JP2006152223A - Aluminum lake pigment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an acidic dye aluminum lake pigment which has a large dye rate, a large coloring power, and excellent light resistance. <P>SOLUTION: A crystallized acidic dye aluminum lake pigment crystal is provided. The aluminum lake pigment crystal, wherein the acidic dye is an edible dye is provided. The aluminum lake pigment crystal, wherein the acidic dye is an acidic dye prepared by diazocoupling 1-(4-sulfophenyl) 3-methyl-5-pyrazolone with an aromatic sulfonic acid compound is provided. In addition, a method for producing the aluminum lake pigment crystal comprises forming the lake of an acidic dye with aluminum polychloride having two or more aluminum atoms and crystallizing the lake. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a crystalline aluminum lake pigment of an acid dye.

Acid dyes, especially food colorings, are generally widely used as dyes or as aluminum lakes. Among these, acidic dyes including food coloring dyes are used in a system that dissolves in water, while aluminum lake pigments are used by dispersion because they are insoluble or hardly soluble in water.
Representative examples of the aluminum lake pigments currently available on the market include edible red No. 2, No. 3, No. 40, yellow No. 4, No. 5, blue No. 1 and No. 2 aluminum lakes. It is made by a method of producing a dyed pigment, that is, a method of dyeing the surface of an aluminum hydroxide body.

  The concept of the structure of the pigment produced by this dyed pigment production method can be expressed by the following formula.

In the above formula, A is an amorphous aggregate of hydrated alumina and is generally called a body.
B is a residue of an acid dye.

  As shown by the above formula, this pigment has a dye sulfone group bonded to the surface of the amorphous aggregate of hydrated alumina. And it does not exist as a dye crystal, but exists in an amorphous state. The fact that the pigment is amorphous means that the diffraction X-ray spectrum of the commercially available aluminum lake pigment Edible Blue No. 2 obtained by X-ray diffraction, which is effective for measuring the crystal state, is as shown in FIG. This can be confirmed by showing only a broad peak. In FIG. 2, the vertical axis represents the diffraction angle (2θ), and the horizontal axis represents the intensity (count number).

The proportion of the dye in the pigment prepared by this dyed pigment manufacturing method is at most about 20% to 30%, and the remainder is occupied by aluminum hydroxide. For this reason, the coloring power of the pigment is inferior by the small amount of the pigment. If the proportion of aluminum hydroxide is reduced, that is, if the proportion of pigment is increased, the raked product obtained will dissolve in water, and the insoluble or poorly soluble properties of water, which is the original pigment function, will be lost. .
For this reason, unlike conventional pigments used in printing inks, aluminum lake pigments containing acidic dyes have drawbacks such as low coloring power and poor light resistance.
Japanese Patent Publication No.36-7624

  An object of the present invention is to improve the above-mentioned drawbacks, and to provide a crystalline aluminum lake pigment with an acid dye having a high pigment ratio, a large coloring power, and excellent light resistance.

  As a result of intensive investigations to solve the above problems, the present inventors have found that by crystallizing the pigment, the aluminum component contained in the pigment can be greatly reduced and the pigment component can be increased. . The present invention has been made based on this finding.

That is, the present invention comprises (1) crystals of an acid dye aluminum lake pigment,
(2) The crystal of the aluminum lake pigment according to (1), wherein the acidic dye is an edible dye,
(3) The crystal of the aluminum lake pigment according to (1), wherein the acid dye is an acid dye obtained by diazo coupling of a 3-methyl-5-pyrazolone compound and an aromatic sulfonic acid amine compound;
(4) The aluminum lake pigment according to any one of (1) to (3), wherein the acid dye is laked and crystallized using polyaluminum chloride having two or more aluminum atoms. Crystal manufacturing method,
(5) Food, cosmetics, pharmaceutical or agricultural chemical coating material or printing marker, stationery, writing instrument, printing ink obtained by mixing or dispersing the crystals of the aluminum lake pigment according to any one of (1) to (3) (Printing inks for ordinary printed materials, food packaging materials, napkins, etc.), inkjet inks, metal inks (including metal inks used for printing alumite and metal cans), paints, plastic colorants, color toners, or A color filter is provided.

