industrially manufactured and used.

1 (II) is used as a heat-resistant epoxy diluent because of its extremely low viscosity, but it is highly toxic and causes problems such as severe irritation of the skin of workers.

(III) has few impurities and a low hue, and its cured product has a high heat deformation temperature, but has a problem of poor water resistance due to ester bonds.

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

The present invention was developed as a result of intensive research to develop a new epoxy resin in view of these problems.
We have discovered an epoxy resin that can be formed into any shape from liquid to solid, has excellent water resistance, heat resistance, and, oh, excellent reactivity, and has accomplished the present invention.

That is, the present invention relates to an epoxy resin represented by the following general formula.

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

n, , R2, . . . n is an integer of 0 or 100, and the sum thereof is 1 to 100.

l represents an integer from 1 to 100.

A is an oxycyclohexane skeleton having a substituent X and is represented by the following formula.

5- Contains one or more in the resin.

Next, the present invention will be explained in detail.

In the novel epoxy resin represented by formula (I) of the present invention, R8 is an organic residue having active hydrogen, and examples of the organic substance having active hydrogen, which is a precursor thereof, include alcohols and phenols.

Examples include carboxylic acids, amines, thiols, and the like.

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

6- Examples evaporated methanol, ethanol, propatool.

Aliphatic alcohols such as butanol, pentanol, hexanol, octatool, aromatic alcohols such as benzyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, fluoropylene glycol, dipropylene glycol, 1.3 phthanediol, 1 .4 phthanediol,
Bentanediol.

■, 6-hexanediol, neopentyl glycol.

Oxypivalic acid neopentyl glycol ester, cyclohexane dimetatool, glycerinol.

diglycerin, polyglycerin, trimethylolpropane, tyl)) tyrolethane, pentaerythritol,
Examples include polyhydric alcohols such as dipentaerythritol.

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

Hydroquinone monomethyl ether, bisphenol A
, bisphenol F14,4'-dihydroxybenzophenone, bisphenol S, phenol resin, cresol novolac resin, and the like.

Carboxylic acids include formic acid, acetic acid, propionic 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, isophthalic 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.

Hexylamine, cyclohexylamine, octylamine, dodecylamine, 4,4. '・Diaminodiphenylmethane, isophoronediamine, toluenediamine, hexamethyldiamine, xylenediamine, diethylenetriamine, triethylenetetramine, ethanolamine, etc.

Examples of thiols include mercapto compounds such as methyl mercaptan, ethyl mercaptan, propyl mercaptan, and phenyl mercaptan, mercaptopropionic acid, and polyhydric alcohol esters of mercaptopropionic acid 7t.
Examples include (haethylene coul) dimercaptobrobionic acid ester, trimethylolpropane trimercaptopropionic acid nispur, pentaerythritol pentamercaftofuropionic acid ester, and the like.

In addition, as compounds having active hydrogen, polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, f-pump, cellulose, cellulose fucetate, cellulose acetate butyrate, hydrocarbon diethyl cellulose,
Ac 11 polyol resin, styrene allyl alcohol copolymer resin, /2 Methylene! Leic acid copolymer resin, alkyd resin.

Polyester polyol resin, polyester carboxylic acid resin, polycaprolactone polyol resin.

Examples include polypropylene polyol, polyetra, methylene glycol, etc.

Further, the compound having active hydrogen may have an unsaturated type 2 bond in its skeleton, and the following is a specific example.

So, allyl alcohol, acrylic acid, methacrylic acid,
Examples include 3-cyclohexenemethanol and tetrahy-9-dolphthalic acid. The unsaturated double bonds of these compounds may also have an epoxidized structure.

In the general formula CI), n, n2...nt are 0 or an integer from 1 to 100, and the sum is 1 to 1 (10, but if it exceeds 100, the resin has a high melting point and is difficult to handle, so in practice The top is not usable.

l is an integer from 1 to 1001.

