JP2537663B2 - Alkali Bull-pigment composition - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a blue pigment used for paints, printing inks, plastics and the like, and an alkali blue pigment composition suitable as a toner for black ink.

(Prior Art) Alkali blue pigment is a highly polar pigment having an amino group or a sulfonic acid group, and during its production, it strongly aggregates in the process of drying and crushing an aqueous slurry, making it difficult to knead in a dispersion medium, As a result, it has been difficult to obtain a pigment having excellent coloring power. Usually, the alkali blue pigment employs a so-called flushing method in which an aqueous slurry of the alkali blue pigment is mixed with an oil-based vehicle and dispersed and mixed with the oil-based vehicle while evaporating water. However, according to this flushing method, the solid content concentration of the pigment is as low as 40% or less because it is already dispersed and mixed in the oil-based color-developing agent, and there is a limit to the selection of the color-developing agent as a dispersion medium for paints and printing inks. Yes,
It also has the drawback that it cannot be used for plastics.
Therefore, an alkali blue pigment having a high effective pigment concentration and applicable to various media is desired. As described above, the alkali blue pigment strongly aggregates in the drying process, and it is difficult to obtain a pigment having excellent coloring power. As a treatment method for the purpose of improving the coloring power of the alkali blue pigment, a method of treating with an alkaline aqueous solution containing an acidic resin in U.S. Pat.No. 3,635,745, a treatment with an anionic dispersant in an alkaline aqueous solution in U.S. Pat.No. 4,032,357. A method of treating with an oily varnish under acidic conditions, a method of treating with an alkaline aqueous solution containing phenols in U.S. Pat.No. 4,189,328, U.S. Pat.
No. 373,662 shows a method of treating an acidic slurry of pigments with a tertiary amine acetate and ammonia, and US Pat. No. 4,456,485 shows a method of treating an acidic slurry of pigments with a long chain alkylamine.

(Problems to be Solved by the Invention) However, the alkali blue pigment obtained by these treatment methods has a drawback that satisfactory performance cannot be obtained in terms of coloring power and dispersibility.

The object of the present invention is an alkali suitable for paints, printing inks, plastics, or as a toner for black ink, which is easy to grind without agglomerating in the manufacturing process, solves the above problems, and can be dispersed in various dispersion media. It is to provide a blue pigment composition.

(Means for Solving the Problems) A sulfated product of a roseaniline derivative, which is a starting material for the alkali blue pigment composition of the present invention (hereinafter referred to as a material)
Is a roseaniline derivative represented by the following general formula [I].

(In the formula, X1, X2, X3, and X4 are hydrogen or 1 to 3 carbon atoms.
Alkyl groups, R1 and R2 are hydrogen or a phenyl group or an alkyl group-substituted phenyl group having 1 to 3 carbon atoms) Phospholipids used in the present invention, egg yolk or soybean oil, rapeseed oil, linseed oil Phosphatidylcholine, phosphatidylethanolamine (ethanol / kephalin), phosphatidylserine, obtained from vegetable oils and fats such as
It refers to complex lipids such as phosphatidylinositol, phosphatidylic acid, lysolecithin, and lysokephalin.

Then, the phospholipid is added in the range of 0.5 to 40 parts by weight to 100 parts by weight of the raw material and treated. The amount of phospholipid is 0.
If it is less than 5 parts by weight, no effect is obtained, and if it exceeds 40 parts by weight, it is diluted with a treating agent, a high-concentration pigment composition cannot be obtained, and the coloring power is insufficient.

When the raw material is dissolved in an aqueous alkali solution, the alkali may be an inorganic alkali such as sodium hydroxide, potassium hydroxide, lithium hydroxide, or any of an organic amine and ammonia.

Further, the acid used for the acid treatment may be an inorganic acid such as hydrochloric acid, sulfuric acid or phosphoric acid, or an organic acid such as acetic acid or citric acid.

