DE3710849A1 - USE OF LAYERED SILICATES LOADED WITH QUARTAINE AMMONIUM COMPOUNDS AS SOAP AIDS IN SOAP PROCESSES FOR FIXING DYES - Google Patents

Abstract

Natural bentonite-type swelling lamellar silicates and synthetic lamellar silicates with a smectic-like crystalline phase but with large contents bound alkalies and silicates and a swelling capacity in aqueous suspension considerably lower than that of pure lamellar silicates of this type can be used as saponifying agents for dyes and prints on textile materials after charging with 1 to 50 % of their weight of quaternary ammonium compounds.

Description

The present invention relates to the use of soap additives containing quaternary ammonium compounds (QAV) contain layered silicates, especially for removing dyes from aqueous Systems.

In practice, washing processes after dyeing and Printing on fabrics generally as soaps or after-soaps designated.

The aim of re-soaping dyeings and prints is Achieving good fastness and an optimal product appearance. The soap processes are used to avoid unwanted Remove substances from textile surfaces (K. Schumann et al, Deutscher Färberkalender, 1979, pages 246 to 257).

US Pat. No. 4,292,035 relates to plasticizer compositions to soften the laundry during the washing process, which is a combination of an anionic surfactant Substance and a complex of different Smectites with various organic amines, their salts and various quaternary compounds consists. Such compositions have properties  of fabric softeners, which accordingly Laundry after-treatment agent when rinsing the laundry or added directly to detergents during washing can be.

DE-OS 29 10 583 (additional application to DE-OS 28 17 427) describes the use of finely divided, water-insoluble Alkaline aluminum silicates as soap aids for dyeing and printing on textile material and in particular for the treatment of dyeings and prints with naphthol dyes, reactive dyes and dis persion dyes on cellulose and synthetic fiber material.

The present invention is based on the object Soap aids based on layered silicates To provide the improved color fastness of textiles and improved dye absorption capacity compared to known soap aids.

It has now surprisingly been found that with QAV layered silicates loaded with a large amount of dyes can bind and thus eliminate from the wash liquor. Loaded synthetic ones are particularly suitable Layered silicates.

The present invention relates to the use of quaternary ammonium compounds natural and / or preferably synthetically produced Layered silicates as soap aids in soaping processes for fixing dyes, the Layered silicates with 1 to 50% of their weight at least one or mixtures of water soluble  or water-dispersible quaternary dialkyl-di alkylammonium and / or monoalkyl trialkylammonium compounds of the general formulas

are loaded and

R₁ for a straight chain and / or branched chain saturated 8 to 20 carbon atoms, R₂ for an alkyl having 1 to 4 carbon atoms and / or hydroxyalkyl radical and X represents bromine and chlorine and in the event that R₂ represents a methyl radical, optionally also stands for a sulfate residue.

A preferred embodiment of the present invention consists in the fact that bentonite is used as layered silicate and / or a synthetic hectorite is used.

An embodiment of the present invention exists in that the alkyl ammonium compounds are selected are made from distearyldimethyl, lauryltrimethyl, Ditalgalkyldimethyl-, cocoalkyltrimethyl- and cetyltrimethylammonium chloride group.

Soap aids according to the invention can either can be used alone in the soaping process mentioned or, according to a preferred embodiment, as Additive, for example in a pre-cleaning agent for rayon wool and synthetic fibers on the basis of non-surfactant and anionic additives in one  Amount of 5 to 95 wt .-%, based on the weight of the Pre-cleaning agents are added.

In the event that the soap aids according to the invention used in conjunction with a pre-cleaning agent it is preferred to use an aqueous solution or dispersion with a total amount of pre-cleaning agent and with quaternary ammonium compounds loaded layered silicates from 0.02 to 0.5% by weight to manufacture.

From the concept of layered silicates in the sense of the present Invention becomes naturally occurring sound that is swellable in water and has a high ion exchange capacity has included. Examples of such swellable Clays with an ion exchange capacity of at least 50 milliequivalents / 100 g are volchonskoit, Nontronite, sauconite and in particular montmorillonite, Hectorite and saponite. It also includes synthetic finely divided, water-insoluble layered silicates with smectite-like crystal phase, but increased Contained in bound alkali and silicate and one in Compared to pure layered silicates of this type reduced swelling capacity in aqueous suspension with the oxide sum formula

MgO · a M₂O · Al₂O₃ · b · c n H₂O SiO₂,

wherein
M stands for sodium, optionally together with lithium, with the proviso that the molar ratio Na / Li is at least 2 and in which further
a , b , c and n each have a number in the ranges
a = 0.05 to 0.4;
b = 0 to 0.3;
c = 1.2 to 2.0;
n = 0.3 to 3.0
mean and n stands for the water bound in the crystal phase. Synthetic layered silicates in which the parameters a , b and c are in the following ranges are preferred:
a = 0.15 to 0.30;
b = 0 to 0.10;
c = 1.3 to 1.5
wherein the ratio a / b is preferably equal to or greater than 3.

