WO1988007603A1

WO1988007603A1 - Use of lamellar silicates charged with quaternary ammonium compounds as saponifying agents in saponification processes for fixing dyes

Info

Publication number: WO1988007603A1
Application number: PCT/EP1988/000245
Authority: WO
Inventors: Wolfgang Von Rybinski; Winfried Wichelhaus; Milan-Johann Schwuger
Original assignee: Henkel Kommanditgesellschaft Auf Aktien
Priority date: 1987-04-01
Filing date: 1988-03-24
Publication date: 1988-10-06
Also published as: DE3710849A1; EP0308469A1; ES2006621A6

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

Use of SchiehtsiIkate loaded with quaternary ammonium compounds as a soaping agent in soaping processes for fixing dyes

The present invention relates to the use of soap auxiliaries which contain layered silicates loaded with quaternary ammonium compounds (QAC), in particular for removing dyes from aqueous systems.

In practice, washing processes after dyeing and printing fabrics are generally referred to as soaps or after-soaps.

The aim of re-soaping dyeings and prints is to achieve good fastness properties and an optimal product appearance. The soaping processes serve to remove unwanted substances from textile surfaces (K. Schumann et al., Deutscher Färberkalender, 1979, pages 246 to 257).

US Pat. No. 4,292,035 relates to softening compositions for softening laundry during the washing process, which consists of a combination of an anionic surfactant and a complex of different smectites with various organic amines, their salts and various quaternary compounds. Such compositions have properties of fabric softeners, which can accordingly be added as laundry aftertreatment agents when rinsing the laundry or directly to the detergents during the laundry.

DE-OS 29 10 583 (additional application to DE-OS 28 17 427) describes the use of finely divided, water-insoluble alkali aluminum silicates as soaping agents for dyeings and prints on textile materials and in particular for the aftertreatment of dyeings and prints with naphtho dyes, reactive dyes and disperse dyes on cellulose and Synthetic fiber material. The present invention has for its object to provide soap aids based on layered silicates, which have improved color fastness of the textiles and improved dye absorption capacity compared to known soap aids.

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

The present invention relates to the use of layered silicates loaded with quaternary ammonium compounds, natural and / or preferably synthetically produced, as soaping aids in soaping processes for fixing dyes, the layered silicates having from 1 to 50% 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

R _{1 is} a straight-chain and / or branched-chain saturated 8 to 20 C-alkyl radical, R _{2 is} an 1 to 4 C-alkyl and / or hydroxyalkyl radical and X is bromine and chlorine and in the case that R ₂ represents a methyl radical, optionally also for one

SuIfatrest stands.

A preferred embodiment of the present invention is that bentonite and / or a synthetic hectorite is used as layered silicate. One embodiment of the present invention is that the alkylammonium compounds are selected from the group consisting of DistearyIdimethyI, LauryItrimethyI, DitaIgaIkyIdimethyI, KokosaIkyItrimethyI and CetyltrimethyIammoniumchloride.

Soap aids according to the invention can either be used alone in the soaping process mentioned or, according to a preferred embodiment, as an additive, for example in a pre-cleaning agent for rayon wool and synthetic fibers based on nonionic and anionic additives in an amount of 5 to 95% by weight. -%, based on the weight of the Vorrei cleaning agent, are added.

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

The term layered silicates in the sense of the present invention encompasses naturally occurring clay which is swellable in water and has a high ion exchange capacity. Examples of such swellable clays with an ion exchange capacity of at least 50 million equivalents / 1010 g are VoIchonskoit, Nontronit, Sanconit and in particular MontmoriIIonit, Hectorit and Saponit. Also included are synthetic, finely divided, serum-insoluble layered silicates with smectite-like crystal phase, but increased contents of bound alkali and silicate and a significantly reduced swelling capacity in aqueous suspension with the oxide sum form compared to pure layered silicates of this type

MgO. aM ₂ O. bAl ₂ O ₃ . cSiO ₂ . nH ₂ O, wherein

M stands for sodium, optionally together with lithium, with the proviso that the molar ratio Na / Li is at least 2 and furthermore 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.

