JPH09151238A - Novel compound having (meth)acrylic group on its side chain and use thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prepare a novel compd. having a (meth)acrylic group which, upon irradiation with an actinic energy radiation, can yield a cured film having excellent flexibility, adhesion to a substrate, solvent resistance, and glossiness by adding a particular compd. to a predetermined epoxy compd. SOLUTION: A compd. selected from compds. having a COOH group and a (meth)acrylic group, pref. (meth)acrylic acid, and compds. represented by formulae II and III (R<3> represents H or CH3 ; R<4> represents a 2-6C alkylene; R<5> represents a 3-10C alkylene, alkenyl, or phenylene; (n) is 1 to 10; and (m) is 1 to 5) is added to an epoxy compd. prepd. by epoxidating an unsatd. fatty acid deriv. represented by formula I (R<1> represents H or a 1-10C alkyl; R<2> represents R<1> , an aryl, an alkenyl, (meth)acrylic, or an alkoxysilyl; and (x) and (y) are 1 to 20).

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention provides a cured film excellent in flexibility, adhesiveness to a substrate, solvent resistance and glossiness by irradiating active energy rays such as ultraviolet rays and electron beams. The present invention relates to a compound having a (meth) acrylic group in its side chain and an active energy ray-curable composition containing the compound. The compound having a (meth) acrylic group in the side chain of the present invention is used in various coating fields such as ink, plastic paint, paper printing, film coating, metal coating, and furniture coating, linings, adhesives, and electronics fields. It can be applied to many fields such as insulating varnish, insulating sheet, laminated board, printed board, resist ink, and semiconductor encapsulant.

[0002]

2. Description of the Related Art An active energy ray-curable resin composition which is cured by irradiating an active energy ray such as an ultraviolet ray or an electron beam has been developed for various uses such as printing, coating and electrical insulation, and is practically used. It is used. The advantages are (1) solventless and low pollution type, (2) curing rate is extremely fast and product productivity is high, and (3) solid content is so small that volume change before and after curing is extremely small, (4) ) Since there is no heat loss or heat effect on the material, it has been developed for various paints and adhesives such as plastic, paper and inorganic materials.

[0003]

As an active energy ray-curable resin widely used for paints, inks, adhesives, etc., epoxy (meth) obtained by ring-opening reaction of acrylic acid or methacrylic acid with epoxy group of epoxy resin. There is an acrylate resin. However, this epoxy (meth) acrylate resin is not only hard and brittle, but also has a drawback that the shrinkage upon curing is large. For example, when it is used as an ink for printing paper, there is a problem that when the paper surface after printing is bent, cracks occur in the ink portion. Also, when it is used for paints on metals such as iron and aluminum, if the metal plate coated with the paint is bent, the coating film will crack and cannot be processed, or it will be applied on metals such as iron and aluminum. May have poor adhesion. The present invention has improved the defects found in such active energy ray-curable epoxy (meth) acrylate resin and active energy ray-curable epoxy resin, and has excellent flexibility, adhesiveness, and solvent resistance. An object is to provide a compound capable of providing an active energy ray-curable resin composition.

[0004]

In view of the above circumstances, the present inventors have earnestly studied the development of a curable compound that gives an excellent cured product, and as a result, the compound having a (meth) acryl group in the side chain of the present invention. Found, and by using a curable composition characterized by further containing the compound, imparts appropriate flexibility, adhesion, heat resistance, solvent resistance, gloss,
It was found that a cured product such as a coating film having excellent chemical resistance can be obtained, and the present invention was completed.

That is, according to the present invention, a compound (b) having a carboxyl group and a (meth) acryl group in the epoxy compound (a) obtained by epoxidizing the derivative of the unsaturated fatty acid represented by the general formula (1). A compound having a (meth) acrylic group in its side chain, which is obtained by adding a compound, and various uses containing the compound are provided. Hereinafter, the present invention will be described in more detail.

[0006]

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[0007]

BEST MODE FOR CARRYING OUT THE INVENTION An epoxy compound obtained by epoxidizing a derivative of an unsaturated fatty acid represented by the general formula (1) of the component (a) in the present invention is an unsaturated compound represented by the general formula (1). It can be easily obtained by epoxidizing a derivative of a fatty acid with an oxidizing agent. Examples of the alkyl group represented by R ¹ and R ² in the formula 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. Examples of the alkoxy group of the alkenyl group having 1 to 10 carbon atoms and the alkoxysilyl group represented by R ² include the groups corresponding to the above alkyl groups. R ¹
Is preferably an alkyl group having 2 to 5 carbon atoms, and R ² is preferably an ethyl group.

