JPH1121282A - Epoxy compound and tacky composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new compound high in reactivity with an amine-based curing agent and capable of giving cured products excellent in impact resistance, flex resistance and adhesion. SOLUTION: This new compound is shown by formula I R<1> is a (branched) 1-10C alkyl; R<2> is a substituent bearing an epoxy ring at least on chain end or side chain, such as of formula II [R<3> is a (branched) 1-10C alkylene; X<1> is H, etc.], or formula III [R<4> is a (branched) 3-12C alkylene; R<5> is a bond O-C, etc.; X<2> is H, etc.; (k) is 1-20]; (m1+m2) and (n) are each 1-20; (m1) is 1-10; (m2) is 0-10; the binding order for respective (m1), (m2), (n) groups are arbitrary}, e.g. docosahexaenoic allyl ester epoxide. The compound of formula I is obtained by epoxidation of a compound of formula V (R<12> is a substituent bearing at least one C=C double bond at chain end or side chain) formed a compound of formula IV (R<11> is H, R<1> , etc.; (m) and (n) are each 1-20; the binding order for respective (m), (n) groups are arbitrary) through oxidation.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to an epoxy ring in the same molecule together with an epoxy ring inside the molecular chain (hereinafter referred to as an epoxy ring except in the examples, including an epoxy ring in which a hydrogen atom is substituted by a methyl group). At least one at the molecular end or side chain
The present invention relates to an epoxy compound having two epoxy rings, and a pressure-sensitive adhesive composition comprising the epoxy compound, which is easily cured with an amine-based curing agent and has excellent flex resistance, impact resistance, and adhesion.

[0002]

2. Description of the Related Art Bisphenol A type and F type epoxy resins and novolak type epoxy resins obtained from phenol and cresol are known as epoxy resins, but these cured products are hard. Often brittle.

On the other hand, epoxy compounds of unsaturated fatty acids or rubber compounds having an epoxy ring obtained by oxidizing a carbon-carbon double bond in the molecular chain have a flexible carbon chain structure itself. And is flexible after curing. However, the epoxy ring inside the molecular chain has low reactivity with the amine compound, so that low-temperature curing is often impossible. For this reason, epoxy resins having an internal epoxy ring have no heat resistance or cannot be cured by heat, and are not often used for bonding.

[0004] On the other hand, from the viewpoint of environmental protection, aqueous compositions have recently attracted attention as one of the movements of desolvation of adhesive compositions such as paints. However, an epoxy compound having an epoxy ring in the molecular chain is inferior in hydrophilicity because it is difficult to react with an amine, and is not used as a hydrophilic adhesive composition. Therefore, the development of a new epoxy compound having flexibility and the development of a pressure-sensitive adhesive composition having a cured product excellent in bending resistance, impact resistance and adhesion and having hydrophilicity are expected.

[0005]

Means for Solving the Problems The present inventors have found that an epoxy compound having an epoxy ring at a molecular terminal or a side chain together with an epoxy ring inside a molecular chain in the same molecule has excellent reactivity with an amine-based curing agent. Further, the obtained cured product was found to be excellent in impact resistance, bending resistance, and adhesion, and the present invention was completed.

That is, the present invention provides an epoxy compound represented by the formula (1). Further, the present invention provides an epoxy compound, wherein R ² in the formula (1) is a substituent represented by the formulas (2), (3) and (4). Further, the present invention provides an adhesive composition comprising the epoxy compound. Hereinafter, the present invention will be described in detail.