Suitable for the purposes of the invention are synthetic layered silicates which, after suspension in water (16 ° dH, room temperature), have a swelling capacity - determined as the quotient of the sediment volume (V _s ) / total volume (V) after previous treatment with excess soda solution, careful washing and 20 hours after suspension in 9 parts by weight of water / one part by weight of layered silicate - of V _s / V less than 0.6, in particular 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 structure I

correspond to what applies

x = 0 - 0.3 preferred: 0 0.1 y = 0 - 0.5 0 - 0.4 x + y = 0.1 - 0.5 0.2 - 0.4 z = 1 - 22 1 - 14 m = 0.1 - 0.5 0.1 - 0.3 n = 0 - 8 2 - 6

Such synthetic layered silicates contain excess alkali, in particular sodium hydroxide or soda, which is not incorporated into the crystal structure, and / or are present in intimate admixture with, in particular, water-soluble salts, preferably alkali sulfates and / or carbonates. The sheet silicates mentioned and their preparation are described in the earlier patent application EP 86 / 109717.8. Reference is hereby expressly made to this patent application. The use of synthetic layered silicates loaded with quaternary ammonium compounds with a smectite-like crystal phase and significantly reduced swelling capacity is preferred.

The layered silicates are loaded by the methods known in the art, as described, for example, in column 13 of US Pat. No. 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 des

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 RD), loaded with 20% by weight lauryltrimethylammonium chloride.

Comparative Example 1

1 g / l pre-cleaning agent for rayon cells and synthetic 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 cellulose and synthetic fibers based on ethoxylated fatty alcohol condensation products with anion-active additives with the addition of zeolite A (Sasil).

SeifhilfsmitteI according to Examples 1 and 2 and according to Comparative Examples 1 and 2 were prepared and tested on a tissue which is particularly problematic in practical use. The fabric is cotton plush with a PA base fabric, dyed with procion turquoise (procion blue AS). Experiments were carried out with pre-cleaning agents for rayon cells and synthetic fibers based on ethoxylated fatty alcohol condensation products with anion-active additives and with the addition of the loaded visual silicates according to the invention to the above-mentioned pre-cleaning agent at a washing temperature of 90 ° C with a liquor ratio of 1:12 over the course of 30 min. The evaluation was carried out according to known methods in a launderometer. The absorption of the washing liquor after the washing process was determined using an absorption band (= 651 nm) which is characteristic of the dye.

Table 1 below gives the absorption, i.e. the dye content of the soapy water, again in extinction units.

Table 1

Example absorption

Example 1 0.60 Example 2 0.58 Comparative Example 1 0.62

When the loaded sheet silicates are added to the pre-cleaning agent according to Examples 1 and 2, the adsorption, i.e. the dye content of the wash liquor clearly decreases, the effect being greatest in the formulation according to Example 2.

In addition to the abovementioned tests, the washing liquor obtained according to Comparative Example 2 was aftertreated after the tissue had been separated off with the loaded layered silicates at different temperatures (25 ° C. and 60 ° C.). After the layered silicate had been separated off by centrifugation, the solutions showed an absorption, as shown in Table 2. The wash liquor obtained as above according to Comparative Example 2 (absorption 0.86) was aftertreated with 1 g / l of the layered silicates according to the invention loaded with quaternary ammonium compounds in accordance with the compositions of Examples 3 and 5 at 25 and 60 ° C. Table 2

Example of absorption temperature

Comparative Example 2 0.86 Example 3 0.08 25 ° C

Example 3 0.01 60 ° C

Example 4 0.60 25 ° C

Example 4 0.58 60 ° C

When the loaded layered silicates are added, the dye concentration decreases significantly compared to the pure pre-cleaning agent in the liquor. When using the synthetic hectorite according to Example 3, almost the entire amount of dye is removed from the solution. The dye elimination increases with increasing temperature. The divergent results in the presence and absence of the tissue are probably explained by the fact that the amount of dye detached from the tissue is greater when the tissue is present and the layered silicate is added. By adding the visual silicate, dye is removed from the wash liquor, the dye balance is shifted and further dye that is not fixed on the tissue can be detached. This effect can be compensated for with a higher use concentration of the layered silicate.

