JPS6035950B2 - Method for solubilizing dyes in hydrocarbon solvents - Google Patents

Description

Detailed Description of the Invention The present invention uses n-hexane, diethylbenzene, isopropylbenzeso, p-cymene, tetralin, chlorotoluene, ligroin, xylene, styrene, Solvesso-10
0 and 150 (Esso Chemical Co. product), DOSB (Shell Chemical Co. product), ASL-100 (Kureha Chemical Co. product),
This invention relates to a method for solubilizing dyes in hydrocarbon solvents such as tri- and tetramethylbenzene.

More specifically, the general formula of the present invention {wherein R,, R2 represents an alkyl group having 1 to 19 carbon atoms and a hydroxyalkyl group (these alkyl groups may be unsaturated alkyl groups), and R3 represents a lower alkyl group, R4 represents a lower alkyl group, hydroxyalkyl group, or benzyl group, and R5 represents a saturated or unsaturated alkyl group having 8 to 18 carbon atoms.

} using a higher fatty acid salt of a long-chain alkyl or hydroxy long-chain alkylamine as a solubilizer,
The present invention relates to a method for solubilizing a 2:1 type metal rust salt dye or steel phthalocyanine dye in a hydrocarbon solvent. Up to now, as solvent-soluble dyes, 2:1 type metal key salt dyes are treated with aliphatic amines, alicyclic amines, or heterocyclic amines (Japanese Patent Publication No. 41-12915, specification). , Samuraiko No. 6397, 1973), and those treated with aliphatic quaternary ammonium salts (Japanese Patent Application Laid-open No. 1973-
No. 8316 Specification), and as steel phthalocyanine dyes, copper phthalocyanine dyes having sulfonic acid groups have been salt-formed with alkyl amines (Pomelo Fast Blue HFL, BASF product, Dye Handbook, New Edition, 865).
Page, Organic Synthetic Chemistry Association Green) or those treated with salt formation with alkoxyalkyl amines (Specification of Japanese Patent Publication No. 44-3218), and acid dyes treated with salt formation with alicyclic amines (Pomelo Fast Yellow CGG, BASF Company products such as Dye Handbook (840 pages, Organic Synthetic Chemistry Association line) are publicly known.

However, all of these dyes are soluble in polar organic solvents such as ethanol, acetone, methyl cellosolve, methyl ethyl ketone, ethylene glycol, ethyl acetate, and n-butanol, and are soluble in benzene, toluene, xylene, styrene, cymene, and naphthalene. , Tetralin, Sorbetso 100. It hardly dissolves in hydrocarbon solvents such as DOSB, and even if it does dissolve, the amount is very small. In contrast, the present inventors
As a result of various studies on metal salt dyes soluble in hydrocarbon solvents, it was found that by simply physically mixing with a higher fatty acid salt of the longest chain alkyl or hydroxy long chain alkylamine represented by the general formula {1}. , these dyes include n-hexane, tetralin, ligroin, xylene, sorbetso-100 and 150, DOSB, ASL-1
They found that hydrocarbon solvents such as 00 had better solubility than expected, and completed the present invention.