[0007]

Embedded image

[0008]

Embedded image

[0009]

Embedded image

[0010]

Embedded image

[0011]

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, the alkyl group having 1 to 10 carbon atoms which may include a branch of R ¹ includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group,
Examples thereof include a heptyl group, an octyl group, a nonyl group, and a decyl group. Among them, an alkyl group having 2 to 5 carbon atoms is preferable. R ² is a substituent having an epoxy ring at least at a chain end or a side chain;
It is preferably a substituent represented by (3) or (4). As a preferred substituent represented by the formula (2),
3-epoxypropyl group, 3,4-epoxybutyl group,
2-methyl-3,4-epoxybutyl group, 3-methyl-
A 3,4-epoxybutyl group can be exemplified. Preferred examples of R ⁴ in the formula (3) include trimethylene, tetramethylene, methyltetramethylene, pentamethylene, propylene, and hexyltetramethylene. Further, as a preferable example of the substituent represented by the formula (4), a polyene chain having an epoxy ring in the inside of the group and a side chain and having a number average molecular weight of 500 to 5,000 is exemplified. Further, a compound in which an epoxidized unsaturated fatty acid residue constituting the formula (1) is ester-bonded to the terminal is exemplified. In the formula (1), m1 represents an integer of 1 to 10, and particularly preferably 2 to 6. M2 is 0 to 10
And particularly preferably 0 to 1. Further, the sum of m1 and m2 represents an integer of 1 to 20, and particularly preferably 4 to 6. This is because sufficient adhesiveness can be exhibited in this range. n represents an integer of 1 to 20, and particularly preferably 1 to 7. In addition, m1, m2
And the bonding order of each of the n groups is arbitrary. This is because unsaturated fatty acids are often obtained as a mixture, and the physical properties of the cured product do not greatly differ depending on the bonding position.

Production Method of Epoxy Compound (1) Raw Material The epoxy compound of the present invention is obtained by adding an unsaturated fatty acid represented by the following formula (6) or a derivative (A) thereof to a carbon-carbon double bond at least at a molecular terminal or a side chain. Esterified with a monovalent or divalent alcohol having a bond to obtain an unsaturated fatty acid derivative (B) represented by the following formula (7), and then epoxidized the unsaturated fatty acid derivative (B) by an oxidation reaction to produce can do.

[0013]

Embedded image

In the unsaturated fatty acid represented by the formula (6) or its derivative (A), 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 ¹¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group,
Examples include a heptyl group, an octyl group, a nonyl group, and a decyl group. Examples of the aryl group include a phenyl group, an o-toluyl group, an m-toluyl group, a p-toluyl group, and an α-naphthyl group. Examples of the alkenyl group include a vinyl group, a propenyl group, and an isopropenyl group. Among them, 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 (6) 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), having 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 for producing the epoxy compound of the present invention, a methyl ester or an ethyl ester of the above unsaturated fatty acid is preferable.

The monohydric or dihydric alcohol having a carbon-carbon double bond at least at a molecular chain terminal or a side chain to be reacted with the compound represented by the formula (6) is represented by the following formulas (8), (9), The compound represented by (10) can be exemplified.

[0017]

Embedded image

Preferred compounds represented by the formula (8) include allyl alcohol, 2-methylallyl alcohol and isoprenol. As preferred compounds represented by the formula (9), γ-butyrolactone, ε-caprolactone, δ-
Lactones such as valerolactone and δ-decalactone
There is an ester bond of up to 20, more preferably 1 to 10, polymers with the compound represented by (7) above. In the formula (10), k6 and k7 are each preferably 1 to 150, more preferably 2 to 130. Preferred compounds represented by the formula (10) include:
Hydroxyl-terminated polybutadiene having a number average molecular weight of 500 to 5,000 ("G-1000" manufactured by Nippon Soda Co., Ltd .;
"G-3000", Idemitsu Petrochemical Co., Ltd. "R-15H"
T "," R-45HT "). From this, equation (7)
R ¹² in the formula (8) is preferably an alcohol residue of the compound represented by (9) or (10).
In addition, when the compound of the formula (10) is used, both ends thereof may be esterified with the unsaturated fatty acid or the derivative (A) thereof.

A method for obtaining an unsaturated fatty acid derivative (B) by reacting an unsaturated fatty acid or its derivative (A) with a monohydric or dihydric alcohol having a carbon-carbon double bond at least at a molecular terminal or a side chain. Although there is no particular limitation, esterification, transesterification, and the like via an acid chloride using a normal acid catalyst or a carboxylic acid chlorinating agent are preferred.

