JPH10330370A - Epoxy compound, its production and photosetting resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce the subject compound, excellent in compatibility with a bisphenol type or a novolak type epoxy resin and capable of providing a cured product excellent in impact and flex resistances and adhesion by binding an unsaturated fatty acid, etc., to a specific compound and then epoxidizing the resultant compound. SOLUTION: This epoxy compound represented by formula I R<1> is a 1-10C alkyl; R<2> is a mono- or a polyfunctional (k)-valent alcohol residue having an aromatic ring; [(m1)+(m2)] and (n) are each 1-20; (m1) is 1-10; (m2) is 0-10; (k) is >=1} is obtained by reacting (A) an unsaturated fatty acid represented by formula II [R<3> is H, a 1-10C alkyl, an aryl or an alkenyl; (m) and (n) are each 1-20] or its derivative with (B) a mono- or a polyfunctional (k)-valent alcohol having an aromatic ring (preferably benzyl alcohol, etc.), providing (C) an unsaturated fatty acid derivative represented by formula III and then epoxidizing the resultant component C by an oxidizing reaction.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy compound having an aromatic ring in its structure, which has good compatibility with other resins and whose cured product is excellent in impact resistance, bending resistance and adhesion. The present invention relates to a compound and a photocurable resin composition comprising the epoxy compound.

[0002]

2. Description of the Related Art Epoxy resins having a benzene ring include bisphenol A type and F type epoxy resins and novolak type epoxy resins obtained from phenol or cresol. However, these cured products are generally hard and brittle. Further, since the resin structure has a benzene ring, the weather resistance is poor, and the distance between the phenol structure portion and the epoxy structure portion has poor compatibility with other resins.
In order to improve the fragility of such a cured product, epoxy copolymers such as SBS and SIS using a rubber material have been developed.

[0003]

However, when these epoxy resins are used, their cured products are improved in terms of impact resistance and bending resistance as compared with the above-mentioned bisphenol type and novolak type epoxy resins. However, its high molecular weight makes it incompatible with other resins and poorly soluble in solvents,
It is difficult to handle when used as a paint or adhesive.

Further, in recent years, development of solvent-free paints and coating agents in consideration of environmental problems has been actively pursued. Among these, there are photocationically curable coatings, which are being used.
On the other hand, in the field of coating of beverage cans, a metal part of a can coated with a polyethylene terephthalate (PET) film is being used in order to improve the storage stability and productivity of the contents. The alicyclic epoxy used as a main component in the photocationically curable paint has poor adhesion to the film.

Therefore, it is an epoxy compound having excellent curability, has good compatibility with other resins, and its cured product has excellent impact resistance, flex resistance, and adhesion, and when used as a paint or adhesive. It is desired to develop an epoxy compound that is easy to handle, and a photocurable resin composition that has excellent adhesion to polyester-based resins such as PET by adding a compound that has cationic reactivity and has a benzene ring. It is rare.

[0006]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that an epoxy compound obtained by bonding a compound having an aromatic ring to an unsaturated fatty acid or the like, and then epoxidizing the compound, The inventors have found that the cured product has excellent compatibility with bisphenol-type and novolak-type epoxy resins and has excellent impact resistance, bending resistance, and adhesion, and has completed the present invention.

That is, the present invention provides an epoxy compound represented by the formula (1). Further, an unsaturated fatty acid represented by the following formula (2) or a derivative thereof (A)
Is reacted with a monofunctional or higher-valent alcohol having an aromatic ring to obtain an unsaturated fatty acid derivative (B) represented by the formula (3), and then the unsaturated fatty acid derivative (B) is epoxidized by an oxidation reaction. A method for producing the epoxy compound is provided. Further, the present invention provides a method for producing the epoxy compound, wherein the monofunctional or higher valent alcohol having an aromatic ring is any one of benzyl alcohol, p-nitrobenzyl alcohol and 2-phenoxyethanol. In addition, the present invention provides a photocurable resin composition comprising the epoxy compound. Hereinafter, the present invention will be described in detail.