In the practice of the present invention, an alkaline aqueous solution is added to an aqueous slurry of a raw material, and the mixture is heated to 50 to 100 ° C, preferably 90 to 100 ° C and stirred, and the raw material exhibits a brown color and is dissolved. Phospholipid is added to this solution in the range of 0.5 to 40 parts by weight with respect to 100 parts by weight of the solid content of the raw material, and the mixture is heated to 15 to 100 ° C and stirred. After that, an inorganic or organic acid is added to this solution to adjust the pH to an acidic side, preferably to pH 4 or less, 40 to 80 ° C, preferably 50 to 70 ° C.
A precipitate is formed when heated and stirred. This acidic slurry is heated at 90 to 100 ° C for 15 minutes or more, the formed precipitate is filtered, washed with water, the residue is dried at 100 ° C or less, and can be applied to various dispersion media by pulverization, and the coloring power can be obtained. An excellent alkali blue pigment composition can be obtained.

As described above, the material to be one component of the pigment composition such as phospholipids in the aqueous slurry of the raw material is added, mixed, heated or cooled, the pH is adjusted, a precipitate is formed, and filtered, A commonly used process for producing a pigment or a pigment composition, such as washing with water, drying, and crushing, is called a treatment.

In addition to the above-mentioned phospholipid treatment, a petroleum solvent is further added for treatment, whereby an alkali blue pigment composition which can be easily dispersed in a dispersion medium can be obtained. The petroleum solvent refers to solvents produced from each fraction in a petroleum refining process, which is a mixture of various hydrocarbons such as aliphatic, naphthenic, and aromatic.

That is, the treatment of the raw material with the petroleum solvent used in the present invention alone does not produce the effect of easy dispersibility, but when used in combination with the phospholipid treatment, the alkali blue pigment composition having excellent easy dispersibility can be obtained. Addition of less than 1 part by weight of this solvent to 100 parts by weight of the solid content of the raw material has no effect, and if treated in an amount of more than 50 parts by weight, it becomes tacky after drying and becomes difficult to pulverize. If the boiling point is less than 140 ° C, the solvent may scatter during drying, which is not preferable in production.

To obtain an easily dispersible alkali blue pigment composition, first add an aqueous alkali solution to the aqueous slurry of the raw material, and then add 50 to 100
When heated to and stirred at 90 ° C, preferably 90 to 100 ° C, the raw material turns brown and dissolves. Add phospholipids to this solution as raw material solids
Add 0.5 parts by weight or more and 40 parts by weight or less to 100 parts by weight, heat to 15 to 100 ° C., and stir. After that, add an inorganic or organic acid to this solution to adjust the pH to the acidic side, preferably pH.
To 4 or less and heated to 40 to 80 ° C., preferably 50 to 70 ° C., with stirring, the boiling point is 140 ° C. or higher. Parts or less and the total weight part with the phospholipid is 60 or less. This slurry is heated at 90 to 100 ° C for 15 minutes or longer, treated coprecipitate is filtered and washed with water, and the residue is dried at 100 ° C or less and crushed to easily prepare various dispersion media. It is possible to produce an alkali blue pigment composition that can be dispersed in

The treatment method with a phospholipid and a petroleum-based solvent is not particularly limited to a method of treating the phospholipid in an alkaline aqueous solution and then with a petroleum-based solvent under acidic conditions. As long as it is treated with the above method, either a method of treating both in an alkaline aqueous solution of the raw material or a method of treating both in an acidic slurry of the raw material may be used.

(Example) An example is shown below. In Examples, "parts" means "parts by weight". Although lecithin is a typical phospholipid, the present invention was carried out using soybean lecithin in Examples 1 and below.

Example 1 To an aqueous slurry containing 40 parts of raw materials, an alkaline aqueous solution prepared by dissolving 15 parts of sodium hydroxide in 120 parts of water was added, and heated to 100 ° C. with stirring to dissolve. The raw material becomes a brown aqueous solution. 0.2 parts by weight of soybean lecithin is added to this alkaline solution and stirred. Cold water is added to cool to 70 ° C., and this solution is added to 600 parts of a 1.7% hydrochloric acid aqueous solution at 70 ° C. to precipitate the pigment as an acidic slurry. 1 at 90-100 ° C with stirring
After heating for 5 minutes, water was added, the mixture was cooled to 50 ° C or lower, and the precipitate was filtered. The precipitate was washed with warm water of 50 ° C. until the pH of the washing water became 5 or more, the water-containing paste was dried at 80 ° C. or less, and pulverized with a sample mill. This gives a solid content of 10
A finely powdered alkaline blue pigment composition was obtained which was treated by adding soy lecithin in an amount of 0.5 part by weight to 0 part by weight.