Are suitable according to the invention, synthetic phyllosilicates that after suspension in water (16 ° dH, room temperature) a swelling power - thorough washing determined as the quotient of the sediment volume (V _s) / total volume (V) after previous treatment with excess soda solution, and 20 hours after slurrying in 9 parts by weight of water / one part by weight of layered silicate - of V _s / V less than 0.6, especially less than 0.4. Suitable synthetic layered silicates are of mixed-crystalline design and have structure-determining saponite and / or hectorite-like crystal phases, which are interspersed in an irregular arrangement with crystalline alkali polysilicate, the mixed crystal systems of the structural formula

[Na _{x + y} (Mg _{3- x} Li _x ) (Si _{4- y} Al _y ) O₁₀ (OH) ₂] · m [Na₂Si _z O _{2 z + 1} ] · n H₂O

correspond to what applies

Such synthetic layered silicates contain excess not integrated into the crystal structure Alkali, especially sodium hydroxide or soda, and / or are in intimate mixture with in particular water-soluble salts, preferably alkali sulfates and / or carbonates. The layered silicates mentioned and their manufacture are in the earlier patent application EP 86 / 109717.8. On this patent application is hereby expressly referred to. The use of with quaternary ammonium compounds loaded with synthetic layered silicates smectite-like crystal phase and significantly reduced Swelling power is preferred.

The layered silicates are loaded according to the in methods known in the art, such as in Column 13 of U.S. Patent 4,292,035.

Example 1

1 g / l pre-cleaning agent for rayon cellulose and synthetic fibers based on ethoxylated fatty alcohol condensation products with anion-active additives with the addition of 1 g / l of bentonite Bentone ^R 34, NL Industries, which is modified with a quaternary ammonium compound.

Example 2

1 g / l pre-cleaning agent for rayon cellulose and synthetic fibers based on ethoxylated fatty alcohol condensation products with anion-active additives with the addition of 1 g / l of a synthetic hectorite (Laponite ^R RD), loaded with 20 wt .-% lauryl trimethylammonium chloride.

Comparative Example 1

1 g / l pre-cleaning agent for rayon wool and syn thesis fibers based on ethoxylated fatty alcohol Condensation products with anion-active additives without additives.

Comparative Example 2

1 g / l pre-cleaning agent for rayon wool and syn thesis fibers based on ethoxylated fatty alcohol Condensation products with anion-active additives with the addition of zeolite A (Sasil).

Soap aids according to Examples 1 and 2 and in accordance with Comparative Examples 1 and 2 were manufactured and used in a practical Application of particularly problematic tissue examined. The fabric is made of cotton plush with PA base fabric, dyed with procion turquoise (procion blue AS). Experiments were carried out with pre-cleaning agents for rayon Cellulose and synthetic fibers based on ethoxylated Fatty alcohol condensation products with anion-active Additions and with the addition of the invention loaded sheet silicates to the above  Pre-cleaning agent at a washing temperature of 90 ° C with a liquor ratio of 1:12 in the course of 30 min. The evaluation was carried out after known methods in a launderometer.

The absorption of the wash liquor after the washing process was determined using an absorption band characteristic of the dye ( λ = 651 nm).

Table 1 below shows the absorption, ie the dye content of the soapy water, in extinction units.
Example absorption

Example 10.60 Example 20.58 Comparative Example 10.62

When adding the loaded layered silicates to the previous one detergent according to Examples 1 and 2 takes Adsorption, d. H. the dye content of the wash liquor, significantly, the effect of the recipe according to Example 2 is the largest.

In addition to the above attempts, the Wash liquor obtained according to Comparative Example 2 after detaching the tissue with the loaded ones Layered silicates at different temperatures (25 ° C and 60 ° C) aftertreated. After disconnection of the layered silicate by centrifugation the solutions have an absorption as shown in Table 2.  The wash liquor obtained as above according to the comparative example 2 (absorption 0.86) was at 1 g / l of the invention with quaternary ammonium compounds loaded layered silicates according to Zu compositions of Examples 3 and 5 at 25 and 60 ° C. aftertreated.

Table 2

With the addition of the loaded layered silicates, the Dye concentration compared to the pure pre detergents in the fleet. In the Use of the synthetic hectorite according to the example 3 is almost the entire amount of dye from the solution away. With increasing temperature it increases dye removal too. The divergent results explain in the presence and absence of tissue presumably by the fact that in the presence of the fabric and with the addition of the layered silicate, the amount of dye detached from the tissue is greater. By the addition of the layered silicate is made from the dye Wash liquor removed, the dye balance with it moved and there can be no more, on the tissue fixed dye can be removed. With a higher one The use concentration of the layered silicate can be Effect can be compensated.  