The present inventors have already applied for patents in Japanese Patent Application No. 48-60325 and Japanese Patent Application No. 48-44223 for a method for producing a 2:1 type metal tin salt dye that is soluble in hydrocarbon solvents. All of these methods are characterized in that a sodium salt, potassium salt, or ammonium salt of a 2:1 type metal tin salt dye is subjected to salt formation treatment with a fatty acid salt of an N-alkyl-substituted alkylene dizamine. In addition, as a method for solubilizing 2:1 type metal dyes in hydrocarbon solvents,
We are currently applying for a patent No. 5, which is a method of mixing an aliphatic ammonium salt or alicyclic ammonium salt of a 2:1 type metal mirror salt dye with a fatty acid salt of an N-alkyl-substituted alkylene dizamine. . Furthermore, a patent application was filed in 1973 for a method for producing copper phthalocyanine dyes soluble in hydrocarbon solvents.
-59698 patent is pending, which relates to salt formation treatment of sodium salt, potassium salt, and ammonium salt of copper phthalocyanine sulfonic acid with fatty acid salt of N-alkyl substituted alkylene dizamine. In addition, a patent is pending in Tokubuta No. 501-48653 for a method of solubilizing copper phthalocyanine dyes in hydrocarbon solvents, which describes the method of solubilizing copper phthalocyanine dyes in N- The present invention relates to a method of mixing an alkyl-substituted alkylene diamine with a fatty acid salt. In contrast, the method of the present invention uses the general formula (
A higher fatty acid salt of the longest chain alkyl or hydroxy long chain alkylamine represented by 1) and a 2:1 type metal rust salt dye or steel phthalocyanine dye (hereinafter simply referred to as dye) are simply mixed in a hydrocarbon solvent. By mixing, the dye can be easily solubilized in a hydrocarbon solvent.

That is, in the method of the present invention, a dye is dispersed in a hydrocarbon solvent such as xylene, n-hexane, diethylbenzene, tetralin, styrene, SORBETSO-15 DOSB, ASL-100, etc., and the dye is dispersed at room temperature while stirring to obtain the general formula {
The higher fatty acid salt of a long-chain alkyl or hydroxy long-chain alkylamine represented by 1} can be easily solubilized in the above solvent by adding at least 50% or more, preferably 100 to 150% or more of the amount of the dye used. .

In this case, the higher fatty acid salt of the longest chain alkyl or hydroxy long chain alkylamine is dissolved in the hydrocarbon solvent, but the completely dissolved solution may be used as it is as a concentrated dye solution; The used solvent may be recovered and used in the form of a paste. The higher fatty acid salts of various long-chain alkyl or hydroxy long-chain alkyl amines used in the method of the present invention have the following general formula (wherein,
, e3 represent a halogen atom and R, , R2, R3 and R4 are as defined above.

) is dissolved in water or aqueous alcohol, and the following general formula R5-COOX2{8) (wherein, X2 represents hydrogen and sodium atoms, R
5 is as defined previously.

A higher fatty acid or a higher fatty acid salt represented by the general formula (wherein R,, R2, R3, R4 and R5 are as defined above) is precipitated by adding a higher fatty acid or a higher fatty acid salt.

) is separated, washed with water, and dried.

Next, the dye is dispersed in a hydrocarbon solvent, a fatty acid salt of a long-chain alkyl or hydroxy long-chain alkylamine represented by the general formula m is added, and the mixture is stirred at room temperature to easily dissolve the dye.

Suitable examples of the quaternary ammonium alkyl or hydroxyalkylamine represented by the general formula (2) include the following.

Further, preferable higher fatty acids or higher fatty acid salts represented by the general formula {31 are, for example, CI7day35CO
OH C 18 days 37 COOH C, 7 days 35 COONa C 8 days 17 COO days CI rainbow 29 COO days C, 7 days 33 COONa C, 4 days 29 COONa C, 2 days 23 COONa and C, 8 days 37 COONa.

Furthermore, among the preferred dyes used in the method of the invention, two
: Type 1 metal lead salt dyes include, for example, C.I. 1. Acid Yellow 99 (Neoline Yellow GR, CIBA product), C. 1. Solvent Yellow 19 (Pomelo Fast Yellow GR, BASF product) C. 1. Acid Red 183 (Neolan Red GRE, CIB company product),
C. 1. Solvent Red 83 (Eisenspiron Red BEH, Hodogaya Chemical Co., Ltd. product), C.I. 1. Solvent Black 22 (Eisen Black BH, Hoya Kagakusha product), C.I. 1. Solvent Black 23 (Eisenspiron Black GSH Special, Hodogaya Chemical Co., Ltd. product), C
．． 1. Acid Blue 161 (Eisen Opal Black BH, Hodogaya Chemical Products) Among suitable dyes, copper phthalocyanine dyes include, for example, C.I. 1. Direct Flu-86 (Mitsui Acid Milling Turkey Flu 30, Mitsui Chemicals product), C.I. 1. Solvent Plue 2
5 (Pomelo Fast Blue HFL, BASF product). The forms that are soluble in hydrocarbon solvents obtained by the method of the present invention are dye solutions in solubilizing solvents and pastes obtained by recovering solubilizing solvents, and these pastes may be mixed with solvents depending on the purpose. It is also possible to make a liquid product with an appropriate concentration by adding .