(2) Esterification For example, in a transesterification reaction, a monohydric or dihydric alcohol having a carbon-carbon double bond at least at a molecular terminal or a side chain is added to 100 parts by weight of the unsaturated fatty acid derivative (A). It is preferable to use 50 to 200 parts by weight, especially 60 to 190 parts by weight. The reaction may be carried out under normal pressure or under reduced pressure. When the reaction is carried out under reduced pressure, it is 600 mmHg or less, preferably 500 mHg.
It is performed under reduced pressure of mHg or less. Reaction temperature is 120-25
It is preferably carried out at 0 ° C, particularly at 150 to 220 ° C.
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 oxidizing agents such as peracetic acid, formic acid, perpropionic acid, perbenzoic acid, etc. Examples include hydroperoxides such as t-butyl hydroperoxide, cumyl hydroperoxide, tetralyl hydroperoxide, diisopropylbenzene hydroperoxide, and hydrogen peroxide. Among them, it is preferable to use anhydrous peracetic acid. This is because ring opening of the epoxy 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 a hydroperoxide is used as an oxidizing agent, a mixture of tungstic acid and caustic soda is used together with hydrogen peroxide, an organic acid is used together with hydrogen peroxide, or molybdenum hexacarbonyl is used together with t-butyl hydroperoxide. can do.

The molar ratio of the oxidizing agent to one 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. It is preferably in the range of ~ 2. When the molar ratio is larger than 3, it is preferable in terms of the conversion of the double bond in the unsaturated fatty acid derivative and the shortening of the reaction time, but the side reaction due to excess oxidizing agent, the selectivity of the oxidizing agent and the unreacted It is not preferable because a large cost is required for recovering the oxidizing agent. Conversely, when the molar ratio is 0.
When it is less than 05, it is preferable in terms of the conversion and selectivity of the oxidizing agent, and the side reaction of the product due to the oxidizing agent is prevented. There are drawbacks such as high cost.

At the time of epoxidation, the epoxidation ratio and the number of epoxy rings can be adjusted by changing the amount of the oxidizing agent used or changing the reaction time. In the present invention, the epoxidation epoxidizes the unsaturated fatty acid derivative (B) to the same extent as the carbon-carbon double bond inside the molecule and the carbon-carbon double bond at the molecular terminal or side chain.

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. If 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 dilution of an 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. Note that the reaction is preferably performed in a nitrogen atmosphere to prevent coloring of the raw materials and products.

The aging time after completion of the dropping of the oxidizing agent is usually 1 to 5 hours, though it varies depending on the reaction rate. 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 the oxidizing agent in the reaction crude liquid containing the epoxy compound, the reaction crude liquid is washed with water or neutralized to remove the organic acid in order to prevent ring opening of the epoxy product. Is preferred. Examples of the aqueous alkaline solution used for neutralization include NaOH, KOH, K ₂ CO ₃ , N ₂
An aqueous solution such as a ₂ CO ₃ , NaHCO ₃ or NH ₃ can be used. After neutralization, it is preferable to wash with water. Next, the reaction crude liquid containing the epoxy compound can be purified by distillation using a thin film evaporator.

Applications The epoxy compound of the present invention has an epoxy ring at a molecular terminal or a side chain, and is selected according to a type such as a two-part type, a one-part type, a thermosetting type, and a photo-setting type. The composition can be used as an adhesive, a sealant, and a coating composition, and the strength and heat resistance of these cured products can be increased. Adhesive composition containing these,
Hydrophilic paints, sealants, coatings, inks,
Useful as fiber, FRP, SMC, asphalt, polymer alloy.

Hereinafter, the composition and the adhesive composition which can be used in producing an adhesive composition using the epoxy compound of the present invention will be described. (1) Curing agent Examples of the amine-based curing agent that can be added to the epoxy compound of the present invention include ethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenediamine, diethylaminopropylamine, hexamethylenediamine, and mensendiamine. , 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 the acid anhydride-based curing agents include methylnadic anhydride, dodecenylsuccinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylchondmethylenetetrahydrophthalic anhydride, crotonic anhydride, and ethylene glycol trimellitic anhydride. Esters, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride and the like.