[0008]

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[0009]

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[0010]

BEST MODE FOR CARRYING OUT THE INVENTION Epoxy compound The epoxy compound of the present invention is a compound represented by the above formula (1). In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group and a decyl group. Of these, an alkyl group having 2 to 5 carbon atoms is preferable. R ²
Is a monofunctional or higher functional k-valent alcohol residue having an aromatic ring, and examples of the monovalent alcohol residue include a benzyl group and p
-Nitrophenyl group, 2-phenoxyethyl group and the like. As R ² , a benzyl group, a p-nitrophenyl group and a 2-phenoxyethyl group, which are monovalent alcohol residues, are particularly preferable. m1 represents an integer of 1 to 10,
Especially preferably, it is 2-6. M2 represents an integer of 0 to 10, and particularly preferably 0 to 1. Furthermore, m
The sum of 1 and m2 represents an integer of 1 to 20, particularly preferably 4 to 6. The reason is that if it is 3 or less, the introduced amount of epoxy group is reduced, and the physical properties of the cured product are not obtained.
This is because those with more than 7 are difficult to obtain. n is 1 to
It represents an integer of 20 and is particularly preferably 1 to 7. The bonding order of m1, m2 and n groups is arbitrary. The reason for this is that inexpensive unsaturated fatty acids are often a mixture, and it is difficult to imagine that there will be a large difference in physical properties depending on the bonding position.

Production Method of Epoxy Compound (1) Raw Materials The epoxy compound of the present invention is obtained by mixing an unsaturated fatty acid represented by the following formula (2) or a derivative thereof (A) with an alcohol having a monofunctional or higher k-valent alcohol having an aromatic ring. To obtain an unsaturated fatty acid derivative (B) represented by the following formula (3):
It can be produced by epoxidizing the unsaturated fatty acid derivative (B) by an oxidation reaction.

[0012]

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In the formula (2), R ¹ is the same as R ^{1 in the} formula (1) representing an epoxy compound. Examples of the alkyl group having 1 to 10 carbon atoms for R ³ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Further, as the aryl group, a phenyl group, o
-Toluyl group, m-toluyl group, p-toluyl group, α-
An example is a naphthyl group. Examples of the alkenyl group include a vinyl group, a propenyl group, and an isopropenyl group.
Of these, an alkyl group having 2 to 5 carbon atoms is preferable, and an ethyl group or a methyl group is particularly preferable.
This is because it is easy to obtain and purify.

The unsaturated fatty acid represented by the formula (2) or its derivative (A) is preferably a compound having 16 to 2 carbon atoms.
2, especially ester derivatives of 20 to 22 unsaturated fatty acids, wherein m is 4 to 6 and n is 1 to 7. As unsaturated fatty acids, hexadecatrienoic acid having 16 carbon atoms (6,10,14-hexadecatrienoic acid, 6,9,1
2-hexadecatrienoic acid, 7,10,13-hexadecatrienoic acid), hexadecatetraenoic acid, carbon number 18
Octadecatetraenoic acid (4,8,12,15-octadecatetraenoic acid), H 21 eicosapentaenoic acid having 21 carbon atoms (6,9,12,15,18-Hene eicosapentaenoic acid), 20 carbon atoms Of eicosatetraenoic acid (5,8,11,14-eicosatetraenoic acid, 4,
8,12,16-eicosapentaenoic acid), eicosapentaenoic acid (5,8,11,14,17-eicosapentaenoic acid, 4,8,12,15,18-eicosapentaenoic acid), which has 22 carbon atoms Docosatetraenoic acid (10,1
3,16,19-docosatetraenoic acid), docosapentaenoic acid (7,10,13,16,19-docosapentaenoic acid), docosahexaenoic acid (4,7,10,13,1)
6,19-docosahexaenoic acid, 4,8,12,15,
18,21-docosahexaenoic acid, 4,8,11,1
4,17,20-docosahexaenoic acid). As the unsaturated fatty acid derivative that can be used in the production method of the present invention, a methyl ester or an ethyl ester of the above unsaturated fatty acid can be preferably used. In addition, these can be obtained from natural fats and oils, such as a fish oil, and can also be used in addition to other mixtures of high-purity products, or distillation residues containing unsaturated fatty acids and their derivatives.

