JPS6258376B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a method for producing epoxy (meth)acrylate. More specifically, the present invention relates to a method for stably producing epoxy (meth)acrylate without gelation when producing epoxy (meth)acrylate from an epoxy resin and a carboxylic acid component containing (meth)acrylic acid. In this specification, the term (meth)acrylic acid is used as a general term for acrylic acid and/or methacrylic acid.
Furthermore, the term epoxy (meth)acrylate will be used as a general term for compounds having an atomic group produced by the reaction of an epoxy resin with acrylic acid and/or methacrylic acid. In recent years, epoxy (meth)acrylates have been rapidly expanding as low-volatile polymerizable monomers, low-volatile resins, anaerobic resins, heat-resistant/corrosion-resistant resins, and ultraviolet curing resins, and are usually used in the temperature range of 70 to 150°C. It is produced by a method in which an epoxy resin and (meth)acrylic acid are reacted in the presence of a reaction catalyst and a radical polymerization inhibitor. However, since (meth)acrylic acid and epoxy (meth)acrylate produced by reaction have high radical polymerizability, the entire system tends to polymerize and gel during the production reaction. This gelation during the production reaction is likely to occur when a commonly used iron-based reaction apparatus or raw materials stored in an iron-based container are used, and is a problem in the production of epoxy (meth)acrylate. It has become a big problem. In order to prevent gelation during this manufacturing reaction, if the amount of a conventional radical polymerization inhibitor such as hydroquinone is increased, the resulting epoxy (meth)acrylate will contain a large amount of the radical polymerization inhibitor. If such epoxy (meth)acrylate is used directly without purification, a new problem arises in that the curability is significantly deteriorated. In view of the current situation, the present inventors have conducted intensive research on a method for preventing gelation during the reaction when producing epoxy (meth)acrylate from epoxy resin and (meth)acrylic acid.
Gelation can be prevented by coexisting a specific nitrogen atom-containing chelating agent in the reaction system for producing epoxy (meth)acrylate from epoxy resin and (meth)acrylic acid. ) acrylate can be obtained, leading to the completion of the present invention. Therefore, an object of the present invention is to provide a method for stably producing epoxy (meth)acrylate with excellent hue from an epoxy resin and (meth)acrylic acid without gelation. That is, the method for producing epoxy (meth)acrylate of the present invention comprises an epoxy resin (A) and a carboxylic acid component (B) containing 30% or more of (meth)acrylic acid in terms of carboxyl group equivalents (hereinafter referred to as carboxylic acid component). acid component (B)) in the presence of a catalyst and a radical polymerization inhibitor while stirring the reaction system.
When producing epoxy (meth)acrylate by reacting in the temperature range of It is characterized by the coexistence of both. In the present invention, epoxy (meth)acrylate is obtained from an epoxy resin (A) and a carboxylic acid component (B), but the epoxy resin (A) has two or more epoxy groups in one molecule. , what is usually called an epoxy resin can be used.
(Epoxy resins are introduced in detail in many explanatory books and reports.For example, "Epoxy Resins" edited by Hiroshi Kakiuchi (Showa Do, published September 30, 1972), pp. 51-108, Pages 151 and 154 or “Epoxy Resin” edited by Kuniyuki Hashimoto (Nikkan Kogyo Shimbun, Showa
Published October 30, 1944, Plastic Materials Course (1) pp. 13-48. ) Among these epoxy resins,
So-called bisphenol type epoxy resin which is a condensate of bisphenol A and epichlorohydrin;
So-called novolac-type epoxy resin, which is a condensation product of novolac resin such as phenol or cresol, and epichlorohydrin; So-called glycol-type epoxy resin, which is a condensation product of glycol and epichlorohydrin; triglycidyl isocyanurate; diglycidyl hydantoin; 1.1. 3-tris (4
-glycidyloxyphenyl)propane; 1.
