JP2001181284A - Method for producing cyclic aluminum oxide acylate, gelling agent composition for printing ink and gelling agent composition for coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an economic method producing a cyclic aluminum oxide acylate not through a cyclic aluminum oxide alcoholate, having no gelation/ solidification of reaction solution, slightly causing a by-product of ester, discoloration, cloudiness, etc., of product. SOLUTION: This method for producing the cyclic aluminum oxide acylate comprises dividing a mixed solution of an organic solvent for solubilizing a carboxylic acid and water-the carboxylic acid-water into two or more stages and dripping an aluminum trialkoxide to the mixed solution in reacting the aluminum trialkoxide with the carboxylic acid and water. The amounts of the carboxylic acid and water at the first stage of the mixed solution to be dividedly dripped at the two or more stages are 0.6-0.8 mol and 0.3-0.4 mol based on 1 mol of the aluminum trialkoxide, respectively and the molar ratio of water/carboxylic acid is 1/1.50 to 1/2.67.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel method for producing a cyclic aluminum oxide acylate useful as a gelling agent for printing inks or a crosslinking agent for coatings, a gelling agent composition for printing inks, and a gelling agent for coatings. The present invention relates to an agent composition.

[0002]

2. Description of the Related Art Hitherto, the following examples have been known for producing cyclic aluminum oxide acylate.

In US Pat. No. 4,324,670, an aluminum trialkoxide is reacted with 2 mol of a carboxylic acid to obtain an aluminum monoalcolate diacylate as an intermediate, which is obtained. A method is disclosed in which the product is further heated to obtain a mixture of cyclic aluminum oxide acylate and carboxylic acid ester.

However, this method uses 2 moles of carboxylic acid per mole of aluminum trialkoxide, so that a large amount of carboxylic acid ester is produced, and the amount of carboxylic acid used is large, which is economically disadvantageous. Is the way.

In US Pat. No. 2,979,497, an aluminum trialkoxide is dissolved in a solvent such as xylene, and a solution obtained by mixing and diluting a carboxylic acid and water in a solvent such as an alcohol is dropped, followed by a by-product. alcohol,
A method is disclosed in which xylene as a solvent is removed under reduced pressure to obtain a cyclic aluminum oxide acylate.

However, in this method, the viscosity of the reaction solution sharply increases due to the aluminum soap generated as an intermediate during the reaction, so that it is difficult to keep the reaction solution in a constantly stirrable state. Further, if the amount of the solvent used is small, the reaction solution is solidified, so that a desired product may not be obtained in some cases. Further, handling was difficult because the obtained product was a very viscous liquid or solid.

In US Pat. No. 3,054,816, cyclic aluminum oxide alcoholate is obtained by heating a solution of water and an alcohol to form a mixed vapor with an aluminum trialkoxide and introducing the mixture. Or, the aluminum trialkoxide is heated to a high temperature of 250 ° C. or more to remove the alkoxy group,
A method for obtaining a cyclic aluminum oxide acylate by distilling ether generated by condensation to obtain a cyclic aluminum oxide alcoholate and then dropping an arbitrary carboxylic acid to the obtained cyclic aluminum oxide alcoholate is disclosed. Have been.

However, in this method, in order to obtain a cyclic aluminum oxide acylate, it is necessary to first produce a cyclic aluminum oxide alcoholate, and at that time, an apparatus for evaporating water and an alcohol solution is required. Therefore, it is economically disadvantageous. Also, 2
When heated to 50 ° C. or higher, there is a disadvantage that the product is easily colored. Furthermore, in order to obtain a cyclic aluminum oxide acylate, it is necessary to carry out an acylation reaction by reacting a cyclic aluminum oxide alcoholate with a carboxylic acid.

Under such circumstances, it has been desired to develop a method for efficiently producing a cyclic aluminum oxide acylate.

[0010]

An object of the present invention is to provide a method for producing a cyclic aluminum oxide acylate useful as a gelling agent for printing inks or a crosslinking agent for paints, via a cyclic aluminum oxide alcoholate. In addition, there is no problem of gelation or solidification of the reaction solution, and there are few by-products of the ester, coloring of the product, turbidity and the like, and an economical production method is provided.

[0011]

Means for Solving the Problems In order to solve the above problems, the present inventors have made intensive studies and as a result, using aluminum trialkoxide as a raw material, a mixed solution of water, carboxylic acid, and an organic solvent at a specific composition ratio. It has been found that the step of dropping by dividing into two or more stages is effective, and the present invention has been completed.