Preferred unsaturated fatty acid derivatives represented by the general formula (1) are unsaturated fatty acids having 16 to 22 carbon atoms, and particularly preferred are those having 20 carbon atoms. ~ 22, and further x
Is 4 to 6 and y is 1 to 7. Specifically, when it is shown as an unsaturated fatty acid, hexadecatrienoic acid (6,10,14-hexadecatrienoic acid, 6,6,6,6 carbon atoms,
9,12-hexadecatrienoic acid, 7,10,13-hexadecatrienoic acid), hexadecatetraenoic acid, octadecatetraenoic acid having 18 carbon atoms (4,8,12,15)
-Octadecatetraenoic acid), heneicosapentaenoic acid having 21 carbon atoms (6,9,12,15,18-heneicosapentaenoic acid), and eicosatetraenoic acid having 20 carbon atoms (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) derivatives of each unsaturated fatty acid are exemplified. These are obtained from natural fats and oils such as fish oil, and can be used in any of high-purity products, mixtures thereof, or distillation residues containing derivatives of these unsaturated fatty acids.

The oxidizing agent to be used is not particularly limited as long as it can epoxidize an unsaturated bond and can be industrially produced, and organic peracids such as peracetic acid, performic acid, perpropionic acid and perbenzoic acid. , T-butyl hydroperoxide, cumyl hydroperoxide, tetralyl hydroperoxide, hydroperoxides of diisopropylbenzene hydroperoxides, hydrogen peroxide and the like can be mentioned as examples.

A catalyst can be used if necessary in the epoxidation. For example, in the case of peracid, an alkali such as sodium carbonate or an acid such as sulfuric acid is used as a catalyst. In the case of hydroperoxides, a catalytic effect can be obtained by using a mixture of tungstic acid and caustic soda with hydrogen peroxide, an organic acid with hydrogen peroxide, or molybdenum hexacarbonyl with t-butyl hydroperoxide. Can be.

The molar ratio of the oxidizing agent used to the double bond in the unsaturated fatty acid derivative represented by the general formula (1) is theoretically 1, but in the range of 0.01 to 10 actually. , Preferably in the range of 0.05 to 2. When the molar ratio is greater than 10, it is preferable in terms of the conversion rate of double bonds in the unsaturated fatty acid derivative and the shortening of the reaction time. It is not preferable because recovery of the oxidant requires a large amount of cost. On the contrary, when the molar ratio is less than 0.05, the conversion rate of the oxidant, the selectivity,
Although it is preferable from the viewpoint of preventing side reaction of the product due to the oxidizing agent, it has drawbacks such that the introduction rate of the epoxy group is too low and the recovery of the unreacted unsaturated fatty acid derivative requires a great deal of cost.

During the epoxidation, the epoxidation rate and the number of epoxy groups can be freely controlled by changing the amount of the oxidizing agent used or by changing the reaction time to deactivate the excess oxidizing agent. . Remaining double bonds are useful after the final adhesive, sealant, or coating has cured, especially when it is very flexible and elastic.

The reaction temperature for the epoxidation is lower than the upper limit value so that the epoxidation reaction has priority over the decomposition reaction of the oxidant. For example, when peracetic acid is used, the temperature is 70 ° C. or lower, t
When using -butyl hydroperoxide, 1
50 ° C. or lower is preferred. When the reaction temperature is low, it takes a long time to complete the reaction.
If butyl hydroperoxide is used, both are 2
It is preferably performed at 0 ° C. or higher.

Although a solvent may not be used in the reaction, aromatic compounds such as benzene, toluene, xylene, chloroform, dimethyl chloride, carbon tetrachloride, chlorobenzene, etc. may be used for the purpose of stabilization by dilution of the oxidizing agent. Ester compounds such as halides, ethyl acetate and butyl acetate, ketone compounds such as acetone and methyl isobutyl ketone, 1,
Ether compounds such as 2-dimethoxyethane can be used. Further, during the reaction, it is preferable to carry out the reaction under a nitrogen atmosphere in order to prevent coloring of the raw materials and products.