1,2,2-tetrakis(4-glycidyloxyphenyl)ethane and the like are particularly useful as the epoxy resin (A) of the present invention. The carboxylic acid component (B) in the present invention is (meth)
Acrylic acid expressed as carboxyl group equivalent: 30
% or more (however, 1 equivalent of carboxylic acid anhydride group is calculated as 2 equivalents of carboxyl group. The same applies hereinafter). When the content of (meth)acrylic acid is less than 30%, the polymerizability of the obtained epoxy (meth)acrylate decreases, which is not preferable. Acid components other than (meth)acrylic acid are used for the purpose of adjusting the molecular weight of epoxy (meth)acrylate, adjusting polymerization reactivity, or improving physical properties such as flexibility, thermal properties, and flammability of cured products. Any carboxylic acid or carboxylic acid anhydride that can react with the epoxy resin can be selected and used. Examples of such carboxylic acids and carboxylic acid anhydrides include monovalent carboxylic acids such as acetic acid, butyric acid, octylic acid, naphthenic acid, benzoic acid, salicylic acid or linseed oil fatty acids; acrylic anhydride or methacrylic anhydride, etc. Monovalent carboxylic acid anhydrides; maleic acid, succinic acid, adipic acid, malic acid, phthalic acid, fumaric acid, tetrahydrophthalic acid, 3,6-endomethylenetetrahydrophthalic acid, dimer acid, alkenylsuccinic acid, tetrahydrophthalic acid, Bromphthalic acid, tetrachlorophthalic acid, 4,5-dibromotetrahydrophthalic acid,
3,6-endomethylenehexachlorophthalic acid,
Sodium 5-sulfoisophthalate, trimellitic acid, pyromellitic acid or 1,2,3,4-
Polyhydric carboxylic acids such as tetracarboxybutane and their acid anhydrides; maleic acid monomethyl ester, maleic acid mono(2-hydroxyethyl) ester, or ethylene obtained by ring-opening addition of 2 moles of maleic anhydride to 1 mole of ethylene glycol. Examples include half esters of polycarboxylic acids such as glycol dimaleate and alcoholic hydroxyl group-containing compounds. The usage ratio of the epoxy resin (A) and the carboxylic acid component (B) in the present invention is 1 equivalent of the carboxyl group contained in the carboxylic acid component (B) per 1 equivalent of the epoxy group contained in the epoxy resin (A). It is preferable that the above is the case. If the ratio of carboxyl groups is less than 1 equivalent, the amount of epoxy groups will be relatively large and coloration will occur easily due to side reactions, which is not preferable. As the catalyst used for reacting the epoxy resin (A) and the carboxylic acid component (B), those commonly used in the technical field can be used.
Examples of such catalysts include metal hydroxides such as potassium hydroxide and lithium hydroxide; metal halides such as lithium chloride, potassium bromide, tin chloride, potassium chloride, lithium bromide, zinc chloride, and zirconium chloride. Class: ethanolamine, laurylamine, aniline, dibutylamine, morpholine, piperidine, diphenylamine, triethylamine, dimethylaniline, triethylenediamine, pyridine, diethylamine hydrochloride, dimethylamine acetate, trimethylamine hydrochloride, tetramethylalmonium bromide, trimethylbenzyl Amines such as ammonium chloride, their inorganic and organic acid salts, and quaternary ammonium salts; amides such as N/N-dimethylformamide; organic acid alkali metal salts such as potassium acetate and sodium phthalate; benzene phosphon Acids, phosphonic acids and phosphonium salts such as triphenylmethylphosphonium iodide; sulfonic acids and sulfonium salts such as para-toluenesulfonic acid and triphenylsulfonium chloride; Lewis acid type compounds such as boron trifluoride, etc. and one or two of these compounds
More than one species can be used. Among them, amines and their inorganic and organic acid salts, as well as
A compound selected from the group consisting of ammonium salts can be used as a particularly advantageous catalyst since it causes few side reactions. The amount of such a catalyst used is usually in the range of 0.001 to 5 parts by weight, based on 100 parts by weight of the total amount of the epoxy resin (A) and the carboxylic acid component (B). In the reaction between the epoxy resin (A) and the carboxylic acid component (B), a radical polymerization inhibitor is used together with the catalyst described above, and (meth)acrylic acid contained in the carboxylic acid component (B) used in the present invention Usually,