As a curing catalyst for reacting the epoxy compound with the acid anhydride curing agent, quaternary ammonium salts such as benzyltriethylammonium chloride or bromide, tetramethylammonium chloride or bromide, dimethyltin bis (methylmalate), dimethyltin Tin catalysts such as bis (ethylmalate), dimethyltinbis (butylmalate) and dibutyltinbis (methylmalate), or phosphorus compounds such as triphenylphosphine, tetraphenylphosphonium chloride or bromide, imidazole, 2-methylimidazole and 2-ethyl- 4-methylimidazole, 2
-Phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1-benzyl-2
Imidazoles such as -methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-undecylimidazole, aluminum An aluminum-based catalyst such as isopropoxide can also be used.

Examples of the hydroxyl group-based curing agent include alcohols such as butanol, ethanol, propanol, ethylene glycol and trimethylolpropane;
-Hydroxyethyl (meth) acrylate or β-
Polymerizable monomer obtained by adding caprolactone to hydroxyethyl (meth) acrylate (PCLFA manufactured by Daicel Chemical Industries, Ltd.)
-L, PCLFM-1), 4-hydroxybutyl (meth) acrylate, hydroxyl group-containing such as polymerizable monomers obtained by adding ethylene oxide or propylene oxide to (meth) acrylic acid (Blenmer PP, Blenmer PE manufactured by NOF Corporation) An acrylic polymer of a monomer can be exemplified.

As the catalyst for reacting the epoxy compound with the hydroxyl group-based curing agent, amine-based, alkali-based and acid-based catalysts can be suitably used. As such a catalyst,
Imidazoles such as methylimidazole, tertiary amines such as tris (dimethylamino) 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 contain from 0.1 ppm to 10%, preferably from 10 ppm to 2%, based on the sum of the epoxy compound and the curing agent.
% Range. If it is 0.1 ppm or less, the effect of accelerating the curing is poor, and if it is 10% or more, the physical properties of the coating film deteriorate.

Examples of the curing agent include those having a silanol group or a hydrolyzable alkoxysilyl group and compounds obtained by introducing the same into an acrylic resin. Specifically, γ- (meth) acryloxypropyltrimethoxysilane, γ- (meth) acryloxypropyltriethoxysilane, γ- (meth) acryloxypropyltripropoxysilane, γ- (meth) acryloxypropylmethyldimethylsilane Ethoxysilane, γ- (meth) acryloxypropylmethyldipropoxysilane, γ- (meth) acryloxybutylphenyldimethoxysilane, γ- (meth) acryloxybutylphenyldiethoxysilane, γ- (meth) acryloxybutylphenyl Dipropoxysilane,
γ- (meth) acryloxypropyldimethylmethoxysilane, γ- (meth) acryloxypropyldimethylethoxysilane, γ- (meth) acryloxypropylphenylmethylmethoxysilane, γ- (meth) acryloxypropylphenylmethylethoxysilane, etc. Can be used.

As a catalyst for reacting an epoxy compound with a silanol group or a hydrolyzable alkoxysilyl group,
A known aluminum chelate, titanium chelate, or zirconium chelate compound catalyst that promotes the cationic polymerization reaction and provides 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 desirable. 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 having a hydroxyl group at the β-position (such as salicylaldehyde), esters having a hydroxyl group at the β-position (eg, methyl salicylate), and the like. In particular, acetoacetic esters and β-diketones are preferably used. 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,
The range is preferably 0.01 to 30 parts by weight, more preferably 0.05 to 15 parts by weight, and still more preferably 0.5 to 10 parts by weight. The amount of catalyst is 0.01
If the amount is less than the weight part, 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 may cause deterioration of the water absorption and weather resistance of the coating film.

As the curing agent, urea derivatives, polymercaptan-based curing agents, methylol group-containing compounds such as phenolic resins, urea resins and melamine resins, polyisocyanates, and aromatic diazonium salts which are ultraviolet curing catalysts are used. can do. These may be used in combination of two or more at the same time.