  In the present invention, the edible pigment is edible red No. 2, edible red No. 3, edible red No. 40, edible red No. 102, edible red No. 104, edible red No. 105, edible red No. 106, edible red No. 106, which are prescribed by the enforcement regulations of the Food Sanitation Act. Edible yellow 4, edible yellow 5, edible green 3, edible blue 1, and edible blue 2.

The crystal of the aluminum lake pigment of the present invention improves the physical properties such as light resistance of the pigment, and can reduce the aluminum content as compared with commercially available lake pigments, so that the coloring power becomes 2 to 4 times. In addition, the range of application can be expanded by improving coloring power and physical properties of pigments, and can be used not only for foods and cosmetics but also for general-purpose pigments such as inks.
In particular, crystals of aluminum lake pigments for edible dyes have a sense of security that can be used for edible purposes, and are likely to be used indefinitely as environmentally friendly pigments.

  One embodiment of the present invention is a crystal of an acid dye aluminum lake pigment. Each crystallized aluminum lake pigment has its own X-ray diffraction pattern due to its chemical structure. The edible blue No. 2 aluminum lake crystal of the present invention typically has a diffraction X-ray spectrum as shown in FIG. The horizontal axis in FIG. 1 is the diffraction angle (2θ), and the vertical axis is the intensity (count number).

  When compared with the broad X-ray diffraction pattern of the commercially available aluminum lake pigment shown in FIG. 2, it can be clearly seen that the crystal has a diffraction peak and is crystallized.

  The acid dye used in the present invention is not limited thereto, but examples thereof include edible pigments. Among these, food coloring can be preferably used from the viewpoint of safety and environment.

Since the crystal of the aluminum lake pigment of the present invention does not contain an aluminum body, the ratio of the pigment component of the acidic dye to the aluminum can be higher than that of the conventional aluminum lake pigment. If the ratio of the pigment component is high, the coloring power, which is an inherent function of the pigment, is increased. For example, the ratio of the dye component of the conventional aluminum lake pigment is 20 to 30%, whereas the ratio of the dye component of the crystal of the aluminum lake pigment of the present invention is 55 to 80%, which is a ratio of 2 to 4 times. It becomes an improvement.
In addition, the light resistance and dispersibility are improved, and the hue is also sharpened. For example, when the light resistance of edible blue No. 2 is examined with a fade meter under the same conditions, a general commercially available aluminum lake fades in 20 hours, whereas the crystallized aluminum lake of the present invention can withstand 80 hours. I know it.

In another preferred embodiment of the present invention, the acidic dye is a diazo-coupled acidic dye of a 3-methyl-5-pyrazolone compound and an aromatic sulfonic acid amine compound. The 3-methyl-5-pyrazolone compound used in the present invention is preferably 1- (4-sulfophenyl) 3-methyl-5-pyrazolone or 1-phenyl-3-methyl-5-pyrazolone. . Examples of the aromatic sulfonic acid compound used include 2-amino-5-methylbenzenesulfonic acid (4B acid), 2-aminobenzenesulfonic acid (ortanylic acid), 2-amino-3, 5-dimethylbenzene. Examples include sulfonic acid (xylidinesulfonic acid).
1- (4-sulfophenyl) 3-methyl-5-pyrazolone or 1-phenyl-3-methyl-5-pyrazolone and aromatic sulfonic acid amine compound diazo-coupled acid dye crystallized aluminum lake pigment Is particularly useful because its hue is close to that of a yellow pigment for general-purpose printing inks in printing ink applications. Since yellow pigments for printing inks are mostly made from dichlorobenzidine, there are toxicity problems during synthesis, and alternative pigments are desired. In this respect, since this pigment is non-dichlorobenzidine and a non-chlorine compound, it is promising as an alternative pigment.