Since a radical polymerization inhibitor is added to prevent polymerization during storage, the reaction with the epoxy resin (A) can be carried out without adding a radical polymerization inhibitor again. However, it can be further added and used if necessary. Examples of such radical polymerization inhibitors include P-benzoquinone, naphthoquinone, p-toluquinone,
2,5-diphenyl-P-benzoquinone, 2,6
- Quinones such as dichloroquinone; polyhydric phenols such as hydroquinone, pt-butylhydroquinone, tolhydroquinone, catechol, pt-butylcatechol, tetrachlorohydroquinone, pyrogallol, hydroquinone monomethyl ether, and their alkyl ethers ; Phenols such as di-t-butyl para-cresol and phenol; Copper salts such as copper naphthenate and copper chloride; Nitro compounds such as picrylic acid, dinitrophenol and trinitrotoluene; and one of these compounds. A species or two or more species can be used. The amount of such a radical polymerization inhibitor to be used, including the amount if the (meth)acrylic acid contains a radical polymerization inhibitor, is based on the amount of the epoxy resin (A) and the carboxylic acid component (B). total amount
The amount is usually in the range of 0.0001 to 0.5 parts by weight per 100 parts by weight. In the present invention, the epoxy resin (A) and the carboxylic acid component (B)
The reaction with is carried out within the temperature range of 70-150°C. When the reaction temperature is higher than this range, the reaction system tends to gel, and when it is lower than this range, the reaction takes a long time, both of which are unfavorable. In the present invention, it is necessary to stir the reaction system in order to proceed the reaction uniformly without gelation. The degree of stirring that is commonly used in the technical field is sufficient, and the stirring method that is commonly used in the technical field can be appropriately used. Nitrogen-containing chelating agent (C) used in the present invention
As the compound, one or more compounds selected from the group consisting of nitrogen atom-containing carboxylic acids, salts and complex salts of the carboxylic acids are used. Examples of such compounds include amino acids such as glycine, N-methylglycine, alanine, β-alanine, α-aminobutyric acid, cysteine, threonine, hydroxyproline, glycylglycine, N·N-dimethylglycine; Acetic acid, iminodipropionic acid, N-methyliminodiacetic acid, N-(3.
3-dimethylbutyl)iminodiacetic acid, N-phenyliminodiacetic acid, N-(2-hydroxyethyl)
Iminodiacetic acid, N-(2-mercaptoethyl)iminodiacetic acid, N-(2-hydroxyethyl)iminodipropionic acid, N-(3-hydroxypropyl)iminodipropionic acid, N-(2-hydroxycyclohexyl)iminodiacetic acid , N-(2-methoxyethyl)iminodiacetic acid, N-(2-hydroxybenzyl)iminodiacetic acid, N-(3-carboxyphenyl)iminodiacetic acid, N-(carbamoylmethyl)iminodiacetic acid, N-(2-amino Ethyl)iminodiacetic acid, N-(2-aminoethyl)iminodipropionic acid, nitrilotriacetic acid, N-carboxymethyliminodipropionic acid, nitrilotripropionic acid, N-(2-carboxyethyl)iminodiacetic acid, N-(2- Methyl-2-carboxyethyl)iminodiacetic acid, N・N′-ethylenediaminediacetic acid, N・N′-ethylenediaminedipropionic acid, N・N′-di(2-hydroxyethyl)ethylenediaminediacetic acid, N-n-butyl Ethylenediaminetriacetic acid, N-cyclohexylethylenediaminetripropionic acid, N-(2
-hydroxycyclohexyl)ethylenediaminetriacetic acid, N-(2-hydroxyethyl)ethylenediaminetriacetic acid, N-benzylethylenediaminetriacetic acid, ethylenediaminetetraacetic acid, ethylenediaminetetrapropionic acid, N・N'-
Di(2-carboxyethyl)ethylenediaminediacetic acid, N・N'-di(1-carboxyethyl)ethylenediaminediacetic acid, 1,2-propylenediaminetetraacetic acid, trimethylenediaminetetraacetic acid, tetramethylenediaminetetraacetic acid, pentamethylene Diaminetetraacetic acid, octamethylenediaminetetraacetic acid, octamethylenediaminetetrapropionic acid, N・N'-(2-carboxyethyl)octamethylenediaminediacetic acid, 1,2-cyclopentyldiaminetetraacetic acid, 1,2-cyclohexyldiaminetetraacetic acid Acetic acid, 1,2-cyclohexyldiaminetetrapropionic acid, 1,3-
Cyclohexyldiaminetetraacetic acid, 1,4-cyclohexyldiaminetetrapropionic acid, 1.