When an organic acid is used as an oxidant, the crude product solution of the epoxy compound obtained by the reaction is washed with water or neutralized to reduce the boiling point in order to prevent ring opening of the epoxy group of the product. It is preferable to remove the components. Examples of the alkaline aqueous solution used for neutralization include NaOH, KOH, and K.
Aqueous solutions such as ₂ CO ₃ , NaCO ₃ , NaHCO ₃ , NH ₃ etc. can be used, the concentration of which can be freely used within a wide range. After neutralization, if the low-boiling components are removed and the product is made into a product without washing with water, a neutralized salt will remain in the product. Therefore, it is preferable to wash with water after the neutralization. In order to remove low boiling components from the reaction crude liquid which has been neutralized or washed with water, it is preferable to use a thin film evaporator.

The concentration of oxirane oxygen contained in the thus obtained component (a) epoxy compound is 1 to 22% by weight, preferably 6 to 16% by weight. When the oxirane oxygen concentration is less than 1% by weight, (meth)
If the proportion of the acrylic group introduced cannot be increased, curing failure will occur. On the other hand, if it exceeds 22% by weight, the coating film cured after introducing the (meth) acrylic group becomes hard and brittle, which is not preferable.

The compound having a (meth) acrylic group in the side chain of the present invention is an epoxy compound (a) obtained by epoxidizing the derivative of the unsaturated fatty acid represented by the general formula (1) obtained by the above method. It is obtained by adding the compound (b) having a carboxyl group and a (meth) acrylic group to the epoxy group. Examples of the compound (b) that can be used in the present invention include methacrylic acid, acrylic acid, compounds represented by the general formula (2) and compounds represented by the general formula (3).

[0018]

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As the compound represented by the general formula (2),
For example, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2- (meth) acrylic acid 2-
Hydroxyalkyl (meth) acrylates such as hydroxypentyl can be converted to δ-valerolactone, β-methyl-δ-valerolactone, ε-caprolactone, 3,3,5-trimethylcaprolactone, 3,5,5-trimethylcaprolactone and the like. Examples thereof include compounds in which a terminal hydroxyl group of a compound modified with a lactone is acid-modified with a polybasic acid or a polybasic acid anhydride. These compounds represented by the general formula (2) may be used alone or in combination.

As the compound represented by the general formula (3),
Unsaturated carboxylic acid, such as (meth) acrylic acid, is converted into δ-valerolactone, β-methyl-δ-valerolactone, ε-
Examples thereof include compounds modified with lactones such as caprolactone, 3,3,5-trimethylcaprolactone and 3,5,5-trimethylcaprolactone. These compounds represented by the general formula (3) may be used alone or in combination.

The compound (b) having a carboxyl group and a (meth) acryl group is in the range of 0.1 to 2.0 equivalents, preferably 0.95 to 1. Used in the range of 3 equivalents. If the amount is less than 0.1 equivalent, a large amount of epoxy groups remain and there is a problem in storage stability. If it exceeds 2.0 equivalents, the alkali resistance of the cured coating film becomes insufficient.

A well-known method can be applied to the reaction with the epoxy group. For example, a solvent, an epoxy ring-opening addition catalyst, and optionally a polymerization inhibitor are mixed, and the reaction is carried out at 50 to 150 ° C. 50 ℃
In the following, the reaction takes time and the productivity becomes poor. 150
At temperatures above ℃, gelation tends to occur during the reaction. Such ring-opening addition reaction of the compound (b) is preferably carried out in the presence of a molecular oxygen-containing gas in order to prevent gelation.
Air is usually used as the molecular oxygen-containing gas and is blown into the reactor.

Epoxy ring-opening addition catalysts include tertiary amines such as dimethylbenzylamine, triethylamine, tetramethylethylenediamine, tri-n-octylamine, tetramethylammonium chloride, tetramethylammonium bromide, tetrabutylammonium bromide and the like. Examples thereof include primary ammonium salts, alkylureas such as tetramethylurea, alkylguanidines such as tetramethylguanidine, phosphine compounds such as triphenylphosphine, and salts thereof.
The above catalysts may be used alone or in combination.