In Examples 2 to 7, the present invention was carried out by changing the addition weight part of soybean lecithin to 100 weight parts of the raw material, and the addition weight part is shown in Table 1 together with the above-mentioned Example 1.

Next, as Comparative Example 1, the same treatment as in Example 1 was carried out without adding soybean lecithin to the aqueous slurry of the raw material to obtain a reference pigment serving as a reference point for evaluating the coloring power. As Comparative Example 2, soybean lecithin was used as the raw material solid content. The same treatment method as in Example 1 was carried out by adding 0.3 parts by weight to 100 parts by weight. Further, as Comparative Example 3, 50 parts by weight of soybean lecithin was added and treated in the same manner. The added amount is shown in Table 2.

40 parts of the alkali blue pigment compositions obtained in Examples 1 to 7 and Comparative Examples 1 to 3 and 60 parts of heat-polymerized squid oil varnish were kneaded 3 times with a three-roll to form a raw material paste, and the coloring power was obtained. In comparison with the reference pigment of Comparative Example 1, those that obtain a + value were evaluated as effective. However, the evaluation method was as follows.

1 part of the pigment paste of Example and 50 parts of sheet-fed offset white ink were kneaded well, and the mixing amount of the white ink required to obtain the same concentration as that of the reference pigment paste of Comparative Example 1 was obtained. The increase or decrease rate of the mixed amount of was calculated. The above evaluation values are shown in Tables 1 and 2. The evaluation values of the coloring power in Tables 1 and 2 indicate the increase or decrease ratio of the white ink, and the + value indicates the improvement of the coloring power.

From Table 1, the amount of soybean lecithin added is 0.5 parts by weight or more 40
When the amount is less than or equal to parts by weight, the evaluation value of the coloring power increases, and from Table 2, when the addition amount is less than 0.5 parts by weight or exceeds 40 parts by weight, the evaluation value of the coloring power is lower than that of the reference pigment. To be

As described above, soybean lecithin was added to the raw material solid content of 100 parts by weight in the range of 0.5 to 40 parts by weight, and treated to form fine powder close to primary particles, and an alkali having excellent coloring power. A blue pigment composition can be obtained.

Next, a petroleum solvent is used to obtain an alkali blue pigment composition that can be easily dispersed in various dispersion media.
15 will be described.

First, as Example 8, to an aqueous slurry containing 40 parts by weight of a raw material, an alkaline aqueous solution prepared by dissolving 15 parts of sodium hydroxide in 120 parts of water is added and heated to 100 ° C. with stirring to dissolve. The raw material becomes a brown aqueous solution. 0.2 parts by weight of soybean lecithin is added to this alkaline solution and stirred. Add cold water and cool to 70 ° C.
In addition to 00 parts, an acidic slurry is prepared to precipitate the pigment. Naphthesol L (Nippon Oil Co., Ltd., boiling point of petroleum solvent)
188 ° C), 0.4 part by weight, and heated to 90-100 ° C with stirring. Water was added, the mixture was cooled to 50 ° C. or lower, and the precipitate was filtered. The precipitate was washed with warm water of 50 ° C. until the pH of the washing water became 5 or more, the water-containing paste was dried at 80 ° C. or less, and pulverized with a sample mill. As a result, an easily dispersible finely divided alkali blue pigment composition was obtained which was treated with 0.5 part by weight of soybean lecithin and 1 part by weight of petroleum solvent relative to 100 parts by weight of the solid content of the raw material. Examples 9 to 15 are examples in which the addition amount of soybean lecithin and naphthezol L in Example 8 was changed, or xylene, K-solvent or 300 solvent was used instead of naphthezol L.
This addition amount is shown in Table 3 together with the addition amount of Example 8.

