JPH09137078A - Curable ester base and curable composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a curable ester base excellent in stability in preservation, excellent in polymerization reactivity, namely curability, capable of forming a cured uniform material excellent in adhesivity and flexibility in curing and a curable composition containing the ester base. SOLUTION: This curable ester base is a monoester or a polyfunctional ester comprising a mixed fatty acid containing a fatty acid having a conjugated double bond and a polyhydric alcohol. The ratio of a fatty acid residue containing a conjugated double bond in a mixed fatty acid residue linked by an ester bond is 35-70mol%. More preferably the curable ester base is composed of an ester amounting to >=50% the sum of trans-trans form, cis-cis form, cis- trans form and trans-trans form in the content of geometrical isomerism of the fatty acid residue containing the conjugated double bond. The objective curable composition comprises the curable ester base.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention can be used in the fields of paints, inks, resin processing, paper sizing agents, wood, bottles, metals, surface treatment agents for cans, etc. and is curable to light and / or heat. The present invention relates to an excellent ester base and a curable composition containing the same. The curable ester base of the present invention and the composition containing the same have high curing reactivity to light and heat, and are excellent in uniformity, adhesion and flexibility in a film or cured product formed by the reaction. It has the property of.

[0002]

2. Description of the Related Art Fatty acids constituting ordinary animal and vegetable fats and oils include unsaturated fatty acids having an unsaturated bond represented by a carbon-carbon double bond (hereinafter, simply referred to as a double bond). It is known that the polymerization reaction of unsaturated fatty acids and derivatives thereof having two or more double bonds is accelerated by heat or light, and the properties of highly unsaturated ones change from paste to solid. ing. Unsaturated fatty acids having a large number of double bonds have been used in various fields, for example, making use of this property to form films such as paints and inks and plate-like molded products such as laminates.

In general, the rate of polymerization of unsaturated fatty acids having double bonds and derivatives thereof is affected, in part, by the number of double bonds, so that the larger the number of double bonds, the faster the polymerization reaction speed. Further, the position of the double bond greatly affects the polymerization reactivity. Specifically, two or more double bonds is in the generally "pentadiene type" and 1,4-position relationship called _{(CH- -CH = CH-CH 2} -CH =),
Normal liquid fats and oils produced in large quantities for industrial or edible use, such as soybean oil, rapeseed oil, corn oil, sunflower oil, rice oil, safflower oil, sesame oil, olive oil, cottonseed oil, linseed oil, etc. For example, linoleic acid and trienoic acid (for example, linolenic acid) have such a positional relationship. These oils and fats, by applying light and heat,
Alternatively, if the film is left in the air for a long time, the film changes into a paste or a gel, and further, a film is formed or solidified. However, the speed of the property change is very slow.

On the other hand, a 1,3-position positional relationship (-C) which is called "conjugated type" having high polymerization reactivity (drying property).
Some have a double bond at H = CH-CH = CH-). Tung oil is an example of a natural product containing a relatively large amount of conjugated double bonds. This is composed mainly of conjugated trienoic acid called eleostearic acid, which is the highest reactivity among natural fats and oils, but the film formed by this is called wrinkle called chijimi. There was a problem of occurrence of.

The constituent fatty acids of natural fats and oils (linoleic acid, linolenic acid, etc.) can be used as a starting material to perform light (UV) irradiation treatment, heat treatment, or a conjugation reaction using a catalyst to increase the conjugation rate. Possible (eg oil chemistry, 38th)
Vol., Pp. 949 and 959, 1989). Conjugated linseed oil, dehydrated castor oil, and the like are examples of conjugated fats and oils that have been implemented on an industrial scale, and the conjugation rate of any of these was limited to about 30 mol%. Conjugated fatty acid by thermal isomerization reaction using an alkali catalyst such as sodium hydroxide, and hydienoic acid (manufactured by Soken Chemical Co., Ltd.) conjugated with castor oil hydrolyzed fatty acid as a raw material by dehydration reaction are about 60 mol%. However, since the terminal carboxyl group is free,
The range of use was limited.

[0006] As described above, due to the content of conjugated double bonds in natural fats and oils and their fatty acids and functional restrictions, the field of utilizing the hardening function of natural fats and fatty acid derivatives is currently Although not so wide, it is a raw material that can be obtained from planned cultivation resources for petroleum-based raw materials that are fossil resources, in particular, from the viewpoint that high biodegradability can be expected, etc. The momentum for reconsidering natural fats and oils and their fatty acid derivatives is increasing.