That is, the present invention provides a compound of the general formula (1) Al (OR ¹ ) ³ (1) wherein R ¹ represents a linear or branched alkyl or alkenyl group having 1 to 4 carbon atoms. With respect to the aluminum trialkoxide represented by the general formula (2) R ² COOH (2) wherein R ² is a straight-chain or branched-chain having 1 to 21 carbon atoms which may be substituted by a hydroxy group. A carboxylic acid represented by the formula (3):

[0013]

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Wherein R ² is the same as defined above. In the method for producing a cyclic aluminum oxide acylate represented by the formula (1), a mixed solution obtained by mixing a carboxylic acid represented by the general formula (2) and water in an organic solvent for solubilizing carboxylic acid and water is divided into two or more steps. And the general formula (1)
A method for producing a cyclic aluminum oxide acylate represented by the general formula (3) by dropwise addition to an aluminum trialkoxide represented by the formula: Is in the range of 0.6 to 0.8 mol per mol of aluminum trialkoxide, and the amount of water in the first stage is in the range of 0.3 to 0.4 mol per mol of aluminum trialkoxide. And the molar ratio of water / carboxylic acid is 1/1.
A method for producing a cyclic aluminum oxide acylate represented by the general formula (3), characterized by containing 50 to 1 / 2.67, and a cyclic aluminum oxide acylate produced by the production method. The present invention relates to a gelling composition for printing inks or paints.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The aluminum trialkoxide of the general formula (1) used as a raw material in the present invention is not particularly limited as long as R ¹ is a hydrocarbon group of ¹ to 4. Propoxide, aluminum triethoxide, aluminum tri-
sec-butoxide and the like, and aluminum triisopropoxide is particularly preferred because it is easily available.

In the reaction, the aluminum trialkoxide of the above general formula (1) is dissolved in toluene, xylene or a hydrocarbon solvent such as Solvent No. 7, Solvent AF No. 5, Solvent AF No. 7 (manufactured by Mitsubishi Nisseki Co., Ltd.). It is preferable to keep it.

R ² COO in the cyclic aluminum oxide acylate represented by the general formula (3) is an acyl group derived from a carboxylic acid represented by the general formula (2), and may be a single composition or a mixed composition.

Examples of the carboxylic acid represented by the general formula (2) include caproic acid, caprylic acid, 2-ethylhexanoic acid, isononanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, isopalmitic acid, Linear or branched saturated or unsaturated carboxylic acids such as stearic acid, isostearic acid, oleic acid and linoleic acid, or natural products such as coconut fatty acid, soybean fatty acid, rice bran fatty acid, palm stearic acid and palm kernel oil fatty acid Carboxylic acids having an alkyl composition derived therefrom are exemplified.

The total amount of the carboxylic acid used for the acylation is preferably 0.8 to 1.3 mol, more preferably 0.1 to 1.3 mol, per mol of aluminum trialkoxide.
85 to 1.15 mol.

If the total amount of the carboxylic acid added is less than 0.8 mol per 1 mol of aluminum trialkoxide, the amount of unreacted alkoxy groups increases, the flash point decreases, and the resulting product When is used as a gelling agent, it is not preferable because alcohol is generated.

On the other hand, if the total amount of the carboxylic acid added exceeds 1.3 mol per 1 mol of the aluminum trialkoxide, it is not preferable because an ester is formed as a by-product and causes odor. Furthermore, the reaction solution is gelled or solidified by the by-product of aluminum soap, which is not preferable.

The total amount of water used for the hydrolysis contained in the dropping solution is preferably 0.8 to 1.1 mol, more preferably 0.85 to 1.0 mol, per mol of aluminum trialkoxide. is there.

If the total amount of water added is less than 0.8 mol per mol of aluminum trialkoxide, hydrolysis is insufficient, cyclization is insufficient, and unreacted raw materials remain.

On the other hand, when the total amount of water exceeds 1.1 mol per 1 mol of aluminum trialkoxide, a cyclic compound is formed, but aluminum hydroxide is by-produced, which causes the product to become cloudy.

The organic solvent that dissolves water and carboxylic acid is
There is no particular limitation as long as it can solubilize water and a carboxylic acid. For example, alcohols such as ethanol, isopropanol and cyclohexanol, diethyl ether,
Examples include ether compounds such as tetrahydrofuran, ethyl cellosolve, glyme, and propylene glycol monomethyl ether acetate, dimethylformamide, N-methylpyrrolidone, and the like, and an arbitrary amount for uniformly mixing water and a carboxylic acid is required. Isopropanol is preferred from the viewpoints of high solubility of both water and carboxylic acid, easy removal at a low boiling point, and economy.

A mixed solution obtained by adding the carboxylic acid represented by the general formula (2) and water to the above-mentioned organic solvent is divided into two or more stages, and the mixture is dropped and reacted. More specifically, the split dropping method is a method for improving the above-mentioned problem by supplying a molar ratio of water and a carboxylic acid at a predetermined reaction temperature in such a range that each is optimal. The procedure is as follows.

In the first stage of dropping, the reaction temperature is 80 to 15
Add dropwise at 0 ° C. In the first stage, in a region where the ratio of aluminum alkoxide is high, the molar ratio of water to 1 mol is 0.3 to 0.4, and the molar ratio of carboxylic acid is 0.6.
~ 0.8, that is, the molar ratio of water / carboxylic acid is 1 /
It is preferable to perform dropping within a range of 1.50 to 1 / 2.67.

When a mixed solution of water and a carboxylic acid is dropped, an aluminum soap which is relatively stable against hydrolysis is formed.
This molar ratio is within a range in which an increase in the viscosity of the reaction solution can be suppressed.