These catalysts are contained in the epoxy compound (a) in an amount of 0.01 to 10% by weight, preferably 0.5 to 3.0.
Use by weight%. If it is less than 0.01% by weight, the catalytic effect is low and it is not necessary to add an amount exceeding 10% by weight.

Raw materials and (meth) used as a solvent
There is no particular limitation as long as it dissolves a compound having an acrylic group in its side chain, and examples thereof include aromatic hydrocarbons such as benzene, toluene and xylene, alcohols such as methanol, ethanol and 2-propanol, and acetone.
Ketones such as methyl ethyl ketone and methyl isobutyl ketone, ethers such as diethyl ether, dibutyl ether and dioxane, ethyl acetate, isobutyl acetate,
Esters such as ethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol monoacetate, ethylene glycol monoalkyl ethers, diethylene glycol monoalkyl ethers, propylene glycol monoalkyl ethers, dipropylene glycol monoalkyl ethers,
Butylene glycol monoalkyl ethers, ethylene glycol dialkyl ethers, diethylene glycol dimethyl ether, diethylene glycol diethyl ether and other diethylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, diethylene glycol monoalkyl ether acetates, dimethylformamide, dimethylacetamide and other amides , Halogenated hydrocarbons such as carbon tetrachloride and chloroform are used. These solvents may be used alone or as a mixture. These solvents can be included as they are in product applications containing compounds having a (meth) acrylic group in the side chain.

Since the compound having a (meth) acrylic group in the side chain of the present invention can be cured by active energy rays, an active energy ray-curable composition containing this and other components added as necessary are included. The composition can be used in various applications such as an adhesive composition, a sealant composition, and a coating composition.

The composition obtained by mixing the compound having a (meth) acryl group in the side chain of the present invention obtained above with a photopolymerization initiator and a photosensitizer, alone or in combination, promotes active energy ray crosslinking. be able to.

Examples of the photopolymerization initiator include benzophenone, acetophenone benzyl, benzyl dimethyl ketone, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, dimethoxyacetophenone, dimethoxyphenylacetophenone, diethoxyacetophenone, diphenyldisulfite. , Diaryliodonium, alkoxy-substituted diaryliodonium, triarylsulfonium, dialkylphenacylsulfonium, and dialkyl-4-hydrophenylsulfonium salts are used alone or in combination. These photopolymerization initiators are sensitizers for enhancing conversion of absorption energy of active energy rays into polymerization initiation free radicals, for example, thioxanthone and its halogen and alkyl derivatives, anthracene, perylene,
It may also contain tetracene, phenothiadione, 1,2-benzanthracene, coronene and tertiary amines. Such a compound is used in an amount of 0.01 to 5.0% by weight, preferably 0.05 to 3.0%, based on the compound having a (meth) acrylic group in its side chain. If it is used in an amount of 0.01% or less, the effect is insufficient. On the other hand, if it exceeds 5.0%, the molecular weight will increase too much. It is important to select the photoinitiator and the photosensitizer that are compatible with the compound having a (meth) acrylic group in the side chain to be crosslinked and the active energy ray source that can be used.

The compound having a (meth) acrylic group in the side chain of the present invention can be used as a mixture with alcohol, vinyl ether, epoxide, polymerizable monomer or polymerizable oligomer. The polymerizable monomer is a compound having a radical-polymerizable double bond represented by an acrylic acid ester or methacrylic acid ester compound, a vinyl aromatic compound such as styrene, and an amide unsaturated compound. Typical acrylic acid ester or methacrylic acid ester is as follows. (Meth) acrylic acid alkyl esters such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, 2-hydroxyethyl (Meth) acrylic acid esters having a hydroxyl group such as (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, and caprocactone-modified 2-hydroxyethyl (meth) acrylate, methoxydiethylene glycol (meth) acrylate, ethoxy Diethylene glycol (meth) acrylate, isooctyloxydiethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, methoxy Triethylene glycol (meth) acrylate, methoxy polyethylene glycol # 400-
(Meth) acrylates such as (meth) acrylate,
Bifunctional (meth) acrylic acid esters such as 1,6-hexanediol di (meth) acrylate and neopentyl glycol di (meth) acrylate, trifunctional (meth) acrylic acid esters such as trimethylolpropane tri (meth) acrylate Kinds etc. are used. Examples of the polymerizable prepolymer or the polymerizable oligomer include (meth) acrylic acid esters of polyester polyol, (meth) acrylic acid esters of polyether polyol,
Examples thereof include an adduct of polyepoxy and (meth) acrylic acid and a resin obtained by introducing hydroxy (meth) acrylate into a polyol via polyisocyanate. The above-mentioned polymerizable monomer and the like can be blended in a necessary amount, for example, in the range of 0 to 300 parts by weight, preferably 0 to 100 parts by weight, with respect to the compound having a (meth) acrylic group in the side chain.
When the amount of the polymerizable monomer or the like is more than 300 parts, the characteristics of the compound having a (meth) acrylic group in the side chain are reduced.