Among the substituents X of A in formula (I) \ HOR1 That's true.

That is, in the present invention, the substituent X is 110- 8 Sentence 7 is the main one.

0 Specifically, the novel epoxy resin represented by the formula (I) of the present invention is produced by using an organic compound having active hydrogen as an initiator.
A polyether resin obtained by ring-opening polymerization of vinylcyclohexene-1-oxide, that is,
It can be produced by epoxidizing the present cenoxide polymer to polycyclo having a vinyl group side chain with an oxidizing agent such as a peracid.

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

When 4-vinylcyclohexene-1-oxide is polymerized in the presence of active hydrogen, it is preferable to use a catalyst.

As the 71I111 medium, methylamine, ethylamine,
Amines such as propylamine and piperazine, organic basic acids 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 alcoholades such as sodium methylate, alkalis such as KOH and NaOH, BF3
Examples include ZnC62, Aicg3, 5nC64, etc. (Dk), and organometallic compounds such as sulfuric acid or its complexes, triethylaluminum, and diethylzinc.

These catalysts can be used in an amount of 0.01-IQ, preferably 0.1-5% based on the reactants.

The reaction temperature is -70 to 200°C, preferably -30°C to
The temperature is 100°C.

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

i.e., ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, benzene, toluene,
Aromatic solvents such as xylene, ethers, aliphatic hydrocarbons, esters, etc. can be used.

Now, in step 1 of producing the novel epoxy resin of formula (T) of the present invention by epoxidizing the thus synthesized polycyclohexene oxide polymer having a vinyl group side chain, peracids, hydrobaronesides, nodolphins, etc. If you use ka, you can make shi.

Peracids and 1-2 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.

Kusha butyl hydroperoxide, cumene oxide, etc. can be used.

A catalyst can be used during epoxidation if necessary. For example, in the case of peracid, alkali 11 such as soda carbonate
Acids such as sulfuric acid and sulfuric acid can be used as catalysts. In addition, in the case of Hydropero Honside, a mixture of tungstic acid and caustic soda is mixed with hydrogen peroxide, or an organic acid is mixed with hydrogen peroxide.
Alternatively, molybdenum hexacarbonyl can be used with tert-butylhydride 13-lobar oxide to achieve catalytic effect.

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.

Depending on the conditions of the epoxidation reaction, the substituents in the raw materials undergo side-reaction with the epoxidizing agent, etc. 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 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. When the epoxidizing agent is peracetic acid, it mainly has the structure shown below, and is generated from the generated epoxy group and the by-produced acetic acid.

1. The target compound can be extracted from the reaction crude solution by ordinary chemical industrial means such as concentration.

By crosslinking with phenol novolak resin or other curing agents, the novel epoxy compound obtained by this method has 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 semiconductor encapsulants, paints, etc.

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

Example-1 116 g (2 moles) of allyl alcohol, 496 g (4 moles) of 4-vinylcyclohexene-1-oxide and 3.19 g of BF3 etherate 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, absorption due to epoxy groups at sio and 5sol-', which were observed in the raw materials, is absent, and absorption due to ether bonds is present at 1080 and 1150cTL-'.

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 since there was an absorption of OH group at 50 cmIrL-'.

434 g of this compound was dissolved in ethyl acetate and charged into a reactor, and 388 g of peracetic acid #1 was dissolved in ethyl acetate.
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 4x61 portions of sodium carbonate, and then thoroughly washed with distilled water.

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

This compound has an oxirane oxygen content of 9.97%,
In the infrared absorption spectrum, characteristic absorption due to epoxy groups was observed at 1260 cIIL-'. Furthermore, 1640c
Absorption due to residual vinyl groups is observed in m-', 34
Since absorption is observed by OH group at 50-1 and 17--〇〇- group at 1730-1, this compound has the structure of general formula (I) (R: glycidyl group or allyl group, n= It was confirmed that the average value was 2. (containing some groups in which acetic acid was added to epoxy groups).

