EP1634991A2 - Liquid additive for treating and finishing textile products - Google Patents

Abstract

A bleach-free and alkali-free auxiliary composition (A) for industrial treatment or finishing of textile products comprises a mixture of peroxide activator(s) (I) and surfactant(s) (II), where (i) (I) forms at least 35 (preferably at least 50) wt. % of (A) and (ii) (I), (II) and (A) are all in the form of liquids at room temperature, : An independent claim is included for a method for finishing or treating textiles, including treatment with (A).

Description

The invention relates to a liquid at room temperature aid for the treatment and finishing of textile fiber material and / or textile products and a corresponding method.

In the textile industry, the textile substrate is refined, for example bleached, to prepare it for dyeing or finishing. For bleaching textiles different chemicals are used. Oxidative bleaching agents such as hydrogen peroxide, sodium hypochlorite, sodium chlorite or reductive bleaching agents such as thiourea dioxide are known in the art. For quite some time, a bleach activator, the less water-soluble powdered tetraacetylethylenediamine (TAED), has also been used in some cases. Also in the commercial or industrial laundry of textile products. In the treatment of textile products, said bleaching agents are used for stain removal or disinfection in the event of contamination by microorganisms.

Chlorine-based bleaching components such as sodium hypochlorite and sodium chlorite form organohalogen compounds during the bleaching process that are classified as harmful to health. In addition to the resulting organohalogen compounds, depending on the bleaching agent, it can also lead to the formation of harmful gases and to strong odor nuisance, eg by formation of chlorine dioxide, come during the bleaching. Furthermore, bleaching with sodium chlorite is only possible on special machines, which must be made of special materials.

Because of these disadvantages, hydrogen peroxide bleaching is the most common bleaching process.

To be able to bleach with hydrogen peroxide, however, this must first be activated. Furthermore, if the bleaching liquor is insufficiently stabilized, there is a risk that a great potential of bleaching-active oxygen will be lost.

The activation of the hydrogen peroxide takes place primarily with alkali. Caustic soda is used almost exclusively for the bleaching of cellulose fibers, while sodium carbonate is used for bast fibers.

Alkali-sensitive fibers such as protein fibers or some synthetic fibers can not be treated with the alkaline peroxide bleach. Otherwise, damage may occur until the fibers are destroyed during alkaline bleaching. Furthermore, some fiber-blending substances and fiber impurities can not be oxidatively destroyed with an alkaline peroxide bleach.

In addition to bases, hydrogen peroxide can also be activated in other ways, for example, by chemical reaction of the hydrogen peroxide to form peracids or by activation by means of special metal catalysts.

P. Wurster, Textile Practice International (1992), October, p. 961, discloses the use of peracetic acid in textile bleaching. Peracetic acid is obtained in the textile industry from acetic acid hydride and hydrogen peroxide. Acetic anhydride is explosive in the gaseous state with air. In addition, it has a pungent smell, etches and burns the skin. The formation of peracetic acid from acetic anhydride and hydrogen peroxide can lead to the formation of diacetylperoxoid. This chemical is poorly soluble and has a strong irritant effect on the skin. Furthermore, it reacts explosively when heated.

The handling of the acetic anhydride and the production of peracetic acid are likely to be the reason why the peracetic acid is used as a bleaching agent in the textile industry practically no use.

In addition to the peroxide activation methods mentioned, a number of chemical compounds are also suitable as activators for hydrogen peroxide to form peracids.

According to W. Nay, Textile Practice International, 1974, pages 1392 to 1402 and 1552 to 1565), particularly those compounds are efficient which have a large number of peracid-forming acyl groups with the smallest possible relative molar mass. This requirement exists, for example, in the case of the solids tetraacetylethylenediamine (TAED) and tetraacetylglycoluril (TAGU).

Typical solid bleach activators are usually used in household detergents in admixture with other excipients as powder or granules.

Instead of solid bleach activator blends, liquid suspensions may also be of interest. Suspensions would be of interest because of their dust-free utility, ease of pumping and generally better and faster solubility in the textile industry. For reasons of application safety, such agents must be present as stable homogeneous products. In the case of the suspensions, however, the stability of the components used is a problem. It can come to the separation or decomposition of the individual components. The blends are steadily losing activity and the agents have reduced bleaching performance.

As prior art, there are some suggestions for bleach activators as well as for liquid blends with powdered bleach activators.

DE OS 1 695 219 describes the use of acylated glycolurils, mainly TAGU, as a bleach activator in the bleaching of fibers of all kinds.