Particularly in recent years, there has been a demand for shortening and improving the efficiency of raw material processing in various industrial fields. For this reason, for example, in the case of coating a protective film on a metal surface of an automobile, machine, ship, etc., In addition, as in the case of carton printing, metal printing, form printing, sticker printing, curved surface printing, printed circuit board, overprinting, etc., the curing reaction technology by ultraviolet (UV) irradiation is applied, and it is mainly used as a raw material to be processed. Chemically synthesized raw materials such as acrylic acid compounds and compositions having these as main constituents have been used. However, improvements in functional disadvantages of acrylic acid compounds (such as skin irritation and the necessity of volatile organic solvents) have been pointed out, and from the viewpoint of environmental protection, the shift from chemically synthesized raw materials to natural raw materials has been pointed out. With the progress of the conversion, there is a demand for the effective utilization of raw materials utilizing natural oils and fats and their fatty acids in the various fields mentioned above.

[0008]

As described above, excluding tung oil, not only vegetable oils and fats but also derivatives thereof such as conjugated linseed oil and dehydrated castor oil, etc., in which the conjugation rate is generally improved are generally used. Tung oil has been studied for applications where the polymerization reactivity or curability is insufficient, or where higher reactivity is expected. However, paulownia oil has problems such as wrinkles and has been used only in limited fields. Therefore, an object of the present invention is to have high polymerization reactivity, that is, curability by irradiation with light (UV) and heating, and also to have good stability during storage and to be homogeneous when cured,
An object is to provide an ester base that forms a cured structure having excellent adhesion and flexibility, and a curable composition containing the same.

[0009]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that in an ester of a mixed fatty acid and a polyhydric alcohol, the content of the conjugated unsaturated fatty acid in the mixed fatty acid is It was found that when the amount is too large, wrinkles are generated in the cured film similarly to tung oil, but wrinkles are not generated until the content of the conjugated unsaturated fatty acid reaches a specific mixing ratio. As a result of further study based on this finding, the polymerization reaction rapidly proceeded by light and heat, the curability was good, the formed film had appropriate strength and flexibility, and wrinkles did not occur. It has been found that a curable composition having a property is obtained. The present invention is based on this finding.

That is, the gist of the present invention is a monoester or polyvalent ester comprising a mixed fatty acid containing a fatty acid having a conjugated double bond (hereinafter referred to as a conjugated unsaturated fatty acid) and a polyhydric alcohol, which is ester-bonded. Of the mixed fatty acid residues, the ratio of conjugated unsaturated fatty acid residues is 35 to 70.
A curable ester base material comprising the above ester in an amount of mol%, and a curable composition containing the ester base material.

Among the monoesters or polyvalent esters, more preferable ones are cis-cis type in which the ratio of trans-trans type as geometric isomer of double bond in the ester-bonded conjugated unsaturated fatty acid residue is 50 in total of cis-trans type and trans-trans type
% Or more.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The curable ester base of the present invention comprises:
It has a structure of an ester (monoester or polyvalent ester) of a polyhydric alcohol having two or more hydroxyl groups in the molecule and a mixed fatty acid, and the conjugated unsaturated fatty acid residue is 35 to 70 among the ester-bonded mixed fatty acid residues. It consists of said ester in a molar proportion of preferably 40 to 60 mol%.

The ester according to the present invention is an unsaturated fatty acid having a double bond capable of esterifying a mixed fatty acid containing a conjugated unsaturated fatty acid and a polyhydric alcohol into a monoester or a polyvalent ester, or a conjugating double bond. It is produced by subjecting a monoester or polyvalent ester of a mixed fatty acid containing it and a polyhydric alcohol to a conjugate isomerization reaction.

The conjugated unsaturated fatty acid is conjugated octadecatrienoic acid (eleostearic acid) which is a constituent fatty acid of tung oil.
Such a hydrolyzed oil or fat containing a naturally occurring conjugated unsaturated fatty acid can be obtained by subjecting it to appropriate fractionation and purification treatments. Further, linoleic acid and linolenic acid constituting soybean oil, rapeseed oil, safflower oil, sesame oil, cottonseed oil, linseed oil, eno oil, etc., i.e., oils and fats containing a large amount of unsaturated fatty acids having a double bond capable of being conjugated to conjugated isomers. There is also a method for purifying conjugated unsaturated fatty acids such as conjugated octadecadienoic acid and conjugated octadecatrienoic acid by subjecting the same to a hydrolyzing treatment. In this case, a conjugate reaction is performed on the oil or fat alone or in a mixture, and then a hydrolysis treatment is performed to obtain a conjugated unsaturated fatty acid mixture, or the oil or fat alone or mixed is hydrolyzed. A conjugated unsaturated fatty acid mixture may be obtained by subjecting the mixture to a fatty acid and subjecting it to a conjugation reaction. Furthermore, the mixture of the conjugated unsaturated fatty acid thus obtained and the other kind of fatty acid is subjected to a treatment such as solvent fractionation, silica gel column fractionation or the like, if necessary, or conjugated by mixing another kind of fatty acid. It is also possible to adjust the purity of the unsaturated fatty acids.