In the second and subsequent stages, the dropping solution is not particularly limited, but the total amount of the carboxylic acid used in the mixture of the carboxylic acid, water, and the organic solvent to be divided and dropped is, for the reasons described above, aluminum. 0.1 per mole of trialkoxide.
It is necessary that the amount of water used is 8 to 1.3 mol, and similarly the amount of water used is 0.8 to 1.1 mol.

The remainder of the one-step dropping may be entirely dropped in the second step, but it is preferable to drop it in three or more steps as described later.

The case of performing three-part dropping as one embodiment of the present invention will be described in detail below.

First, as a dropping solution in the first stage, water 0.1.
A mixed solution of 3 to 0.4 mol, a carboxylic acid represented by the general formula (2) of 0.6 to 0.8 mol, and an amount of an organic solvent necessary for homogenizing water and the carboxylic acid is prepared. The reaction liquid temperature is 80 to 150 ° C., preferably 12 to 1.0 mol of the aluminum alkoxide represented by the formula (1).
At 0 to 130 ° C., while distilling off by-product alcohol, 1
It is preferable to drop the solution within 2 hours.

As the dropping solution in the second stage, water 0.05 to
0.15 mol, 0.1% of the carboxylic acid represented by the general formula (2).
A mixed solution of 1 to 0.5 mol and a necessary amount of an organic solvent for making water and the carboxylic acid uniform is prepared, and the reaction solution is mixed with 1
The mixture is added dropwise at 50 to 190 ° C., preferably 180 to 190 ° C., for 30 minutes to 1 hour while distilling off by-product alcohol.

[0034] As the dripping solution of the third stage, water
0.75 mol, 0.1% of the carboxylic acid represented by the general formula (2).
A mixed solution of 1 to 0.5 mol and a necessary amount of an organic solvent for homogenizing water and a carboxylic acid was prepared, and a reaction temperature of 1
The mixture is added dropwise at 90 to 200 ° C. for 1 to 2 hours while distilling off by-product alcohol. After completion of the dropwise addition, the alcohol remaining in the system is distilled off under reduced pressure.

According to the above-mentioned method, it is possible to keep the reaction solution in an optimum stirring state at all times, and to suppress by-product of ester and production of aluminum hydroxide. Further, by changing the amount of the solvent to be added in advance, it is possible to obtain a product having a desired concentration at the end of the reaction.

Water used for the stoichiometrically required reaction,
The reaction cannot be controlled so that a side reaction does not occur even if a solution obtained by preliminarily mixing a carboxylic acid and a solvent and divided into two or more, that is, a solution containing water and carboxylic acid in a substantially equal molar ratio is divided and dropped. . However, when the divided dropping according to the present invention is performed, the reaction can be controlled.

The reason is that aluminum alkoxide as a raw material is a compound which is very easily hydrolyzed, and in the initial stage of the reaction, water and carboxylic acid are bonded at a ratio of 1/1 to one Al atom. In addition, it is easy to produce aluminum hydroxide which has reacted only with water. This is presumed to be due to the reason that the ratio of added water / carboxylic acid collapses.

The reaction product can be directly used as a gelling agent composition for printing inks or coatings without distilling off the hydrocarbon solvent from the reaction product. However, the solvent is distilled off to obtain a cyclic aluminum oxide acylate compound. May be isolated. The gelling agent composition for printing inks or coatings of the present invention may contain, for example, coconut oil, palm oil, palm kernel oil, soybean oil, rice bran oil and the like in addition to the above-mentioned solvents.

The gelling agent composition of the present invention thus obtained does not generate alcohol at the time of addition in the production of ink or paint, and has a high flash point. Further, the cyclic aluminum oxide acylate compound of the present invention is a suitable compound as a gelling agent composition for crosslinking and thickening resins for inks and coatings.

The gelling agent composition for printing inks or paints of the present invention can be used as a gelling agent for inks or a cross-linking agent for paints.

For example, a printing ink may be prepared by the following method. First, resin (rosin-modified phenolic resin, acrylic resin, urethane resin or petroleum resin),
2 drying oils (tung oil, linseed oil, soybean oil, etc.) and petroleum solvents
After stirring at 00 ° C. for about one hour, 0.1 to 10% by weight of the gelling agent composition for a printing ink of the present invention is added.
What was stirred at 180 ° C. for 1 hour was used as an ink varnish. To this, a pigment (arbitrary organic or inorganic pigment) and a petroleum solvent are added, and the mixture is kneaded and mixed with a bead mill, a three-roll mill or the like to obtain a printing ink.

To prepare a paint, a paint resin (alkyd resin, acrylic resin, urethane resin, epoxy resin, silicone resin, etc.), a solvent, a pigment (arbitrary organic or inorganic pigment), and other additives are used. And the gelling agent composition for paints of the present invention may be added in a pure content of 0.1 to 10% by weight and mixed with a sand mill, bead mill, paint shaker or the like.