Next, as Comparative Example 4, the same treatment as in Example 8 was performed without adding soybean lecithin or a petroleum solvent to obtain a reference pigment serving as an evaluation reference product of dispersibility.
5 parts by weight of xylene, 0.3 parts by weight of soybean lecithin as Comparative Example 6, 1 part by weight of naphthezol L as a solvent, 0.5 parts by weight of soybean lecithin as Comparative Example 7 and 0.8 parts by weight of naphthezol L as a solvent, relative to 100 parts by weight. 15 parts by weight of soybean lecithin as a comparative example, 50 parts by weight of 300 sorbet as a solvent, and 40% of soybean lecithin as a comparative example 9.
Then, the same treatment as in Example 8 was carried out by adding 25 parts by weight of 300 solvent as a solvent.

 Table 4 shows the addition amounts of Comparative Examples 4 to 9.

The dispersibility of the alkali blue pigment compositions obtained in Examples 8 to 15 and Comparative Examples 4 to 9 was evaluated. The test method was that 1 part of the pigment composition and 150 parts of sheet-fed offset white ink were accurately weighed and rotated at 150 pounds for 50 times using a Hoover Mahler, and the color density of the ink was changed to the pigment of Comparative Example 4. Based on the dispersion evaluation value of the composition,
For each pigment composition, the increase or decrease ratio of the amount of white ink mixed was obtained, and those having different evaluation values of +10 or more were determined to be effective for dispersibility. The evaluation value above is the third
It shows in Table and Table 4. In this table, the petroleum-based solvent is manufactured by Nippon Oil Co., Ltd., and the boiling points are 290 ° C. for 300 solvent, 188 ° C. for naphthezol L, 163 ° C. for K-solvent, and 140 ° for xylene.
° C.

From Table 3, phospholipids are added to 100 parts by weight of the solid content of raw materials.
0.5 parts by weight or more and 40 parts by weight or less, and a petroleum solvent having a boiling point of 140 ° C. or more is added in an amount of 1 part by weight or more and 50 parts by weight or less and the total weight part of the phospholipid and the petroleum solvent is 60 or less. It can be seen that the alkali blue pigment composition which can be easily dispersed in the dispersion medium is obtained by treating the raw material in this way. Further, from Table 4, dispersibility is not improved by treatment with only petroleum solvent, and even if phospholipid and petroleum solvent are used, the solid content of the raw material is 10%.
It can be seen that the dispersibility deteriorates when the total weight of both is more than 60 parts by weight, the phospholipid is less than 0.5 parts by weight, and the petroleum solvent is less than 1 part by weight with respect to 0 part by weight.

(Effect of the Invention) As described above, by treating the sulfated product of the rose aniline derivative with a specific amount of phospholipid, it is possible to prevent aggregation between pigment particles and obtain an alkali blue pigment composition having excellent coloring power. Further, by the combined treatment of the phospholipid and the petroleum solvent, it is possible to obtain an alkali blue pigment composition which prevents aggregation between pigment particles and can be easily dispersed in a dispersion medium.

Claims (4)

(57) [Claims] 1. A general formula (In the formula, X1, X2, X3, and X4 are hydrogen or 1 to 3 carbon atoms.
Is an alkyl group, and R1 and R2 are hydrogen or a phenyl group or a phenyl group substituted with an alkyl group having 1 to 3 carbon atoms). A method for producing an alkali blue pigment composition having excellent coloring power, which comprises adding and treating phospholipids at a ratio in the range of 40 to 40 parts by weight. 2. An alkali blue pigment composition having excellent tinting strength produced by the method according to claim 1. 3. General formula (In the formula, X1, X2, X3, and X4 are hydrogen or 1 to 3 carbon atoms.
Is an alkyl group, and R1 and R2 are hydrogen or a phenyl group or a phenyl group substituted with an alkyl group having 1 to 3 carbon atoms). Phospholipids are added at a ratio in the range of 1 to 40 parts by weight, and further treated in the range of 1 to 50 parts by weight, and the total weight part with the phospholipids is 1.
A method for producing a readily dispersible alkali blue pigment composition, which comprises adding a petroleum solvent having a boiling point of 140 ° C. or more at a ratio of 5 or more and 60 or less and treating the composition. 4. An easily dispersible alkali blue pigment composition produced by the method according to claim 3.