Example-2 Allyl alcohol 58S' was prepared in the same manner as in Example-1.
, (1 mol) 4-vinylcyclohexene-1-oxide 868.9 (7 mol) BF3.etherate 4.
7g was reacted to obtain a viscous liquid product.

In the infrared absorption spectrum of the product, the absorption by the epoxy group of 810,850C:rrL-' observed in the raw material has disappeared, 1080,11507m-'
Gas chromatography analysis revealed that there was absorption due to ether bonds in the product, and although there was only a trace amount of allyl alcohol in the product, the infrared absorption spectrum showed that it was 3450 cm.
It was confirmed that this compound has the structure shown by the following formula from the absorption of OH group at "-".

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

This compound has an oxirane oxygen content of 9.27% and an infrared absorption spectrum of 1260. -' characteristic absorption due to epoxy group was observed. Furthermore, absorption due to residual vinyl groups is observed at 1640in-', and 3450CIf
Since absorption is observed by an OH group at L-' and a 1-co- group at l730CTL-', this compound has the structure of general formula (I) (R, nigericidyl group or allyl group, n-average 7. epoxy group). (contains a group with a portion of acetic acid added to).

Example-3 In the same manner as in Example-1, methanol 649C2 mol), 4-vinylcyclohexene-1-oxide 7
449 (6 mol) BFs・etherate 4.1.9
were reacted to obtain a viscous liquid product.

In the infrared absorption spectrum of the product, 810,850. -' absorption due to epoxy group has disappeared, 1080,1150CTL-' has absorption due to ether bond, and gas chromatography analysis shows that allyl alcohol in the product remains in trace amounts, but the infrared absorption spectrum 34506rIL-'
It was confirmed that this compound had the structure shown by the following formula since there was an absorption of OH group in .

Furthermore, 573 g of this compound was reacted with 387 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 9.03.
In the infrared absorption spectrum, characteristic absorption due to epoxy groups was observed at 1260C7rL-. Furthermore, 1640c1r
Absorption due to residual vinyl groups is observed in L-”, 34
This compound has the structure of general formula (1) (R1: methyl group, n-average 3. epoxy group (contains a group to which acetic acid is partially added).

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

The measurement was performed by weighing approximately 2 g of the sample and decomposing and burning it in an oxygen cylinder, and the results shown in Table 1 were obtained. Considering that ordinary epoxy resins using epichlorohydrin 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.

21 - Table 1 Total chlorine content in epoxy resin Application example 1 A curing agent was added to the products of Examples 1 and 2.3, gel time was measured, and the curability of the epoxy resin was investigated. Novolac type phenolic resin (PSF-43) was used as a curing agent.
00 Gunei Chemical Industry Co., Ltd., and 2-
Undecylimidazole (Curezole C, Z, Shikoku Kasei Kogyo 0)) was used. In addition, as a comparative resin,
Using 3,4-epoxycyclohexylmethyl-3/,4/-epoxycyclohexanecarboxylate (Celoxide 2021, Daicel Chemical Industries, Ltd. 0), which is a typical alicyclic epoxy resin, the following formulation was used. , melt-mixed at 120° C. for about 1 minute and then cooled to obtain a blend. The obtained compound was tested according to JIS-C210422.
The gel time at 120° C. was measured by -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.

Blend formula Epoxy resin 1.0 equivalent PSF-43001, 1 equivalent Kyuazole CnZ (based on the formulation) 0.7% by weight Table 2 Gel time application example 2 of the formulation Cured using the compounds of Examples 1 and 2.3 The physical properties of the object were measured.