[0043]

The present invention will be described below with reference to examples. Note that the following examples show one example of the present invention,
The present invention is not limited only to this embodiment.

In the examples, the measurement of the aluminum content was carried out by a chelate titration method. Comparative Example 1 In a 1 L four-necked flask, 204 g (1.0 mol) of aluminum triisopropoxide (trade name "AIPD", manufactured by Kawaken Fine Chemical Co., Ltd.) and 102 g of AF-7 Solvent (manufactured by Mitsubishi Nisseki Co., Ltd.) And heated to 90 to 110 ° C. while stirring. To this solution was added 18.0 water.
A mixed solution of 2 g (1.0 mol), 163 g of isopropanol and 200 g (1.0 mol) of lauric acid was added dropwise over 6 hours. However, turbidity and gelation occurred during the reaction, and the desired product was not obtained. Comparative Example 2 18.0 g (1.0 mol) of water, 200 g of lauric acid
A mixed solution of (1.0) mol and 172 g of isopropanol is prepared in advance and divided into three equal parts.

In a 1 L four-necked flask, 204 g (1.0 mol) of aluminum triisopropoxide and 102 g of Solvent AF-7 were charged, and stirred at 120 to 1 g.
The mixture was heated to 30 ° C. and added dropwise over 2 hours while distilling off isopropanol, which is a by-product of 1/3 of the mixed solution of water, lauric acid and isopropanol.

Next, the mixture was heated to 180 ° C., and 1/3 of the mixed solution of water, lauric acid and isopropanol was further heated to 190 ° C., and the remaining 1/3 of the mixed solution of water, lauric acid and isopropanol was mixed. 3 was added dropwise over 2 hours while distilling off isopropanol as a by-product. Although the viscosity of the reaction solution hardly increased, the product was a cloudy liquid. Example 1 A 1-L four-necked flask was charged with 81.7 g (0.40 mol) of aluminum triisopropoxide and 40.8 g of AF-7 solvent, and heated to 120 to 130 ° C with stirring. 2.70 g (0.15 mol) of water was added to this solution,
A mixed solution of 34.6 g (0.24 mol) of 2-ethylhexanoic acid and 24.3 g of isopropanol was added dropwise over 2 hours while distilling off by-produced isopropanol.

Next, the reaction solution was heated to 180 ° C., and 0.90 g (0.050 mol) of water, 11.5 g (0.08 mol) of 2-ethylhexanoic acid, and 8.1 g of isopropanol were used.
After dropping isopropanol as a by-product of the mixed solution of 0 g in 30 minutes while distilling off, the reaction solution was heated to 190 ° C., and 3.60 g (0.20 mol) of water and 11.5 g of 2-ethylhexanoic acid were added. (0.08 mol), isopropanol 3
2.4 g of the mixed solution was dropped in 1 hour and 30 minutes while distilling off isopropanol as a by-product.

After the completion of the dropwise addition, the inside of the system was depressurized to remove isopropanol, and 119 g of a pale yellow transparent liquid (yield 9
8%). The total amount of water used in the reaction was 7.2 g
(0.40 mol), the total amount of 2-ethylhexanoic acid is 5
It was 7.6 g (0.40 mol).

Further, in order to confirm the formation of the compound, the aluminum content and the infrared absorption spectrum were measured.

Aluminum content: 9.13% (theory 9.16%) IR spectrum (cm ^-1 ) 2,960-2,850 (C of -CH ₂ -and -CH ₃
-H stretching vibration) 1,610,1,464 (COOAl stretching vibration)

The carboxylic acid used as the raw material is a dimer-specific OH
Wide absorption band due to expansion and contraction (3,300 to 2,500cm
^-1 ) and absorption of C = O stretching vibration (1,706c
m ^-1 ) was observed, but the resulting compound lost this absorption, and instead replaced the COOAl stretching vibration of the acylate (1,6).
10cm ^-1, 1,464cm ^-1 1) it was confirmed. From this, it is considered that the target compound was obtained.

Example 2 In a 1 L four-necked flask, 204 g (1.0 mol) of aluminum triisopropoxide, AF-7 Solvent 10
Charge 2 g and heat to 120-130 ° C. with stirring. 6.75 g (0.38 mol) of water and coconut fatty acid (manufactured by NOF CORPORATION, neutralization value 278.5 mg KO) were added to this solution.
A mixed solution of 121 g (0.60 mol) of H / g and 61.0 g of isopropanol was added dropwise over 2 hours while distilling off by-produced isopropanol.

Next, the reaction solution was heated to 180 ° C., and 2.26 g (0.12 mol) of water and 40.3 g of coconut fatty acid were added.
(0.20 mol) and 30 g of a mixed solution of 20.0 g of isopropanol while distilling off by-produced isopropanol.
After dropping in minutes, the reaction solution was heated to 190 ° C., and 9.01 g (0.50 mol) of water and 40.3 g of coconut fatty acid
(0.20 mol), and a mixed solution of 81.0 g of isopropanol was added dropwise over 1 hour and 30 minutes while distilling off isopropanol as a by-product.

