JPS601264A - Stable high concentration liquid dispersion of anionic dye - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Anionic dyes are usually commercially available in fine powder form, so
Even after being treated with anti-dust oil, it still tends to generate dust. Handling large quantities of such dusty products causes undesirable environmental pollution and hygiene problems for those who handle these products. Atmospheric dye particles can also cause undesirable bleeds on textiles, reducing their cost.

Furthermore, in order to color textiles or paper, the required dye powder must be allowed to stand, moistened, boiled to form a solution, and filtered to ensure that any insoluble solids are removed. Therefore, such methods of preparing the necessary dye solutions are labor-intensive, time-consuming and energy-consuming, resulting in large expenses for dye manufacturers. In many cases, the solubility of the dye in water is insufficient, especially when the dye solution is allowed to cool before being added to the final dyebath. The limited solubility of many dyes in their normal powder state is such that these Makes the dye unfit for use.

To avoid processing powders and take advantage of liquids, many manufacturers have resorted to the use of organic solvents. The drawbacks of this are high costs, increased burden on wastewater treatment facilities, and in many cases the respective anionic dyes have limited solubility. Ta.

The present invention relates to and is directed to highly concentrated, fluid, stable aqueous dispersion compositions of anionic dyes and methods for their preparation.

Prior literature [e.g. U.S. Pat. No. 4,110.0]
No. 73 Mollet (Mn1let) etc. August 2, 1978
No. 9] discloses the use of anionic dispersant mixtures to obtain stable, flowable dispersions of anionic dyes.

However, in practice higher dye concentrations are desired than can be obtained with many anionic dye and anionic dispersant combinations.

Unfortunately, even higher concentrations and stable aqueous dispersions of anionic dyes can be obtained by using nonionic dispersants, and furthermore, particle sizes of less than 10 microns can be obtained by mixing these. discovered. Nonionic dispersants are
These include ethoxylated ethers, ethoxylated fatty acids, ethoxylated aliphatic alcohols and oils, and alkylene-oxydide block copolymers, which may be used alone or in combination.

The nonionic dispersant used here is preferably a block copolymer of propylene oxide and ethylene oxide, particularly one in which the ethylene oxide component in the polymer is condensed with ethylene glycol, and whose molecular weight is from about 1.000 to about 15,000 is preferred.

To prevent drying out during storage, the stable dispersion may contain from about 5 to about 2 weight percent of a humidity control agent, such as sorbitol, glycerin, ethylene glycol, polyethylene glycol, propylene glycol, or polypropylene glycol. I can do it.

High pressure antifoam agents can be used to control the level of foam. Typically, an effective amount of antifoam agent is about 0.01 to about 2 weight percent. Effective anti-foam agents are
Contains silicone emulsion and 2.4.7.9-tetramethyl-5-decyne-4,7-diol. Some of the propylene oxide-ethylene oxide block copolymers preferred as nonionic dispersants also have antifoaming properties, so when using such propylene oxide-ethylene oxide block copolymers as a dispersant, , other antifoam agents may be used in small amounts or not at all.

Wetting agents are used to control viscosity, dispersion, gauze, and stability, and to improve application to substrates such as fibers and paper.

A typical wetting agent is 2,4.7.9-tetramethyl-5
-decyne-4°7-diol, dioctyl sodium sulfosuccinate, and ethylene oxide-ester condensate, used in amounts of about 0.1 to about 20 percent.

To improve the stability of the dispersed anionic dye, an antisettling agent such as alginate, locust bean powder, or other natural or synthetic cellulose gums may be added in an amount of from about 1 to about 10 percent by weight. It can be used in

To increase solubility in hard water, main lattice agents such as sodium hexametaphosphate, tetrasodium pyrophosphate, or tetrasodium ethylenediaminetetraacetate, and hydrotropic agents such as urea, sodium xylene sulfonate, and sodium alkylnaphthalene sulfonate. can be used. Chelating agents and hydrotropic agents are effective in amounts of about 0.5 to about 5.0 weight percent.

To prevent the growth of mold and decomposition by bacteria ((,6-
Antimicrobial and bactericidal agents such as acetoxy-2,4-dimethyl-m-dioxane and gadolinium pentachlorofel can be added in amounts of about 0.01 to about 20 percent.

In the case of very finely divided or very friable dyestuffs, the dispersant is added to the wet press until a homogeneous dispersion with a particle size of at least less than 10 microns is obtained. A dispersion can be produced by mixing with a cake. For more crystalline dyes,
Mechanical abrasion is necessary to obtain a stable concentrated dispersion. Such dispersions are suitably prepared by wet soaking the wet presscake in suspension with the dispersant in a ball mill, heat mill or sand mill. After cooling until the particle size is at least less than 10 microns, the concentrated dispersion is adjusted to standard concentration by adding water.