Next, the manufacturing method of the crystal | crystallization of the aluminum lake pigment of this invention is demonstrated.
In the present invention, polyaluminum chloride having two or more aluminum atoms as a lake forming material (precipitating agent) [Al _n (OH) _m Cl _3n-m , where n represents an integer of 2 or more, and m represents an integer of 5 or more] It is preferable to use a rake. In this case, the pigment particles can be crystallized by appropriately adjusting the lake temperature and the subsequent aging temperature.
Hereinafter, a production method using polyaluminum chloride will be described. In the present invention, polyaluminum chloride is used as a rake material, and unlike the aforementioned so-called dyeing rake method, it is raked by directly bonding aluminum atoms to acidic groups such as sulfone groups. It is.
The concept of the structure of the pigment produced by the production method of the preferred embodiment of the present invention can be represented by the following formula.

  Here, B = acidic dye residue, n = 2 or more, m = 5 or more, x = 1 to 5, and y = 0 to 3.

When aluminum chloride (AlCl ₃ ) is used instead of polyaluminum chloride in the production method of the present invention, the obtained product is not raked and becomes soluble in water. In the present invention, since two or more molecules of aluminum are bonded, they are laked, become insoluble in water, and act as pigments.

  As polyaluminum chloride, polyaluminum chloride having 2 or more aluminum atoms, preferably 2 to 6, is used. Preferably, 0.5 mol or more of polyaluminum chloride is used per 1 mol of the sulfone group of the acid dye.

By performing aging at a high temperature after the rake formation temperature and the rake formation, the raked product changes from an amorphous solid to a crystallized solid, and the suitability as a pigment is improved.
The rake temperature and the aging temperature are required to be 50 ° C. or higher. However, depending on the chemical structure, 90 ° C. may be required, and pressure treatment may be performed to 100 ° C. or higher in order to shorten the processing time.

  In addition, the size of the pigment particles can be controlled by controlling the rake temperature and the aging temperature. If large crystal particles are needed for application, the temperature can be increased, and if small particles are needed, the temperature can be decreased. good. In general, it is said that the particle size distribution is determined by the temperature and speed of rake formation and the particle size is determined by the aging temperature and time, but this general principle can also be applied in the present invention.

In the present invention, the rake temperature is preferably 20 ° C to 100 ° C, more preferably 50 ° C to 90 ° C. The rake time is preferably 1 minute to 120 minutes, more preferably 20 minutes to 80 minutes.
The aging treatment temperature is preferably 30 ° C to 150 ° C, more preferably 40 ° C to 120 ° C. The aging treatment time is preferably 30 minutes to 8 hours, more preferably 1 hour to 6 hours. The pressure in the aging treatment is preferably normal pressure to 0.5 Pa, more preferably normal pressure to 2 Pa.

  The aluminum lake pigments obtained in this way are not only used for food and cosmetics, but also food packaging materials, printing inks for napkins, ink materials for marking printing directly on food, etc. However, it can also be used for coloring toys, printing materials, coloring materials for plastics, stationery, and writing instruments. It can also be used for pharmaceuticals, agricultural chemical coating materials and printing markers, and metal inks used for printing alumite and metal cans. It can also be blended with general printing inks such as planographic printing inks, intaglio inks, and gravure inks. Application to color toners and color filters is also possible. Use as an environmentally friendly pigment is endless.

  Hereinafter, the present invention will be described in more detail with reference to examples.

