JPH0511124B2 - - Google Patents

Description

[Detailed description of the invention]

[Industrial Application Field] The present invention relates to an epoxy resin having an unsaturated group and a method for producing an epoxy resin derivative. [Prior art] Epoxy resin has excellent corrosion resistance, adhesive properties, electrical insulation properties, heat resistance, etc., and is used in paints, adhesives, molding agents,
It is used in various industrial fields such as sealants. By utilizing the epoxy groups at both ends of the epoxy resin, it can be used in combination with compounds having active hydrogen (e.g., polyhydric carboxylic acids, polyhydric alcohols, polyamines, polyamides) to give cured products, and By reacting with a compound containing hydrogen, it can be modified into epoxy esters, epoxy ethers, etc., and can be made into resins with a wide range of properties depending on the purpose of use. However, even epoxy resins with such excellent properties have reactive sites only at both ends of the molecule, and can only react with compounds having active hydrogen. Therefore, the crosslinking reaction thereof is also limited, and in some cases, it has the disadvantage that it only provides a cured product with a low crosslinking density. In order to improve this, it is possible to introduce a carbon-carbon unsaturated group into the epoxy resin. For example, as disclosed in JP-A-59-10373, an epoxy resin is reacted with acrylic acid or methacrylic acid to introduce the above-mentioned unsaturated group at the end of the epoxy resin, and then subjected to a Michael type addition reaction with a polyamine compound or by ultraviolet irradiation. This makes it possible to provide a cured product. However, this method has the drawback that not only the epoxy group disappears due to the reaction with acrylic acid or methacrylic acid, but also that only up to two unsaturated groups can be introduced. [Circumstances of completion of the invention] The applicant has the following formula: [Wherein, R represents H or a lower alkyl group (eg, methyl, ethyl, propyl). ] We have successfully synthesized an alkenoyl isocyanate represented by the following, and are already applying for a patent. α-Alkylacryloyl isocyanate (R: lower alkyl group) is a compound obtained by a new synthesis method in which α-alkylacrylamide and oxalyl halide are reacted (Japanese Patent Application No. 58-225226), and acryloyl isocyanate in which R is H Isocyanate is a compound obtained by reacting acrylamide with oxalyl halide and dehydrohalogenating β-halopropionyl isocyanate (Japanese Patent Application No. 59-241876). This alkenoyl isocyanate [ ] is generally liquid at room temperature and easy to handle. However, it not only has a polymerizable carbon-carbon unsaturated group and an isocyanate group in its molecule, but also has a bond between both of these functional groups. Since a carbonyl group is present adjacent to them, the activity of the carbon-carbon unsaturated group is increased, and the activity of the isocyanate group is also increased, and it is in a state where it can carry out various addition reactions. That is, alkenoyl isocyanate [] can be used in various reactions (e.g., radical polymerization, anionic polymerization,
Dimerization, trimerization, polar addition, addition of active hydrogen): In particular, acyl isocyanate groups have much higher reactivity than isocyanate groups. By utilizing this property, alkenoyl isocyanate [ ] can be made to act on the secondary hydroxyl groups of epoxy resins, which generally have poor reactivity, under non-catalytic and non-heating conditions. - It has been found that carbon unsaturated groups can be introduced to increase the functionality of epoxy resins,
The present invention has now been completed. [Object of the invention] The present invention improves the drawbacks of the above-mentioned epoxy resin, and utilizes the hydroxyl group in the resin to form a carbon-
An object of the present invention is to provide an epoxy resin and its derivatives which have enhanced functionality by introducing a carbon unsaturated group. [Structure of the Invention] According to the method of the present invention, at least one hydroxyl group of an epoxy resin and/or an epoxy resin derivative having a hydroxyl group is expressed by the formula: [In the formula, R has the same meaning as above. ] A reaction product having a structure substituted with a group represented by the following is provided. More specifically, in the method of the present invention, the epoxy resin is first dissolved in an inert solvent, and in the case of xylene, for example, the solvent is refluxed at about 150°C to remove water in the resin. -20～
The temperature is returned to +50°C, preferably 0 to 20°C, and the above reaction product is obtained by dropping alkenoyl isocyanate [ ] while stirring under a nitrogen stream. Since the reaction mixture generates heat when alkenoyl isocyanate [ ] is added, it may be cooled, for example, in a water bath. Alkenoyl isocyanate [] may be added as is, but it is preferably used after diluting with an inert solvent. The amount of alkenoyl isocyanate [] to be added may be appropriately selected depending on the desired amount for substituting the hydroxyl group in the epoxy resin with the group of the above formula []. The end point of the reaction is NCO at 2240 cm ^-1 in the infrared absorption spectrum of the reaction mixture.