3,5-triaminocyclohexanehexaacetic acid,
2-hydroxytrimethylenediaminetetraacetic acid, 2,2'-ethyl etherdiaminetetraacetic acid, 2,2'-ethylthioetherdiaminetetraacetic acid, bis(ethyl iminodiacetate) methylamine, diethylenetriaminepentaacetic acid, diethylenetriaminepentapropionic acid, 2 -(2-Iminodiacetic acid ethoxy)-2'-iminodiacetic acid-ethyl ether, trimethylenetetraminehexaacetic acid, triethylenetetraminehexapropionic acid, N・N′-dimethyltriethylenetetramine-N″・N″・N・N -Tetraacetic acid, N・N'-
Dimethyltriethylenetetramine-N″・N″・N
- Aminopolycarboxylic acids and polyaminopolycarboxylic acids such as N-tetrapropionic acid; examples include ammonium salts, metal salts, and metal complexes of these compounds. The metals that form such metal salts and metal complexes include lithium, sodium, potassium, magnesium,
Examples include calcium, barium, lead, gallium, manganese, cobalt, nickel, copper, zinc, zirconium, cadmium, lanthanum, cerium, and gadolinium. The amount of the nitrogen atom-containing chelating agent (C) used is preferably 0.0001 part by weight or more, based on 100 parts by weight of the total amount of the epoxy resin (A) and carboxylic acid component (B). . If the amount used is less than this, the excellent effects of the present invention will not be fully exhibited, which is not preferable. Nitrogen atom-containing chelating agent (C)
The upper limit of the amount used is not particularly limited, but usually an amount of 2 parts or less per 100 parts of the total amount of epoxy resin (A) and carboxylic acid component (B) is sufficient to achieve its effect. Demonstrate. The nitrogen atom-containing chelating agent (C) can be made to coexist in the reaction system, for example, by the following method. However, the present invention is not limited to these examples. (a) Prior to the start of the reaction, it is mixed in advance with the epoxy resin (A) and/or the carboxylic acid component (B). (b) At the start of the reaction, it is charged into the reactor along with other raw materials. (c) After the epoxy resin (A) and the carboxylic acid component (B) are reacted to some extent, a nitrogen atom-containing chelating agent (C) is added to the reaction system. However, it must be added before the reaction is completed. The epoxy (meth)acrylate thus obtained according to the present invention can be used for various purposes in the same manner as conventionally known epoxy (meth)acrylates. For example, the obtained epoxy (meth)acrylate can be used as paint resin, FRP molding resin, casting resin, etc. with or without addition of polymerizable monomers as necessary. . Based on the present invention, it is possible to produce epoxy (meth)acrylate which has such a wide range of uses stably and with good color without gelling during the production reaction, making a great contribution to the technical field. be. Although it is not theoretically clear why the method of the present invention exhibits such excellent effects in preventing gelation and coloring during the production of epoxy (meth)acrylate, it is difficult to explain why the method of the present invention exhibits excellent effects in preventing gelation and coloring during the production of epoxy (meth)acrylate. Compared to the cases where C) is not present or when other chelating agents are present, the gelling and coloring prevention effects are surprising. Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples, but it goes without saying that the present invention is not limited to these Examples. In the examples, "parts" represent "parts by weight" unless otherwise specified, and the numbers in parentheses after "parts" represent the equivalent weight of the epoxy group or the equivalent weight of the carboxyl group. Example 1 Total condenser, thermometer, gas introduction pipe,
In a stainless steel (SUS 304) reaction vessel equipped with a heating device, a cooling device, a stirring device, and a raw material inlet, 2492 parts (14 603 parts (7 equivalents) of methacrylic acid, 0.4 parts of bydroquinone, 10 parts of triethylamine, and 0.4 parts of ethylenediaminetetraacetic acid were added, and the temperature was raised to 105°C with stirring in an air atmosphere, and the temperature was maintained at that temperature for 1 hour. After the reaction, 603 parts (7 equivalents) of methacrylic acid was further added and the reaction was carried out at a temperature of 105° C. for 8 hours to obtain epoxy methacrylate with an acid value of 2.1. Next, this epoxy methacrylate 65
1 part was dissolved in 35 parts of styrene to obtain resin (1). The hue, viscosity, curing properties, and mechanical properties of the cured product (cast plate) of this resin (1) were measured. Results first
Shown in the table. Comparative Example 1 When an attempt was made to produce epoxy methacrylate in the same manner as in Example 1 except that 0.4 part of ethylenediaminetetraacetic acid was not used, the entire system gelled 4.5 hours after the start of the reaction. The reaction solution extracted 10 minutes before gelation has an acid value.