The amount of the curing agent used is usually preferably such that the amount of active hydrogen groups contained in the curing agent is substantially equimolar to that of the epoxy ring. Further, the type and appropriate amount of the curing accelerator can be appropriately selected and used according to the type of the curing agent to be used and the curing conditions.

(2) General-purpose epoxy compound Since the epoxy compound of the present invention has a low viscosity, by mixing with the general-purpose epoxy compound, the viscosity of the composition containing the epoxy compound can be reduced.
Because of crosslinking, 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 ,
Heterocyclic epoxy compounds, epoxy compounds derived from polyolefin polymers or copolymers, epoxy compounds obtained by (co) polymerization of epoxy-containing (meth) acrylates, epoxy compounds obtained from glycerides of highly unsaturated fatty acids, Polyalkylene ether type epoxy compounds and the like can be mentioned. 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% by weight in the composition, the crosslink density does not increase and the strength of the cured product becomes insufficient.
Not preferred.

(3) Adhesive Composition When the epoxy compound of the present invention and the general-purpose epoxy compound are blended, the adhesive composition of the present invention contains one part of a curing agent per 100 parts by weight of the total. To 100 parts by weight, more commonly used additives, tackifiers, softeners, known adhesive composition components, leveling agents, defoamers, ultraviolet absorbers, light stabilizers, antioxidants, pigments, Add a thickener, antisettling agent, antistatic agent, antifogging agent, organic solvent, etc. to 0.00
It can be blended and prepared in the range of 1 to 50 parts by weight. Hot melt adhesives, solvent-soluble adhesives, pressure-sensitive adhesives, sealants and the like can be produced depending on the type of compounding agent used. The adhesive composition of the present invention can obtain a uniform adhesive composition by kneading at a temperature of 25 to 125 ° C. for less than 3 hours. The obtained adhesive composition can be used as it is or after being diluted with a solvent or water. As a method of applying the adhesive composition of the present invention, brush coating, spray coating, dip coating,
Methods such as spin coating and curtain coating are used.
The curing of the pressure-sensitive adhesive composition of the present invention may be promoted by heating the adhesive before and after bonding in order to increase the adhesiveness, in addition to leaving at room temperature, and irradiating the radiation before and after the bonding. By doing so, the curing can be accelerated.

[0043]

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.
For NMR, “GXS270WB” manufactured by JEOL Ltd.
PC was manufactured by Shimadzu "HPLC LC-6A SYST"
EM "(column: polystyrene column, solvent: THF)
Was used.

Example 1 300 g of docosahexaenoic acid ethyl ester (GC purity: 50%: residue after distilling active ingredient from fish oil / iodine value: 354), allyl alcohol 4
8.9 g and 0.35 g of tetrabutoxytitanium were charged into a flask equipped with a dehydration tube and reacted at 220 ° C. for 24 hours. As a result, 295.4 g of docosahexaenoic acid allyl ester (A-1) was obtained. In addition, the reaction product was analyzed by NMR.
That the internal double bond peaks δ 5.1 to 5.4 and the terminal double bond peaks δ 4.8 to 5.0 exist.
And GC confirmed that the peak of allyl alcohol had almost disappeared. Next, 150 g of ethyl acetate was added to 295 g of (A-1), and 1499.5 g of an ethyl acetate solution of peracetic acid (peracetic acid concentration: 29.
1%) was added dropwise. After completion of the dropwise addition of the peracetic acid solution, the reaction was aged at 50 ° C. for 6 hours to complete the reaction. The reaction crude solution was washed with water at 50 ° C., and the low-boiling components were distilled off at 70 ° C./10 mmHg to obtain 340.9 g of an epoxidized docosahexaenoic acid allyl ester (A-2). Epoxidized product (A-2) is NMR
The peak δ of the internal epoxy ring is 2.9 to 3.3 ppm in the measurement.
And the peak δ 2.1 to 2.8 ppm of the terminal epoxy ring
Existed, and the molecular end and the inside of the molecule were epoxidized. The properties of the obtained product are oxirane oxygen concentration 1
4.9% by weight, viscosity 860 cP / 25 ° C.