This can be confirmed by the disappearance of absorption. As the above-mentioned epoxy resin, ordinary ones may be used, and examples thereof include bisphenol A type epoxy resin, aliphatic type epoxy resin, alicyclic epoxy resin, and the like. Epoxy resins that themselves have hydroxyl groups can be used as they are. In the case of products that do not have hydroxyl groups (e.g., diglyndyl ether of bisphenol A), 1 mole of dicarboxylic acid (e.g., azelaic acid) is reacted with 2 moles of such epoxy resin in accordance with a conventional method to remove the epoxy groups. It can be used by retaining a hydroxyl group by forming a hydroxyl group by ring opening with a carboxyl group. In addition,
If there is no problem even if the epoxy group disappears, a hydroxyl group is formed by acting with the above-mentioned compound having an active hydrogen that is reactive with the epoxy group, or for example, ethanolamine is allowed to act on the epoxy resin to form a first It may also be used by introducing a class hydroxyl group. In the present invention, products obtained by modifying such epoxy resins are collectively referred to as epoxy resin derivatives. In the following description, only the term epoxy resin will be used for simplicity. The inert solvent used for the epoxy resin and, if necessary, the alkenoyl isocyanate [] may be any inert solvent that does not contain active hydrogen, such as aliphatic hydrocarbons such as pentane, hexane, and heptane, benzene, Aromatic hydrocarbons such as toluene and xylene, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, and decalin, hydrocarbon solvents such as petroleum ether and petroleum benzene, and halogens such as carbon tetrachloride, chloroform, and 1,2-dichloroethane. carbonated hydrocarbon solvent,
Ether solvents such as ethyl ether, isopropyl ether, anisole, dioxane, tetrahydrofuran, acetone, methyl ethyl ketone,
It can be appropriately selected and used from ketones such as methyl isobutyl ketone, cyclohexanone, acetophenone, and isophorone, esters such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, cellosolve acetate, acetonitrile, dimethylformamide, dimethyl sulfoxide, etc. can. For epoxy resins, the use of the above-mentioned aromatic hydrocarbons is preferred. The α-alkyl acryloyl isocyanate [ ] in which R is a lower alkyl group is a combination of α-alkylacrylamide (e.g., methacrylamide) and oxalyl halide (e.g., oxalyl chloride), as described in the specification of the above-mentioned patent application. ~0.1:1,
-10 to +150 °C, preferably 0 to 80 °C, preferably in the presence of the above inert solvent, preferably the above halogenated hydrocarbon solvent, in a molar ratio of 1.5 to 0.7:1.
It is obtained by reacting at a temperature of °C. When α-alkyl acryloyl isocyanate [] is isolated from the reaction mixture, it may be carried out by a conventional method (eg, distillation, vacuum distillation). Further, acryloyl isocyanate [ ] in which R is H can be obtained as described in the specification of the above patent application. That is, acrylamide and the above oxalyl halide (especially oxalyl chloride)
-50 to +150°C, usually in the absence of a solvent, preferably in the presence of the above-mentioned inert solvent (particularly a halogenated hydrocarbon solvent), in a molar ratio of 10 to 0.1:1, preferably 1.5 to 0.7:1. Preferably -30~+100℃
A reaction mixture containing β-halopropionyl isocyanate as the main product is obtained.