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. For molding, the temperature was raised from 60°C to 170°C in about 30 minutes under a pressure of 90~lookgf/ffl.
Further, after being left under pressure at 170°C for 10 minutes, it was post-cured for 2 hours in an open air set at 180°C. The obtained cured product was made into a test piece by cutting and tested according to JIS-K-691.
The physical properties were measured using No. 1, 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 amendment of cured product (voluntary) IS date March 1985 Manabu Shiga, Director General of the Patent Office1, Ibaraki Patent Application No. 14859 filed in 19822, Title of the invention: New epoxy resin3, Person making the amendment Relationship to the case Patent applicant Postal code: 590 Address: Sakai, Osaka Prefecture 1 Ichiteppo-cho Name (290) Daicel Chemical Industries, Ltd. 1) Section 1, “Claims” in the specification (1) “Detailed explanation of the patent” on the 11th line from the bottom of page 2 of the specification. Corrected to "Detailed Description of the Invention."

(2) Correct r((1111)J in the 7th line from the bottom of the 4th page to r([[l)J.

(3) In the third line from the bottom of page 4, "1, the present invention, etc." is corrected to "the present inventors, etc.".

(4) "Any shape" in the first line from the bottom of page 4 is corrected to "any property."

(5) Correct "Oh," in the first line of page 5 to "and."

(6) On page 5, line 3, ``Montta.'' is corrected to ``Ritata.''

(7) General formula (1) on page 5 of the same I am corrected.

(8) Change "or 100" in the fifth line from the bottom of page 5 to J "
or 1-100”.

(9) The statement in parentheses on page 6 of the same is corrected to 1. (2 is any one of H, an alkyl group, an alkylcarzenyl group, or an arylcarzenyl group.)

On ``Phenol'' in the first line from the bottom of page 7 is corrected to ``Funol Nozerak''.

01) “Phthalic acid” on page 8, line 5 of the same page is “phthalic acid”
I am corrected.

Correct "Mercapto" in the second line from the bottom of page 8 of O2 to "Mercaptan."

0.1 "Ethylene glycol dimercaptopropionic acid ester" in lines 1 to 2 on page 9 is corrected to "ethylene glycol bismercaptopropionic acid ester."

a4 Correct "trimethylolpropane trimercaptopropionic acid ester" in lines 2 to 4 of page 9 to read "trimethylolpropane trimercaptopropionic acid ester."

a9 "Pentaerythritol pentamercaptopropionic acid ester" in lines 4 to 5 on page 9 is corrected to "pentaerythritol tetrakismercaptopropionic acid ester."

0e "Polyetramethylene glycol" in lines 6 to 5 from the bottom of page 9 is corrected to "I-litetramethylene glycol."

07) "Double bond" in the second line of page 10 is corrected to "double bond."

α杓 In the 3rd line from the bottom of page 10, replace “I. Especially” with “ku,”
On the contrary,” he corrected.

α■ "Oxide" in lines 4 to 5 on page 11 is corrected to "oxide."

(a) "Polycyclohexene oxide polymer" on page 11, line 7 of the same page is replaced with "polycyclohexene oxide polymer".
I am corrected.

Qυ Same page 11, line 9 from the bottom θ) Correct "Oxide wa" to "Oxide wa".

(c) On page 11, line 5 from the bottom, "Oxide o" is corrected to "Oxide o".

(c) "Active hydrogen" in the fourth line from the bottom of page 11, "
," is deleted.

041 On page 12, line 1, "1 organic base acid" is corrected to "1 organic base."

(c) "AlCl3" on page 12, line 5 of the same page is rAlc/
Correct it to 3J.

Kan: "Polycyclohexene oxide polymer" in the second line of page 13 is corrected to "polycyclohexene oxide polymer."

Reference: On page 13, line 4, "hydroperoxides" is corrected to "hydroperoxides."

CI'l Correct "and metamorphosis" in the third line from the bottom of page 14 to "and metamorphosis."

(To) "Transformation" in the second line of page 15 is corrected to "denaturation."

(To) "Oxide" in the 7th line from the top of page 16 is corrected to "Oxide".

OD "1 oxide" in the 10th line from the top of page 16 of the same page as "
Oxide,” he corrected.