When the conjugated unsaturated fatty acid is used alone, the curing speed is high as described above, but wrinkles are formed on the cured film. Therefore, it is necessary to use the conjugated unsaturated fatty acid in combination with other fatty acids. It is. Non-conjugated fatty acids are preferable as other fatty acids to be mixed for such a purpose, and examples thereof include acetic acid, butyric acid, caproic acid, caprylic acid, nonanoic acid, capric acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitin. Acids, linear saturated fatty acids such as heptadecanoic acid, stearic acid and behenic acid, 2-ethylhexanoic acid, 3,5,5-trimethylhexanoic acid, 2-
Hexyldecanoic acid, 2-heptylundecanoic acid, side chain saturated fatty acids such as polymethyl group branched isostearic acid manufactured by Emery Corporation, palmitooleic acid, oleic acid, elaidic acid, linoleic acid, linolenic acid, erucic acid, etc. Unsaturated fatty acids.

The properties of the ester according to the present invention can be controlled by selecting the type of these non-conjugated fatty acids. Selecting a fatty acid having a lower molecular weight can lower the viscosity of the ester, and selecting a fatty acid having a higher degree of unsaturation can lower the freezing point (melting point). The melting point can be lowered.

On the other hand, polyhydric alcohols for constituting the ester according to the present invention include, for example, ethylene glycol, propylene glycol, 1,3-butanediol,
Polyhydric alcohols such as 1,4-butanediol, octanediol, decanediol, glycerin, neopentyl glycol, trimethylolethane, trimethylolpropane, trimethylolbutane, and pentaerythritol; diglycerin, triglycerin, decaglycerin, etc. Polyhydric alcohol dehydration condensates such as polyglycerin, diethylene glycol, dipropylene glycol and dipentaerythritol, sugar alcohols such as sorbitol, mannitol and xylitol, and sugars such as glucose, sucrose, xylose and maltose can be used. Among these polyhydric alcohols, in the present invention, two hydroxyl groups are present in the molecule.
Those having up to 6 are preferred.

In the present invention, a monoester or a polyester can be obtained by appropriately combining the mixed fatty acid comprising the conjugated unsaturated fatty acid and another fatty acid with the polyhydric alcohol and subjecting the mixture to an esterification reaction. As the esterification method, a conventional method may be used,
For example, using a known esterification catalyst such as a metal or an oxide or chloride thereof, or an acidic or alkaline substance, heating to cause dehydration condensation, or a derivative of the mixed fatty acid (acid chloride, acid anhydride) Etc.) to facilitate the progress of the esterification reaction, or enzymes (lipases)
A method such as esterification utilizing the method can be appropriately employed. In the present invention, in order to handle conjugated unsaturated fatty acids whose stability to light and heat is inferior to ordinary unsaturated fatty acids, it is desirable to select methods and conditions that are as mild as possible in the ester production process.

In addition to the method using the esterification reaction as described above, a fat or oil containing a conjugated unsaturated fatty acid and a polyhydric alcohol ester esterified with an arbitrary fatty acid are used for transesterification reaction such as sodium methylate or lipase. For transesterification using a catalyst, or for polyhydric alcohol esters containing unsaturated fatty acids such as linoleic acid and linolenic acid that can be conjugated and isomerized as constituents, for conjugated isomerization reactions such as iodine and methyl iodide It is also possible to produce the specific ester according to the present invention by carrying out conjugation using a catalyst.

In producing the ester according to the present invention, it is usually desirable that the degree of esterification is almost perfect, but a structure in which a part of the hydroxyl groups of the polyhydric alcohol remains depending on the purpose and use of the ester ( It may be a monoester or a polyvalent ester), or may be a mixed ester with the complete ester containing at least one or more of these partial esters.