Example 1
9.7 parts by weight of edible blue No. 2 (pure 9.3 parts by weight) and 400 parts by weight of water were placed in a beaker and stirred at a temperature of 80 ° C., and polyaluminum chloride 1 (Al ₄ (OH) ₉ Cl 23 wt% aqueous solution of a ₃ alumina component was added dropwise hereinafter the same) 19.5 parts by mass over about 1 hour through the dropping pump a solution obtained by diluting 150 parts by weight of water. After completion of dropping, aging treatment was performed at 80 ° C. for 5 hours. After cooling to room temperature, filtering and washing with a small amount of water, the resulting wet cake was dried in a dryer at 80 ° C. for 4 hours. This was pulverized to obtain 14.4 parts by mass of a blue powder pigment.
When this pigment is measured with an X-ray diffractometer, it has a diffraction peak as a main peak at diffraction angles (2θ) of 4.208, 6.546, 7.634, 8.589, 26.245 and is crystallized. I understand.
When this pigment was kneaded with a varnish for printing ink by a Hoover muller and evaluated as an offset ink, the coloring power was 2.5 times better than that of a commercially available edible blue No. 2 aluminum lake pigment. When this offset ink was spread on paper and examined for light resistance with a fade meter, it did not fade even after 80 hours. Commercially available aluminum lake pigments faded in 20 hours, while exhibiting excellent light resistance.

Example 2
Food Yellow No. 5 (9.7 parts by mass) (pure content: 9.0 parts by mass) and water (400 parts by mass) were placed in a beaker and heated with stirring to a temperature of 80 ° C. A solution obtained by diluting 19.5 parts by mass of polyaluminum chloride 1 into 150 parts by mass of water was dropped into the solution through a dropping pump over about 1 hour. After completion of the dropwise addition, the temperature was set to 80 ° C., and an aging treatment was performed for 4 hours. This was brought to room temperature, filtered, washed with water, dried and pulverized to obtain 14.8 parts by weight of a yellow-orange powder pigment.
When this pigment was measured with an X-ray diffractometer, it was found that the main peaks had diffraction peaks at diffraction angles (2θ) of 4.269, 6.807, 7.689, and 8.509 and were crystallized.
When this pigment was kneaded with a varnish for printing ink by a Hoover muller and evaluated as an offset ink, the coloring power was four times better than that of a commercially available yellow No. 5 aluminum lake pigment.

Example 3
Edible Red No. 102, 14.0 parts by mass (pure 12.6 parts by mass) and 400 parts by mass of water were placed in a beaker and heated with stirring to a temperature of 80 ° C. A solution obtained by diluting 29.2 parts by mass of polyaluminum chloride 1 into 150 parts by mass of water was dropped into the solution through a dropping pump over about 1 hour. After completion of the dropwise addition, the temperature was set to 80 ° C. and aging treatment was performed for 3 hours. This was brought to room temperature, filtered, washed with water, dried and pulverized to obtain 21.1 parts by mass of a red powder pigment.
When this pigment was measured with an X-ray diffractometer, it was found that the main peaks had diffraction peaks at diffraction angles (2θ) of 4.440, 5.270, 7.034, and 8.426 and were crystallized.
When this pigment was kneaded with a printing ink varnish by a Hoover muller and evaluated as an offset ink, the coloring power was three times better than that of a commercially available red No. 102 aluminum lake pigment.

Example 4
12.4 parts by mass (pure 11.3 parts by mass) of acid yellow 17 and 300 parts by mass of water were placed in a beaker and heated with stirring to a temperature of 80 ° C. A solution obtained by diluting 19.5 parts by mass of polyaluminum chloride 1 into 60 parts by mass of water was dropped into the solution through a dropping pump over about 1 hour. After completion of the dropping, the temperature was set to 80 ° C. and aging treatment was performed for 3 hours. This was brought to room temperature, filtered, washed with water, dried and pulverized to obtain 16.4 parts by mass of a greenish yellow powder pigment.
When this pigment was measured with an X-ray diffractometer, it was found that the main peaks had diffraction peaks at diffraction angles (2θ) of 5.59 and 7.60 and were crystallized.

Comparative Example 1
When the same treatment as in Example 4 was performed except that calcium chloride was used instead of polyaluminum chloride 1, the product was dissolved and no pigment was obtained.