It was a brown liquid with a weight of 12.3. 65 parts of this extracted reaction solution was dissolved in 35 parts of styrene to obtain a resin (hereinafter referred to as comparative resin (1)). This comparison resin
Regarding (1), various physical properties were measured in the same manner as in Example 1. The results were as shown in Table 1. Comparative Example 2 Epoxy methacrylate was obtained in the same manner as in Example 1, except that 6 parts of hydroquinone was used in place of 0.4 part of ethylenediaminetetraacetic acid. The acid value of this epoxy methacrylate was 2.7. Using this epoxy methacrylate, a resin (hereinafter referred to as comparative resin (2)) was obtained in the same manner as in Example 1. Table 1 shows the physical properties of comparative resin (2) measured in the same manner as in Example 1. The Hazen value of hue was high and the curing properties were also poor.

【table】

[Table] Examples 2 to 10 and Comparative Examples 3 to 6 Examples except that in Example 1, various nitrogen atom-containing chelating agents (C) listed in Table 2 were used in place of 0.4 part of ethylenediaminetetraacetic acid. Each resin which is each epoxy methacrylate and its mixture with styrene was obtained in the same manner as in Example 1. Table 2 shows the type and amount of the nitrogen atom-containing chelating agent (C), the acid value of each epoxy methacrylate obtained, and the hue and viscosity of each resin. Table 2 also shows the results of similar evaluations using chelating agents other than the nitrogen atom-containing chelating agent (C).

【table】

[Table] Example 11 In Example 1, all parts of the reactor that come into contact with the reaction liquid were made of glass, and methacrylic acid 1206
(14 equivalents) instead of stainless steel (SUS304)
Acrylic acid 1008 stored in a drum for 6 months
An epoxy acrylate was obtained in the same manner as in Example 1 except that 14 parts (14 equivalents) were used. There was no gelation of the reaction system, and the acid value of the obtained epoxy acrylate was 1.9. The resin liquid (styrene content: 35%, same hereinafter) had a Hazen of 170. Comparative Example 7 In Example 11, an attempt was made to produce epoxy acrylate in the same manner as in Example 19 except that 0.4 part of ethylenediaminetetraacetic acid was not used, but the entire system gelled 4 hours after the start of the reaction. The acid value of the reaction solution 7 minutes before gelation was 17. Example 12 In Example 11, 1 part of ethylenediaminetetraacetic acid was added in place of 0.4 part of ethylenediaminetetraacetic acid.
Epoxy acrylate with an acid value of 2.3 was obtained in the same manner as in Example 19 except that 0.4 part of calcium salt was used. Example 13 Epoxy acrylate was prepared in the same manner as in Example 11, except that instead of adding 0.4 part of ethylenediaminetetraacetic acid into the reaction system from the beginning of the reaction, it was added into the reaction system 3.5 hours after the start of the reaction. I got it. The acid value of the obtained epoxy acrylate was 2.0. Moreover, the Hazen of the resin liquid was 230. Example 11 “Araldite GY250” (manufactured by Ciba Corporation, epoxy equivalent
185 bisphenol type epoxy resin) and 0.5 parts of hydroquinone were added.