The reaction mixture is subjected to conventional isolation methods (e.g. distillation, vacuum distillation) to obtain β-halopropionyl isocyanate, which is then treated with a dehydrohalogenating agent in the presence or absence of the above-mentioned inert solvent. 0.1 to 100 per mole of the isocyanate, preferably
The desired acryloyl isocyanate [ ] can be obtained by processing at a temperature of -50 to +200°C, preferably 0 to 150°C, at a molar ratio of 0.1 to 10. In addition, when isolating acryloyl isocyanate [ ] from the reaction mixture, a normal method may be employed in the same manner as described above. In addition, using the above-mentioned β-halopropionyl isocyanate and acting on the epoxy resin in place of the above-mentioned alkenoyl isocyanate [],
The formula for the hydroxyl group of epoxy resin is: [In the formula, Hal represents a halogen. R has the same meaning as above. ] The desired reaction product can also be obtained by substituting a group represented by the following formula and then converting it into the above formula [] by treating with a dehydrohalogenating agent as described above. The by-produced hydrogen halide product may be separated by a conventional method (eg, filtration). The above-mentioned dehydrohalogenating agent includes not only β-halopropionyl isocyanate or a dehydrohalogenating agent in the ordinary sense, which requires the use of at least an equimolar amount of β-halopropionyl isocyanate with respect to the above functional group provided thereby. , includes dehydrohalogenation catalysts that can achieve the desired purpose even in relatively small amounts of equimolar or less, and specific examples thereof include the following: triethylamine, 1,8 −Diazabicyclo [5.4.0]
Amines such as undecene-7, pyridine, quinoline, alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, copper oxide, magnesium oxide, calcium oxide, alumina, oxide Metal oxides like iron, metal complex compounds like ( _Ph3P ) _2Ru (CO) ₃ , ( _Ph3P ) _3Pt , metals like lithium chloride, titanium tetrachloride, aluminum chloride, sodium chloride halides, metal salts such as zinc naphthenate, nickel acetate, barium sulfate, potassium phosphate, metal alkoxides such as potassium t-butoxide, sodium ethoxide, sodium isopropoxide, molecular sieves, porous glass. Synthetic zeolites such as boric acid, oxirane, metallic zinc, etc. Among these, it is particularly preferable to use those selected from amines, metal oxides, metal halides, synthetic zeolites, and the like. During the above reaction and distillation operations, a polymerization inhibitor may be present in order to avoid unnecessary polymerization of terminal double bonds. Specific examples of polymerization inhibitors include hydroquinone, p-methoxyphenol, 2,
6-di-t-butyl-4-methylphenol, 4
-t-butylcatechol, bisdihydroxybenzylbenzene, 2,2'-methylenebis(6-t-
butyl-3-methylphenol), 4,4'-butylidenebis(6-t-butyl-3-methylphenol), 4,4'-thiobis(6-t-butyl-3
-methylphenol), p-nitrosophenol,
Diisopropylxanthogen sulfide, N-nitrosophenylhydroxylamine ammonium salt, 1,1-diphenyl-2-picrylhydrazyl, 1,3,5-triphenylferdazyl,
2,6-di-t-butyl-α-(3,5-di-t
-butyl-4'-oxo-2,5-cyclohexadien-1-ylidene)-p-trioxy, 2,2,
6,6-tetramethyl-4-piperidone-1-oxyl, dithiobenzoyl sulfide, p,p'-
Examples include ditolyl trisulfide, p,p'-ditolyl tetrasulfide, dibenzyl tetrasulfide, and tetraethylthiuram disulfide. The reaction product obtained by the above method of the present invention is a pale yellow, transparent, viscous liquid containing a solvent. In addition, the introduction of the group of the above formula [] into the reaction product is due to the fact that the infrared absorption spectrum of the reaction mixture is 2240 cm ^-1 (NCO) as described above.
absorption has disappeared, the nonvolatile content of the reaction mixture is consistent with the theoretical value, and the signal of H of the olefin bond in the magnetic resonance spectrum is δ (ppm) of alkenoyl isocyanate [ ].
This can be confirmed by the shift from 6.15 and 5.75 to δ (ppm) = 5.56 and 5.31 in high magnetic fields. The residual epoxy group is reflected in the infrared absorption spectrum.
