JP2959707B2 - UV curable paint base and UV curable paint containing the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention is applicable to 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. it relates excellent paints base and UV-curable paints which comprises it to. UV curable paint base of the present invention and comprising the same
Paints have high curing reactivity to light and heat, and exhibit properties such as excellent uniformity, adhesion, and flexibility in films and cured products formed by the reaction.

[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 have a 1,4-position positional relationship (-CH = CH-CH2-CH = CH-) generally called "pentadiene type",
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 natural products containing a relatively large amount of conjugated double bonds. This is composed mainly of conjugated trienoic acid called eleostearic acid, which is the most reactive of the natural fats and oils. There was a problem of occurrence.

[0005] It is also possible to increase the conjugation rate by using a fatty acid (linoleic acid, linolenic acid, etc.) constituting natural fats and oils as a starting material and performing a conjugation reaction using light ( ultraviolet ) irradiation treatment, heat treatment or a catalyst. Possible (eg oil chemistry, third
8, 949 and 959, 1989). Examples of conjugated oils and fats that have been implemented on an industrial scale include conjugated linseed oil and dehydrated castor oil, and the like.
In any case, the conjugation rate was limited to about 30 mol%. Also, about 60 mol% of a conjugated fatty acid obtained by a thermal isomerization reaction using an alkali catalyst such as sodium hydroxide or a hydienoic acid (manufactured by Soken Chemical Co., Ltd.) conjugated by a dehydration reaction using castor oil hydrolyzed fatty acid as a raw material. 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 curing function of natural fats and oils and their fatty acid derivatives is currently limited. Although it is not very wide, it is a raw material that can be obtained from planned cultivation resources for petroleum-based raw materials, which is a fossil resource, especially from the viewpoint of high biodegradability. Motives for reviewing natural fats and oils and their fatty acid derivatives are increasing.

In recent years, in particular, in various industrial fields, there has been a demand for shortening and improving the efficiency of raw material processing steps. For this reason, for example, in the case of coating a protective film on a metal surface of an automobile, a machine, a ship, or the like, In addition, as in the case of printing such as carton printing, metal printing, form printing, seal printing, curved surface printing, printed circuit board, overprinting, etc., curing reaction technology by ultraviolet ( ultraviolet ) irradiation is applied. Chemically synthesized raw materials such as acrylic acid compounds and paints containing 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, tung 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 ( ultraviolet light ) or heating, good stability during storage, uniformity when cured, and excellent adhesion and flexibility. To provide an ester base forming a cured structure and a curable paint containing the ester base.

[0009]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, the content of the conjugated unsaturated fatty acid in the mixed fatty acid in the ester of the mixed fatty acid and the polyhydric alcohol has been studied. When the content is too large, wrinkles are formed on the cured film as in the case of tung oil, but it was found that wrinkles were not observed until the content of the conjugated unsaturated fatty acid reached a specific mixing ratio. As a result of further study based on this finding, the polymerization reaction proceeds rapidly by light and heat, the curability is good, the resulting film has appropriate strength and flexibility, and it does not generate wrinkles It has been found that curable paints that also exhibit properties can be obtained. The present invention is based on this finding.

That is, the gist of the present invention is to provide a monoester or a polyhydric 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, wherein Of the mixed fatty acid residues, the ratio of the conjugated unsaturated fatty acid residues is 35 to 70.
Purple, characterized in that it consists of the esters are mole%
External curable paints bases, and the UV curable paints which comprises the paints base.

Among the above-mentioned monoesters or polyesters, more preferred are those in which the ratio of trans-trans form as a geometric isomer of double bond in the conjugated unsaturated fatty acid residue having an ester bond is cis-cis type, 50 of the total of cis-trans and trans-trans
% Or more.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION The UV-curable paint base of the present invention comprises an ester (monoester or polyester) of a polyhydric alcohol having two or more hydroxyl groups in a molecule and a mixed fatty acid. It is composed of the above-mentioned ester having a structure and containing 35 to 70 mol%, preferably 40 to 60 mol% of conjugated unsaturated fatty acid residues in the mixed fatty acid residues having ester bonds.