The temperature was raised to 105° C. with stirring under an air atmosphere. Next, a mixture of 1206 parts (14 equivalents) of methacrylic acid, 10 parts of 1,2-cyclohexyldiaminetetraacetic acid, and 20 parts of trimethylbenzylammonium chloride was added dropwise over 3 hours from a dropping device installed at the raw material input port. did. During this time, the reaction temperature was controlled so as not to exceed 110°C. Thereafter, the reaction was further carried out for 7 hours at 105°C to obtain epoxy methacrylate with an acid value of 2.7. Comparative Example 8 Example 14 except that 10 parts of 1,2-cyclohexyldiaminetetraacetic acid was not used in Example 14.
An attempt was made to produce epoxy methacrylate in the same manner. However, the entire system gelled 3.5 hours after the start of the reaction. Example 15 The following experiment was carried out using a reaction apparatus similar to that used in Example 19 except that the volume was 2, and using 520 parts of methacrylic acid freshly purified by vacuum distillation as the methacrylic acid. I did it. 1110 parts of “Araldite GY250” (6
equivalent), 260 parts (3 equivalents) of the 520 parts of the above methacrylic acid, 0.16 part of hydroquinone, 0.03 part of iron naphthenate () (metal content 5%) (0.9 ppm as iron ions based on the total amount of the reaction mixture) Equivalent to.)
8 parts of triethylamine and 0.16 parts of ethylenediaminetetraacetic acid were added, the temperature was raised to 100°C while stirring in an air atmosphere, and after reacting at that temperature for 1 hour, the remaining 260 parts (3 equivalents) of the above methacrylic acid were added. was added and subsequently reacted at a temperature of 100°C for 10 hours to obtain epoxy acrylate with an acid value of 3.2. Comparative Example 9 In Example 15, an attempt was made to produce epoxy methacrylate in the same manner as in Example 15 except that 0.16 part of ethylenediaminetetraacetic acid was not used, but the entire system gelled 5.5 hours after the start of the reaction. Comparative Example 10 In Example 15, additional methacrylic acid 260
After adding 50% of the mixture, the mixture was stirred at a temperature of 100° C. for 3 hours to react, and then the stirring was stopped and the reaction was continued, and the reaction system turned into a gel 2 hours after the stirring was stopped. Comparative Example 11 In the same reactor used in Example 15, 1110 parts (6 equivalents) of "Araldite GY250" and 216 parts ( 3 equivalents), 0.15 parts of hydroquinone, 7 parts of triethylamine and 0.3 parts of ethylenediaminetetraacetic acid,
Raise the temperature to 100℃ while stirring in an air atmosphere,
After reacting at that temperature for 1 hour, the remaining 144 parts (2 equivalents) of acrylic acid was added and reacted at 100° C. for 5 hours to obtain epoxy acrylate with an acid value of 0. About this epoxy acrylate,
When the content of epoxy groups was measured by the hydrochloric acid-dioxane method, it was found to be 0.05 equivalent/100 g. Further, the Hazen of this epoxy acrylate resin liquid was 500 or more. Comparative Example 12 In Comparative Example 11, an attempt was made to produce epoxy acrylate in the same manner as in Comparative Example 11, except that 0.3 parts of acetylacetone was used instead of 0.3 parts of ethylenediaminetetraacetic acid, but the entire system turned into a gel 4 hours after the start of the reaction. It became. Example 16 In a reaction vessel similar to that used in Example 1, 2775 parts (15 equivalents) of "Araldite GY250" and 602 parts of methacrylic acid were added.
(7 equivalents), 13 parts of triethylamine, 0.4 parts of hydroquinone, and 0.4 parts of diethylenetriamineheptaacetic acid were added, and the temperature was raised to 100°C with stirring in an air atmosphere. After reacting at that temperature for 1 hour, methacrylic acid was further added. Add 430 parts (5 equivalents) and 441 parts (9 equivalents) of maleic anhydride to make 100
The reaction was carried out for 8 hours at a temperature of .degree. C. to obtain epoxy methacrylate having an acid value of 21. Hazen of the resin liquid is
It was 230. Example 12 In a reaction vessel similar to that used in Example 1, 1850 parts (10 equivalents) of “Araldite GY250” and methacrylic acid were added.