The "monofunctional or higher valent alcohol having an aromatic ring" to be reacted with the unsaturated fatty acid or its derivative (A) is a compound having an alcoholic hydroxyl group on the aromatic ring, and naphthalene, Also includes those in which a plurality of rings are connected, such as anthracene, pentalene, azulene, biphenylene and the like. In the aromatic ring,
Even if it has other substituents in addition to the alcoholic hydroxyl group,
There is no particular limitation as long as the substituent is not acidic or alkaline. Preferred examples of the substituent include a nitro group, a phenyl group, an alkyl group, an alkenyl group, an alkoxy group, a phenoxy group, and a halogen. Examples of the monofunctional or higher valent alcohol having an aromatic ring include benzyl alcohol, p-nitrophenol, and monovalent alcohol.
-Phenoxyethanol and the like can be exemplified, and it is particularly preferable to use a monohydric alcohol.

The method for obtaining the unsaturated fatty acid derivative (B) by reacting the unsaturated fatty acid or its derivative (A) with a monofunctional or more-functional k-valent alcohol having an aromatic ring is not particularly limited, but a common acid is used. An esterification method and a transesterification method via an acid chloride using a catalyst or a carboxylic acid chlorinating agent are preferred.

(2) Esterification For example, in a transesterification reaction, 100 parts by weight of the unsaturated fatty acid derivative (A) is converted into one or more functional groups having an aromatic ring.
50 to 200 parts by weight of the alcohol having a valency, especially 60 to 1
It is preferable to use 90 parts by weight. The reaction may be carried out under normal pressure or under reduced pressure. When the reaction is performed under reduced pressure, the reaction is preferably performed under reduced pressure of 600 mmHg or less, preferably 500 mmHg or less. The reaction temperature is 120 to 250 ° C, particularly 150 to 220 ° C.
It is preferable to carry out in. This is to prevent coloring and gelling during the reaction.

A catalyst can be used for the transesterification. As a catalyst that can be used, a tin compound, a titanium compound, an aluminum compound, a zinc compound, a molybdenum compound, a zirconium compound, and the like can be used. Among these, tin compounds, titanium compounds, and antimony compounds are preferably used in terms of ease of handling, low toxicity, reactivity, non-coloring property, heat stability, and the like. Examples of the tin compound include stannous chloride, stannous octylate, monobutyltin compounds such as monobutyltin oxide and monobutyltin tris (2-ethylhexylhexanate), and dibutyltin compounds such as dibutyltin oxide. Examples of the titanium compound include tetrabutoxy titanate, tetrabutyl titanate, and tetraisopropyl titanate. As antimony compounds,
Antimony trioxide and the like can be mentioned. These catalysts may be used alone or in combination of two or more.

(3) Epoxidation The epoxy compound provided by the present invention can be obtained by epoxidizing the unsaturated fatty acid derivative (B) by an oxidation reaction. The oxidation reaction can be performed using an oxidizing agent.

The oxidizing agent is not particularly limited as long as it can epoxidize the unsaturated bond and can be produced industrially.
Organic peracids such as peracetic acid, formic acid, perpropionic acid, and perbenzoic acid; hydroperoxides such as t-butyl hydroperoxide, cumyl hydroperoxide, tetralyl hydroperoxide, and diisopropylbenzene hydroperoxide; Hydrogen peroxide and the like can be mentioned as examples. Among them, it is preferable to use anhydrous peracetic acid. This is because ring opening of the epoxy group during the reaction can be prevented.

At the time of epoxidation, a catalyst can be used if necessary. For example, when a peracid such as peracetic acid is used as the oxidizing agent, an alkali such as sodium carbonate or an acid such as sulfuric acid can be used as a catalyst. When using hydroperoxides as an oxidizing agent,
Mixtures of tungstic acid and caustic soda can be used with hydrogen peroxide, organic acids with hydrogen peroxide, or molybdenum hexacarbonyl with t-butyl hydroperoxide.

The molar ratio of the oxidizing agent to the double bond of the unsaturated fatty acid derivative (B) is theoretically 1, but it is actually in the range of 0.05 to 3, especially 0.1 to 2 Is preferably within the range. If the molar ratio is greater than 3,
It is preferable in terms of conversion rate of double bonds in unsaturated fatty acids and their derivatives and shortening of reaction time, but it is very costly for side reaction due to excess oxidizing agent, selectivity of oxidizing agent and recovery of unreacted oxidizing agent. Is required, which is not preferable. On the contrary, when the molar ratio is less than 0.05, it is preferable in terms of the conversion rate of the oxidizing agent, the selectivity, and the side reaction of the product due to the oxidizing agent, but the introduction rate of the epoxy group is too low, and the unreacted unreacted There are drawbacks such as a large amount of cost for recovering saturated fatty acids and their derivatives.