Example 2 300 g of docosahexaenoic acid ethyl ester (GC purity: 50%: residue after distilling active ingredient from fish oil / iodine value: 354), isoprenol
5 g and 0.37 g of tetrabutoxytitanium were charged into a flask with a dehydrating tube and reacted at 220 ° C. for 24 hours. As a result, 330.5 g of docosahexaenoic acid isoprenyl ester (B-1) was obtained. In addition, the reaction product was analyzed by NMR.
That the internal double bond peaks δ 5.1 to 5.4 and the terminal double bond peaks δ 4.8 to 5.0 exist.
And it was confirmed by GC that the peak of isoprenol almost disappeared. Next, 160 g of ethyl acetate was added to 330 g of (B-1), and 1558.6 g of a peracetic acid solution (peracetic acid concentration: 29.20 g) was added over about 2 hours so that the temperature in the reaction system became 50 ° C. while blowing nitrogen gas. 1%) was added dropwise. After completion of the dropwise addition of the peracetic acid solution, the mixture was aged at 50 ° C. for 3 hours to complete the reaction. The reaction crude solution was washed with water at 50 ° C and dried at 70 ° C / 10
The low-boiling components were distilled off at mmHg to obtain 386 g of an epoxidized docosahexaenoic acid isoprenyl ester (B-2). The epoxidized product (B-2) has an internal epoxy ring peak δ 2.9 to 3.3 ppm and a terminal epoxy ring peak δ 2.1 to 2.8 ppm by NMR measurement,
The terminal and the inside of the molecule were epoxidized. The properties of the obtained product were an oxirane oxygen concentration of 13.1% by weight and a viscosity of 1060 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), allyl alcohol 4
8.9 g, 95.9 g of ε-caprolactone and 0.45 g of tetrabutoxytitanium were charged into a flask equipped with a dehydrating tube and reacted at 220 ° C for 24 hours. Thereby, 399.4 g of ε-caprolactone-modified docosahexaenoic acid allyl ester (C-1) was obtained. The reactant was found to have a molecular weight of 350 in terms of styrene by GPC measurement of the molecular weight distribution.
Near peaks have almost disappeared, NMR indicates that internal double bond peaks δ 5.1 to 5.4 and terminal double bond peaks δ 4.8 to 5.0 exist, and GC
As a result, it was confirmed that the peaks of allyl alcohol and ε-caprolactone almost disappeared. Then, (C-1) 3
200 g of ethyl acetate was added to 99 g, and 1548 g of a peracetic acid solution (peracetic acid concentration: 29.1) was added over about 2 hours so that the temperature in the reaction system became 50 ° C. while blowing nitrogen gas.
%) Was added dropwise. After the addition of the peracetic acid solution is completed,
After aging for a while, the reaction was completed. The reaction crude solution was washed with water at 50 ° C., and the low boiling point was distilled off at 70 ° C./10 mmHg to obtain 430.2 g of an epoxidized ε-caprolactone-modified docosahexaenoic acid allyl ester (C-2). The epoxidized product (C-2) has a peak δ of 2.9 to 3.3 ppm for the internal epoxy ring and a peak δ 2.1 to 2.8 ppm for the terminal epoxy ring by NMR measurement, and the molecular terminal and the inside of the molecule are epoxidized. I was The properties of the obtained product were as follows: oxirane oxygen concentration 11.3% by weight, viscosity 2560
cP / 25 ° C.

