JPS61272226A - Epoxy resin and derivative thereof having unsaturated group - Google Patents

Abstract

PURPOSE:The titled resin, obtained by substituting hydroxyl groups of a hydroxyl group-containing epoxy resin or a derivative thereof with a specific carbon- carbon unsaturated group and capable of assuming a wide range of reaction forms due to improved functionality and giving tougher cured articles than the conventional articles, etc. CONSTITUTION:A hydroxyl group-containing epoxy resin or a derivative thereof or both are reacted with an isocyanate compound expressed by formula I (R is H or lower alkyl), preferably in an insert solvent at 0-20 deg.C to give the aimed resin having a structure, in which the hydroxyl groups in the above- mentioned resin and/or derivative thereof are substituted by groups expressed by formula II. The compound expressed by formula I (R is lower alkyl) is obtained by reacting, e.g. an alpha-alkylacrylamide, with an oxalkyl halide. The compound expressed by formula I (R is H) is obtained by reacting, e.g. acrylamide, with the oxalyl halide and dehydrohalogenating the resultant reaction product.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to epoxy resins and epoxy resin derivatives having unsaturated groups and methods for producing them.

[Prior Art] Epoxy resins have excellent corrosion resistance, adhesive properties, electrical insulation properties, heat resistance, etc., and are used in various industrial fields such as paints, adhesives, molding agents, and 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 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 disadvantage that not only the epoxy group disappears due to the reaction with acrylic acid or methacrylic acid, but also that the unsaturated group can only be introduced up to 21[1].

[Circumstances of Completion of the Invention] The present applicant has the following formula: % Formula % [1 [In the formula, 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 (Patent application No.
225226), acryloyl isocyanate in which R is H 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 both of these functional groups. Since there is a carbonyl group 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 [I] can undergo various reactions (e.g., radical polymerization, anionic polymerization, trimerization, trimerization, (polar addition, addition of active hydrogen): in particular, acylisocyanate groups have a much higher reactivity than isocyanate groups. Utilizing this property, it is possible to cause alkenoyl isocyanate [I] to act on the secondary hydroxyl group of an epoxy resin, which generally has poor reactivity, under non-catalytic and non-heating conditions. It was discovered that carbon-carbon unsaturated groups can be introduced to enhance the functionality of epoxy resins, leading to the completion of the present invention.

[Object of the invention] The present invention improves the above-mentioned drawbacks of epoxy resins, and provides an epoxy resin whose functionality is enhanced by introducing carbon-carbon unsaturated groups using hydroxyl groups in the resin. and derivatives thereof.

[Configuration of the Invention] According to the present invention, an epoxy resin having a hydroxyl group and/or
Or, at least one of the hydroxyl groups of the epoxy resin derivative has the formula: % formula % [1] [wherein 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, the reaction product of the present invention is produced by first dissolving an epoxy resin in an inert solvent, and, in the case of xylene, for example, refluxing the solvent at about 150°C to remove water in the resin. Next, the resin solution is returned to a temperature of -20 to +50°C, preferably 0 to 20°C, and alkenoyl isocyanate [I] is added dropwise with stirring under a nitrogen stream to react. Since the reaction mixture generates heat when alkenoyl isocyanate [1] is added, it may be cooled, for example, in a water bath. Alkenoyl isocyanate [1] may be added as is, but it is preferably used after diluting with an inert solvent. The amount of alkenoyl isocyanate [I] added may be appropriately selected depending on the desired amount of substituting the hydroxyl groups in the epoxy resin with the groups of the above formula [II]. The end point of the reaction is NG at 2240 cm-' in the infrared absorption spectrum of the reaction mixture.
This can be confirmed by the disappearance of O 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, and alicyclic epoxy resin. Epoxy resins that themselves have hydroxyl groups can be used as they are. In the case of substances that do not have hydroxyl groups (e.g. diglyndyl ether of bisphenol A),
It is used by retaining the hydroxyl group by reacting 1 mole of dicarboxylic acid (e.g. azelaic acid) with 2 moles of the epoxy resin according to a conventional method to form a hydroxyl group by ring opening of the epoxy group with the carboxyl group. be able to. In addition, if there is no problem even if the epoxy group disappears, the above-mentioned compound having an active hydrogen that is reactive with the epoxy group may be applied to form a hydroxyl group, or, for example, ethanolamine may be allowed to act on the epoxy resin. It may be used by introducing a primary 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 [I] may be any inert solvent that does not have active hydrogen, such as pentane,
Aliphatic hydrocarbons such as 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. Carbonized hydrocarbon solvents, ether solvents such as ethyl ether, isopropyl ether, anisole, dioxane, and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, and isophorone, ethyl acetate, butyl acetate, propylene glycol monomethyl It can be appropriately selected and used from esters such as ether acetate and cellosolve acetate, acetonitrile, dimethylformamide, dimethyl sulfoxide, and the like. For epoxy resins, the use of the above-mentioned aromatic hydrocarbons is preferred.