This is due to the drawbacks of conventional solvent-soluble dyes, which are generally used in the form of powders or flakes, which have slow dissolution rates, are difficult to handle, and are only slightly soluble in hydrocarbon solvents. This means that the disadvantages of requiring extra equipment for dissolving the dye can be solved. Furthermore, one of the major features of the method of the present invention is that by simply mixing the dye with a higher fatty acid salt of a long-chain alkyl or hydroxy long-chain alkylamine, it becomes soluble in a hydrocarbon solvent, which is a non-polar solvent. This is very advantageous from an industrial standpoint.

Another major feature is that it has greater solubility than existing oil-soluble dyes. The dye solution of the solubilizing solvent obtained by the present invention and the paste obtained by recovering the solubilizing solvent can be used in a wide range of fields due to their chemical and physical properties, such as for various inks and lacquers. It has a wide range of uses, including as an excellent coloring agent for wood, oils, natural and synthetic waxes, synthetic resins, etc., and as a color modifier for gasoline, lubricating oils, and other petroleum products.

EXAMPLES The present invention will be explained in detail with reference to examples below, but the present invention is not limited to the following examples.

Unless otherwise specified, parts and percentages in the text mean parts by weight and percentages by weight. Example 1 7.5 parts of a dye represented by the following structural formula (Eisenspiron Black BH, a product of Hodogaya Chemical Co., Ltd.) was dispersed in 10 parts of trimethylbenzene, and while stirring, hydroxyl represented by the following structural formula was dispersed into the dye. 5 parts of a higher fatty acid salt of a long-chain alkylamine were added and stirred for 1 hour at 25-30°C to completely dissolve the dye, yielding 112.5 parts of a uniform black solution.

This solution has a wide range of uses, including various writing inks, inkjet inks, and various resin colorants. When used in these applications, the printed or colored matter will have a high density, clear hue, and light resistance. The temperature was extremely good. On the other hand, in the case of the dye that was not subjected to this mixing treatment, the dispersion was nonuniform and did not fall into the solvent. Example 2 8 parts of a dye represented by the following structural formula were dispersed in 10 parts of Sol-Besso-150 (product of Esso Chemical Co., Ltd.), and while stirring, a hydroxy long-chain alkylamine represented by the following structural formula was dispersed into this mixture. 5 parts of a higher fatty acid salt were added and stirred at 50 to 6,000 for 1 hour to completely dissolve the dye and obtain 113 parts of a black homogeneous solution.

This solution has a wide range of uses, including various writing inks, inkjet inks, and colorants for various resins. When used in these applications, the printed or colored materials will have a high density, clear hue, and light resistance. The fastness was extremely good. On the other hand, in the case of the dye without this treatment, the dispersion was non-uniform and did not fall into the solvent. Example 3: A dye represented by the following structural formula, 1 Ikarito, was dispersed in 120 parts of tetralin,
While stirring, 4 parts of a higher fatty acid salt of the highest chain alkylamine represented by the following structural formula was added to the mixture, and the mixture was stirred at room temperature for 2 hours to completely dissolve the dye, yielding 134 parts of a red homogeneous solution.

This solution has a wide range of uses, including various writing inks, inkjet inks, and various resin colorants. When used in these applications, the printed or colored matter will have a high density, clear hue, and light resistance. The temperature was extremely good.