345 parts (4 equivalents), 0.4 parts of hydroquinone, 15 parts of trimethylbenzylammonium chloride, and 0.2 parts of ethylenediaminetetraacetic acid were added, and the temperature was raised to 100°C while stirring in an air atmosphere, and the mixture was reacted at that temperature for 30 minutes. 172 parts (2 equivalents) of methacrylic acid and 1856 parts of tetrabromophthalic anhydride
(8 equivalents) and reacted at a temperature of 100° C. for 9 hours to obtain epoxy methacrylate with an acid value of 3.8. (The resin liquid had a Hazen rating of 170.) Next, 65 parts of this epoxy methacrylate, styrene
35 parts, antimony trioxide 5 parts, cobalt octenoate (8% metal content) 0.3 parts and methyl ethyl ketone peroxide (oxide content 55%)
A resin composition obtained by blending 1.5 parts was cast between glass plates to obtain a flat plate with a thickness of 3 mm. As a result of testing the flammability of this flat plate using the oxygen index method,
The oxygen index was 31. Example 18 Acrylic acid containing N-(2-hydroxyethyl)iminodiacetic acid in an amount of 0.1 parts per 100 parts of acrylic acid and stored for 6 months in a stainless steel (SUS304) drum was used as acrylic acid. Using. In Example 1, ethylenediaminetetraacetic acid was not used, and 1206 parts (14 equivalents) of methacrylic acid was used.
An epoxy acrylate having an acid value of 2.0 was obtained in the same manner as in Example 1 except that 1008 parts (14 equivalents) of the above acrylic acid was used instead. The resin liquid had a Hazen of 230. Example 19 Acrylic acid was added to the same reaction vessel as used in Example 1.
720 parts (10 equivalents), 861 parts (10 equivalents) of methacrylic acid, 12 parts of triethylamine, 0.4 parts of hydroquinone
1.0 parts of N-(2-hydroxyethyl)ethylenediaminetriacetic acid and 536 parts (5 equivalents) of diethylene glycol diglycidyl ether as an epoxy resin were added, and the temperature was raised to 100°C with stirring in an air atmosphere, and at that temperature. After reacting for 30 minutes, 536 parts (5 equivalents) of diethylene glycol diglycidyl ether was added three times at 30 minute intervals while maintaining the temperature at 100°C. Then 100℃
The mixture was reacted for 5 hours at a temperature of 5.3 to obtain epoxy (meth)acrylate with an acid value of 5.3. The resin liquid had a Hazen of 200. Example 20 “Araldite” was placed in the same reaction pot as in Example 1.
GY250” 740 parts (4 equivalents), “Epicote 154” 1780
(10 equivalents), 0.4 parts of hydroquinone, 10 parts of triethylamine, 603 parts (7 equivalents) of methacrylic acid, and 0.4 parts of ethylenediaminetetraacetic acid, and placed in an atmosphere of a mixture consisting of 1 part air and 4 parts nitrogen. The temperature was raised to 110°C with stirring, and the reaction was carried out at that temperature for 1 hour. Then, 504 parts (7 equivalents) of acrylic acid was added, and the reaction was carried out at 110°C for 5 hours to produce epoxy (meth) with an acid value of 7.0. Obtained acrylate. The resin liquid had a Hazen of 190.

Claims (1)

[Claims] 1. An epoxy resin (A) and a carboxylic acid component (B) containing 30% or more of (meth)acrylic acid expressed as carboxyl group equivalents in the presence of a catalyst and a radical polymerization inhibitor. 70 to 150 while stirring the reaction system.
When producing epoxy (meth)acrylate by reacting in the temperature range of A method for producing epoxy (meth)acrylate with excellent hue, characterized by coexisting with epoxy (meth)acrylate. 2 Add nitrogen atom-containing chelating agent (C) to epoxy resin
The total amount of (A) and (meth)acrylic acid component (B) is 100
The method for producing epoxy (meth)acrylate according to claim 1, which is used in an amount of 0.0001 parts by weight or more as parts by weight.