This can be confirmed from the fact that the absorption of epoxy groups at 905 to 920 cm ^-1 did not change before and after the reaction. [Effect of the invention] The reaction product has all or a part of the hydroxyl group, which generally has poor reactivity, converted to the group of the above formula Depending on the reactivity of the epoxy resin as well as the functionality provided by the group of formula [], a wide range of reaction configurations can be achieved. A typical example of the reaction product is as follows. [In the formula, n represents an integer of 1 or more. ] Various reactions can be expected due to the conjugated double bond of the A moiety introduced here. For example, (a) When reacted with amines, a Michael type addition reaction occurs and amines are added. When a polyamine is used as a curing agent, it reacts with the epoxy group and also with the carbon-carbon unsaturated group, resulting in a tough cured product with a high crosslink density. (b) Since it has radical polymerizability, it is possible to copolymerize with an ethylenic monomer and synthesize a graft polymer having carbon-carbon bonds as resin chains. Furthermore, since polymerization occurs in the presence of a general free radical catalyst or by ultraviolet rays or electron beams, it is possible to cause the reaction product to self-crosslink. (c) Easily undergoes radical addition when reacted with mercaptan compounds. Additionally, Lewis acids such as hydrogen halides are easily added. (d) Carbon-
It is possible to convert carbon unsaturated groups to epoxy groups, and polyepoxides can be synthesized. Of course, in the reaction product, since the epoxy group can be left as is, it is also possible to inherit the reactivity of conventional epoxy resins as is. As described above, the reaction product exhibits various interesting reactivities in many directions, so it can be used in many applications, for example in the field of paints. For example, when polyamine is used for curing, it is possible to provide a coating film that has a higher crosslinking density than conventional ones and also has stronger adhesive strength due to the acyl urethane bonds. The use of free radical catalysts, ultraviolet light, or electron beams can provide cured coatings through self-crosslinking, which is absent with conventional epoxy resins. By grafting acrylic resin to the reaction product, a wide range of properties (e.g. hardness, gloss,
Flexibility) can be freely designed. The characteristics of the reaction product can be utilized not only in the field of paints described above, but also in the fields of adhesives, molding resins, resins for electronic parts, and the like. As described above, the method of the present invention can produce an epoxy resin having a unique reactivity. [Example] Next, the present invention will be specifically explained by giving reference examples, examples, comparative examples, and application examples. Note that parts refer to parts by weight. Reference example 1 (Synthesis of methacryloyl isocyanate) Methacrylamide 17.9 in 100ml of chloroform
A solution of 20 ml of oxalyl chloride in 15 ml of chloroform was added dropwise to a suspension of 0.18 g of hydroquinone and 0.18 g of hydroquinone under ice cooling at 0° C. in a nitrogen stream. After dripping,
The mixture was returned to room temperature and stirred for about 100 minutes. 0.18 g of hydroquinone was added, and the mixture was further heated and stirred at 60°C for 4 hours. After cooling, the reaction solution was concentrated under reduced pressure, and the concentrate was further distilled under reduced pressure to obtain methacryloyl isocyanate as a colorless liquid (22.2 g; yield 94%) boiling at 52-53°C/39 mmHg. According to the infrared absorption spectrum of methacryloyl isocyanate obtained here, 2250 cm ¹
(NCO) and 1705cm ¹ (CO). Also, according to the nuclear magnetic resonance spectrum, δ (ppm) = 6.15 (1H, s), 5.75 (1H, s),
1.87 (3H, s) was observed. Reference Example 2 (Synthesis of acryloyl isocyanate) Add 95.25 g (0.75 mol) of oxalyl chloride to 150 ml of 1,2-dichloroethane at -30 to 0°C.
A solution of 35.5 g (0.5 mol) of acrylamide and 0.54 g of hydroquinone in 200 ml of 1,2-dichloroethane was added dropwise over about 30 minutes. After dropping, heat under reflux for about 1 hour, allow to cool, and perform vacuum distillation to obtain β.
-44.7 g of chloropropionyl isocyanate were obtained as a colorless liquid with a boiling point of 74-75°C/25 mmHg. The above β-chloropropionyl isocyanate
Add 20 g of Molecular Sieve 4A to a 20 ml solution of 13.35 g (100 mmol) in toluene, and in a nitrogen stream,
Heat to reflux for 13.5 hours. After cooling, the molecular sieve was filtered off, and the filtrate was distilled under reduced pressure to obtain acryloyl isocyanate. Boiling point 82-83
℃. According to the infrared absorption spectrum of acryloyl isocyanate obtained here, 2250 cm ¹ (NCO)
A peculiar absorption was observed at 1750 cm ¹ (CO). Also, according to the nuclear magnetic resonance spectrum, δ
(ppm) = 6.40-6.60 (1H, dd), 6.24-6.34 (1H,
d), 6.80 (1H, m) was observed. Example 1 Formulation Amount used (parts) [A] Bisphenol A type epoxy resin (“YD-011” manufactured by Toto Kasei Co., Ltd., epoxy equivalent 450-500,
2 hydroxyl groups/molecule, molecular weight 990-1000) 41.7 Xylene 12.5 [B] Propylene glycol monomethyl ether acetate (Dow Chemical Co., Ltd. “Dowanol
PMA'') 29.2 [C] Methacryloyl isocyanate 4.6 Pour mixture [A] into a 200ml four-necked flask equipped with a stirrer, thermometer, decanter, dropping funnel, and nitrogen blowing tube, heat to an internal temperature of 150°C, and leave for about 2 hours. The water in the epoxy resin was removed by refluxing the xylene. Next, blend [B] was added and diluted while the internal temperature was lowered to room temperature, and then blend [C] was added dropwise from the dropping funnel over a period of 20 minutes under a nitrogen stream.