After completion of the dropwise addition, the system was depressurized to remove isopropanol, and 341 g of a pale yellow transparent liquid was obtained (yield: 9).
9%). The total amount of water used in the reaction was 18.02
g (1.0 mol), the total amount of coconut fatty acids is 201.6 g
(1.0 mol).

In order to confirm the formation of the compound, the aluminum content and the infrared absorption spectrum were measured.

Aluminum content: 7.88% (theory 7.90%). IR spectrum (cm ^-1 ) 2,960 to 2,850 (C of -CH ₂ -and -CH ₃
-H stretching vibration) 1,588, 1,470 (COOAl stretching vibration)

The starting carboxylic acid is a dimer-specific OH
Wide absorption band due to expansion and contraction (3,300 to 2,500cm
^-1 ) and absorption of C = O stretching vibration (1,710c
m ^-1 ), the absorption of the resulting compound disappeared, and instead the COOAl stretching vibration of the acylate (1,5)
88cm ^-1, 1470cm ^-1) has been confirmed. From this, it is considered that the target compound was obtained.

Example 3 In a 1 L four-necked flask, 102 g (0.50 mol) of aluminum triisopropoxide, AF-7 solvent 5
1 g was charged and heated to 120 to 130 ° C. with stirring. To this solution, a mixed solution of 3.38 g (0.19 mol) of water, 60.1 g (0.30 mol) of lauric acid, and 30.4 g of isopropanol was added dropwise over 2 hours while distilling off by-produced isopropanol. .

Next, the reaction solution was heated to 180 ° C., and 1.14 g (0.063 mol) of water and 20.0 g of lauric acid were added.
(0.10 mol) and a mixed solution of 10.0 g of isopropanol were added to the solution while distilling out by-produced isopropanol.
After dropwise addition in minutes, the reaction solution was heated to 190 ° C., and 4.50 g (0.25 mol) of water and 20.0 g of lauric acid were added.
(0.10 mol), and a mixed solution of 40.0 g of isopropanol was added dropwise over 1 hour and 30 minutes while distilling off isopropanol as a by-product.

After completion of the dropwise addition, the pressure in the system was reduced to remove isopropanol, and 170 g of a pale yellow transparent liquid (yield: 9%) was obtained.
9%). The total amount of water used in the reaction was 9.02 g
(0.50 mol), the total amount of lauric acid is 100.1 g
(0.50 mol).

Further, in order to confirm the formation of the compound, the aluminum content and the infrared absorption spectrum were measured.

Aluminum content: 7.92% (theoretical 7.92%) IR spectrum (cm ⁻¹ ) 2,960-2,850 (C of —CH ₂ — and —CH ₃ )
-H stretching vibration) 1,589, 1,465 (COOAl stretching vibration)

The carboxylic acid used as a raw material is OH specific to the dimer.
Wide absorption band due to expansion and contraction (3,300 to 2,500cm
^-1 ) and absorption of C = O stretching vibration (1,710c
m ^-1 ), the absorption of the resulting compound disappeared, and instead the COOAl stretching vibration of the acylate (1,5)
89cm ^-1, 1,465cm ^-1) has been confirmed. From this, it is considered that the target compound was obtained.

Example 4 153 g (0.75 mol) of aluminum triisopropoxide and AF-7 Solvent 7 were placed in a 1 L four-necked flask.
6.0 g was charged and the reaction temperature was 120 to 13 while stirring.
Heated to 0 ° C. 4.32 g of water (0.24 g) was added to this solution.
Mol), 39.0 g of isopropanol, isopalmitic acid (manufactured by Higher Alcohol Industry Co., Ltd., neutralization number 216.0)
A mixed solution of 117 g (0.45 mol) of mgKOH / g was added dropwise over 2 hours while isopropanol produced as a by-product was distilled off.

Next, at a reaction temperature of 180 ° C., 2.43 g of water
(0.14 mol), a mixed solution of 20.0 g of isopropanol and 39.0 g (0.15 mol) of isopalmitic acid were added dropwise over 30 minutes while distilling off by-produced isopropanol. 6.67 g (0.3
7 mol), 60.0 g of isopropanol and 39.0 g (0.15 mol) of isopalmitic acid were added dropwise over 1 hour and 30 minutes while distilling off by-produced isopropanol.

After completion of the dropwise addition, the system was depressurized to remove isopropanol, and 388 g of a pale yellow transparent liquid (yield 9%) was obtained.
9%). The total amount of water used in the reaction was 13.42
g (0.75 mol), the total amount of isopalmitic acid is 19
It was 5 g (0.75 mol).

Further, in order to confirm the formation of the compound, the aluminum content and the infrared absorption spectrum were measured.

