JP2001181283A - Cyclic aluminum oxide acylate compound, gelling agent composition for printing ink and gelling agent composition for coating - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a cyclic aluminum oxide acylate compound useful for printing ink suitable for high-speed/automatic printing in an ink field. SOLUTION: This cyclic aluminum oxide acylate compound is represented by general formula [R1CO, R2CO and R3CO are each a mixed fatty acid residue constituting natural oils and fats and the composition ratio of saturated fatty acid residue contained in the mixed fatty acid residue is >=10%].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel cyclic aluminum oxide acylate compound and a gelling composition for printing inks or paints containing the compound.

[0002]

BACKGROUND OF THE INVENTION For many years, metal organic compounds such as aluminum organic compounds have been used in the production of printing inks. Metal organic compounds play an important role in controlling fluidity in ink production technology, and improving performance such as glossiness, pigment dispersion, and dryness. Mainly, when a gelling agent or a thickening agent is used as a fluidity control, the effects are as follows: gloss, yield value, pigment wettability, penetration power,
Explained.

[0003] In recent years, the printing technology has been remarkably advanced, and there has been a demand for higher-performance printing inks in order to achieve higher printing speed and automation of printing. When printing is performed at high speed, misting and stains on the guide roller become problems. In order to improve these drawbacks, it is necessary to make the viscoelasticity of the printing ink proper by an appropriate gelling reaction at the time of producing a gel varnish of the printing ink, and the gelling agent has been improved.

Heretofore, as a gelling agent for a printing ink, a metal which is generally a metal soap such as aluminum octylate, an aluminum alcoholate such as aluminum isopropylate and an aluminum chelate such as ethyl acetoacetate aluminum diisopropylate Organic compounds were used.

[0005] For example, metal soap is used for the gelation reaction of hydrocarbon oil in ink production. Metal soap is
In the vehicle, a fibrous network is formed by hydrogen bonds and coordinate bonds. However, since there is no covalent bond between the metal soap and the oil or between the metal soap and the resin, this structure is easily broken by a small amount of energy such as heating, friction, and vibration. In addition, metal soap is excellent in stability in air, but cannot be handled as a solution because it gels when dissolved in a solvent. Further, metal soap is poor in workability such as being scattered during handling because it is a fine and light solid powder. In addition, at the time of ink production, if the addition temperature is high, the gel is locally immediately gelled before being uniformly dispersed to form a partial gel,
The desired quality of the product was not obtained.

On the other hand, aluminum alcoholate or aluminum chelate reacts with a carboxyl group or a hydroxyl group in a resin to form a covalent crosslinked structure, thereby increasing the molecular weight and increasing the viscosity. Moreover, this covalent bond structure is not destroyed by the shearing force. Further, an aluminum hydroxide intermediate is formed by a trace amount of water contained in the resin, and gelation occurs by an interaction like soap. Aluminum alcoholate and aluminum chelate are easy to handle because they dissolve in organic solvents without thickening.However, when exposed to air, they are immediately decomposed by a small amount of moisture, such as moisture, and therefore have poor stability in air. It has the drawback of poor flash point due to these properties.

In addition, aluminum alcoholate and aluminum chelate generate VOC (Vo), which has recently become a problem because alcohol, which is a volatile component, is produced during ink production.
Latile Organic Compounds (Volatile Organic Compounds) It is not preferable from the point of regulation, and the alkoxy group in the chelate has high reactivity, and therefore has a drawback that a partial gel is formed by a local reaction before it is uniformly dispersed. Further, the use temperature of aluminum alcoholate and aluminum chelate is limited to 100 to 150 ° C., and if it is lower than 100 ° C., alcohol as a by-product cannot be removed, and 150 ° C.
When the temperature exceeds ℃, there is a problem that the hydrogen bond and the coordination bond are broken, and the desired quality of the product cannot be obtained.

As a gelling agent which solves the above problems, a cyclic aluminum oxide acylate compound is mentioned, and derivatives such as 2-ethylhexanoic acid, stearic acid, oleic acid, linoleic acid and tall oil fatty acid are known. Have been.