The reaction temperature rose to 50°C. After about 30 minutes, the infrared absorption spectrum of the reaction mixture was measured at 2240 cm ¹
After confirming that the absorption of (NCO) has disappeared,
The reaction has ended. Note that the above raw materials other than the epoxy resin were dried using a molecular sieve 4A for one day or more before use. Methacryloyl isocyanate was handled with particular care to avoid exposure to air. The properties of the obtained reaction product solution are as shown in Table 1. Example 2 Formulation Amount used (parts) [A] Bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd. "YD-014", epoxy equivalent 950, number of hydroxyl groups 3.7/molecule, molecular weight 1400) 28.6 Xylene 18.5 [B] Cellosolve Acetate 37.0 [C] Methacryloyl isocyanate 8.3 1,2-dichloroethane 7.6 The same procedure as in Example 1 was conducted except that the raw materials in the above formulation were used. Table 1 shows the properties of the reaction product solution obtained. Example 3 Formulation Amount used (parts) [A] Bisphenol A and hydrogenated bisphenol A
Epoxy resin composed of and epichlorohydrin (“ST-5100” manufactured by Toto Kasei Co., Ltd., epoxy equivalent: 950) 20 Xylene 11 [B] Propylene glycol monomethyl ether acetate 21 [C] Methacryloyl isocyanate 1.58 Other than using the raw materials in the above formulation , carried out in the same manner as in Example 1. Table 1 shows the properties of the reaction product solution obtained. Example 4 Formulation Amount used (parts) [A] Bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd. "YD-014") 147.8 Xylene 72.1 [B] Azelaic acid (manufactured by Emerox Co., Ltd.) 12.3 Dimethylbenzylamine 0.3 [C] Propylene glycol monomethyl ether acetate 168.2 [D] Methacryloyl isocyanate 8.9 1,2-dichloroethane 22.9 Charge blend [A] into a 500 ml four-necked flask, dehydrate in the same manner as in Example 1, cool the internal temperature to 180°C, and blend [B] was added. The reaction temperature was raised to 140° C., and the reaction was continued for 4 hours. When the acid value of the reaction mixture became 0.7 or less, the reaction was terminated. After cooling the reaction mixture to 100°C, formulation [C] was added to dilute it. Below, add formulation [D] in the same manner as in Example 1,
Made it react. Table 1 shows the properties of the reaction product solution obtained. Example 5 Formulation Amount used (parts) [A] Bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd. "YD-014") 147.8 Xylene 72.1 [B] Azelaic acid (manufactured by Emerox Co., Ltd.) 12.3 Dimethylbenzylamine 0.3 [C] Propylene glycol monomethyl ether acetate 168.2 [D] Methacryloyl isocyanate 22.2 The same procedure as in Example 4 was conducted except that the raw materials in the above formulation were used. Table 1 shows the properties of the reaction product solution obtained. Example 6 Formulation Amount used (parts) [A] Bisphenol A type epoxy resin (manufactured by Toto Kasei Co., Ltd. "YD-014") 147.8 Xylene 72.1 [B] Azelaic acid (manufactured by Emerox Co., Ltd.) 12.3 Dimethylbenzylamine 0.3 [C ] Propylene glycol monomethyl ether acetate 168.2 [D] Methacryloyl isocyanate 57.7 The same procedure as in Example 4 was carried out except that the raw materials in the above formulation were used. Table 1 shows the properties of the reaction product solution obtained. Example 7 Formulation Amount used (parts) [A] Bisphenol A type epoxy resin (“YD-014” manufactured by Toto Kasei Co., Ltd.) 20 Xylene 15 Cellosolve acetate 10 [B] β-chloropropionyl isocyanate 7 [C] Butyl acetate 100 [D] Triethylamine 6 Blend [A] was charged into a four-necked flask equipped with a stirrer, thermometer, nitrogen blowing tube, and decanter, and refluxed for 1 hour to dissolve the epoxy resin and remove water in the resin. After the resin solution was cooled to room temperature, formulation [B] was added dropwise from the dropping funnel over 30 minutes. The temperature of the reaction solution rose from 25°C to 35°C. Blend [C] was added little by little to this reaction solution from the dropping funnel to dilute it. Formulation [D] was then added to perform dehydrochlorination. After the addition was complete, stirring was continued for 3 hours, and the resulting crystals were filtered out using a glass filter.