Aluminum content: 5.20% (theoretical value: 5.21%) IR spectrum (cm ⁻¹ ) 2,960 to 2,850 (CH stretching vibration of —CH 2 — and —CH 3) 1,592; 1,467 (COOAl stretching vibration)

The carboxylic acid used as a raw material is OH specific to the dimer.
Wide absorption band due to expansion and contraction (3,300 to 2,500cm
^-1 ) and absorption of C = O stretching vibration (1,704c
m ^-1 ), the absorption of the resulting compound disappeared, and instead the COOAl stretching vibration of the acylate (1,5)
92cm ^-1, 1,467cm ^-1) has been confirmed. From this, it is considered that the target compound was obtained. Example 5 In a 1 L four-necked flask, 204 g (1.0 mol) of aluminum triisopropoxide, AF-7 Solvent 10
2 g was charged and heated to 120 to 130 ° C. with stirring. 6.75 g (0.38 mol) of water and palm stearic acid (neutralization value 205.1 mgKOH / g) 1
64 g (0.60 mol), 61.0 g of isopropanol
Was added dropwise over 2 hours while isopropanol produced as a by-product was distilled off.

Next, the reaction solution was heated to 180 ° C., and 2.26 g (0.12 mol) of water and 5% of palm stearic acid were added.
4.7 g (0.20 mol), isopropanol 20.0
g of the mixed solution was added dropwise over 30 minutes while distilling off by-produced isopropanol, and then the reaction solution was heated to 190 ° C., and 9.01 g (0.50 mol) of water and 54.7 g of palm stearic acid (0 mol) were added. .20 mol), isopropanol 8
0.0 g of the mixed solution was added dropwise over 1 hour and 30 minutes while distilling off by-produced isopropanol.

After completion of the dropwise addition, the pressure inside the system was reduced to remove isopropanol, and 415 g of a pale yellow transparent liquid was obtained (yield: 9%).
9%). The total amount of water used in the reaction was 18.02
g (1.0 mol), the total amount of palm stearic acid is 27
It was 3.4 g (1.0 mol).

Further, in order to confirm the formation of the compound, the aluminum content and the infrared absorption spectrum were measured.

Aluminum content: 6.48% (theoretical 6.49%) IR spectrum (cm ⁻¹ ) 2,960-2,850 (C of —CH ₂ — and —CH ₃
-H stretching vibration) 1,589,1,468 (COOAl stretching vibration)

The carboxylic acid used as a raw material is OH specific to the dimer.
Wide absorption band due to expansion and contraction (3,300 to 2,500cm
^-1 ) and absorption of C = O stretching vibration (1,705c)
m ^-1 ), but this absorption disappeared in the obtained compound, and instead, the COOAl stretching vibration of the acylate (1, ¹ ) was observed.
589 cm ^-1 and 1468 cm ^-1 ). From this, it is considered that the target compound was obtained.

Example 6 In a 1 L four-necked flask, 204 g (1.0 mol) of aluminum triisopropoxide, AF-7 Solvent 10
2 g was charged and heated to 120 to 130 ° C. with stirring. 6.75 g (0.38 mol) of water and isostearic acid (manufactured by Nissan Chemical Industries, Ltd., neutralization number 19) were added to this solution.
A mixed solution of 172 g (0.60 mol) of 6.0 mg KOH / g) and 61.0 g of isopropanol was added dropwise over 2 hours while distilling off by-produced isopropanol.

Next, the reaction solution was heated to 180 ° C., and 2.26 g (0.12 mol) of water and 57.2 g of isostearic acid were added.
A mixed solution of 3 g (0.20 mol) and 20.0 g of isopropanol was added dropwise over 30 minutes while distilling off by-produced isopropanol, and then the reaction solution was heated to 190 ° C.
9.01 g (0.50 mol) of water, isostearic acid 5
7.3 g (0.20 mol), isopropanol 81.0
g of the mixed solution was dropped in 1 hour and 30 minutes while distilling off isopropanol as a by-product.

After completion of the dropwise addition, the inside of the system was depressurized to remove isopropanol, and 426 g of a pale yellow transparent liquid was obtained (yield: 9).
9%). The total amount of water used in the reaction was 18.02
g (1.0 mol), the total amount of isostearic acid is 28
It was 6.6 g (1.0 mol).

Further, in order to confirm the formation of the compound, the aluminum content and the infrared absorption spectrum were measured.

Aluminum content: 6.29% (theoretical 6.32%) IR spectrum (cm ⁻¹ ) 2,960-2,850 (C of —CH ₂ — and —CH ₃
-H stretching vibration) 1,588, 1,463 (COOAl stretching vibration)

The carboxylic acid used as the starting material is a dimer-specific OH
Wide absorption band due to expansion and contraction (3,300 to 2,500cm
^-1 ) and absorption of C = O stretching vibration (1,709c
m ^-1 ), but this absorption disappeared in the obtained compound, and instead, the COOAl stretching vibration of the acylate (1, ¹ ) was observed.
588 cm ^-1 and 1463 cm ^-1 ). From this, it is considered that the target compound was obtained.

Example 7 In a 1 L four-necked flask, 204 g (1.0 mol) of aluminum triisopropoxide, AF-7 Solvent 10
2 g was charged and heated to 120 to 130 ° C. with stirring. 6.75 g (0.38 mol) of water and soybean oil fatty acid (manufactured by NOF CORPORATION, neutralization value: 199.9 mg) were added to this solution.
A mixed solution of 168 g (0.60 mol) of KOH / g and 61.0 g of isopropanol was added dropwise over 2 hours while distilling off by-produced isopropanol.