Example 5
Edible Red No. 2 14.1 parts by mass (pure 12.7 parts by mass) and 300 parts by mass of water were placed in a beaker and heated with stirring to a temperature of 80 ° C. A solution obtained by diluting 29.2 parts by mass of polyaluminum chloride 1 into 100 parts by mass of water was dropped into the solution through a dropping pump over about 1 hour. After completion of the dropwise addition, the temperature was set to 90 ° C. and aging treatment was performed for 3 hours. This was brought to room temperature, filtered, washed with water, dried and pulverized to obtain 22.3 parts by mass of a reddish purple powder pigment.
When this pigment was measured with an X-ray diffractometer, it was found that the main peaks had diffraction peaks at diffraction angles (2θ) of 4.41, 5.06, and 6.49 and were crystallized.

Example 6
Edible red No. 40 10.7 parts by mass (pure 9.8 parts by mass) and 300 parts by mass of water were placed in a beaker and heated with stirring to a temperature of 80 ° C. A solution obtained by diluting 19.5 parts by mass of polyaluminum chloride 1 into 100 parts by mass of water was dropped into the solution through a dropping pump over about 1 hour. After completion of the dropping, the temperature was set to 90 ° C. and aging treatment was performed for 3 hours. This was brought to room temperature, filtered, washed with water, dried and pulverized to obtain 15.7 parts by weight of a bluish red powder pigment.
When this pigment is measured with an X-ray diffractometer, it has a diffraction peak at diffraction angles (2θ) of 4.20, 5.11, 6.59, 7.66, and 8.58 as a main peak, and is crystallized. I understand.

Example 7
23.8 parts by mass of 1- (4-sulfophenyl) 3-methyl-5-pyrazolone is added to 300 parts by mass of water, and further 26.7 parts by mass of sodium carbonate is added and dissolved under stirring to obtain a solution. It was.
Separately, 18.7 parts by weight of 2-amino-5-methylbenzenesulfonic acid (4B acid) was added to 300 parts by weight of water, 24.0 parts by weight of 35% hydrochloric acid was added, and the mixture was brought to 0 ° C. with ice. Diazotization was performed by adding 18.9 parts by mass of sodium nitrite. This was stirred for 30 minutes or more and then dropped into the above solution over about 30 minutes to carry out a coupling reaction.
The obtained reaction solution was stirred for 1 hour to complete the reaction, and then 70 parts by mass of sodium chloride was added for salting out. After stirring for 1 hour, yellow crystals were precipitated. This was filtered and dried to obtain 49 parts by mass of 95% pure acid dye.
Next, 10.4 parts by mass of the obtained acidic dye and 300 parts by mass of water were placed in a beaker and heated with stirring to set the temperature at 80 ° C. A solution obtained by diluting 19.5 parts by mass of polyaluminum chloride 1 into 50 parts by mass of water was dropped into the solution through a dropping pump over about 1 hour. After completion of the dropping, the temperature was set to 90 ° C. and aging treatment was performed for 3 hours. This was brought to room temperature, filtered, washed with water, dried and pulverized to obtain 13.7 parts by mass of a bright yellow powder pigment.
When this pigment is measured with an X-ray diffractometer, it has a diffraction peak at diffraction angles (2θ) of 4.86, 6.90, 7.67, 9.47, and 9.80 as main peaks and is crystallized. I understand.

Comparative Example 2
As a comparative example, except that calcium chloride was used instead of polyaluminum chloride 1, an attempt was made to make a lake in the same manner as in Example 7, but it was dissolved and no pigment was obtained.