These dispersions can be used in automated liquid metering systems and have the advantage of containing little or no organic solvents, resulting in better environmental outcomes after the dye is applied to the fiber. It gives These anionic dye dispersions are very suitable for continuous dyeing processes.

Examples are shown below, but these examples do not limit the present invention.

Example 1 A dye having the following structural formula, 56.0 f/, was mixed with 89.8
fF water, 'lo, 0! i'propylene glyco-J 0.3
2.4.7.9-tetramethyl-5-decyne-4°7-diol, 0.3 L? 6-acetoxy-2゜4
-dimethyl-n]-dioxane, 0.87 formulated silicone emulsifier (DB-I 10A from Dow Corning),
Ethylene oxide/composed of about 20 percent poly(oxypropylene) and 80 percent poly(oxyethylene) with a molecular weight of about 14,000 of 22.4 y.
propylene oxide block copolymer, a copolymer of ethylene oxide and propylene oxide with a similar composition of 5.6!7 and a molecular weight of 8.35Of, and a copolymer of 5.6!7 with a molecular weight of 8.35Of;
Addition of sodium hexametaphosphate to a solution consisting of sodium hexametaphosphate with stirring 1. The resulting suspension was either thoroughly homogenized by continuous stirring or passed through a colloid mill to promote the disintegration of aggregates. . Using a ball mill, the particle size of the dye is 10
The mixture was gently dispersed until it was less than μ. Similar results were obtained using sand, glass sports balls, or a shot mill.

Next, 10' of propylene glycol, 2.8 f of Natural Cam Thickener (Super Clear 11.
0-N), and 9.6L? of water was added.

The dispersion was completely homogenized by stirring (1.) or by passing it through a homogenizer.

The dye dispersion made in this way has a low viscosity (<4
No deterioration occurred during storage for several months at 00CP/20°C). This dispersion is ready for use and is used directly in the preparation of dyebaths and is particularly suitable for direct metering systems applied to large-scale dyeing of polynamide fibers.

Example 2 Dye 51.2 f (i:, 77
．． 11 water, 16.0? of ethylene glycol, 6.37-2
．． 4.7.9-Tetramethyl-5-decyne-4,7-thiol, 0.31% of 6-acetoxy-2,4-dimethyl-1]]-dioxane was added to the solution with stirring to produce The suspension was subsequently stirred or passed through a colloid mill to ensure thorough homogenization.

Molecular weight 14.000 and molecule i 8 used in Example 1
．． 350 ethylene oxide-propylene oxide block copolymer with total addition of 3.81 and 1.3y
1'', and then dispersed in a whole mill until the particle size of the entire dye was less than IOμ.

This liquid dispersion was then mixed with 6.07% ethylene glycol and 64%. Of water was added. The dispersion was then thoroughly homogenized by stirring or passing through a homogenizer. The product obtained by this operation has a low viscosity (1
50CP/20°C) and was stable even after storage for several months.

Example 3 Following the procedure of Example 1, a dye of the formula 40.07 and 82.7! water, 16. Ofi' ethylene glycol 0.3 g 6-acetoxy-2,4-dimethyl-1'l
- dioxane, a 2-ethoxylated lauryl ether with an average of 4I and 221 ethoxy ether units, respectively. Using O'y'e and 15.02 water in place of the ingredients and amounts described in Example 1, a fluid and stable dispersion with good physical properties similar to Example 1 was obtained. Ta.

Example 4 A free-flowing, stable dispersion with physical properties similar to the product of Example 1 was prepared using the following ingredients.

40, Of dye of formula 3.87 of water, 16. (J# ethylene glycol 10
．． 37 2.4.7.9-Tetramethyl-5-decyne-
4,7-thiol, 0.37 6-acetoxy-2,4
-m-dioxane, 0.6 g formulated silicone emulsion D
B-110A, Example 10 Ethylene oxide-propylene oxide block copolymer with a molecular weight of 14,000 4.
Of, and 1, 5.09 water in the procedure of Example I.

Example 5 A fluid, stable dispersion with physical properties similar to the product of Example 1 was obtained using the following ingredients'ftc.

40, (J? dye of the following formula 79.7? water, 16.Of propylene glycol,
0.39 6-acetoxy-2,4-dimethyl-In
-Dioxane, 0.2f! 2.4.7.9-(tetramethyl-5-decyne-4,7-diol, 0.8
7 formulated silicone emulsion DB-], 10A.