The α-alkylacryloyl isocyanate [I] 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. lθ~0.1:1. Preferably 1.5 to 0.7:
-10 to +150°C in the presence of the above-mentioned inert solvent, preferably the above-mentioned halogenated hydrocarbon solvent at a molar ratio of 1
, preferably by reacting at a temperature of 0 to 80°C. When isolating α-alkyl acryloyl isocyanate [1] from the reaction mixture, the usual method (
For example, distillation, vacuum distillation).

In addition, acryloyl isocyanate [l] in which R is H,
Obtained as described in the specification of the above patent application. That is, acrylamide and the above oxalyl halide (especially oxalyl chloride) are mixed in a ratio of lO to 0.1:1. Preferably in a molar ratio of 1.5 to 0.7:1 (usually in the absence of a solvent, preferably in the presence of the above-mentioned inert solvent (particularly a halogenated hydrocarbon solvent), -50 to +150 ℃, preferably at a temperature of -30 to +100℃ to obtain a reaction mixture containing β-halopropionyl isocyanate as the main product.This reaction mixture is subjected to a conventional isolation method (e.g., distillation, vacuum distillation). Then, β-halopropionyl isocyanate is obtained, which is then treated with a dehydrohalogenating agent in the presence or absence of the above-mentioned inert solvent at a concentration of 0.1 to 100, preferably 0.1 to 100, per mole of the isocyanate. -50 to +200°C in a molar ratio of 1-10, preferably 0 to 1
By processing at a temperature of 50°C, the desired acryloyl isocyanate [■] is obtained. In addition, when isolating acryloyl isocyanate [I] from the reaction mixture, a conventional method may be employed in the same manner as described above.

In addition, using the above β-halopropionyl isocyanate and acting on the epoxy resin in place of the above-mentioned alkenoyl isocyanate [■], the hydroxyl group of the epoxy resin is converted to the formula: %Formula% [In the formula, Hal represents a halogen] . R has the same meaning as above.

] The desired reaction product can also be obtained by substituting with a group represented by the following and then converting it into the above formula [11] by treating with a dehydrohalogenating agent as described above.

The hydrogen halide product produced as a by-product may be separated by a conventional method (eg, filtration).

The above-mentioned dehydrohalogenating agent is not limited to β-halopropionyl isocyanate or a dehydrohalogenating agent in the usual sense, which requires the use of β-halopropionyl isocyanate in a theoretically at least equimolar amount to the above-mentioned functional group provided by it, etc. It includes dehydrohalogenation catalysts that can achieve the desired purpose even in relatively small amounts of moles or less, and specific examples thereof include the following: triethylamine, 1,8-diazabicyclo [5,4,0
] Undecene-7, pyridine, amines such as quinoline, alkali metal or alkaline earth metal hydroxides such as sodium hydroxide, potassium hydroxide, magnesium hydroxide, copper oxide, magnesium oxide, calcium oxide,
Metal oxides such as alumina, iron oxide, (Ph3P)t
Ru(CO)3, (ph3p).

Metal complex compounds such as Pt, metal halides such as lithium chloride, titanium tetrachloride, aluminum chloride, sodium chloride, metal salts such as zinc naphthenate, nickel acetate, barium sulfate, potassium phosphate, potassium t
- Metal alkoxides such as butoxide, sodium ethoxide, sodium isopropoxide, molecular sieves, synthetic zeolites such as porous glasses, boric acid, oxiranes, 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-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-triphenylfeldazyl, 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'-ditolyl trisulfide, p, p'-ditolyl tetrasulfide, dibenzyl tetrasulfide, tetraethylthiuram disulfide, etc. It will be done.