Examples of the epoxide include bisphenol A type epoxy resin, bisphenol S type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, N-glycidyl type epoxy resin, and alicyclic type. Included are epoxy resins, epoxidized soybean oil and linseed oil, and fatty acids. Examples include 4-vinylcyclohexene-1-oxide, 5-vinylbicyclo [2.2.1] hept-2-ene 2-oxide, limonene monoxide,
Trivinylcyclohexane monoxide, divinylbenzene monoxide, butadiene monoxide, 1,2-
There are epoxy-9-decene and the like, for example, AOE X24, AOE X68, AOE manufactured by Daicel Chemical Industries, Ltd.
There are Y08 and the like, and these can be used.
Further, ethylene oxide, propylene oxide, cyclohexyl oxide, styrene oxide, vinylcyclohexene dioxide can also be used. Further, if necessary, an epoxy compound having two or more alicyclic epoxy groups can be used. Examples of commercially available products thereof include CELLOXI manufactured by Daicel Chemical Industries, Ltd.
DE 2021, CELLOXIDE 2021P, C
ELLOXIDE 2081, CELLOXIDE 2
083, CELLOXIDE 2085, etc., and they can be used. Further, ERL4289 and ERL4299 manufactured by Union Carbide Co., which is an adipic ester-based aliphatic cyclic epoxy compound, can also be used. In addition, Daicel Chemical Industries Ltd. EPOLEAD GT400, EPOLEAD GT4
01, EPOLEAD GT403, etc., and these can be used. The above epoxides having one or more epoxy groups may be used alone or in combination of two or more. These epoxy compounds are required in the required amount, for example, compound 1 having a (meth) acrylic group in the side chain.
0 to 100 parts by weight is added to 00 parts by weight. When the amount of the epoxy compound is more than 100 parts, (meth) of the present invention
The characteristics of the compound having an acrylic group in the side chain are reduced.

The compound having a (meth) acrylic group in the side chain of the present invention is a crosslinkable substance, and includes adhesives (including pressure-sensitive adhesives, pressure-sensitive adhesives, laminating adhesives and assembly adhesives), sealants, It is useful for coatings, films (such as those requiring heat resistance and solvent resistance) and the like. An adhesive composition product prepared by compounding a compound having a (meth) acrylic group in a side chain and an optional curing aid or curing agent to meet properties required for individual applications is a tackifier. , Other ingredients such as, plasticizers, fillers, solvents and stabilizers may be included in various combinations.

The adhesive composition containing the compound having a (meth) acrylic group in the side chain of the present invention may also contain a plasticizer such as a rubber plasticizer or a compounding oil. Compounding oils for rubber are well known to those skilled in the art, and include highly saturated compound-containing oils and highly aromatic compound-containing oils. The amount of the rubber compounding oil used in the adhesive composition of the present invention is 0 to 500 parts by weight, preferably 0 to 100 parts by weight, and further 100 parts by weight of the compound having a (meth) acrylic group in the side chain. It is preferably in the range of 0 to 60 parts by weight.

The coating composition containing the compound having a (meth) acrylic group in the side chain of the present invention may contain various fillers and pigments. This is especially true in exterior paints where fillers are added to also improve paint properties such as weather resistance. Suitable fillers include calcium carbonate, clay, talc, zinc oxide, titanium dioxide and the like. Further, examples of protective pigments capable of improving the decomposition resistance by exposure to sunlight include carbon black, zinc oxide, titanium dioxide and the like. The amount of the filler is 0 to 70% by weight based on the solvent contained in the paint at an arbitrary ratio depending on the type of the filler usually used and the intended use.