Further, at the time of epoxidation, the epoxidation rate and the number of epoxy groups can be adjusted by changing the amount of the oxidizing agent or changing the reaction time and treating the excess oxidizing agent.

The reaction temperature of the epoxidation is lower than the upper limit such that the epoxidation reaction has a higher priority than the decomposition reaction of the oxidizing agent.
When butyl hydroperoxide is used, 1
50 ° C. or lower is preferred. When the reaction temperature is low, it takes a long time to complete the reaction. Therefore, when using peracetic acid or t-butyl hydroperoxide, it is preferable to perform the reaction at 20 ° C. or higher.

In the epoxidation reaction, a solvent can be used for stabilization by diluting the oxidizing agent. Specifically, aromatics such as benzene, toluene, and xylene; halides such as chloroform, dimethyl chloride, carbon tetrachloride, and chlorobenzene; ester compounds such as ethyl acetate and butyl acetate; ketone compounds such as acetone and methyl isobutyl ketone And ether compounds such as 1,2-dimethoxyethane. During the reaction,
In order to prevent coloring of raw materials and products, it is preferable to carry out the reaction under a nitrogen atmosphere.

The aging time after the completion of the dropping varies depending on the reaction rate, but is usually 1 to 5 hours. When the aging time is less than 1 hour, the conversion of double bonds is low and not practical.
Further, when the time is 5 hours or longer, for example, when peracetic acid is used as the peroxide, the addition reaction between the epoxidized compound and acetic acid increases, which causes a decrease in yield and an increase in viscosity of the product, which is not preferable.

When an organic acid is used as an oxidizing agent, the reaction crude liquid containing an epoxy compound is washed with water or neutralized to prevent ring-opening of the epoxy group of the product, and to reduce the low boiling components. Is preferably removed. Examples of the alkaline aqueous solution used for neutralization include, for example, NaOH, KOH, K ₂
Aqueous solutions such as CO ₃ , NaCO ₃ , NaHCO ₃ or NH ₃ can be used. After neutralization, it is preferable to wash with water. The crude reaction liquid can be purified and distilled using a thin film evaporator to remove low boiling components.

Use The epoxy compound of the present invention has a large number of epoxy groups relatively close to the molecular terminals, and can be crosslinked with a photopolymerization initiator or the like by various methods. For example, two-pack type, one-pack type,
It is selected according to the type such as a thermosetting type and a photocuring type, and can be used as a photocurable resin composition, an adhesive, a sealant, and a coating composition to increase strength and heat resistance. In addition, any curing agent, general-purpose epoxy compound,
Various components such as a thermoplastic resin, a curing aid, a tackifier, a plasticizer, a solvent, and a stabilizer are added or mixed to form a photocurable resin composition, an adhesive, a sealant composition, a coating agent, or an ink. , Fiber, FRP, SMC, asphalt, polymer alloy.

(1) Curing agent As a curing agent for the epoxy compound of the present invention having an epoxy group, for example, ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, diethylaminopropylamine, hexamethylenediamine, and menine. Senediamine, isophoronediamine, bis (aminomethyl) cyclohexane, N-aminoethylpiperazine, 3,9-bis (3-
Aminopropyl) -2,4,8,10-tetraoxaspiro (5,5) undecane, m-xylylenediamine,
Aromatic polyamines such as diaminodiphenylmethane, diaminodiphenylsulfone, diaminodiethyldiphenylmethane, benzyldimethylamine, 2- (dimethylaminomethyl) phenol, tetramethylguanidine, N,
N-dimethylpiperazine, triethylenediamine, 1,
Seconds such as 8-diazabiscyclo [5.4.0] undecene, triethanolamine, piperazine, pyrrolidine, polyamidoamine, and boron fluoride monoethylamine complex
And tertiary amines.

Examples of acid anhydride-based curing agents include methyl nadic acid anhydride, dodecenyl succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcondomethylenetetrahydrophthalic anhydride, crotonic anhydride, and ethylene glycol trimellitic anhydride. Examples thereof include esters, methyltetrahydrophthalic anhydride and methylhexahydrophthalic anhydride.