However, no studies have been made on the fatty acid composition of the cyclic aluminum oxide acylate compound and its performance as a gelling agent for printing inks. Oleic acid and linoleic acid, which are unsaturated fatty acids, and tall oil fatty acids whose composition is 90% or more of the unsaturated fatty acids, when used as a gelling agent for vehicles for printing inks or vehicles for coatings, may cause coloring or odor. And there is a problem in stability over time.

[0010]

The problem to be solved by the present invention is to provide a cyclic aluminum oxide acylate compound suitable for a printing ink suitable for high-speed and automatic printing in the ink field, a vehicle for a printing ink and a vehicle for a paint. An object of the present invention is to provide a gelling agent composition free from problems such as coloring, odor and stability over time even when added.

[0011]

Means for Solving the Problems In order to solve the above-mentioned problems, in the case of cyclic aluminum oxide acylate compounds, the present inventors have determined the composition ratio of the saturated and unsaturated fatty acid residues of mixed fatty acid residues constituting natural fats and oils. Is considered to be the cause of coloring, odor and stability over time. As a result of intensive studies, the use of a fatty acid having a composition derived from natural fats and oils having a composition ratio of saturated aliphatic groups of 10% or more enables the use of a gel for printing ink. The present inventors have found a cyclic aluminum oxide acylate compound having good performance as an agent and free from the above-mentioned problems, and have completed the invention.

That is, the present invention provides a compound represented by the general formula (1):

[0013]

Embedded image

[Wherein R ₁ CO, R ₂ CO and R ₃ CO
Is a mixed fatty acid residue constituting natural fats and oils, and the composition ratio of the saturated fatty acid residue contained in the mixed fatty acid residue is 10
Wt% or more. The present invention further relates to a gelling agent for a printing ink, comprising a cyclic aluminum oxide acylate compound represented by the general formula (1). The present invention relates to a composition and a gelling agent composition for paint.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The cyclic aluminum oxide acylate compound of the present invention is a compound represented by the above general formula, and can be produced, for example, by the following method.

The cyclic aluminum oxide alcoholate is dissolved in an aprotic solvent, a mixed fatty acid constituting a natural fat or oil is added to the solution, and an acylation reaction is carried out to obtain the cyclic aluminum oxide represented by the general formula (1). An aluminum oxide acylate compound can be obtained. Examples of the aprotic solvent include toluene, xylene, and petroleum solvents such as No. 7 solvent, AF No. 5 solvent, and AF No. 7 solvent (Nippon Oil Co., Ltd.)
And other hydrocarbon-based solvents.

Examples of the cyclic aluminum oxide alcoholate used as a raw material include cyclic aluminum oxide ethylate, cyclic aluminum oxide isopropylate, cyclic aluminum oxide-sec-butylate, and cyclic aluminum oxide mono-sec-butylate diisopropylate. However, cyclic aluminum oxide isopropylate is preferred in terms of high reactivity, economical availability, and easy availability.

The mixed fatty acids constituting the natural fats and oils used as raw materials include coconut oil fatty acids, palm oil fatty acids, palm kernel oil fatty acids, soybean oil fatty acids, rice bran oil fatty acids, and the like, in which the composition ratio of saturated aliphatic groups is 10 Wt% or more. More preferably 15 Wt%
The mixed fatty acids described above are exemplified.

The composition ratio of saturated fatty acids in the mixed fatty acids constituting the above natural fats and oils is as follows. (Composition ratio of saturated fatty acids) Palm oil fatty acids 88-93 Wt% Palm oil fatty acids 42-54 Wt% Palm kernel oil fatty acids 80-89 Wt% Soybean oil fatty acids 10-25 Wt% Rice bran oil fatty acids 10-30 Wt% Also constitutes natural fats and oils The number of ligands of the mixed fatty acid is preferably from 1 to 1.2 per atom of aluminum. If it is less than 1, the alkoxy group remains, so that the flash point becomes low. If it exceeds 1.2, aluminum soap is generated, which may cause a problem of gelation of the solution, which is not preferable.