It is important that the curable ester base of the present invention comprises an ester which satisfies the following conditions. That is, the fatty acids that make up the ester are mixed fatty acids,
The molar ratio of the conjugated unsaturated fatty acid to the total mixed fatty acid is 35 to 70%, preferably 40 to 60%.
When the amount of the conjugated unsaturated fatty acid in the mixed fatty acid is less than 35 mol%, it is difficult to secure sufficient polymerization reactivity and curing speed, and the strength of the obtained film is weak. On the other hand, when the conjugated unsaturated fatty acid exceeds 70 mol%, wrinkles in the film, such as those found in tung oil, occur.

It should be noted that the content ratio of the conjugated unsaturated fatty acid residue is not limited to the present invention even if the ester having a high concentration of the conjugated unsaturated fatty acid residue and the ester having no conjugated unsaturated fatty acid residue or a small amount of the ester are simply mixed. Although it is possible to obtain the same ester as the above-mentioned, a simple cured film of such an ester cannot obtain a uniform cured film.

Further, in the ester constituting the curable ester base of the present invention, the double bond of the ester-bonded conjugated unsaturated fatty acid residue is in the trans form and the trans form (referred to as trans-trans type. The same applies hereinafter). The ratio of cis-cis, cis-trans and trans-trans is 5% of the total amount of geometric isomers.
It is preferably 0% or more. More preferably, it is 70 to 100%. When the ratio is less than 50%,
The curing rate becomes slower, and when compounded in the UV curable composition, the tendency to delay the curing rate becomes greater.

The curable ester base of the present invention comprising an ester satisfying the above-mentioned conditions can be used as it is for the above-mentioned esterification reaction product as it is for the production of various cured products. It may be used after being subjected to purification treatment such as deoxidation, decolorization and deodorization to the extent that the conjugated structure of saturated fatty acids is not deteriorated. The ester base of the present invention has high polymerization reactivity or curability, has good stability during storage, is homogeneous when cured, and forms a cured structure excellent in adhesion and flexibility. Have characteristics.

Next, the curable composition of the present invention will be described. The curable composition of the present invention is a mixture of the curable ester base of the present invention and various known components used in a conventional curable substance or a composition containing the same, making use of the above-mentioned properties of the curable ester base of the present invention. It is. At this time, the compounding ratio of the curable ester base of the present invention is in principle arbitrary, and it is considered that the curable ester base of the present invention is used as a main component in the composition and as a additive. Can be When the curable ester base is contained as a main component, the compounding amount is 40 to 95% by weight, preferably 60 to 90% by weight based on the whole curable composition. When it is used as an additive, it is added in an amount of 1 to 30% by weight, preferably 3 to 15% by weight, based on the entire curable composition.

The known components include lower carboxylic acids having a conjugated unsaturated bond such as acrylic acid, methacrylic acid and sorbic acid, which are polymerized by heat treatment or light irradiation treatment, and their derivatives (esters, ethers, salts). , Amide, etc.), urethane prepolymers that also polymerize by heating or light irradiation, stand oil partially polymerized by heating or oxygen addition, polymerized oils and fats such as boil oil, and reduction of viscosity. Polymerization initiators (2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl) which accelerate the polymerization reaction by various organic solvents for compatibilizing mutually insoluble components and heat or light. -Ketone etc.), resins, pigments, dyes and the like.

The curable composition of the present invention is a coating material, ink, or the like which forms a film or a cured product by irradiation with light (UV) or heating.
A surface treatment agent such as paper or metal, a laminate, etc., and their base compositions may be prepared according to the required functions and use conditions. For example, in paints, the ester base of the present invention is used as a main component of a film-forming element, and in inks, the ester base of the present invention is used as a drying oil or a processed product thereof (heat-polymerized oil, maleated oil, urethanized) Can be used as a partial or complete replacement for oil, etc.).

As a specific example, in the case of general paints and inks, resins are dissolved in a mixture containing the ester base of the present invention, an organic solvent and, if necessary, an oily component (mineral oil, ester oil, etc.), Alternatively, the ester base of the present invention or a mixture thereof with a resin is partially reacted, or a vehicle is prepared by adding a thickener, a gelling agent or the like to any of the above mixtures, and a pigment or dye is added thereto. Is added and kneaded to form a mill base, and if necessary, an organic solvent and other additives are blended to produce a curable composition. In the case of a highly curable composition such as a UV curable ink, a photopolymerizable monomer or a prepolymer thereof, such as an acrylic acid compound, is used as a main film-forming component, and a photopolymerization initiator and A suitable amount of the ester base of the present invention is added to form a base composition, and if necessary, a pigment and a stabilizer are added, followed by heating and mixing to produce a curable composition.