The ester according to the present invention is obtained by subjecting a mixed fatty acid containing a conjugated unsaturated fatty acid and a polyhydric alcohol to an esterification reaction to a monoester or a polyhydric ester, or an unsaturated fatty acid having a double bond capable of being conjugated. It is produced by subjecting a monoester or polyester of a mixed fatty acid 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. Also, linoleic acid and linolenic acid constituting soybean oil, rapeseed oil, safflower oil, sesame oil, cottonseed oil, linseed oil, eno oil, etc. 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. Further, the mixture of the conjugated unsaturated fatty acid and the other fatty acid thus obtained is subjected to a treatment such as solvent separation, silica gel column fractionation or the like, if necessary, or conjugated by mixing with another 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 preferred as other fatty acids to be mixed for such purpose, for example, acetic acid, butyric acid, caproic acid, caprylic acid, nonanoic acid, capric acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid Linear saturated fatty acids such as acid, heptadecanoic acid, stearic acid, and behenic acid; 2-ethylhexanoic acid; 3,5,5-trimethylhexanoic acid;
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 above-mentioned method using an esterification reaction, an oil or fat containing a conjugated unsaturated fatty acid and a polyhydric alcohol ester esterified with an arbitrary fatty acid are used for a transesterification reaction such as sodium methylate or lipase. For transesterification using a catalyst or for conjugate isomerization reaction of iodine, methyl iodide, etc. to polyhydric alcohol ester containing unsaturated fatty acid which can be conjugate isomerized such as linoleic acid or linolenic acid as a constituent element By performing conjugation using a catalyst, the specific ester according to the present invention can be produced.

In producing the ester according to the present invention, the degree of esterification is generally desirably almost perfect. However, depending on the purpose and use of the ester, a structure in which a part of the hydroxyl groups of the polyhydric alcohol is left ( A monoester or a polyester), and a mixed ester with the complete ester containing at least one of these partial esters.

It is important that the UV curable paint base of the present invention comprises an ester satisfying the following conditions.
That is, the fatty acid constituting the ester is a mixed fatty acid, and 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 amount of the conjugated unsaturated fatty acid exceeds 70 mol%, wrinkles in a film such as those found in tung oil are generated.

Further, in the ester constituting the base of the ultraviolet-curable paints of the present invention, the double bond of the ester-bonded conjugated unsaturated fatty acid residue is referred to as a trans form and a trans form (hereinafter referred to as a trans-trans form). The ratio occupied by the same is preferably 50% or more of the total amount of the three types of geometric isomers of cis-cis, cis-trans and trans-trans types. More preferably, it is 70 to 100%. When the ratio is less than 50%, the curing speed becomes slow, and when it is blended into an ultraviolet curable paint, the curing speed tends to be slow.

The UV-curable paint base of the present invention comprising an ester satisfying the above conditions can be used as it is for the preparation of various cured products by using, for example, the esterification reaction product as described above. The conjugated unsaturated fatty acid may be used after being subjected to a purification treatment such as deacidification, decolorization, and deodorization to such an extent that the conjugated structure of the conjugated unsaturated fatty acid does not deteriorate. The paint base of the present invention has high polymerization reactivity or ultraviolet curability , has good stability during storage, and forms a cured structure that is homogeneous when cured, and has excellent adhesion and flexibility. Etc.

Next, the UV curable coatings of the present invention will be described. UV-curable paints of the present invention, Purple present invention
By utilizing the above-mentioned properties of the base material of the external curable paint, it is mixed with a conventional curable substance or various known components used in paints containing the same. At this time , the blending ratio of the UV-curable paint base of the present invention is in principle arbitrary, and the UV-curable paint base of the present invention is
It is conceivable that it is used as a main component in paints or as an additive. When an ultraviolet-curable paint base is contained as a main component, the compounding amount thereof is 40 to 95% by weight, preferably 60 to 90% by weight based on the whole ultraviolet-curable paints . UV curing when used as an additive
1 to 30 wt% based on the total sexual paints, preferably 3 to
It is good to mix 15% by weight.