Example 4 300 g of docosahexaenoic acid ethyl ester (GC purity: 50%: residue after distilling an active ingredient from fish oil / iodine value: 354) and hydroxyl-terminated polybutadiene (“G-1000” manufactured by Nippon Soda Co., Ltd.) 648
g and tetrabutoxytitanium (0.45 g) were charged into a flask equipped with a dehydration tube and reacted at 200 ° C. for 24 hours. Thereby, docosahexaenoic acid polybutadiene ester (D-
903.4 g of 1) was obtained. GPC for molecular weight distribution of reactants
, The peak near a molecular weight of 350 in styrene conversion almost disappeared, the peak δ5.1-5.4 of the internal double bond and the peak δ4.8-5.5 of the side chain double bond were confirmed by NMR. 0 was confirmed to be present. Then
(D-1) 400 g of ethyl acetate and 200 g of ethyl acetate were charged into a flask, and while blowing nitrogen gas, the temperature in the reaction system was raised to 50 ° C. for about 2 hours, and the peracetic acid solution 1334 was taken.
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 5 hours to complete the reaction.
The reaction crude liquid was washed with water at 50 ° C., and low boiling was distilled off at 70 ° C./10 mmHg to obtain 410.2 g of an epoxidized docosahexaenoic acid polybutadiene ester (D-2). The properties of the obtained product were an oxirane oxygen concentration of 9.7% by weight and a viscosity of 32400 cP / 25 ° C. Epoxidized (D
-2) is a peak δ of an internal double bond determined by NMR measurement.
5.1 to 5.4 ppm and peak δ of side chain double bond
4.8-5.0 ppm decreased, a peak δ 2.9-3.3 ppm of the internal epoxy ring, a peak 2.1-2.8 ppm of the side chain epoxy ring appeared, and docosahexaenoic acid polybutadiene ester (D-1) appeared. ) Was confirmed to be epoxidized.

(Examples 5 to 10, Comparative Examples 1 and 2) The epoxy compound obtained in Examples 1 to 4 and a bisphenol A type epoxy resin (“Epicoat 828” manufactured by Yuka Shell Co., Ltd.):
Epoxy equivalents 189) and amine curing agents ("Fujicure 4025" manufactured by Fuji Kasei Co., Ltd.) were used as curing agents, and paints were prepared according to the blending ratios in Table 1. This paint was applied to a test piece (SPTE) using a bar coater to a film thickness of 4
It was applied so as to have a thickness of 0 μm and dried at room temperature of 23 ° C. for 7 days to form a coating film. The obtained coating film was tested for adhesion, bending resistance, impact resistance, and pencil hardness, and the results are shown in Table 2.

[0049]

[Table 1]

[0050]

[Table 2]

[Measurement Items] (1) Adhesion In accordance with the grid tape method of JIS K5400 8.5, cuts with a gap of 1 mm were made in a grid pattern, and an adhesive tape was stuck on the grid and peeled off. The state of adhesion of the subsequent coating film was visually observed and evaluated on a 10-point scale. (2) Flex resistance According to JIS K5400.8.1, the diameter of the mandrel should be 2
The appearance of the coating film was visually observed when the coating film was bent to a thickness of mm, and was evaluated as ○ when no cracking or peeling was observed, and as × when observed. (3) Impact resistance According to JIS K5400 3.3.2, the height of the weight without cracking or peeling of the coating film was indicated using a DuPont impact deformation tester. (4) Pencil hardness According to JIS K5400 8.4, the hardness of the pencil at the time when the coating film began to be damaged was displayed using Mitsubishi Uni (manufactured by Mitsubishi Pencil Co., Ltd.).

[0052]

The epoxy compound of the present invention has an epoxy ring inside the molecular chain and at least one epoxy ring at the molecular terminal or side chain in the same molecule. Therefore, it is easily cured with an amine-based curing agent, and using the epoxy compound,
An adhesive composition can be produced. The pressure-sensitive adhesive composition of the present invention is excellent in bending resistance, impact resistance, and adhesion.

Claims (5)

[Claims] 1. An epoxy compound represented by the formula (1). Embedded image 2. The epoxy compound according to claim 1, wherein R ² is a substituent represented by the formula (2). Embedded image 3. The epoxy compound according to claim 1, wherein R ² is a substituent represented by the formula (3). Embedded image 4. The epoxy compound according to claim 1, wherein R ² is a substituent represented by the formula (4). Embedded image 5. An adhesive composition comprising the epoxy compound according to claim 1.