03 On page 18, line 2, "1 glycidyl group" is corrected to "glycidyl ether group."

(To) "Allyl group" on page 18, line 3 is corrected to "allyloxy group."

(Incorporated Foundation), page 18, lines 7-8, ``Oxide'' is corrected to ``-and.-''.

(To) Change the "glycidyl group" in the 6th line from the bottom of page 19 to "
Glycidyl ether group” is corrected.

0η On page 19, line 5 from the bottom, "allyl group" is corrected to "allyloxy group."

(To) Delete "1 copy" from the 5th to 4th lines from the bottom of page 19.

Ol Page 19, line 4 from the bottom, insert ``some'' before ``includes.''

(41, p. 20, line 1, "1 oxide" is corrected to "oxide."

(41) [Allyl alcohol] on page 20, lines 8-9
is corrected to "methanol".

12 On page 21, line 6, "methyl group" is corrected to "methoxy group."

θta, page 21, line 7, copy 11” is deleted.

0. Insert "some" in front of "contains" on page 21, line 7.

(49, page 21, 1st line from the bottom, “less” means “less”)
I am corrected.

00 Same page 22, line 4 σ) Correct "I went." to "I did it."

0η On page 24, line 9 of the same text, ``do'' is corrected to ``do.''

4. p. 24, line 12 from the top σ) “Cure Sol G1
Correct 1Z J to "Curezol C11Z".

Claims: A novel epoxy resin represented by the general formula (1) provided that R
1 is an organic compound residue having l active hydrogens.

nl, R2,... nl is 0 or an integer from 1 to 100, and the sum thereof is from 1 to 100.

l represents an integer from 1 to 100.

A is an oxycyclohexane skeleton having a substituent and is represented by the following formula.

u　OH0R2 R2ui, H, alkyl group, alkylcarzenyl group.

Contains one or more in the resin.

Procedural amendment (spontaneous) March 19, 1985 1. Indication of the case 1982 Patent Application No. 14859 2. Title of the invention New epoxy resin 3. Person making the amendment Relationship to the case Patent applicant Postal code: 590 Address: 1 Teppo-cho, Sakai City, Osaka Prefecture Contents of amendments to Column 5 of “Detailed Description of the Invention” of the specification (1) The following “Embodiments -
4 134 g (1 mol) of trinol-1-rol propane and 18635' (15 mol) of vinylcyclohexene monoepoxide were reacted in the same manner as in Example 1 to obtain a product.

The obtained product was analyzed by elemental analysis, I1%, and NMIR, and it was confirmed that it had the structure shown in (Tokoro Niha).

n+, "* + ns" = average 5 TI' (in the analysis, as in Example-1, the absorption of epoxy groups at 810, 850 and 1850 am' disappeared, and 1
A new absorption of the ether bond at 080 m' was generated.

Furthermore, 2-910cm' and 1640cm' did.

Absorption of vinyl groups remains.

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

Theory value 75.82 9.73 From the above results, the structure of formula M was confirmed.

573 g of this compound and 387 g of peracetic acid were reacted in the same manner as in Example 1. A viscous transparent liquid? It was 8.

This compound had an oxirane oxygen content of 9.03%, and a characteristic absorption due to the epoxy group was observed at 1260 cm' in the infrared absorption spectrum. Furthermore, absorption due to the residual vinyl group is observed at 1640 m-', and absorption due to the 1-C〇- group is observed at 3450 cm' and 1730 (-m'). Confirm that the structure is (R, nitrimethylolpropane residue l = 3, n, , n, , n, = average 5, including one group in which acetic acid is added to the epoxy group) 3-4-

Claims (1)

[Claims] A novel epoxy resin represented by the general formula (I) provided that R6
teeth! An organic compound residue having active hydrogen. n, , nfi...nj are integers of 0 or 100, and the sum thereof is 1-100. j represents an integer from 1 to 100. A is an oxycyclohexane skeleton having a substituent and is represented by the following formula. Contains one or more in the indicated resin.