2.07 sodium xylene sulfonate, ethylene oxide-propylene oxide 1 having a molecular weight of about 1900 and consisting of about 50 percent poly(oxypropylene) and 50 percent poly(oxyethylene).
Tsuku copolymer 6. and in the operation of Example 1], 5. Of water.

Example 6 Dye 40.0 P having the following structural formula was 8 2.7
P of water, 0.37 of 6-acetoxy-2,4-dimethyl-
m-dioxane, 0.37% 2.4.7.9-tetramethyl-5-decyne-4,7-diol, 0.87% silicone emulsion DB-11OA1 molecular weight 8.350 Example 1 It was added with stirring to a solution consisting of ethylene oxide/propylene oxide block copolymer 6, (Jfl, and the tetrasodium pyrophosphate salt of 6.07), and the resulting suspension was thoroughly homogenized by continued stirring. If available, a colloid mill can be used to promote the disintegration of aggregates; no wetting is necessary.

Next, 4.0! dialkyl ester of polyglycol, ie, Acrytul TT-678 manufactured by Rohm and Haas; and 15. Of water was added.

Next, the dispersion was thoroughly stirred.

The dispersion thus produced was ready for use and exhibited good storage stability and flow properties similar to those prepared by the method of Example 1.

Example 7 Dye 51.02 having the following structural formula was 64.6
r water, 1.7.5y ethylene glycol, 0.3g 2.4.7.9-tetramethyl-5-decyne-4,7-
diol, 0.37 6-acetoxy-2,4-dimethyl-m-dioxane, 0.77 formulated silicone emulsion DB7] 1 OA, 2.8 g polyoxyethylene (
200) monolaurate, 207 polyoxyethylene (20) stearyl ether, 3.5 f natural gum thickener (Super Clear 100N), and 3 1.85' water □ ↓ in the procedure of Example 1. A fluid and stable dispersion having physical properties similar to those of the product of Example 1 was obtained.

Procedural amendment July 20, 1980 Mr. Manabu Shiga, Commissioner of the Patent Office ■ Case description 1982 Patent Application No. 79364 3 Person making the amendment Relationship to the case: Patent applicant name Civer Geigi Akchengesellschaft 4 Agent 5 Subject of amendment (1) “Detailed description of the invention” in the specification
Column 6: Contents of the amendment Attachment (1) [Polyoxyethylene (200) J in page 18, line 6 of the specification is corrected to ``Polyethylene glycol (molecular weight 200) J.''

(2) "20g of polyoxyethylene (20) stearyl ether" on the 7th to 8th lines of the same Lth page is replaced with "20g of polyoxyethylene (20) obtained by adding 20 equivalents of ethylene oxide to stearyl alcohol". ) stearyl ether,” corrected.

Claims (1)

[Scope of Claims] 1. A dye composition comprising an aqueous solution of an anionic dye containing a nonionic dispersant and in which insoluble particles of dye having a diameter of 10 μm or less are dispersed, the composition comprising:
about 40 to about 80 weight percent water and about 15 to about 4
A dye composition consisting essentially of 0 weight percent dye and about 1 to about 25 weight percent dispersant. 2 The dispersant is propylene oxide ethylene oxide floc copolymer, polypropylene-polyethylene glycol polymer, aryl polyoxyethylene ether,
Claim 1, which is a dispersant selected from the group consisting of fatty acid/ethylene oxide condensates, polyoxyethylated aliphatic alcohols, and polyoxyethylated vegetable oils.
Compositions as described in Section. 3 The dispersant has a molecular weight of about 1,000 to about 15,000.
3. The composition according to claim 2, which is a block copolymer of propylene oxide and ethylene oxide, or a mixture of these copolymers. 4. The composition according to claim 3, wherein the ethylene oxide component of the floc copolymer is condensed with ethylene glycol. 5.Furthermore, it contains an effective amount of at least one additive selected from the group consisting of bactericidal agents, antimicrobial agents, humidity regulators, anti-settling agents, wetting agents, chelating agents, hydrotropic agents, and anti-foaming agents. The composition according to claim 1, characterized in that: 6 The effective amount of each additive is in the following weight percentages: Bactericidal agents 0.01 to 1 percent Antimicrobial agents 0.01 to 1 percent Humidity regulators 5 to 30 percent Antisettling agents 0.1 to 10 percent Wetting agent 0.1 to 5 percent Chelating agent 0.5 to 5 percent Hytrotropic agent 0.5 to 5 percent Antifoam agent 0.01 to 2 percent. thing.