The above-mentioned 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 derivatives thereof (esters, ethers, salts). , Amides, etc.), polymerized fats and oils such as stand oil and boil oil partially polymerized by heating and oxygen addition treatment, urethane prepolymers that are also polymerized by heating or light irradiation, Various organic solvents for compatibility of mutually insoluble components, polymerization initiators for promoting polymerization reaction by heat or light (2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl-phenyl) -Ketone, etc.), resins, pigments, dyes and the like.

The UV-curable coatings of the present invention can be used in light ( ultraviolet)
Line ) Paint that forms a film or cured product by irradiation or heating,
Ink, surface treatment agents such as paper and metal, laminated boards and the like and base paints thereof may be prepared according to required functions and use conditions. For example, in paints, the paint base of the present invention as a main component of the film-forming element,
In the ink, the paint base of the present invention can be used as a substitute for part or all of a drying oil in a vehicle or a processed product thereof (a heat polymerization oil, a maleated oil, a urethane oil, etc.). This
Here, in the present invention, ultraviolet curable paints are ultraviolet rays
Used for hardening metal surfaces of automobiles, machines, ships, etc.
Paints, carton printing, metal printing, sticker printing, songs
Ink used for surface printing and special overprinting
Surface treatment agents for tinks, wood, bottles, metals, cans, etc.
U.

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

The UV-curable paints thus obtained are:
It has high polymerization reactivity that is easily cured by heat treatment or light ( ultraviolet ) irradiation treatment, and forms a homogeneous film or cured product excellent in adhesion and flexibility. Therefore, the present invention
UV-curable paints are used in fields where petrochemical raw materials represented by acrylic acid monomers have been mainly used, such as special paints that require particularly high polymerization reactivity,
It can be used in applications such as resin processing for performing ultraviolet curing treatment, ink, and paint. Generally, as a curable raw material utilizing heat or light, the paint base of the present invention has a low polarity , whereas a petrochemical raw material has a relatively high polarity. Insoluble pigments and dyes can be used in combination, and it is possible to give cured products having properties that are difficult to obtain with petrochemical raw materials such as high flexibility of the film and good adhesion. . While still in the manufacture of laminates such as is mainly the use of tung oil Conventionally, ultraviolet-curable coating material of the present invention as the replacement
It is possible to use a base material or a UV-curable paint containing the same.

[0029]

EXAMPLES In the following examples, the ratio of the conjugated unsaturated fatty acid residues in the mixed fatty acid residues constituting the ester is determined by the conjugation ratio (conjugated dienoic acid content and / or conjugated trienoic acid content) of the mixed fatty acid. 2.4.15-71 of “Standard Fat and Oil Analysis Test Method” edited by Japan Oil Chemical Association.
Based on the method described in the section of Conjugated Unsaturated Fatty Acids (Spectral Method), 233, 262, 268, and 27 of a 0.01 g / liter sample solution were prepared using cyclohexane as a solvent.
At 4, 308, 315, 322 and 346 mμ
It was determined by measuring the ultraviolet absorbance and calculating the content of the conjugated unsaturated fatty acid from a prescribed calculation formula. Eleostearic acid content was determined using the same method as described above.
The ultraviolet absorbance at 1.5 and 276.5 mμ was measured and determined from the prescribed formula described in the above-mentioned literature.

The ratio of the trans-trans geometric isomer 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,
The ester is hydrolyzed to methyl ester the constituent fatty acid, and each component is separated, identified and quantified by capillary gas chromatography (GLC).
It was calculated as a percentage of the total amount of each of the cis-trans and trans-trans isomers. When conjugated trienoic acid is contained, the content of conjugated dienoic acid and conjugated trienoic acid is determined by the above method, and ester hydrolysis, methyl esterification,
The content of each geometric isomer was determined by GLC analysis, and as for the cis-trans-trans form of the conjugated trienoic acid, each of the cis-trans form and the trans-trans form was one.
With respect to the unit and all-trans type, the trans-trans type was regarded as 2 units, and the percentage to the total number of conjugated double bonds was calculated.