When the paint is prepared with a solvent solution,
There is no particular limitation as long as it can dissolve or disperse a compound having a (meth) acrylic group in its side chain, and examples thereof include aromatic hydrocarbons such as benzene, toluene, xylene, methanol, ethanol, and 2 -Alcohols such as propanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethers such as diethyl ether, dibutyl ether and dioxane, ethyl acetate, isobutyl acetate, ethylene glycol monoacetate, propylene glycol monoacetate, dipropylene glycol Esters such as monoacetate, ethylene glycol monoalkyl ethers, diethylene glycol monoalkyl ethers,
Diethylene glycol dialkyl ethers such as ethylene glycol dialkyl ethers, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, ethylene glycol monoalkyl ether acetates, diethylene glycol monoalkyl ether acetates, amides such as dimethylformamide, dimethylacetamide, carbon tetrachloride, chloroform, etc. Halogenated hydrocarbons and the like are used. These solvents may be used alone or as a mixture. The amount of solvent depends on the particular solvent chosen and the amount of functional groups of the compound having a (meth) acrylic group in the side chain. Normal,
The amount of solvent used is 0-80% by weight in the coating composition.

Antioxidants and light stabilizers have been added to the composition in order to protect the product against oxidation during preparation or use of the coating composition of the present invention or degradation by exposure to sunlight. obtain. The combination of stabilizers is often more effective due to the degradation of different mechanisms that various polymers undergo.

Antioxidants include hindered phenol antioxidants, phosphite antioxidants, and thioether antioxidants, and commercially available antioxidants include, for example, ADEKA STAB AO-60 and AO-. 80, PEP-8, PE
P-36, HP-10, AO-412S (manufactured by Asahi Denka Co., Ltd.) and zinc dialkyldithiocarbamate are also included, and they can be used alone or in various combinations. These antioxidants are usually used in an amount of 0.05-5% by weight in the composition.

As the light stabilizer, there are hindered amine light stabilizers, benzotriazole light stabilizers, and benzophenone UV absorbers. Commercially available light stabilizers are, for example, ADEKA STAB LA-32, LA-36, LA-. 51,
LA-52, LA62, LA-63, LA-77 (manufactured by Asahi Denka Kogyo Co., Ltd.) and a UV absorber containing a metal are also included, and they can be used alone or in various combinations. These light stabilizers are usually used in an amount of 0.05 to 10% by weight in the coating composition.

Further, the coating composition of the present invention comprises
If necessary, a leveling agent, a defoaming agent, a thickening agent, an anti-settling agent, an antistatic agent, an antifogging agent and the like can be added.

As a coating method of the coating composition of the present invention, a brush coating method, a spray coating method, a dip coating method, a spin coating method, a curtain coating method and the like are used.
Further, as the active energy ray for crosslinking the compound having a (meth) acrylic group in the side chain of the present invention, a high pressure mercury lamp, a metal halide lamp, or the like is used, which is 100 to 40.
Ultraviolet rays of 0 nm, electron beams, etc. can be used.

[0040]

EXAMPLES Next, the present invention will be described with reference to Examples and Comparative Examples. All (parts) in Examples and Comparative Examples mean (parts by weight). Moreover, the measurement and evaluation in Examples and Comparative Examples were performed by the following methods.