On the other hand, in the case of the above dyes that do not undergo this mixing treatment,
The dispersion was insoluble and non-uniform in the solvent. Example 4 One part of the dye represented by the following structural formula was dispersed in a mixed solvent of five parts of tetramethylbenzene and six parts of ○-chlorotene, and while stirring, a higher class of long mirror alkylamine represented by the following structural formula was dispersed. 5 parts of fatty acid salt were added and stirred at room temperature for 1 hour to completely dissolve the dye, yielding 125 parts of a yellow homogeneous solution.

This solution has a wide range of uses, including various writing inks, inkjet inks, and various resin colorants. When used in these applications, the printed or colored matter will have a high density, clear hue, and light resistance. The temperature was extremely good.

On the other hand, in the case of the above dyes that do not undergo this mixing treatment,
The dispersion was insoluble and non-uniform in the solvent. Example 5 7 parts of a dye represented by the following structural formula were dispersed in 1 volume of Solvesso-150 (product of Esso Chemical Co., Ltd.), and while stirring, 3 parts of a higher fatty acid salt of a long-chain alkylamine represented by the following structural formula were dispersed into the solution. 0.5 parts were added and stirred at room temperature for 1 hour to completely dissolve the dye, yielding 120.5 parts of a dark brown homogeneous solution.

This solution has a wide range of uses, including various writing inks, inkjet inks, and various resin colorants. When used in these applications, the printed or colored matter will have a high density, clear hue, and light resistance. The temperature was extremely good. On the other hand, in the case of the dye that was not subjected to this mixing treatment, the dispersion was insoluble and non-uniform in the solvent. Example 6 Dye 1, represented by the following structural formula, was dispersed in 130 parts of triethylbenzene, and while stirring, 6 parts of a higher fatty acid salt of a long-chain alkylamine represented by the following structural formula was added, and 25 to
The dye was stirred for 2 hours at 300° C. to completely dissolve the dye, and 146 parts of a red homogeneous solution was obtained.

This solution has a wide range of uses, including various writing inks, inkjet inks, and various resin colorants. When used in these applications, the printed or colored matter will have a high density, clear hue, and light resistance. The temperature was extremely good. On the other hand, when the dye was not subjected to this mixing treatment, it was insoluble in the solvent and was a non-uniform dispersion. Example 7 9 parts of a dye represented by the following structural formula (C rudder C na (S03H)2) were dispersed in 100 parts of isopropylbenzene, and while stirring, a higher fatty acid salt of a hydroxy long-chain alkylamine represented by the following structural formula was added. Add 4 parts and stir at room temperature for 1 hour to completely dissolve the dye.
A uniform blue solution was obtained.

This solution has a wide range of uses, including various writing inks, inkjet inks, and various resin colorants. When used in these applications, the printed or colored matter will have a high density, clear hue, and light resistance. The temperature was extremely good. On the other hand, in the case of the dye that was not subjected to this mixing treatment, the dispersion was insoluble and non-uniform in the solvent. Various homogeneous solutions were obtained in the same manner as in Example 1 using the dyes shown in the following table.

Claims (1)

[Claims] 1 The following general formula ▲ There are numerical formulas, chemical formulas, tables, etc. ▼ {In the formula, R_1 and R_2 are alkyl groups and hydroxyalkyl groups having 1 to 19 carbon atoms (these alkyl groups are unsaturated and ), R_3 represents a lower alkyl group, R_4 represents a lower alkyl group, hydroxyalkyl group, or benzyl group, and R_5 represents a carbon number of 8
represents a saturated or unsaturated alkyl group from up to 18. } Solubilization of a 2:1 type metal complex dye or copper phthalocyanine dye in a hydrocarbon solvent, characterized by using a higher fatty acid salt of a long-chain alkyl or hydroxy long-chain alkylamine represented by } as a solubilizer. Method.