As a curing catalyst for the reaction between the epoxy group and the carboxyl group, quaternary ammonium salts such as benzyltriethylammonium chloride or bromide, tetramethylammonium chloride or bromide, dimethyltin bis (methylmalate), dimethyltinbis (ethylmalate), dimethyl Tin-based catalysts such as tin bis (butylmalate) and dibutyltinbis (methylmalate), phosphorus compounds such as triphenylphosphine, tetraphenylphosphonium chloride or bromide, imidazole, 2-methylimidazole, 2-
Ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1-benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-
Imidazoles such as cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, and aluminum-based catalysts such as aluminum isopropoxide can be used.

Examples of those having a hydroxyl group as a functional group which reacts with the epoxy group include alcohols such as butanol, ethanol, propanol, ethylene glycol and trimethylolpropane, β-hydroxyethyl (meth) acrylate and β-hydroxy. Polymerizable monomer obtained by adding caprolactone to ethyl (meth) acrylate (PCLFA-1, PCLF manufactured by Daicel Chemical Industries, Ltd.)
M-1), acrylics of hydroxyl group-containing monomers such as polymerizable monomers (Plenmer PP and Blenmer PE manufactured by NOF Corporation) to which 4-hydroxybutyl (meth) acrylate, ethylene oxide or propylene oxide of (meth) acrylic acid is added. A polymer can be exemplified.

As a reaction catalyst for a hydroxyl group that reacts with an epoxy group, an amine-based, alkali-based, or acid-based catalyst can be suitably used. As such a catalyst, imidazoles such as 4-methylimidazole, tris (dimethylamino)
Tertiary amines such as phenol and N, N-dimethylbenzylamine, inorganic alkalis such as KOH and NaOH, and alcoholates such as sodium alcoholate can be used.
Examples of the acid-based catalyst include phosphoric acid and phosphoric acid esters which promote a cationic polymerization catalyst reaction, and (phosphoric acid) -containing (meth) acrylate, oxalic acid, succinic acid, trimellitic acid, p-toluenesulfonic acid, and the like. It is desirable to contain a highly acidic catalyst. These catalysts are used in an amount of 0.1 to the total of the epoxy compound and the curing agent. A range of 1 ppm to 10%, preferably 10 ppm to 2% is desirable. 0. If it is less than 1 ppm, the effect of promoting the curing is poor.
If it is 0% or more, the physical properties of the coating film deteriorate.

A compound having a silanol group or a hydrolyzable alkoxysilanol group as a functional group that reacts with an epoxy group, and a compound obtained by introducing the same into an acrylic resin are also examples of the curing agent. Specifically, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth)
Acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltripropoxysilane, γ-
(Meth) acryloxypropylmethyldiethoxysilane, γ- (meth) acryloxypropylmethyldipropoxysilane, γ- (meth) acryloxybutylphenyldimethoxysilane, γ- (meth) acryloxybutylphenyldiethoxysilane, γ -(Meth) acryloxybutylphenyldipropoxysilane, γ- (meth) acryloxypropyldimethylmethoxysilane, γ- (meth)
Acryloxypropyldimethylethoxysilane, γ-
(Meth) acryloxypropylphenylmethylmethoxysilane, γ- (meth) acryloxypropylphenylmethylethoxysilane and the like can be used. As a catalyst for the reaction of an epoxy group with a silanol group or a hydrolyzable alkoxysilanol group, a known aluminum chelate, titanium chelate or zirconium chelate compound catalyst that promotes a cationic polymerization reaction and gives a suitable pot life can be contained. .