The curable composition thus obtained has a high polymerization reactivity that is easily cured by heat treatment or light (UV) irradiation treatment, and is a homogeneous film or cured product excellent in terms of adhesion and flexibility. To form. Therefore, the curable composition of the present invention is subjected to a field in which petrochemical raw materials represented by acrylic acid monomers have been mainly used in the past, for example, special coating or UV curing treatment requiring particularly high polymerization reactivity. It can be used in applications such as resin processing, inks and paints. Further, as a curable raw material generally utilizing heat or light, the petroleum-based raw material has a relatively high polarity, whereas the ester base of the present invention has a low polarity,
It is possible to use pigments and dyes that were not compatible with conventional raw materials in combination, and the cured product has properties that are difficult to obtain with petrochemical raw materials, such as high film flexibility and good adhesion. Can be given. Further, the use of tung oil has hitherto been mainly used in the production of laminated plates and the like, but the curable ester base of the present invention or a curable composition containing the same can be used as an alternative.

[0030]

EXAMPLES In the following examples, the ratio of the conjugated unsaturated fatty acid residue in the mixed fatty acid residue constituting the ester is determined by the conjugation rate (conjugated dienoic acid content and / or conjugated trienoic acid content) of the mixed fatty acid. Evaluation shall be made by the Japan Oil Chemistry Association, “Standard Oil and Fat Analysis Test Method”, 2.4.15-71.
Based on the method described in the section of conjugated unsaturated fatty acid (spectral method), 233, 262, 268, 27 of 0.01 g / l concentration sample solutions using cyclohexane as a solvent.
It was determined by measuring the UV absorbance at 4, 308, 315, 322 and 346 mμ and calculating the content of conjugated unsaturated fatty acid from the specified calculation formula. For the content of eleostearic acid, 269, 271.
UV absorbance at 5 and 276.5 mμ was measured,
It was calculated from the prescribed calculation formula described in the above-mentioned document.

The ratio of trans-trans geometric isomers in the double bond of the conjugated unsaturated fatty acid residue was determined by the following method. That is, in the case of conjugated dienoic acid,
After the ester is hydrolyzed to convert the constituent fatty acid into a methyl ester and each component is separated, identified and quantified by capillary gas chromatography (GLC), cis-cis type,
It was calculated as a percentage of the total amount of cis-trans and trans-trans isomers. Further, in the case of containing conjugated trienoic acid, the content of conjugated dienoic acid and conjugated trienoic acid is obtained by the above method, and ester hydrolysis as in the case of the conjugated dienoic acid, methyl esterification,
The content of each geometrical isomer was determined by GLC analysis. Conjugated trienoic acid had 1 cis-trans type and 1 trans-trans type, respectively.
Regarding the unit and all-trans type, the trans-trans type was 2 units, and the percentage was calculated with respect to the total number of conjugated double bonds, and the content was calculated by adding the conjugated dienoic acid and conjugated trienoic acid contents.

Production Example 1 In a 500 ml flask equipped with a thermometer, a condenser, a water separator and a stirrer (hereinafter, the same except for capacity), tung oil 85 g, linseed oil 15 g, distilled water 200 g and lipase (Meito Sangyo Co., Ltd. ), Lipase OF) (0.2 g) was added, and the mixture was stirred at 50 ° C. for 5 hours to cause a hydrolysis reaction.
After completion of the reaction, the aqueous layer was removed and the oil layer was dried under reduced pressure to obtain tung oil-decomposed fatty acid. The acid value of this mixed fatty acid was 190. 14 g of trimethylolpropane in the mixed fatty acid
(0.10 mol) and 0.2 g of paratoluenesulfonic acid as a catalyst were added, and the esterification reaction was carried out at 180 ° C. for 15 hours. After completion of the reaction, washed with water and dried under reduced pressure,
80 g of the ester base of the present invention was obtained. The conjugated trienoic acid content in the mixed fatty acid that constitutes this ester base is UV
It was 68 mol% as measured by absorbance. The ratio of trans-trans isomer in the conjugated unsaturated fatty acid was 55%.