The reaction product of the present invention obtained by the above production method is
It is a pale yellow, transparent, viscous liquid that contains a solvent. The introduction of the group of formula [11] into the reaction product is due to the disappearance of the absorption of 2 240 c+n-' (NCO) in the infrared absorption spectrum of the reaction mixture as described above, and the fact that the group of formula [11] is introduced into the reaction product. The non-volatile content of the olefin bond in the magnetic resonance spectrum is in agreement with the theoretical value, and the H signal of the olefin bond in the magnetic resonance spectrum is the alkenoyl isocyanate [I].
δ (ppm) = 6.15, 5.75 to δ of high magnetic field
(ppm) = 5,56.

This can be confirmed by the shift to 5.31. The remaining epoxy group is 90% in the infrared absorption spectrum.
This can be confirmed from the fact that the absorption of epoxy groups between 5 and 920 cm-' did not change before and after the reaction.

[Effects of the Invention] The reaction product of the present invention has all or a part of the hydroxyl groups, which generally have poor reactivity, converted to the group of the above formula [11], and also has an epoxy group if necessary. In addition to the reactivity of conventional epoxy resins, the functionality of the group of formula [11] allows a wide range of reaction forms to be taken.

A typical example of the reaction product of the present invention 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 resins. Also,
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) Radical addition occurs easily when reacted with a mercaptan compound. Additionally, Lewis acids such as hydrogen halides are easily added.

(d) It is possible to convert a carbon-carbon unsaturated group into an epoxy group by reacting with an oxidizing agent such as hydrogen peroxide, and a polyepoxide can be synthesized.

Of course, in the reaction product of the present invention, 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 of the present invention exhibits various interesting reactivities in many directions, and therefore 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 an acrylic resin onto the reaction product, it becomes possible to freely design a wide range of properties (eg, hardness, gloss, flexibility). Not limited to the above paint field,
For example, in the fields of adhesives, molding resins, resins for electronic parts, etc., the characteristics of the reaction product of the present invention can be utilized to expand its application.

[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 I (Synthesis of methacryloyl isocyanate) 17.9 methacrylamide in 100 ml of chloroform
A solution of 20 ml of oxalyl chloride in 15 ml of chloroform was added dropwise to a suspension of 18 g of hydroquinone O and 18 g of hydroquinone O under water cooling at 0° C. in a nitrogen stream.

After dropping, 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 is concentrated under reduced pressure, and the concentrate is further distilled under reduced pressure to convert methacryloyl isocyanate into a colorless liquid (boiling at 52 to 39 mmHg).
22.2 g; yield 94%).

According to the infrared absorption spectrum of the methacryloyl isocyanate obtained here, specific absorption was observed at 2250 cm' (Neo) and 1705 cm' (Co). Furthermore, according to the nuclear magnetic resonance spectrum, δ(pp
m) = 6.15 (I H, s), 5.75 (I H, s)
, 1.87 (3H, s) was observed.

Reference Example 2 (Synthesis of acryloyl isocyanate) 95.25 g (0.75 mol) of oxalyl chloride was added to 1.
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 to 150 ml of 2-dichloroethane at -30 to 0° C. over about 30 minutes. After the dropwise addition, heating was carried out under reflux for about 1 hour, and after cooling, vacuum distillation was carried out to obtain 44.7 g of β-chloropropionyl isocyanate with a boiling point of 74 to 7.
Obtained as a colorless liquid at 5°C/25 tnmHg.

The above β-chloropropionyl isocyanate 13.35
Add 20 g of Molecular Sieve 4A to a solution of 10 g (100 n+ mol) in 20 ml of toluene, and add 20 g of Molecular Sieve 4A to a solution of
．． The mixture was heated to reflux for 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°C.

According to the infrared absorption spectrum of the acryloyl isocyanate obtained here, unique absorption was observed at 2250 cm' (NCO) and 1705 cm' (Co). Furthermore, according to the nuclear magnetic resonance spectrum, δ(pp
m) = 6.40 to 6.60 (I H, dd), 6°24
-6.34 (IH, d), 6.08 (IH, n+) were observed.