Among these chelate compounds, a chelate compound containing a compound capable of forming keto or enol tautomerism as a ligand forming a stable chelate ring is preferable. Compounds that can form keto and enol tautomerism include β-diketones (such as acetylacetone), acetoacetates (such as methyl acetoacetate), malonic esters (such as ethyl malonate), and a hydroxyl group at the β-position. Ketones (such as diacetone alcohol), aldehydes having a hydroxyl group at the β-position (such as salicylaldehyde), β
Esters having a hydroxyl group at a position (methyl salicylate) and the like can be used. Especially acetoacetic esters,
It is preferred to use β-diketones. Any one or several of the aluminum chelate compound, the zirconium chelate compound and the titanium chelate compound may be mixed. The compounding amount of the chelate compound is
When the total of the epoxy compound and the curing agent is 100 parts by weight, it is preferably in the range of 0.01 to 30 parts by weight, more preferably in the range of 0.05 to 15 parts by weight, and still more preferably 0.5 to 15 parts by weight. The range is 10 parts by weight. If the amount of the catalyst is less than 0.01 part by weight, the crosslinking curability tends to decrease. Conversely, if the amount of the catalyst is more than 30 parts by weight, the curing catalyst remaining in the cured product reduces the water absorption and weather resistance of the coating film. It can cause deterioration.

In addition, a urea derivative, a polymercaptan type curing agent, a methylol group-containing compound such as a phenol resin, a urea resin and a melamine resin, a polyisocyanate, and an aromatic diazonium salt which is an ultraviolet curing catalyst can be used. Note that two or more kinds of functional groups capable of reacting with the epoxy group may be used at the same time. When a curing agent of a compound having an epoxy group is used, the amount of the curing agent used is usually such that the active hydrogen groups of these curing agents are almost equimolar to the epoxy group. Further, an appropriate amount of the curing accelerator for the epoxy compound is used depending on the type, curing conditions and the like.

(2) Photopolymerization initiator Examples of the photopolymerization initiator which can be blended with the epoxy compound of the present invention include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin butyl ether, benzoin isopropyl ether, benzyl dimethyl ketal and the like. Benzoin initiators, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, diethoxyacetophenone, 2-hydroxy-2.
-Methyl-1-phenylpropan-1-one, 1- (4
-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl)
-2-hydroxy-2-methylpropan-1-one, 4
-(2-hydroxyethoxy) -phenyl- (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropane-1 and the like. Benzophenone-based initiators such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acryloylated benzophenone, and 3,3-dimethyl-4-methoxybenzophenone; thioxanthone; Methylthioxanthone, isopropylthioxanthone, 2,4-diethylthioxanthone, 2,
Examples of the initiator include 4-diisopropylthioxanthone, methylphenylglyoxylate, and compounds represented by the following formulas (4) and (5). These photopolymerization initiators may be used alone or in combination of two or more.

[0038]

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(3) General-purpose epoxy compound Since the epoxy compound of the present invention has a low viscosity, the viscosity of the composition containing the epoxy compound can be reduced by mixing it with a general-purpose epoxy resin, and after curing, it can be crosslinked. Therefore, the strength of the cured product can be maintained. As general-purpose epoxy compounds, for example, condensation products of epichlorohydrin and polyhydric alcohols or polyphenols, condensation products of epichlorohydrin with phenol novolak, novolac such as cresol novolak, cycloaliphatic epoxy compounds, glycidylamine epoxy compounds Epoxy compounds derived from heterocyclic epoxy compounds, polyolefin polymers or copolymers, epoxy compounds obtained by (co) polymerization of epoxy group-containing (meth) acrylates, epoxy obtained from glycerides of highly unsaturated fatty acids And polyalkylene ether type epoxy compounds. These general-purpose epoxy compounds are the same as the epoxy compounds used in the present invention.
It can be used by mixing at a ratio of 99% by weight, preferably at a ratio of 1 to 90% by weight. When the proportion of the epoxy compound of the present invention is less than 1% in the composition, the crosslink density does not increase and the strength of the cured product becomes insufficient, which is not preferable.

(4) Photocurable Resin Composition The photocurable resin composition of the present invention comprises an epoxy compound 100.
It is preferable that the photopolymerization initiator is blended in an amount of 0.1 to 20 parts by weight based on parts by weight. This is because sufficient photocurability is exhibited in this range. Further, in the photocurable resin composition of the present invention, a photo radical initiator and a photo cation initiator may be used alone or in combination. In the present invention, the photocurable resin composition, if necessary, a leveling agent, an antifoaming agent, an ultraviolet absorber, a light stabilizer, an antioxidant, a pigment, a thickener, an antisettling agent, an antistatic agent, Antifogging agents, organic solvents and the like can also be added. As a method for applying the photocurable resin composition of the present invention, brush coating, spray coating, dip coating, spin coating,
A method such as curtain coating is used, and as the active energy ray, it is preferable to use a high pressure mercury lamp, a metal halide lamp, or the like to irradiate ultraviolet rays of 100 to 500 nm. The irradiation atmosphere may be air or an inert gas such as nitrogen or argon. The photocurable resin composition of the present invention thus obtained can be applied to various coating fields such as plastic paint, film coating, metal coating, and painting.