Next, the reaction solution was heated to 180 ° C., and 2.26 g (0.12 mol) of water and 56.1 g of soybean oil fatty acid were obtained.
(0.20 mol) and 30 g of a mixed solution of 20.0 g of isopropanol while distilling off by-produced isopropanol.
After dripping in minutes, the reaction solution was heated to 190 ° C., and 9.01 g (0.50 mol) of water and 56.1 g of soybean oil fatty acid were added.
(0.20 mol), and a mixed solution of 81.0 g of isopropanol was added dropwise over 1 hour and 30 minutes while distilling off isopropanol as a by-product.

After the completion of the dropwise addition, the inside of the system was depressurized to remove isopropanol, and 424 g of a pale yellow transparent liquid (yield: 1) was obtained.
00%). The total amount of water used for the reaction was 18.0
2 g (1.0 mol), the total amount of soybean fatty acids was 280.2
g (1.0 mol).

Further, in order to confirm the formation of the compound, the aluminum content and the infrared absorption spectrum were measured.

Aluminum content: 6.35% (theoretical 6.35%) IR spectrum (cm ⁻¹ ) 2,960-2,850 (C of —CH ₂ — and —CH ₃
-H stretching vibration) 1,590,1,465 (COOAl stretching vibration)

The carboxylic acid used as a raw material is a dimer-specific OH
Wide absorption band due to expansion and contraction (3,300 to 2,500cm
^-1 ) and absorption of C = O stretching vibration (1,712c
m ^-1 ), but this absorption disappeared in the obtained compound, and instead, the COOAl stretching vibration of the acylate (1, ¹ ) was observed.
590 cm ^-1 and 1465 cm ^-1 ). From this, it is considered that the target compound was obtained.

Example 8 In a 1 L four-necked flask, 204 g (1.0 mol) of aluminum triisopropoxide, AF-7 Solvent 10
2 g was charged and heated to 120 to 130 ° C. with stirring. To this solution, 6.75 g (0.38 mol) of water, rice bran fatty acid (manufactured by Kumiai Yushi Co., Ltd., neutralization value 201.5 m)
A mixed solution of 167 g (0.60 mol) of gKOH / g and 61.0 g of isopropanol was added dropwise over 2 hours while distilling off by-produced isopropanol.

Next, the reaction solution was heated to 180 ° C., and 2.26 g (0.12 mol) of water and 55.7 g of rice bran fatty acid were obtained.
(0.20 mol) and 30 g of a mixed solution of 20.0 g of isopropanol while distilling off by-produced isopropanol.
Then, the reaction solution was heated to 190 ° C., and 9.01 g (0.50 mol) of water and 55.7 g of rice bran fatty acid were added.
(0.20 mol), and a mixed solution of 81.0 g of isopropanol was added dropwise over 1 hour and 30 minutes while distilling off isopropanol as a by-product.

After completion of the dropwise addition, the pressure in the system was reduced to remove isopropanol, and 422 g of a pale yellow transparent liquid (yield: 1) was obtained.
00%). The total amount of water used for the reaction was 18.0
2 g (1.0 mol), the total amount of rice bran fatty acid is 278.4
g (1.0 mol).

In order to confirm the formation of the compound, the aluminum content and the infrared absorption spectrum were measured.

Aluminum content: 6.37% (theoretical 6.38%) IR spectrum (cm ⁻¹ ) 2,960-2,850 (C of —CH ₂ — and —CH ₃
-H stretching vibration) 1,586,1,465 (COOAl stretching vibration)

The carboxylic acid used as the starting material is a dimer-specific OH
Wide absorption band due to expansion and contraction (3,300 to 2,500cm
^-1 ) and absorption of C = O stretching vibration (1,708c
m ^-1 ), but this absorption disappeared in the obtained compound, and instead, the COOAl stretching vibration of the acylate (1, ¹ ) was observed.
586 cm ^-1 and 1465 cm ^-1 ). From this, it is considered that the target compound was obtained.

Example 9 In a 1 L four-necked flask, 204 g (1.0 mol) of aluminum triisopropoxide, AF-7 Solvent 10
2 g was charged and heated to 120 to 130 ° C. with stirring. To this solution, a mixed solution of 6.75 g (0.38 mol) of water, 95.0 g (0.60 mol) of isononanoic acid, and 61.0 g of isopropanol was added dropwise over 2 hours while distilling off by-produced isopropanol. .

Next, the reaction solution was heated to 180 ° C., and 2.26 g (0.12 mol) of water and 31.6 g of isononanoic acid were added.
(0.20 mol) and 30 g of a mixed solution of 20.0 g of isopropanol while distilling off by-produced isopropanol.
Then, the reaction solution was heated to 190 ° C., and 9.01 g (0.50 mol) of water and 31.6 g of isononanoic acid were added.
(0.20 mol), and a mixed solution of 81.0 g of isopropanol was added dropwise over 1 hour and 30 minutes while distilling off isopropanol as a by-product.