Example 1 Formulation Amount used (parts) [A]
Bisphenol A type epoxy resin 41.7 (manufactured by Tobu Kasei Co., Ltd. rYD-011J, epoxy equivalent 450-500
, 2 hydroxyl groups/molecule, molecular weight 900-1000) Xylene 12.5 [B] Propylene glycol monomethyl 29.2 Ether acetate (manufactured by Dow Chemical Company [Dowanol PMAJ]) [C] Methacryloyl isocyanate 4.6 Stirrer, thermometer Blend [A] was charged into a 200 ml four-hole flask equipped with a decanter, a dropping funnel, and a nitrogen blowing tube, heated to an internal temperature of 150° C., and xylene was refluxed for about 2 hours to remove water in the epoxy resin. Next, mix [
After adding B] and lowering the internal temperature to room temperature without diluting,
Formulation [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 and was found to be 2240 cm'.
After confirming that the absorption of (NGO) had disappeared, the reaction was terminated.

Note that the above raw materials other than the epoxy resin were dried with Molecular Sieve 4A for one day or more before use. The 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 28.6 (manufactured by Tobu Kasei Co., Ltd. rYD-014J, epoxy equivalent: 9501, number of hydroxyl groups: 3.7/molecule, molecular weight: 1400) Xylene 18.5 [B] Cellosolve acetate 37.0 [C] Methacryloyl isocyanate 8 .31.2-Dichloroethane 7.6 The same procedure as in Example I was carried out except that the above-mentioned raw materials were used. Table 1 shows the properties of the reaction product solution obtained.

Example 3 Formulation Amount used (parts) [A]
Bisphenol A and hydrogenated bis 20 Phenol A
and epichlorohydrin (rsT-5100J manufactured by Tobu Kasei Co., Ltd.,
5Q) Xylene '11 [B] Propylene glycol monomethyl 21 Ether acetate [C Comethacryloyl isocyanate 1.58 The same procedure as in Example 1 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 4 Formulation Amount used (parts) [A]
Bisphenol A type epoxy resin 147.8 (rYD-014J manufactured by Tobu Kasei Co., Ltd.) Xylene 72.1 [B]Azelaic acid (manufactured by Emerox Co., Ltd.) 12.3 Dimethylbenzylamine 0.3 [C] Propylene glycol monomethyl 168.2 Ether Acetate [D] methacryloyl isocyanate 8.91
．． 2-dichloroethane 22.950
Blend [A] was charged into a 0m1 four-hole flask, dehydrated in the same manner as in Example 1, and the internal temperature was cooled to 180°C.
] 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. The following is the same formulation as in Example 1 [
D] was added and reacted. Table 1 shows the properties of the reaction product solution obtained.

Example 5 Formulation Use! (Part) [A]
Bisphenol A type epoxy resin 147.8 (rYD-014J manufactured by Tobu Kasei Co., Ltd.) Xylene 72.1 [B]Azelaic acid (manufactured by Emerox Co., Ltd.) 12.3 Dimethylbenzylamine 0.3 [C] Propylene glycol monomethyl 168.2 Ether Acetate [D] Methacryloyl Isocyanate 22.2 The same procedure as in Example 4 was carried out except that the above-mentioned raw materials were used. Table 1 shows the properties of the reaction product solution obtained.

Example 6 Formulation Usage amount (parts) [A]
Bisphenol A type epoxy resin 147.8 (rYD-014J manufactured by Tobu Kasei Co., Ltd.) Xylene 72.1 [B]Azelaic acid (manufactured by Emerox Co., Ltd.) 12.3 Dimethylbenzylamine 0.3 [C] Propylene glycol monomethyl 168.2 Ether Acetate [D comethacryloyl isocyanate 57.7 The same procedure as in Example 4 was carried out except that the above-mentioned raw materials were used. Table 1 shows the properties of the reaction product solution obtained.

Example 7 Formulation Use 1i (parts) [
A] Bisphenol A type epoxy resin 20 (manufactured by Tobu Kasei Co., Ltd. rYD-014J) Xylene 15 Cellosolve acetate 10 [B] β-chloropropionyl physocyanate [C] Butyl acetate 100 [D Cotriethylamine 6 Stirrer, thermometer, nitrogen blowing Blend [A] was charged into a four-hole flask equipped with a tube and a 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. Next, blend [D] to perform dehydrochlorination.
] was added. After the addition was completed, stirring was continued for 3 hours, and the resulting crystals were filtered off using a glass filter to obtain a solution of the desired reaction product. Its characteristics are shown in Table 1.