(1) Adhesion: A cross-cut reaching the base material at 1 mm intervals was put in the cured film to make 100 1 mm ² cross-cuts, and cellophane tape was attached on top of it, and then rapidly peeled and peeled. 5 depending on the number of crosses
Peeling number 0, 4; Peeling number 1-25, 3: Peeling number 25-5
0 pieces, 2: 50 to 75 pieces of peeling, 1: 75 to 10 pieces of peeling
It was indicated by 0. In addition. An aluminum plate treated with chromium phosphate was used as the base material. (2) Pencil hardness: Performed according to JIS standard. However,
An aluminum plate treated with chromium phosphate was used as a substrate. (3) Solvent resistance: The coated film surface was rubbed 10 times with cotton soaked with xylene, and the surface was observed. Evaluation results
5: No change in appearance, 4: slightly whitened, 3: whitened, 2: considerably whitened, 1: whitened, and peeled. (4) Heat resistance: The cured coating film test piece was evaluated for coloring after standing at 200 ° C. for 1 hour. The evaluation results are indicated by ◯: the cured film is not colored and the appearance is not abnormal, Δ: the cured film is colored, and x: the cured film is strongly colored. (5) Bending resistance: A bending test was performed using a bending tester in accordance with JIS standards, and cracks and peeling of the coating film were visually examined. The diameter of the mandrel was 2 mm, and an aluminum plate treated with chromium phosphate was used as a test plate. The evaluation results were 5: no cracking and peeling, 4: some cracking occurred, 3: cracking occurred, 2: some peeling occurred,
1: It was peeled off and displayed. (6) Chemical resistance: Each was immersed in a 10% hydrochloric acid aqueous solution and a 10% sodium hydroxide aqueous solution at a predetermined temperature for a predetermined time, and the appearance change after the immersion was observed. The evaluation results are indicated by ◯: no change in appearance, Δ: wrinkles and peeling.

(Example 1) 300 g (iodine number: 373) of ethyl docosahexaenoic acid ethyl ester (GC purity 70%; residue after distillation of active ingredient from fish oil) and 300 g of ethyl acetate were charged into a 2-liter jacketed flask, and nitrogen was charged. While blowing gas, the peracetic acid / ethyl acetate solution 1267 was taken for about 3 hours so that the temperature in the reaction system became 40 ° C.
g (peracetic acid concentration: 29.1% by weight) was added dropwise. After the addition of the peracetic acid / ethyl acetate solution was completed, the reaction was completed by aging for 2 hours at 40 ° C. The crude liquid was washed with water at 40 ° C, 70 ° C / 10
Low boiling point was removed at mmHg to obtain 340 g of epoxidized docosahexaenoic acid ethyl ester. The properties of the obtained product are: oxirane oxygen concentration 15% by weight, viscosity 600 cP /
It is 25 degreeC, the peak derived from the double bond of (delta) 5.3-5.7 vicinity disappears from < ¹ > H-NMR, and (delta) 2.9-3.
It was confirmed that a proton peak derived from an epoxy group was generated around 1.

Next, 300 g of the epoxidized docosahexaenoic acid ethyl ester obtained, 115 g of toluene, 3 g of triphenylphosphine, and hydroquinone monomethyl ether.
0.5 g of tellurium was charged, the mixture was heated to 100 ° C. while bubbling air into the reaction system, and 161 g of acrylic acid was added dropwise from a dropping funnel. Furthermore, the reaction was carried out at 100 ° C. for 8 hours, and the residual acrylic acid was less than 0.5% by gas chromatography analysis, so the reaction was terminated.

(Example 2) 550 g (iodine value: 373) of ethyl docosahexaenoic acid ethyl ester (GC purity 70%; residue after distillation of active ingredient from fish oil) and 550 g of ethyl acetate were charged in a 2-liter jacketed flask, and nitrogen was charged. 805 g of peracetic acid / ethyl acetate solution over about 3 hours so that the temperature in the reaction system becomes 40 ° C. while blowing gas.
(Peracetic acid concentration: 28.7% by weight) was added dropwise. Peracetic acid /
After the addition of the ethyl acetate solution was completed, the reaction was completed by aging at 40 ° C. for 1 hour. The crude liquid was washed with water at 40 ° C, 70 ° C / 10m
The mixture was subjected to low boiling point removal with mHg to obtain 620 g of epoxidized docosahexaenoic acid ethyl ester. The properties of the obtained product are oxirane oxygen concentration 6.8% by weight, viscosity 20 cP /
25 ° C., peak of proton derived from epoxy group in the vicinity of δ 2.9 to 3.1 from ¹ H-NMR, δ 5.3 to
A proton peak derived from the residual double bond was detected around 5.7, and it was confirmed that a compound having an epoxy group and an unsaturated double bond was formed in the molecule.

Next, 300 g of epoxidized docosahexaenoic acid ethyl ester obtained, 115 g of toluene, 3 g of triphenylphosphine, hydroquinone monomethyl ether.
0.5 g of tellurium was charged and heated to 100 ° C. while bubbling air into the reaction system, and 73.5 g of acrylic acid was added dropwise from a dropping funnel. Furthermore, the reaction was carried out at 100 ° C. for 7 hours, and the residual acrylic acid was less than 0.5% by gas chromatography analysis, so the reaction was terminated.