(5) Adhesive When the epoxy compound of the present invention is used as an adhesive,
It is preferable to mix 10 to 50 parts by weight of an epoxy compound with respect to 100 parts of a thermoplastic resin such as SBS, SBR and NBR. Normally, mixing at 25 ° C. to 125 ° C. for about 3 hours yields a uniform mixture. In use, the components may be mixed with a solvent or water before use.

(6) Hot Melt Adhesive, etc. The epoxy compound of the present invention is used as many different types of adhesives such as hot melt adhesives, solvent-soluble adhesives, laminating adhesives and pressure-sensitive adhesives. Is also good. The adhesive may consist of an epoxy compound, but generally, the epoxy compound is mixed with known adhesive composition components such as a tackifying resin and a flexibility-imparting agent.
Curing may be promoted by heating the adhesive before and after bonding in order to increase the adhesiveness, and curing may be promoted by irradiating radiation before and after bonding.

(7) Coating composition A coating composition can be prepared using the epoxy compound of the present invention. The epoxy compound acts as a flexibility imparting agent and a strength imparting agent in the coating,
In addition to the epoxy compound, it is composed of variously mixed components such as a coating resin, an optional curing agent, a curing aid, a pigment, a solvent, and a stabilizer. The obtained composition can be applied by a known method. When it is used as a coating agent, it is preferable to mix 50 to 300 parts by weight of the epoxy compound of the present invention with respect to 100 parts by weight of the epoxy resin other than the epoxy compound of the present invention. The kneading of the composition and the like can be prepared according to a conventional method by a known method.

[0044]

EXAMPLES The present invention will now be described specifically with reference to examples, but the present invention is not limited to these examples. “%” Indicates “% by weight” unless otherwise indicated.
NMR refers to JEOL “GXS270WB”, IR refers to J
"FT / IR-5300" manufactured by ASCO and "HPLC LC-6A SYSTEM" manufactured by Shimadzu (column: polystyrene column, solvent: THF) were used for GPC.

Example 1 300 g of docosahexaenoic acid ethyl ester (GC purity: 50%: residue after distilling an active ingredient from fish oil / iodine value: 354), 95.6 g of benzyl alcohol, and 0.40 g of tetrabutoxytitanium were equipped with a dehydrating tube. The flask was charged and reacted at 220 ° C. for 24 hours. When the molecular weight distribution of the reaction product was measured by GPC, the peak at a molecular weight of about 350 in terms of styrene almost disappeared, and a benzyl ester of docosahexaenoic acid could be obtained. Next, 180 g of ethyl acetate was charged, and 1397.8 g of peracetic acid (peracetic acid concentration: 29.1%) was added dropwise over about 3 hours such that the temperature in the reaction system became 40 ° C. while blowing nitrogen gas. After the addition of peracetic acid, 5
The reaction was completed by aging at 0 ° C. for 4 hours. The reaction crude solution was washed with water at 50 ° C., and deboiled at 70 ° C./10 mmHg to obtain epoxy compound A-1 of benzyl docosahexaenoate.
391.2 g was obtained. The properties of the obtained product were an oxirane oxygen concentration of 11.7% by weight and a viscosity of 662 cP / 25 ° C.