After completion of the dropwise addition, the inside of the system was depressurized to remove isopropanol, and 302.0 g (yield 100%) of a pale yellow transparent liquid was obtained. The total amount of water used in the reaction was 1
8.02 g (1.0 mol), the total amount of isononanoic acid was 1
It was 58.2 g (1.0 mol).

Further, in order to confirm the formation of the compound, the aluminum content and the infrared absorption spectrum were measured.

Aluminum content: 8.91% (theoretical 8.92%) IR spectrum (cm ⁻¹ ) 2,960 to 2,850 (C of —CH ₂ — and —CH ₃
-H stretching vibration) 1,590,1,468 (COOAl stretching vibration)

The carboxylic acid used as a raw material is a dimer-specific OH
Wide absorption band due to expansion and contraction (3,300 to 2,500cm
^-1 ) and absorption of C = O stretching vibration (1,708c
m ^-1 ), but this absorption disappeared in the obtained compound, and instead, the COOAl stretching vibration of the acylate (1, ¹ ) was observed.
590 cm ^-1 and 1468 cm ^-1 ). From this, it is considered that the target compound was obtained.

In Examples 1 to 9, there was almost no change in the viscosity of the reaction solution from the start to the end of the dropping, and the stirring state was good.

Example 10 Thickening Test 400 g of a rosin-modified phenolic resin (trade name “Tamanol # 361”, manufactured by Arakawa Chemical Industries, Ltd.), 300 g of linseed oil, AF-7 Solvent (JP) in a 2,000 mL four-necked flask 300 g of the product (produced by Ishi Mitsubishi Co., Ltd.) was charged, and a heat treatment was performed at 200 ° C. for 1 hour under reduced pressure to prepare a resin varnish for testing.

Resin varnish 5 was placed in a 200 mL four-necked flask.
0 g and the compounds of Examples 1 to 9 at 90 ° C.
Is added to be 0.1%. After the addition, the temperature was raised to 180 ° C., the mixture was heated and stirred at 180 ° C. for 3 hours, and then cooled to 2
The viscosity was measured at 5 ° C.

The above results are shown in Table 1 below.

[0103]

[Table 1]

As shown in the measurement results in Table 1, the cyclic aluminum oxide acylate produced by the method of the present invention with respect to the blank was confirmed to have a thickening effect.

[0105]

According to the present invention as described in claim 1 or 2, since the reaction is carried out without passing through the cyclic aluminum oxide alcoholate, there is no problem of gelling or solidification of the reaction solution, ester by-products, and Cyclic aluminum oxide acylate can be produced economically with little coloring, cloudiness and the like.

The present invention as described in claim 3 or 4 has excellent thickening properties as a gelling agent composition for printing inks or coatings.

 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Norio Hayashi 1-3-34 Kitafu, Takefu City, Fukui Prefecture Inside Takefu Fine Chemical Co., Ltd. 4H048 AA02 AB76 AB99 BB14 BB15 BB20 BB24 BB25 BC31 BC37 BD21 BE60 VA20 VA22 VA80 VB10 4J038 EA011 JC38 4J039 BC31

Claims (4)

[Claims] 1. A compound represented by the general formula (1): Al (OR ¹ ) ₃ (1) wherein R ¹ represents a linear or branched alkyl or alkenyl group having 1 to 4 carbon atoms. For the aluminum trialkoxide, a general formula (2) R ² COOH (2) wherein R ² is a linear or branched alkyl group having 1 to 21 carbon atoms which may be substituted with a hydroxy group, or A carboxylic acid represented by the general formula (3): Wherein R ² is the same as defined above. The method for producing a cyclic aluminum oxide acylate represented by the general formula (2):
A mixed solution obtained by mixing a carboxylic acid and water represented by
This is a method for producing a cyclic aluminum oxide acylate represented by the general formula (3) by dropping the aluminum trialkoxide represented by the general formula (1) into two or more steps, which is divided into two or more steps. The amount of the first-stage carboxylic acid of the mixed solution to be dropped is in the range of 0.6 to 0.8 mol per 1 mol of aluminum trialkoxide,
The amount of water in the first step is in the range of 0.3 to 0.4 mol per 1 mol of aluminum trialkoxide, and
Water / carboxylic acid molar ratio of 1 / 1.50 to 1 / 2.67
A method for producing a cyclic aluminum oxide acylate represented by the general formula (3): 2. The total amount of carboxylic acid in the mixed solution is 0.8 to 1.3 mol per mol of aluminum trialkoxide, and the total amount of water is 0.8 to 1.1 mol per mol of aluminum trialkoxide. The method for producing a cyclic aluminum oxide acylate according to claim 1, wherein the amount is molar. 3. A gelling composition for a printing ink, comprising a cyclic aluminum oxide acylate produced by the method according to claim 1 or 2. 4. A gelling composition for paints, comprising a cyclic aluminum oxide acylate produced by the method according to claim 1 or 2.