A solution of the desired reaction product was obtained. Its characteristics are shown in Table 1. Comparative example 1 formulation Usage amount (parts) [A] Bisphenol A type epoxy resin (manufactured by Toto Kasei "YD-014") 147.8 Xylene 72.1 [B] Azelaic acid (manufactured by Emerox) 12.3 Dimethylbenzylamine 0.3 [C] Propylene Glycol monomethyl ether acetate 168.2 The same procedure as in Example 4 was conducted except that the raw materials in the above formulation were used. Table 1 shows the properties of the reaction product solution obtained. Application Examples 1 to 3 “SUNMIDE #305-70” manufactured by Sanwa Kagaku Co., Ltd. (nonvolatile content 70 wt%) was added as a polyamine curing agent to each reaction product solution obtained in Examples 5, 6 and Comparative Example 1.
were mixed in the formulation shown in Table 2 to obtain a curable coating composition. This composition was applied to a clean tin steel plate with a thickness of 0.8 mm using a bar coater so that the dry film thickness was 20 μm, and baked at 100° C. for 30 minutes to obtain a cured coating film. The pencil hardness of this coating film and the xylene rubbing test results are shown in Table 2. In addition, in the xylene rubbing test results, O means that the coating film is not damaged even after 50 rubbings, and × means that the coating film dissolves under the same conditions. Application Examples 4 to 6 Dimethyl phthalate of methyl ethyl ketone peroxide was added to each reaction product solution obtained in Examples 5 and 6 and Comparative Example 1 as a radical curing catalyst.
A curable coating composition was obtained by mixing a 55 wt % solution (eg, "Kayamek A" manufactured by Kayaku Nouri Co., Ltd.) and 6 wt % cobalt naphthenate in the formulation shown in Table 3.
This composition was used in the same manner as in Application Examples 1 to 3 to obtain a cured coating film. The pencil hardness of this coating film and the xylene rubbing test results are shown in Table 3. Application Example 7 2 parts of a photosensitizer ("U-1173" manufactured by Merck & Co.) was added to 100 parts of the reaction product solution obtained in Example 2 to obtain a photocurable coating composition. This composition was applied to a clean tin plate with a thickness of 0.8 mm using a bar coater so that the dry film thickness was 20μ, and this was pre-dried at 70°C for 5 minutes to sufficiently evaporate the solvent in the paint film. Thereafter, actinic light treatment was performed under the following conditions to obtain a cured coating film. This coating film had a pencil hardness of 2H and did not cause any abnormality on the coating surface even in an acetone rubbing test (50 times). Chemical light treatment A high-pressure mercury lamp HI-40N (80W/cm condensing lamp) manufactured by Nippon Battery Co., Ltd. is placed at a height of 80 mm from the conveyor surface with the length direction of the lamp perpendicular to the conveyor traveling direction, and the conveyor speed is Process at 4 m/min.

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Claims (1)

[Claims] 1 Epoxy resin and/or epoxy resin derivative having a hydroxyl group and the formula: [In the formula, R represents H or a lower alkyl group. ] by reacting an isocyanate compound represented by the formula: [In the formula, R has the same meaning as above. ] A method for producing an epoxy resin and an epoxy resin derivative having an unsaturated group, characterized by obtaining a reaction product having a structure substituted with a group represented by the following. 2. The manufacturing method of item 1 above, which uses bisphenol A type epoxy resin as the epoxy resin. 3. The production method according to item 1 above, which uses a reaction product of an epoxy resin and a carboxylic acid as the epoxy resin derivative. 4. The production method of item 1 above, wherein the reaction is carried out in an inert solvent. 5 Epoxy resin and/or epoxy resin derivative having hydroxyl group and formula: [In the formula, Hal represents a halogen. R has the same meaning as above. ] by reacting an isocyanate compound represented by the formula: [Wherein, Hal and R have the same meanings as above. ] and then treated with a dehydrohalogenating agent to form the formula: [In the formula, R has the same meaning as above. ] A method for producing an epoxy resin and an epoxy resin derivative having an unsaturated group, the method comprising obtaining a reaction product having a structure converted into a group represented by the following. 6. The manufacturing method according to item 5 above, wherein a bisphenol A type epoxy resin is used as the epoxy resin. 7. The production method according to item 5 above, which uses a reaction product of an epoxy resin and a carboxylic acid as the epoxy resin derivative. 8. The production method of item 5 above, wherein the reaction is carried out in an inert solvent.