Production Example 2 Linoleic acid (Wako Pure Chemical Industries, Ltd., special grade reagent) 7
0 g (0.21 mol), oleic acid (Wako Pure Chemical Industries, Ltd.)
30 g (0.14 mol) of reagent grade special grade), 7 g (0.11 mol) of ethylene glycol and 0.2 g of paratoluenesulfonic acid as a catalyst were added, and the mixture was added at 180 ° C. for 1 hour.
The esterification reaction was carried out for 5 hours. After the completion of the reaction, alkali deoxidation, washing with water and drying under reduced pressure to give an esterified product 8
8 g were obtained. In addition to this esterification product, n-
100 ml of hexane and 0.1 g of iodine were added, and a high pressure mercury lamp (manufactured by Ushio Inc., model: UM-102, the same applies below) was used to illuminate the lamp with water at a power of 100 watts for 10 hours while cooling the lamp with water. The conjugated isomerization reaction was carried out. After completion of the reaction, the product was washed with a 10% by weight sodium thiosulfate aqueous solution, and n-hexane was distilled off under reduced pressure to obtain 80 g of the ester base material of the present invention. The conjugated dienoic acid content in the mixed fatty acid constituting this ester base was 55 mol% as measured by UV absorbance. The ratio of trans-trans isomer in the conjugated unsaturated fatty acid was 74%.

Production Example 3 65 g of tung oil, 35 g of rapeseed oil, 10 g of glycerin and 10 g of strongly basic ion exchange resin (Diaion PK-208 manufactured by Mitsubishi Chemical Co., Ltd.) were added, and the mixture was stirred at 40 ° C. for 2 hours. A transesterification reaction was performed. After the reaction was completed, the ion exchange resin was filtered off and fractionated by silica gel column chromatography to give a partial ester (hydroxyl value: 87).
101 g of the ester base of the present invention consisting of The conjugated trienoic acid content in the mixed fatty acids constituting this ester base was 44 mol% as measured by UV absorbance.
The ratio of trans-trans isomer in the conjugated unsaturated fatty acid was 52%.

Production Example 4 60 g of tung oil and 40 g of soybean oil were mixed and then sufficiently dried under reduced pressure, and 0.3 g of sodium methylate was added. This was stirred at 100 ° C. for 1 hour to cause a transesterification reaction. Then, it was washed with water to be neutral and dried under reduced pressure to obtain 91 g of the ester base of the present invention. The content of conjugated trienoic acid in the mixed fatty acid that constitutes this ester base is
It was 45 mol% as measured by UV absorbance. The ratio of trans-trans isomer in the conjugated unsaturated fatty acid was 52%.

Production Example 5 100 g of soybean oil hydrolyzed fatty acid, 30 g of trimethylolpropane, and paratoluenesulfonic acid of 0.1 g as a catalyst.
22 g of the mixture was subjected to the esterification reaction at 180 ° C. for 14 hours. After completion of the reaction, the product was washed with water and dried under reduced pressure to obtain 102 g of a partial ester (hydroxyl value: 90). N-
1000 ml of hexane was added, and 0.1 g of iodine was further added to the mixture, which was then illuminated with a high-pressure mercury lamp under the same conditions as in Production Example 10 for 10 hours to cause a conjugated isomerization reaction. After completion of the reaction, the product was washed with a 10 wt% sodium thiosulfate aqueous solution, and then n-hexane was distilled off under reduced pressure to obtain 95 g of the ester base of the present invention. The conjugated dienoic acid content in the mixed fatty acids constituting this ester base was 40 mol% according to the measurement of UV absorbance. The ratio of trans-trans isomer in conjugated unsaturated fatty acid is 7
2%.

Production Example 6 14 g of diglycerin was added to a mixture of 70 g of hydrolyzed fatty acids of safflower oil and 30 g of hydrolyzed fatty acids of rapeseed oil.
Then, 0.2 g of paratoluenesulfonic acid was added as a catalyst, and the esterification reaction was carried out at 180 ° C. for 15 hours. After completion of the reaction, the product was washed with water and dried under reduced pressure to obtain 83 g of an esterified product. Then, 1000 ml of n-hexane was added to the mixture, and 0.15 g of methyl iodide was further added to the mixture, which was irradiated with a high-pressure mercury lamp under the same conditions as in Production Example 10 for 10 hours to perform a conjugated isomerization reaction. I let it. After completion of the reaction, the product was washed with a 10 wt% sodium thiosulfate aqueous solution, and then n-hexane was distilled off under reduced pressure to obtain 95 g of the ester base of the present invention. The conjugated dienoic acid content in the mixed fatty acid constituting this ester base was 30 mol% as measured by UV absorbance. The ratio of trans-trans isomer in the conjugated unsaturated fatty acid was 72%.