Comparative example! Blend Amount used (parts), [A
] Bisphenol A type epoxy resin 147.8 (Tobu Kasei rYD-014J) Xylene 72.1 [B] Azelaic acid (manufactured by Emerox Co., Ltd.) 12.3 Dimethylbenzylamine 0.3 [C] Propylene glycol monomethyl 168.2 Ether Acetate Example 4 was carried out in the same manner as in Example 4, except that the above-mentioned raw materials were used. Table 1 shows the properties of the reaction product solution obtained.

Application Examples 1 to 3 rsUNM manufactured by Sanso Kagaku Co., Ltd. was added to each reaction product solution obtained in Example 5.6 and Comparative Example I as a polyamine curing agent.
IDE#305-70J (70wt% non-volatile content)
A hard flower coating composition was obtained by mixing the compositions shown in the table. This composition was coated on a clean tin steel plate with a thickness of 0°8 mm using a bar coater so that the dry film thickness was 20μ, and then heated at 100°C.
A cured coating film was obtained by baking for 30 minutes. The pencil hardness of this coating film and the xylene rubbing test results are shown in Table 2. Note that the xylene rubbing test results indicate that the coating film was not damaged even by rubbing 50 times, and ×: the coating film was dissolved under the same conditions.

Application Examples 4 to 6 A 55 wt % dimethyl phthalate solution of methyl ethyl ketone peroxide (e.g. "Kayamec A" manufactured by Kayaku Nouri Co., Ltd.) was added as a radical curing catalyst to each reaction product solution obtained in Examples 5 and 6 and Comparative Example 1. and 6 wt % cobalt naphthenate were mixed in the formulation shown in Table 3 to obtain a curable coating composition. 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 (rU-1173J manufactured by Merck & Co., Ltd.) 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 plate with a thickness of 0,
The coating was applied to an 8 mm tin plate using a bar coater to a dry film thickness of 20 μm, and after preliminary drying at 70°C for 5 minutes to sufficiently evaporate the solvent in the coating film, it was treated with actinic light under the following conditions. A cured coating film was obtained. The pencil hardness of this coating film was 2H, and no abnormality was caused on the coating film surface even in an acetone rubbing test (50 times).

Actinic light treatment A high-pressure mercury lamp HI-40N (80 W/cm condensing lamp) manufactured by Nippon Battery Co., Ltd. was 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 was adjusted. Process at 4 m/min.

Claims (1)

[Claims] 1. At least one hydroxyl group of an epoxy resin and/or an epoxy resin derivative having a hydroxyl group is represented by the formula: ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [In the formula, R is H or a lower alkyl group] show. ] A reaction product having a structure substituted with a group represented by the following. 2. The reaction product of item 1 above, wherein the epoxy resin is a bisphenol A type epoxy resin. 3. The reaction product of item 1 above, wherein the epoxy resin derivative is a reaction product of an epoxy resin and a carboxylic acid. 4. Epoxy resins and/or epoxy resin derivatives having hydroxyl groups and formulas: ▲ Numerical formulas, chemical formulas, tables, etc. ▼ [In the formula, R has the same meaning as above. ] At least one of the above hydroxyl groups is reacted with an isocyanate compound represented by the formula: ▲There are numerical formulas, chemical formulas, tables, etc.▼ [In the formula, R has the same meaning as above. ] A method for producing the above reaction product, characterized in that a reaction product having a structure substituted with a group represented by the following is obtained. 5. The production method of item 4 above, wherein the reaction is carried out in an inert solvent. 6. Epoxy resins and/or epoxy resin derivatives having hydroxyl groups and formulas: ▲ Numerical formulas, chemical formulas, tables, etc. are available▼ [In the formula, Hal represents halogen. R has the same meaning as above. [In the formula, Hal and R have the same meanings as above. ], and then treated with a dehydrohalogenating agent to form the formula: ▲There are numerical formulas, chemical formulas, tables, etc.▼ [In the formula, R has the same meaning as above. ] A method for producing the above-mentioned reaction product, characterized in that a reaction product having a structure converted into a group represented by the above is obtained. 7. The production method of item 6 above, wherein the reaction is carried out in an inert solvent.