Production Example 1 85 g of tung oil, 15 g of linseed oil, 200 g of distilled water and lipase (Meito Sangyo Co., Ltd.) were placed in a 500 ml flask equipped with a thermometer, a condenser, a water separator and a stirrer. Lipase OF) was added and 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 a tung oil-decomposed fatty acid. The acid value of this mixed fatty acid was 190. 14 g of trimethylolpropane is added to the mixed fatty acid.
(0.10 mol) and 0.2 g of paratoluenesulfonic acid as a catalyst were added, and an esterification reaction was performed at 180 ° C. for 15 hours. After the completion of the reaction, washed with water and dried under reduced pressure,
80 g of the paint base of the present invention was obtained. The content of conjugated trienoic acid in the mixed fatty acid constituting the paint base was 68 mol% as measured by ultraviolet absorption. The ratio of the trans-trans isomer in the conjugated unsaturated fatty acid was 55%.

Production Example 2 Linoleic acid (special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.) 7
0 g (0.21 mol), oleic acid (Wako Pure Chemical Industries, Ltd.)
30 g (0.14 mol), 7 g (0.11 mol) of ethylene glycol and 0.2 g of paratoluenesulfonic acid as a catalyst.
The esterification reaction was performed for 5 hours. After the completion of the reaction, alkali deacidification, washing with water and drying under reduced pressure give esterified product 8
8 g were obtained. An additional n-
Hexane (100 ml) and iodine (0.1 g) were added, and a high pressure mercury lamp (manufactured by Ushio Inc., model: UM-102; the same applies hereinafter) was used for 10 hours at 100 watts while water-cooling the lamp periphery with water. To carry out a conjugate isomerization reaction. After the completion of the reaction, the mixture was washed with 10 wt% aqueous sodium thiosulfate solution, coating of the present invention the n- hexane was distilled off under reduced pressure
It was obtained Ruimotozai 80g. The conjugated dienoic acid content in the mixed fatty acid constituting the paint base was 55 mol% as measured by ultraviolet absorbance. The ratio of the 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 a strongly basic ion exchange resin (Diaion PK-208, manufactured by Mitsubishi Chemical Corporation) were added, and the mixture was stirred at 40 ° C. for 2 hours. A transesterification reaction was performed. After completion of the reaction, the ion-exchange resin was filtered off and fractionated by silica gel column chromatography to obtain a partial ester (hydroxyl value: 87).
101 g of the paint base of the present invention consisting of This paint
The content of conjugated trienoic acid in the mixed fatty acid constituting the base was 44 mol% as measured by ultraviolet absorbance.
The ratio of the trans-trans isomer in the conjugated unsaturated fatty acid was 52%.

Production Example 4 After mixing 60 g of tung oil and 40 g of soybean oil, the mixture was 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, after washing with water to make it neutral, it was dried under reduced pressure to obtain 91 g of paint base of the present invention. The conjugated trienoic acid content in the mixed fatty acid constituting the paint base is determined by the ultraviolet ray.
According to the measurement of the linear absorbance, it was 45 mol%. The ratio of the trans-trans isomer in the conjugated unsaturated fatty acid was 52%.

Production Example 5 100 g of hydrolyzed fatty acid of soybean oil, 30 g of trimethylolpropane and 0.1 g of paratoluenesulfonic acid as a catalyst.
22 g of the mixture was subjected to an esterification reaction at 180 ° C. for 14 hours. After the 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). This is n-
A mixture containing 1000 ml of hexane and 0.1 g of iodine was illuminated with a high-pressure mercury lamp under the same conditions as in Production Example 10 for 10 hours to cause a conjugate isomerization reaction. After the completion of the reaction, the resultant was washed with a 10% by weight aqueous solution of sodium thiosulfate, and then n-hexane was distilled off under reduced pressure to obtain 95 g of a paint base of the present invention. The conjugated dienoic acid content in the mixed fatty acid constituting the paint base was 40 mol% as measured by ultraviolet absorbance. The ratio of the trans-trans isomer in the conjugated unsaturated fatty acid is 72%.
%Met.