The acylation reaction is carried out at a reaction temperature of 80.degree.
C., more preferably in the range of 120.degree. C. to 200.degree. If the temperature is lower than 80 ° C., the progress of the reaction is slow, and if the temperature is higher than 230 ° C., problems such as poor quality such as coloring due to heat history may occur, which is not preferable. When the alcohol generated by the acylation reaction is distilled off, a cyclic aluminum oxide acylate compound is obtained. 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.

Without distilling off the solvent from the reaction product,
The gelling agent composition for printing ink or paint can be used as it is, but the solvent may be distilled off to isolate the cyclic aluminum oxide acylate compound. The gelling agent composition for printing inks or paints of the present invention, in addition to the solvent, for example, coconut oil, palm oil, palm kernel oil,
A natural fat or oil containing 10 Wt% or more of saturated fatty acid residues such as soybean oil and rice bran oil may be blended.

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.

As the cyclic aluminum oxide acylate compound having a natural oil / fat composition in the gelling agent composition for printing inks or coatings of the present invention, particularly preferred are cyclic aluminum oxide soybean oil fatty acid acylates, Cyclic aluminum oxide rice bran oil fatty acid acylate and the like can be mentioned.

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.

In order 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.

[0027]

The present invention will be described in more detail with reference to the following examples. In the examples, the aluminum content was measured by a chelate titration method.

Example 1 A cyclic aluminum oxide isopropylate (45.93 g, 0.15 mol) was placed in a glass reactor having a capacity of 300 mL.
l) and 45.93 g of AF Solvent 7 were charged,
The mixture was heated to 150 ° C. with stirring to dissolve. To this solution was added soybean oil fatty acid (neutralization value 199.7, saturated fatty acid content 1).
(3.7 Wt%) was added to 126.44 g (0.45 mol).

Further, the temperature of the reaction solution was raised to 180 ° C., and isopropyl alcohol by-produced was distilled off.
1.25 g (yield 100%) of a cyclic aluminum oxide soybean oil fatty acid acylate AF solvent solution was obtained.

The aluminum content and infrared absorption spectrum were measured to confirm the formation of cyclic aluminum oxide acylate.

Aluminum content 6.33% (theoretical 6.35) IR spectrum (cm ^-1 ) 2925, 2854 (CH of -CH ₂ -and -CH ₃ )
Stretching vibration) 1594 (Stretching vibration of C = C and .CO) 1466, 1376 (CH bending vibration) 1175, 1110 (CO stretching vibration or CH bending vibration)

From the results of IR measurement, absorption of C ＝ O stretching vibration (1712 cm ⁻¹ ) of the aliphatic carboxylic acid was observed before the reaction, but this absorption disappeared in the obtained compound, and instead, the acylate was replaced with acylate. C = C and C = O stretching vibration (159
4 cm ^-1 ) was confirmed. This indicates that the COOH group of the hydroxyalkanoic acid condensate reacted with the cyclic aluminum oxide to obtain the desired compound.

Example 2 45.93 g of cyclic aluminum oxide isopropylate (0.15 mol) was placed in a glass reactor having a capacity of 300 ml.
l) and 45.93 g of AF Solvent 7 were charged,
The mixture was heated to 150 ° C. with stirring to dissolve. To this solution is added rice bran oil fatty acid (neutralization value 200.5, saturated fatty acid content 2).
(6.8 Wt%) was added to 125.93 g (0.45 mol).

Further, the temperature of the reaction solution was raised to 180 ° C., and isopropyl alcohol by-produced was distilled off to remove the yellow liquid 19
0.75 g (yield 100%) of a cyclic aluminum oxide rice bran oil fatty acid acylate AF7 solvent solution was obtained.

The aluminum content and infrared absorption spectrum were measured to confirm the formation of cyclic aluminum oxide acylate.