Comparative Production Example 1 Linoleic acid (Wako Pure Chemical Industries, Ltd., reagent grade) 1
00 g (0.35 mol) and glycerin 10 g (0.
Paratoluenesulfonic acid (0.2 g) was added to (11 mol) and the esterification reaction was carried out at 180 ° C. for 15 hours. After the completion of the reaction, alkali deoxidation, washing with water and drying are performed,
81 g of esterified product was obtained. To this esterified product, 800 ml of n-hexane and 0.08 g of iodine were added, and a conjugated isomerization reaction was carried out by irradiating with a high pressure mercury lamp for 10 hours under the same conditions as in Production Example 2. After completion of the reaction, the mixture was washed with a 10% by weight aqueous sodium thiosulfate solution, and then n-hexane was distilled off under reduced pressure to obtain 72 g of an ester. The conjugated dienoic acid content in the mixed fatty acid constituting this ester was 83 mol% as measured by UV absorbance. The ratio of trans-trans isomer in the conjugated unsaturated fatty acid was 75%.

Comparative Production Example 2 A mixed fatty acid of 30 g of tung oil and 70 g of linseed oil was treated in the same manner as in Production Example 1 to obtain a mixed fatty acid, and further 14 g (0.10 mol) of trimethylolpropane was added thereto.
Was added and treated in the same manner to obtain 90 g of an esterified product. The conjugated trienoic acid content in the mixed fatty acid constituting this esterified product was 22% according to the measurement of UV absorbance.
The ratio of trans-trans isomer in the conjugated unsaturated fatty acid was 49%.

Comparative Production Example 3 A mixture of 35 g of tung oil, 65 g of rapeseed oil and 10 g of glycerin was treated in the same manner as in Production Example 3 to obtain 99 g of a partially esterified product (hydroxyl value: 93). The conjugated trienoic acid content in the mixed fatty acid constituting this partially esterified product was 25 mol% according to the measurement of UV absorbance.
The ratio of trans-trans isomer in the conjugated unsaturated fatty acid was 50%.

Comparative Production Example 4 A mixture of 100 g of tung oil and 10 g of glycerin was treated in the same manner as in Production Example 3 to obtain 90 g of a partial esterification product (hydroxyl value: 80) of tung oil constituent fatty acids.
The conjugated trienoic acid content in the mixed fatty acid constituting this partially esterified product was 78 mol% as measured by UV absorption.
Met. The ratio of trans-trans isomer in the conjugated unsaturated fatty acid was 56%.

Examples 1 to 6 and Comparative Examples 1 to 4 Each ester obtained in Production Examples 1 to 6 and Comparative Production Examples 1 to 4 (Examples 1 to 6 and Comparative Examples 1 to 4 respectively)
Corresponding to) was evaluated by the method described below. In order to cure each ester sample and comparative sample, 2,2-dimethoxy-1,2-diphenylethan-1-one (Nippon Ciba-Geigy Co., Ltd.) was used as a polymerization initiator.
Manufactured by Irgacure 651) and added by 1% by weight, and cured by irradiation with light. Storage stability was tested on the above samples only. Table 1 shows the results.

(1) Stability during storage: 2 ml of each ester sample and comparative sample were placed in a test tube having an inner diameter of 15 mm, stored in a constant temperature bath at 50 ° C. for 1 week, and the viscosity of each sample was examined. The evaluation was ◯: there was no change in viscosity to a slight increase in viscosity, Δ: considerable increase in viscosity, x: gelation (no flow).

(2) Curability: Each coating film was prepared on the surface of a transparent glass plate of 20 cm × 20 cm by an applicator so that each ester and the sample for comparison had a thickness of 0.076 mm. A high-pressure mercury lamp (UMIO 102, manufactured by Ushio Inc.) was used, the lamp was placed at a distance of 10 cm from the coating film, and the coating film was illuminated with a light of 100 watts for 100 minutes. Was touched and the degree of adhesion was examined. The evaluation is ◯: no adhesion, Δ: a little adhesion,
X: Adhered.

(3) Homogeneity of cured product: A coating film having a thickness of 0.076 mm was prepared for each sample by the method of the above (2), and light was irradiated under the same conditions (however, for 3 hours) to complete the coating. After curing,
The occurrence of wrinkles on the surface of the coating film was examined. The evaluation was made as ◯: no wrinkle was generated, Δ: Some wrinkle was generated, and X: Wrinkle was generated.