Production Example 6 14 g of diglycerin was added to a mixture of 70 g of safflower oil hydrolyzed fatty acid and 30 g of rapeseed oil hydrolyzed fatty acid.
Then, 0.2 g of paratoluenesulfonic acid was added as a catalyst, and an esterification reaction was performed at 180 ° C. for 15 hours. After the 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 thereto, and 0.15 g of methyl iodide was further added thereto, and the mixture was illuminated with a high-pressure mercury lamp under the same conditions as in Production Example 10 for 10 hours to carry out a conjugate isomerization reaction. I let you. After the completion of the reaction, the reaction mixture was washed with 10 wt% aqueous sodium thiosulfate solution, and distilled under reduced pressure to remove the n- hexane, paints of the present invention
95 g of base were obtained. The conjugated dienoic acid content in the mixed fatty acid constituting the paint base was 30 mol% as measured by ultraviolet absorbance. The ratio of the trans-trans isomer in the conjugated unsaturated fatty acid was 72%.

Comparative Production Example 1 Linoleic acid (special grade reagent, manufactured by Wako Pure Chemical Industries, Ltd.) 1
00 g (0.35 mol) and 10 g of glycerin (0.
(11 mol) was added with 0.2 g of paratoluenesulfonic acid, and an esterification reaction was performed at 180 ° C. for 15 hours. After the completion of the reaction, alkali deacidification, water washing and drying treatment,
81 g of esterification product were obtained. 800 ml of n-hexane and 0.08 g of iodine were added to the esterification product, and conjugate isomerization reaction was performed by illuminating with a high-pressure mercury lamp under the same conditions as in Production Example 2 for 10 hours. After the completion of the reaction, the mixture was washed with a 10% by weight aqueous solution of sodium thiosulfate, 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% according to the measurement of ultraviolet absorbance.
Met. The ratio of the trans-trans isomer in the conjugated unsaturated fatty acid was 75%.

Comparative Production Example 2 A mixed oil 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 added 14 g (0.10 mol) of trimethylolpropane.
Was added and the mixture was treated in the same manner to obtain 90 g of an esterified product. The conjugated trienoic acid content in the mixed fatty acid constituting the esterified product was 22% according to the measurement of ultraviolet absorbance. The ratio of the 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 content of conjugated trienoic acid in the mixed fatty acid constituting the partially esterified product was 25 mol% as measured by ultraviolet absorbance. The ratio of the 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 partially esterified product comprising tung oil constituent fatty acids (hydroxyl value: 80).
The conjugated trienoic acid content in the mixed fatty acid constituting the partially esterified product was 78 mol% as measured by ultraviolet absorbance. In addition, trans-
The ratio of the trans isomer 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)
) Were evaluated by the following methods. 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.
And Irgacure 651) was added and cured by light irradiation. Stability on storage was tested on the above samples only. Table 1 shows the results.

(1) Stability during storage: 2 ml of each of the ester sample and the comparative sample were placed in a test tube having an inner diameter of 15 mm, and stored for 1 week in a thermostat at 50 ° C., and the respective viscosities were examined. The evaluation was ○: no change in viscosity to slight thickening, Δ: considerably thickened, ×: gelled (no flow).

(2) Curability: Each coating film was formed on a surface of a transparent glass plate of 20 cm × 20 cm by an applicator such that the thickness of each ester and the sample for comparison became 0.076 mm. Using a high-pressure mercury lamp (USHIO INC., UM-102 type), place the lamp at a distance of 10 cm from the coating film and illuminate it with 100 watts for 100 minutes. Was touched to examine the degree of adhesion. The evaluation was ○: no adhesion, Δ: slightly adhered,
X: Adhered.

(3) Uniformity of the 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 irradiated with light (for 3 hours) under the same conditions to complete the coating. After curing,
The occurrence of wrinkles on the coating film surface was examined. The evaluation was ○: no wrinkles occurred, Δ: slight wrinkles occurred, ×: wrinkles occurred.