(Example 3) The compounds prepared in Examples 1 and 2 and having a (meth) acrylic group in the side chain were used.
A composition having the composition shown in 1 was applied to an aluminum plate to a film thickness of 10 μm, and a cured coating film was formed by irradiating ultraviolet rays of 100 mJ / cm ² in the air using a high pressure mercury lamp. . The results are shown in Table 1.

[0047]

[Table 1]

[0048]

The active energy ray-curable composition using the compound having a (meth) acrylic group in the side chain of the present invention is
By coating on the surface of a substrate such as metal, and then irradiating with active energy rays (radiation rays) such as ultraviolet rays and electron beams,
It is possible to form a cured film having excellent flexibility (flexibility) and adhesion. Therefore, it can be applied to various coating fields such as ink, plastic paint, paper printing, film coating, metal coating and furniture coating, linings, adhesives and sealants. Also,
The active energy ray-curable composition of the present invention can be used even in a solventless system, and is therefore extremely important from the viewpoint of environmental protection.

Claims (14)

[Claims] 1. An epoxy compound (a) obtained by epoxidizing a derivative of an unsaturated fatty acid represented by the general formula (1).
A compound having a (meth) acrylic group in its side chain, which is obtained by adding a compound (b) having a carboxyl group and a (meth) acrylic group to. Embedded image 2. The compound having a (meth) acryl group in the side chain according to claim 1, wherein the unsaturated fatty acid derivative is an unsaturated fatty acid derivative obtained by purifying fish oil. 3. The epoxy compound (a) has the general formula (1):
The (meth) acryl according to claim 1, which is obtained by epoxidizing a derivative of an unsaturated fatty acid in which R ¹ is a pentyl group, x is 4, y is 2 and R ² is an ethyl group. A compound having a group in the side chain. 4. The epoxy compound (a) has the general formula (1):
The (meth) acryl according to claim 1, which is obtained by epoxidizing a derivative of an unsaturated fatty acid in which R ¹ is an ethyl group, x is 5, y is 2 and R ² is an ethyl group. A compound having a group in the side chain. 5. The epoxy compound (a) has the general formula (1):
The (meth) acryl according to claim 1, which is obtained by epoxidizing a derivative of an unsaturated fatty acid in which R ¹ is an ethyl group, x is 5, y is 3 and R ² is an ethyl group. A compound having a group in the side chain. 6. The epoxy compound (a) has the general formula (1):
The (meth) acryl according to claim 1, which is obtained by epoxidizing an unsaturated fatty acid derivative in which R ¹ is an ethyl group, x is 4, y is 7 and R ² is an ethyl group. A compound having a group in the side chain. 7. The epoxy compound (a) has the general formula (1):
^2. The (meth) acryl according to claim 1, which is obtained by epoxidizing a derivative of an unsaturated fatty acid in which R ¹ is an ethyl group, x is 5, y is 4 and R ² is an ethyl group. A compound having a group in the side chain. 8. The epoxy compound (a) has the general formula (1):
^2. The (meth) acryl according to claim 1, which is obtained by epoxidizing a derivative of an unsaturated fatty acid in which R ¹ is an ethyl group, x is 6, y is 1 and R ² is an ethyl group. A compound having a group in the side chain. 9. The compound having a (meth) acryl group in the side chain according to claim 1, wherein the oxirane oxygen concentration of the epoxy compound (a) is 6 to 16% by weight. 10. The compound (b) having a carboxyl group and a (meth) acrylic group is selected from methacrylic acid, acrylic acid, a compound represented by the general formula (2) and a compound represented by the general formula (3). It is a compound, The compound which has a (meth) acryl group in the side chain in any one of Claims 1-9. Embedded image 11. An active energy ray-curable composition containing the compound having a (meth) acrylic group in its side chain according to any one of claims 1 to 10. 12. An adhesive composition containing the compound having a (meth) acrylic group in its side chain according to any one of claims 1 to 10. 13. A sealant composition containing the compound having a (meth) acrylic group in its side chain according to any one of claims 1 to 10. 14. A coating composition containing the compound having a (meth) acrylic group as a side chain according to any one of claims 1 to 10.