Aluminum content 6.34% (theoretical 6.36) IR spectrum (cm ^-1 ) 2925, 2854 (CH of -CH ₂ -and -CH ₃ )
Stretching vibration) 1590 (Stretching vibration of C = C and .CO) 1465, 1376 (CH bending vibration) 1176, 1111 (CO stretching vibration or CH bending vibration)

From the results of IR measurement, absorption of C ＝ O stretching vibration (1712 cm ⁻¹ ) of the aliphatic carboxylic acid was observed before the reaction, but this absorption disappeared in the obtained compound, and instead, the acylate was replaced by acylate. C = C and C = O stretching vibration (159
0 cm ^-1 ). This indicates that the COOH group of the hydroxyalkanoic acid condensate reacted with the cyclic aluminum oxide to obtain the desired compound.

Example 3 45.93 g of cyclic aluminum oxide isopropylate (0.15 mol) was placed in a glass reactor having a capacity of 300 ml.
l) and 45.93 g of AF Solvent 7 were charged,
The mixture was heated to 150 ° C. with stirring to dissolve. To this solution was added coconut oil fatty acid (neutralization value 263.6, saturated fatty acid content 9
(5.0 Wt%) was added to 95.79 g (0.45 mol).

Further, the temperature of the reaction solution was raised to 180 ° C., and isopropyl alcohol as a by-product was distilled off to remove the yellow liquid.
61 g (yield 100%) of a cyclic aluminum oxide coconut oil fatty acid acylate AF Solvent No. 7 solution was obtained.

The aluminum content and infrared absorption spectrum were measured to confirm the formation of cyclic aluminum oxide acylate.

Aluminum content 7.53% (theoretical 7.56) IR spectrum (cm ^-1 ) 2925, 2854 (--CH of --CH ₂ -and --CH ₃ )
Stretching vibration) 1592 (Stretching vibration of C = C and .CO) 1467, 1376 (CH bending vibration) 1175, 1111 (CO stretching vibration or CH bending vibration)

From the results of IR measurement, absorption of C 吸収 O stretching vibration (1712 cm ⁻¹ ) of the aliphatic carboxylic acid was observed before the reaction, but this absorption disappeared in the obtained compound, and instead, the acylate was replaced with acylate. C = C and C = O stretching vibration (159
2 cm ^-1 ) was confirmed. This indicates that the COOH group of the hydroxyalkanoic acid condensate reacted with the cyclic aluminum oxide to obtain the desired compound.

Comparative Example 1 A cyclic aluminum oxide isopropylate (45.93 g, 0.15 mol) was placed in a glass reactor having a capacity of 300 ml.
l) and 45.93 g of AF Solvent 7 were charged,
The mixture was heated to 150 ° C. with stirring to dissolve. To this solution, 130.15 g (0.45 mol) of tall oil fatty acid (saturated aliphatic composition: 10% or less, neutralization value: 194) was added.

Further, the temperature of the reaction solution was raised to 180 ° C., and isopropyl alcohol as a by-product was distilled off to remove a brown liquid.
0 g (yield 100%) of a cyclic aluminum oxide tall oil fatty acid acylate AF Solvent No. 7 solution was obtained. Further, the obtained composition had a peculiar odor derived from tall oil fatty acids.

Example 4 The hues (Gardner) of the compounds obtained in Examples 1 to 3 and Comparative Example were compared. Hue was measured according to the standard fat test method.

[0046]

[Table 1]

As is clear from the results shown in Table 1, the use of a mixed fatty acid raw material derived from natural fats and oils having a saturated aliphatic composition ratio of 10 Wt% or more improves the hue of the gelling agent composition and improves Can be added to inks and paints.

Example 5 40.0 parts of rosin-modified phenol resin, linseed oil
0 parts, AF Solvent 7 (Nippon Oil Co., Ltd. solvent) 3
0.0 parts was heated and stirred at 200 ° C. for 1 hour to prepare a test resin varnish.

To 100 parts by weight of the resin varnish, 2 parts by weight of the gelling composition for printing inks of Examples 1, 2, and 3 were added. The addition temperature was 90 ° C. These ones
After performing a gelling reaction by heating at 80 ° C. for 3 hours, the odor was measured, and the viscosity was measured at 25 ° C. using a Brookfield viscometer (manufactured by Tokyo Keiki Co., Ltd.). Table 2 shows the results.