Example 8
23.8 parts by mass of 1- (4-sulfophenyl) 3-methyl-5-pyrazolone is added to 500 parts by mass of water, and further 26.7 parts by mass of sodium carbonate is added and dissolved under stirring to obtain a solution. It was.
Separately, 20.1 parts by mass of 2-amino-3,5-dimethylbenzenesulfonic acid (xylidinesulfonic acid) was added to 300 parts by mass of water, 24.0 parts by mass of 35% hydrochloric acid was added, and the mixture was brought to 0 ° C. with ice. Thereafter, 18.9 parts by mass of 40% sodium nitrite was added for diazotization. This was stirred for 30 minutes or more and then dropped into the above solution over about 30 minutes to carry out a coupling reaction.
The obtained reaction solution was stirred for 1 hour to complete the reaction, and then 70 parts by mass of sodium chloride was added for salting out. After stirring for 1 hour, yellow crystals were precipitated. This was filtered and dried to obtain 42 parts by mass of 95% pure acid dye.
11.3 parts by mass of the obtained acidic dye and 400 parts by mass of water were placed in a beaker and heated while stirring to adjust the temperature to 80 ° C. A solution obtained by diluting 19.5 parts by mass of polyaluminum chloride 1 into 50 parts by mass of water was dropped into the solution through a dropping pump over about 1 hour. After completion of the dropwise addition, the temperature was set to 90 ° C. and aging treatment was performed for 3 hours. This was brought to room temperature, filtered, washed with water, dried and pulverized to obtain 13.7 parts by mass of a bright yellow powder pigment.
When this pigment is measured with an X-ray diffractometer, it has diffracted peaks at diffraction angles (2θ) of 4.35, 5.28, 6.16, 6.62, 7.52, and 8.92 as crystallization. I understood that it was.

Example 9
18.8 parts by mass of 1-phenyl-3-methyl-5-pyrazolone was added to 500 parts by mass of water, and 40 parts by mass of 25% sodium hydroxide was added and dissolved under stirring to obtain a solution.
Separately, 18.7 parts by mass of 2-amino-5-methylbenzenesulfonic acid was added to 300 parts by mass of water, 24.0 parts by mass of 35% hydrochloric acid was added, and the mixture was brought to 0 ° C. with ice. .9 parts by mass was diazotized. This was stirred for 30 minutes or more and then dropped into the above solution over about 30 minutes to carry out a coupling reaction.
The obtained reaction solution was stirred for 1 hour to complete the reaction, and then 70 parts by mass of sodium chloride was added for salting out. After stirring for 1 hour, yellow crystals were precipitated. This was filtered and dried to obtain 40 parts by mass of a 95% pure yellow acidic dye.
8.6 parts by mass of the obtained acidic dye was added to 800 parts by mass of water, and 4 parts by mass of a 25% aqueous sodium hydroxide solution was added, followed by heating to 80 ° C. with stirring. A solution obtained by diluting 19.7 parts by mass of polyaluminum chloride 1 into 30 parts by mass of water was dropped into the solution through a dropping pump over about 1 hour. After completion of the dropping, the temperature was set to 80 ° C., and an aging treatment was performed for 3 hours. This was brought to room temperature, filtered, washed with water, dried and pulverized to obtain 10.6 parts by mass of a bright yellow powder pigment.
When this pigment was measured with an X-ray diffractometer, it was found that the main peaks had diffraction peaks at diffraction angles (2θ) of 4.50, 6.59, 7.17, and 9.17 and were crystallized.

It is a figure which shows the diffraction X-ray spectrum of the crystal | crystallization of the edible blue No. 2 aluminum lake pigment of this invention. It is a figure which shows the diffraction X-ray spectrum of commercial aluminum lake pigment edible blue No. 2.

Claims (5)

  Crystals of acid lake aluminum lake pigment.   The crystal of an aluminum lake pigment according to claim 1, wherein the acid dye is an edible dye.   The crystal of an aluminum lake pigment according to claim 1, wherein the acid dye is a diazo-coupled acid dye of a 3-methyl-5-pyrazolone compound and an aromatic sulfonic acid amine compound.   The method for producing crystals of an aluminum lake pigment according to any one of claims 1 to 3, wherein the acid dye is laked and crystallized using polyaluminum chloride having 2 or more aluminum atoms.   A coating material or printing marker for food, cosmetics, pharmaceuticals or agrochemicals, mixed with or dispersed in crystals of the aluminum lake pigment according to any one of claims 1 to 3, a stationery, a writing instrument, a printing ink, an inkjet ink, a metal Ink, paint, plastic colorant, color toner, or color filter.

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