(4) Adhesion of cured product: Cross-cut tape (JIS K 5400-1900 general paint test method)
It was carried out according to 8.5.2). That is, a coating film having a thickness of 0.076 mm and a length of about 10 cm is prepared for each sample on an aluminum thin plate (length 20 cm, thickness 0.3 mm) by the method (2), and light is applied under the same conditions. After irradiation (however, for 3 hours) to completely cure, both ends of the aluminum thin plate were supported and flexed twice around the center with an amplitude of about 3 cm. Then, using a cutter knife, make a checkerboard-like cut (clearance interval: 1 mm, number of grids: 100) on the sample coating film, stick cellophane tape on this coating film, and then in the direction perpendicular to the coating film surface. The cellophane tape was peeled off and the state of scratches on the coating film was observed. The same sample was tested at 5 places, evaluated according to the standard specified in the JIS method, and the average value of 3 evaluation results excluding the maximum and minimum values was displayed. The larger the number, the higher the adhesion.

(5) Flexibility of cured product: Each ester and each sample for comparison were poured into an iron mold and irradiated with light to be completely cured in the same manner as in the above (3), and each side was 5 mm and length was 15 cm. A square column cured product was prepared. One end of this cured product was fixed and placed in a horizontal state, a 400 g weight was hung on the other end, and the distance from the horizontal position of the other end was measured.

[0048]

[Table 1]

From the above results, the ester base of the present invention has good storage stability, a high curing speed and excellent curability, and at the same time excellent in homogeneity, adhesion and flexibility of the cured film. It was confirmed that the properties were exhibited. On the other hand, conventional fats and oils such as tung oil and dehydrated castor oil, esters and acrylic acid derivatives which are not in the present invention have insufficient curing rate, fragile film properties, lack of flexibility, or good adhesion. It wasn't.

Example 7 and Comparative Example 5 The raw materials shown in Table 2 were mixed to prepare a curable composition as a base composition for paints or inks. The curable composition of Example 7 had significantly lower viscosity (200 CPS / 25 ° C.) than that of Comparative Example 5, and the curability of the coating film (thickness 0.076 mm) formed on the glass plate was rapid. The cured coating film was homogeneous and smooth, and had excellent adhesion.

[0051]

[Table 2] *) No. 0 Solvent H manufactured by Nippon Oil Co., Ltd.

Example 8 and Comparative Example 6 The raw materials shown in Table 3 were mixed to prepare a curable composition to be a base composition for ink. The curable composition of Example 8 had a viscosity as low as that of Comparative Example 6 even though no petroleum solvent was used, and formed a film promptly as in Example 7, The appearance was uniform and smooth, and the adhesion was good.

[0053]

[Table 3] *) No. 0 Solvent H manufactured by Nippon Oil Co., Ltd.

Examples 9 and 10 and Comparative Example 7 The raw materials shown in Table 4 were mixed to prepare a curable composition to be a base composition for UV curable ink. The curable compositions of Examples 9 and 10 had almost the same curability (drying property) in comparison with that of Comparative Example 7, and the films obtained were more flexible. In addition, pigments were kneaded with these curable compositions to prepare UV curable inks, and each was used to print on a thin aluminum plate (0.3 cm thick). The printed coatings for the inks using the curable compositions of Examples 9 and 10 were completely adhered to the lamella, whereas the printed coatings for the inks using Comparative Example 7 were as described above. It was observed that the coating film was partially peeled off only by slightly bending the thin plate.

[0055]

[Table 4]

[0056]

According to the present invention, storage stability is good,
Curing, that is, rich in polymerization reactivity by heating and light irradiation,
A curable ester base consisting of a monoester or polyvalent ester that gives a film or a cured product excellent in terms of hardness, adhesion and flexibility without wrinkling, and a curable composition containing the same. Can provide things.

Claims (4)

[Claims] 1. A monoester or polyvalent ester comprising a mixed fatty acid containing a fatty acid having a conjugated double bond and a polyhydric alcohol, wherein a fatty acid residue having a conjugated double bond among ester-bonded mixed fatty acid residues. The ratio of groups is 35-7
A curable ester base comprising the above ester in an amount of 0 mol%. 2. In the double bond of a fatty acid residue having a conjugated double bond, the ratio of trans-trans isomers is cis-cis isomer, cis-trans isomer and trans-trans isomer. 50% or more of the total amount of the curable ester base according to claim 1. 3. A curable composition comprising the curable ester base according to claim 1 or 2. 4. The content of the curable ester base is 1 to 30.
The curable composition according to claim 3, wherein the curable composition is wt%.