[0050]

[Table 2]

As is clear from the results shown in Table 2, the cyclic aluminum oxide acylate compounds of Examples 1, 2, and 3 of the present invention exhibited an effect of increasing the viscosity of the resin varnish. In preparing the varnish, the cyclic aluminum oxide acylates of Examples 1, 2, and 3 of the present invention did not generate volatile components and had no odor.

Example 6 No. 4 varnish (manufactured by Toshin Yushi Co., Ltd.) 1.12 g, pigment (carbon black # 32, manufactured by Mitsubishi Kasei Co., Ltd.) 0.48
g, and 0.06 g of the gelling agent composition for printing inks of Synthesis Examples 1, 2, and 3 were thoroughly kneaded by a Hoover-type Mahler (manufactured by Yasuda Seiki Seisakusho Co., Ltd.) 100 times three times to prepare a paste. The prepared paste was colored on a measuring paper (manufactured by Taisuke Kiki Co., Ltd.) using a steel knife. After sufficiently drying at room temperature, measurement was made at four points using a gloss meter (manufactured by Nippon Denshoku Industries Co., Ltd.) (60 °). Table 3 shows the results.

[0053]

[Table 3]

As is clear from the results shown in Table 3, the ink varnishes using the cyclic aluminum oxide acylate compounds of Examples 1, 2 and 3 of the present invention as a gelling agent composition for printing inks have glossiness. And improved the pigment dispersibility in the varnish. In preparing the paste, the cyclic aluminum oxide acylates of Examples 1, 2, and 3 of the present invention did not generate volatile components and had no odor.

[0055]

The cyclic aluminum oxide acylate compound according to claim 1 or 2 is suitable for a printing ink suitable for high-speed / automatic printing in the ink field.

The gelling agent composition for printing ink according to claim 3 or 4 is free from problems such as coloring, odor and stability over time during the production of the ink. The printing ink prepared using the product is suitable for high-speed and automatic printing.

The gelling agent composition for paints according to claim 5 or 6 is free from problems such as coloring, odor and stability over time in the production of paints.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Naoko Hashimoto 1-3-34 Kitafu, Takefu-shi, Fukui Prefecture F-term in Takefu Fine Chemical Co., Ltd. 4H048 AA01 AA03 AB76 AB99 VA20 VA22 VA80 VB10

Claims (6)

[Claims] 1. A compound of the general formula (1) [R ₁ CO, R ₂ CO and R ₃ CO in the formula are mixed fatty acid residues constituting natural fats and oils, and the composition ratio of saturated fatty acid residues contained in the mixed fatty acid residues is 10 Wt% or more. . ] The cyclic aluminum oxide acylate compound represented by these. 2. The mixed fatty acid residue constituting the natural fat or oil of the general formula (1) is a constituent fatty acid residue of coconut oil, soybean oil, rice bran oil, palm oil or palm kernel oil. The cyclic aluminum oxide acylate compound according to claim 1. 3. A compound of the general formula (1) [R ₁ CO, R ₂ CO and R ₃ CO in the formula are mixed fatty acid residues constituting natural fats and oils, and the composition ratio of saturated fatty acid residues contained in the mixed fatty acid residues is 10 Wt% or more. . ] The gelling agent composition for printing inks which contains the cyclic aluminum oxide acylate compound shown by these. 4. The mixed fatty acid residue constituting the natural fat or oil of the general formula (1) is a constituent fatty acid residue of coconut oil, soybean oil, rice bran oil, palm oil or palm kernel oil. The gelling composition for a printing ink according to claim 3. 5. A compound of the general formula (1) [R ₁ CO, R ₂ CO and R ₃ CO in the formula are mixed fatty acid residues constituting natural fats and oils, and the composition ratio of saturated fatty acid residues contained in the mixed fatty acid residues is 10 Wt% or more. . A gelling agent composition for paints, comprising a cyclic aluminum oxide acylate compound represented by the formula: 6. The mixed fatty acid residue constituting the natural fat or oil of the general formula (1) is a constituent fatty acid residue of coconut oil, soybean oil, rice bran oil, palm oil or palm kernel oil. A gelling composition for a paint according to claim 5.