Example 2 300 g of docosahexaenoic acid ethyl ester (GC purity: 50%: residue after distilling an active ingredient from fish oil / iodine value: 354), 107.9 g of 2-phenoxyethanol, 0.41 of titanium tetrabutoxy
g was charged into a flask equipped with a dehydration tube and reacted at 220 ° C. for 24 hours. When the molecular weight distribution of the reaction product was measured by GPC, the peak at a molecular weight of around 350 in terms of styrene almost disappeared, and 2-phenoxyethyl ester of docosahexaenoic acid could be obtained. Next, 200 g of ethyl acetate was charged, and peracetic acid was added for about 3 hours while blowing nitrogen gas so that the temperature in the reaction system became 50 ° C.
61.7 g (peracetic acid concentration: 29.1%) was added dropwise. After completion of the dropwise addition of peracetic acid, the reaction was aged at 50 ° C. for 3 hours to complete the reaction. The reaction crude solution was washed with water at 50 ° C., and the low boiling point was removed at 70 ° C./10 mmHg to obtain 45% of epoxy compound A-2 of hexaepoxydocosahexaenoic acid 2-phenoxyethyl ester.
0.9 g was obtained. The properties of the obtained product were an oxirane oxygen concentration of 11.0% by weight and a viscosity of 720 cP / 25 ° C.

Example 3 300 g of docosahexaenoic acid ethyl ester (GC purity: 50%: residue after distilling active ingredient from fish oil / iodine value: 354), 135.4 g of p-nitrobenzyl alcohol, 0.1 g of tetrabutoxytitanium
43 g was charged into a flask with a dehydrating tube and reacted at 220 ° C. for 24 hours. When the molecular weight distribution of the reaction product was measured by GPC, the peak at a molecular weight of around 350 in terms of styrene disappeared, and p-nitrobenzyl ester of docosahexaenoic acid could be obtained. Then, ethyl acetate was added to 20
0 g, and the temperature in the reaction system was raised to 1237.
9 g (peracetic acid concentration: 29.1%) was added dropwise. After completion of the dropwise addition of the peracetic acid solution, the mixture was aged at 50 ° C. for 4 hours to complete the reaction. The reaction crude solution was washed with water at 50 ° C., and deboiled at 70 ° C./10 mmHg to obtain 438.4 g of an epoxy compound A-3 of docosahexaenoic acid p-nitrobenzyl ester.
The properties of the obtained product were an oxirane oxygen concentration of 10.8% by weight and a viscosity of 790 cP / 25 ° C.

[Examples 4 to 7, Comparative Example 1] Examples 1 to 3
And the epoxy compound represented by the following formula (6) ("Celoxide 2021P" manufactured by Daicel Chemical Industries, Ltd.) was used to prepare a photocurable resin composition according to the blending ratio in Table 1. . This composition was applied to an aluminum plate, a steel plate or a PET plate manufactured by Nippon Test Panel Co., Ltd. so as to have a film thickness of 10 μm, and irradiated with a high pressure mercury lamp in air to form a coating film. The obtained coating film was tested for adhesion, pencil hardness, and solvent resistance, and the results are shown in Table 2.

[0049]

Embedded image

[0050]

[Table 1]

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[Table 2]

[Measurement Items] (1) Adhesion The adhesion was measured in accordance with JIS K5400 8.5. (2) Pencil hardness The pencil hardness was measured according to JIS K5400 8.4. (3) Solvent resistance The coating film surface was rubbed ten times with cotton impregnated with methyl ethyl ketone, and the surface was observed. 5: No change in appearance,
4: whitened, 3: whitened, 2: fairly white, 1: whitened and peeled.

[0053]

According to the present invention, an epoxy compound based on an unsaturated fatty acid derivative having a specific structure can be obtained. The epoxy compound of the present invention has good compatibility with other resins, and the cured product thereof has excellent adhesion, pencil hardness, and solvent resistance. By using the epoxy compound of the present invention, it is possible to obtain a photocurable resin composition, a pressure-sensitive adhesive composition, a sealant composition, and the like having high strength while maintaining sufficient flexibility.

Claims (4)

[Claims] 1. An epoxy compound represented by the formula (1). Embedded image 2. An unsaturated fatty acid derivative represented by the formula (3) by reacting an unsaturated fatty acid represented by the formula (2) or a derivative (A) thereof with an alcohol having an aromatic ring and a monofunctional or higher valent alcohol. 2. After obtaining (B), the unsaturated fatty acid derivative (B) is epoxidized by an oxidation reaction.
A method for producing the epoxy compound as described above. Embedded image 3. The method for producing an epoxy compound according to claim 2, wherein the monofunctional or more k-valent alcohol having an aromatic ring is any one of benzyl alcohol, p-nitrobenzyl alcohol and 2-phenoxyethanol. 4. A photocurable resin composition comprising the epoxy compound according to claim 1.