(4) Adhesion of cured product: cross cut tape (JIS K 5400-1900 paint general test method)
8.5.2). That is, a coating having a thickness of about 0.076 mm and a length of about 10 cm was formed for each sample on the aluminum thin plate (20 cm in length and 0.3 mm in thickness) by the method (2), and light was irradiated under the same conditions. After irradiation (however, for 3 hours) to completely cure, the aluminum sheet was supported at both ends and bent near the center twice with an amplitude of about 3 cm. Then, a checkerboard-shaped cut (gap: 1 mm, number of squares: 100) is made on the sample coating with a cutter knife, and a cellophane tape is stuck on the coating, and then perpendicular to the coating surface. The cellophane tape was peeled off, and the state of scratches on the coating film was observed. The same sample was tested at five locations, evaluated according to the criteria specified in the JIS method, and expressed as an average of three evaluation results excluding the maximum and minimum values. The larger the value, the higher the adhesion.

(5) Flexibility of the cured product: Each ester and each sample for comparison were poured into an iron mold and irradiated with light in the same manner as in the above (3) to be completely cured, and each sample was 5 mm on a side and 15 cm in length. A square pillar-shaped 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.

[0047]

[Table 1]

From the above results, the paint base of the present invention has good storage stability, a high curing speed, and excellent curability.
It was also confirmed that the cured film exhibited excellent properties in terms of homogeneity, adhesion and flexibility. On the other hand, conventional fats and oils such as tung oil and dehydrated castor oil, esters and acrylic acid derivatives which are not the present invention have insufficient curing speeds, are brittle, have poor flexibility, or have good adhesion. Was not.

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

[0050]

[Table 2]

[0051] the ink-based paints by mixing raw materials shown in Examples 8 and Comparative Example 6 in Table 3 UV-curable coating
Materials were prepared. The UV-curable coatings of Example 8 had almost the same low viscosity as Comparative Example 6 even though no petroleum solvent was used, and formed a film quickly as in Example 7. The appearance of the film is homogeneous and smooth,
The adhesion was also good.

[0052]

[Table 3]

Examples 9 and 10 and Comparative Example 7 The raw materials shown in Table 4 were mixed to prepare UV-curable paints to be used as base paints for UV- curable inks. The UV curable paints of Examples 9 and 10 had almost the same curability (drying property) as those of Comparative Example 7, and the resulting films were more flexible. . Also, pigments are kneaded with these UV curable paints.
UV curable inks were prepared and each was printed on a thin aluminum plate (0.3 cm thick). The printed coating films of the inks using the UV curable coatings of Examples 9 and 10 were completely adhered to the thin plate, whereas the printed coating films of the inks of Comparative Example 7 were A phenomenon was observed in which the coating film was partially peeled off only by slightly bending the thin plate.

[0054]

[Table 4]

[0055]

According to the present invention, storage stability is good,
Curable, that is, rich in polymerization reactivity by heating and light irradiation,
UV curable paint base consisting of a monoester or polyester which gives a film or cured product excellent in hardness, adhesion and flexibility without wrinkle generation, and ultraviolet light obtained by blending it Curable paints can be provided.

Claims (5)

(57) [Claims] 1. A monoester or polyhydric 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 the ester-bonded mixed fatty acid residues. Group ratio is 35-7
0 mol% of the ester
UV curable paint base . 2. The ratio of trans-trans isomer to cis-cis isomer, cis-trans isomer and trans-trans isomer in the double bond of a fatty acid residue having a conjugated double bond. 2. The UV-curable paint base according to claim 1, wherein the curability is 50% or more of the total amount of the UV-curable paint.
Agent . 3. The ultraviolet curable composition according to claim 1, wherein
UV curing characterized by containing paint base
Paints . 4. The ultraviolet-curable paints are ultraviolet-curable paints.
Wherein the content of the ultraviolet-curable paint base is 40 to 9;
The UV-curable coating according to claim 3, which is 5% by weight.
Kind. 5. An ultraviolet-curable coating composition comprising:
Wherein the content of the UV-curable paint base is 1 to 3
The UV-curable coating according to claim 3, which is 0% by weight.
Kind.