In order to be able to make quantitative statements about the absorption capacity of the layered silicates compared to dyes, adsorption measurements were carried out with two different types of cationic and anionic dyes, methylene blue and benzopurpurine. The layered silicates loaded with QAV were compared with an unloaded, natural bentonite (active bentonite B, Erbslöh, Geisenheim), comparative example 3. In addition, the influence of a commercial detergent based on anionic and nonionic surfactants was checked. Comparative Example 3

An aqueous dispersion containing 2 g / l of a natural bentonite (active bentonite B, Erbslöh, Geisenheim) was prepared.

EXAMPLE 3

An aqueous dispersion containing 2 g / l of a synthetic hectorite, loaded with 20% by weight of its weight of laurin trimethyl ammonium chloride, was prepared.

EXAMPLE 4

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

COMPARISON EXAMPLE 4

An aqueous dispersion according to Comparative Example 3 was produced, which additionally contained 1 g / l of a pre-cleaning agent according to Comparative Example 1.

EXAMPLE 5

An aqueous dispersion according to Example 3 was prepared which additionally contained 1 g / l of a pre-cleaning agent according to Comparative Example 1.

EXAMPLE 6

An aqueous dispersion was prepared according to Example 4, which additionally contained 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 act at a solution temperature of 23 ° C for 30 min.

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

Table 3 below shows the amounts adsorbed for the cationic dye methylene blue.

Table 3

Example adsorbed amount (mg / g)

Methylene blue

Comparative Example 3 95

Example 3 30

Example 4 70

Comparative Example 4 95

Example 5 40

Example 6 90

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

Example adsorbed amount (mg / g)

Benzopurpurine

Comparative Example 3 Example 3 40

Example 4 100 Comparative Example 4 20 Example 5 35 Example 6 85

The synthetic hectorite loaded with lauryltrimethylammonium chloride is particularly favorable (Example 4). In the presence of the pre-cleaning agent, the adsorbed amounts of the dye on the loaded layered silicates decrease slightly, which is probably due to a competitive adsorption of the anionic surfactant of the detergent.

Both adsorption test series show that layered silicates loaded with QAV, especially synthetic hectorites, have a high absorption capacity compared to different dyes from aqueous systems. They are therefore particularly advantageous to use in the soaping process, in the formulation of dye-inhibiting detergent formulations and in the elimination of dyes from the waste water.

Claims

Patent claims

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 dialkyldialkylammonium - and / or monoalkyl-triaIkylammoniumverbindungen of general formulas

are loaded and

R _{1 is} a straight-chain and / or branched chain saturated 8 to 20 carbon atom alkyl radical, R _{2 is} a 1 to 4 carbon atom alkyl and / or hydroxyl alkyl radical and X is bromine and chlorine and in the case that R _{2 represents} a methyl radical, optionally also for one

SuIfatrest stands.

2. Use of layered silicates loaded with quaternary ammonium compounds according to claim 1, wherein the layered silicate is selected from bentonite and / or a synthetic hectorite.

3. Use of layered silicates loaded with quaternary ammonium compounds according to claim 1, wherein the layered silicate consists of a synthetic material with a smeetitähniieher crystal phase and significantly reduced swellability.

4. Use of layered silicates loaded with quaternary ammonium compounds according to claim 1, wherein the quaternary ammonium compounds are selected from the group consisting of distrearyldimethyI, lauryltrimethyI, ditaIgdimethyI, KokosaIkyltrimethyI and cetyltrimethylammonium chloride.

5. Use of quaternary ammonium-loaded sight silicates according to claims 1 to 3 as an additive in a pre-cleaning agent for rayon cellulose and synthetic fibers based on nonionic and anionic additives in an amount of 5 to 95% by weight, based on the weight of the Pre-cleaning agents.

6. Use of layered silicates loaded with quaternary ammonium compounds according to claim 4, wherein the total amount of precleaner and layered silicates loaded with quaternary ammonium compounds is 0.02 to 0.5% by weight of an aqueous solution and / or dispersion.