To contrast about the absorption capacity of the layered silicates Dyes make quantitative statements adsorption measurements with two under different types of cationic and anionic dyes, Methylene blue and benzopurpurine. The Layered silicates loaded with QAV were also used an unloaded, natural bentonite (active bentonite B, Erbslöh, Geisenheim), Comparative Example 3 compared. In addition, the influence of a han usual detergents based on anionic and nonionic surfactants checked.

Comparative Example 3

It became an aqueous dispersion containing 2 g / l a natural bentonite (active bentonite B, company Erbslöh, Geisenheim).

Example 3

It became an aqueous dispersion containing 2 g / l a synthetic hectorite, loaded with 20% by weight its weight of laurintrimethylammonium chloride, produced.

Example 4

An aqueous dispersion containing 2 g / l of the Bentonits Bentone 34, NL-Industries, loaded with a quaternary ammonium compound.

Comparative Example 4

It became an aqueous dispersion according to the comparative example 3 produced, the additional 1 g / l of a pre Detergent according to Comparative Example 1 contained.  

Example 5

An aqueous dispersion was prepared in accordance with Example 3, the additional 1 g / l of a pre-cleaning agent according to comparative example 1.

Example 6

An aqueous dispersion was prepared in accordance with Example 4, the additional 1 g / l of a pre-cleaning agent according to comparative example 1.

At a dye concentration of 0.2 g / l the layered silicates according to Examples 3 to 6 and according to Comparative Examples 3 and 4 with a Lö solution temperature of 23 ° C for 30 min.

The adsorbed amounts of dye are at the un treated bentonite according to Comparative Example 3 in total larger, but the dispersion also has Example 4 compared to a very high absorption capacity Methylene blue, especially in the presence of surfactants.

Table 3 below shows the amounts adsorbed for the cationic dye methylene blue.
Sample adsorbed amount (mg / g)
Methylene blue

Comparative Example 395 Example 330 Example 470 Comparative Example 495 Example 540 Example 690

When using the anionic dye benzopurpurin instead of methylene blue in the above procedure, the loaded layered silicates are clearly superior to the untreated bentonite (Table 4). The adsorption effect was carried out at a concentration of 0.2 g / l benzopurpurin.
Sample adsorbed amount (mg / g)
Benzopurpurine

Comparative Example 31 Example 340 Example 4100 Comparative Example 420 Example 535 Example 685

The one with Lauryltrime is particularly favorable synthetic hectorite loaded with thylammonium chloride (Example 4). In the presence of the pre-cleaner take the adsorbed amounts of the dye to the loaded layered silicates slightly, which is probably to competitive adsorption of the anionic surfactant of the detergent.

Both series of adsorption experiments show that with QAV loaded layered silicates, especially synthetic ones Hectorite, a high absorption capacity compared to un different dyes from aqueous systems to have. They are therefore particularly advantageous in the soaping process, in the formulation of stain-inhibiting Detergent formulations and in the elimination of Use dyes from wastewater.

Claims (6)

1. Use of layered silicates loaded with quaternary ammonium compounds, naturally and / or preferably synthetically produced, in soaping processes for fixing dyes, the layered silicates containing 1 to 50% by weight of their weight with at least one or mixtures of water-soluble or water-dispersible quaternary dialkyl dialkylammonium and / or monoalkyl-trialkylammonium compounds of the general formulas are loaded and R₁ is a straight-chain and / or branched-chain saturated 8 to 20 C-alkyl radical, R₂ is an 1 to 4 C-alkyl and / or hydroxyalkyl radical and X is bromine and chlorine and in the event that R₂ is a methyl radical, optionally also stands for a sulfate residue. 2. Use of quaternary ammonium compounds loaded layered silicates according to claim 1, wherein the Layered silicate is selected from bentonite and / or a synthetic hectorite.   3. Use of quaternary ammonium compounds loaded layered silicates according to claim 1, wherein the Layered silicate made from a synthetic material smectite-like crystal phase and significantly reduced Swelling capacity exists. 4. Use of quaternary ammonium compounds loaded layered silicates according to claim 1, wherein the quaternary ammonium compounds are selected from the from Distrearyldimethyl-, Lauryltrimethyl-, Ditalgdimethyl-, Coconut alkyl trimethyl and cetyl trimethyl ammonium chloride existing group. 5. Use of quaternary ammonium compounds loaded sheet silicates according to claims 1 to 3 as Additive in a pre-cleaning agent for rayon wool and synthetic fibers based on non-surfactant and anionic additives in an amount of 5 up to 95 wt .-%, based on the weight of the prepreini agent. 6. Use of quaternary ammonium compounds loaded sheet silicates according to claim 4, wherein the Total amount of pre-cleaning agent and with quaternary Layered silicates loaded with ammonium compounds 0.02 up to 0.5% by weight of an aqueous solution and / or dispersion is.