EP 0 125 641 B1 and US Pat. No. 4,544,503 disclose the use of acyloxibenzolsulfonic acid salts (AOBS) as a bleach activator. The bleach activator is used in the peroxide bleaching of fabrics and as a dyeing assistant in the dyeing of acrylic fibers.

DE 27 19 235 A1 mentions inter alia N-acetylcaprolactam as a bleach catalyst for the clear-wash cycle of an automatic washing machine for the cleaning of textiles.

EP 1 065 262 A1 describes the use of phthalimidoperoxycarboxylic acids as bleaching agents for fabrics and hard surfaces.

EP 0 737 241 B1 describes the mixture of solid acyl lactam bleach activator compounds and additional components for the production of a powder product.

DE PS 1 291 317 discloses a bleaching process which is suitable for removing stains on textiles. The bleach activator used is an organic N-acyl compound. The activating agent for the inorganic persalts used, such as sodium perborate tetrahydrate, sodium perborate and sodium percarbonate, is also called N-acetylcaprolactam. A disadvantage of these processes is the mandatory use of inorganic persalts.

WO 94/27970 describes a process for producing a powdered combination product for commercial laundries. The bleach activator used is a benzoylcaprolactam derivative. The combination product further includes a peroxide supplier such as percarbonate or perborate, a detergent and fillers.

EP 0 584 710 A2 mentions a process for bleaching textile raw materials with the aid of hydrogen peroxide and peracids. The bleach activator used is a carboxylic acid amide, carboxylic acid ester or sulfonic acid salt. The listed bleach activators possess the disadvantage that they can not be used in the textile industry with the dosing designed for liquid products.

In WO 98/00510 a non-aqueous liquid detergent composition with powdery bleach activators dispersed in the surfactant phase by the addition of polycarboxylates and solvents is described.

DE 40 24 531 A1 describes an anhydrous bleach activator-containing liquid detergent with nonionic and anionic surfactants. The liquid matrix contains solvent and as a bleach activator preferably the powdered TAED is used. However, the examples of the invention contain only small amounts of TAED and achieve their storage stability by a high viscosity adjustment. Both are not very desirable for the users, in particular, viscous products can not be processed on conventional dosing.

In the cited prior art, either the peroxide activators alone are added to the liquor or a pulverulent blend or a suspension of a solid bleach activator with various components is used. A fast and efficient distribution in the treatment liquor is not guaranteed in any procedure.

DE 44 12 390 A1 describes the use of N-acyl lactam derivatives as bleach activators. Among other things, N-acetylcaprolactam is used for bleaching textile materials. The listed bleach activators become separate to the treatment liquor added. A disadvantage of this method is the separate addition of the bleach activator. When using this method on a dosing system, a separate dosing unit for the bleach activator is necessary due to the separate addition. Furthermore, the listed bleach activators have no wetting effect on the substrate to be bleached. Only by the addition of an additional wetting agent to the fleet is a sufficiently good wetting of the goods with the fleet and thus ensures efficient bleaching. In addition, the sufficiently rapid homogeneous distribution of the bleach activator in the liquor is not ensured by the separate addition of the bleach activator.

DE 100 11 273 A1 describes "liquid detergent with liquid bleach activators". In these mixtures, in addition to surfactants as main components and activators in an amount of up to 40 wt .-% excipients, for example, perborate used as an oxidizing agent or alkaline substances such as soda or phyllosilicates as insoluble solids. The mixtures described are highly viscous and become liquid only by shear forces. Even at 0.5 rpm, the blends still have viscosities of more than 1000 mPas in the Brookfield viscometer, which makes possible the incorporation of solids but is less suitable for modern industrial metering systems. In addition, it is far more economical in industrial companies to use excipients such as perborate separately as hydrogen peroxide and soda or silicate separately.

The object of the present invention is to provide concentrated low-viscosity peroxide activators for the textile industry, including industrial laundry, which are available from the prior art avoid the known disadvantages of the technology for peroxide activators and their blends. The blends are intended to combine the properties of peroxide activation and wetting power in one product. A further object of the present invention was to provide a stable, liquid, low-viscosity, peroxide-activating and at the same time wetting mixture for the textile industry , which has good storage stability and is rapidly distributed homogeneously in the liquor.

The solution to this problem is achieved by blending liquid bleach activators with liquid surfactants, wherein the activator of the mixture is at least 35 wt .-%, in particular at least 50 wt .-%.

The invention relates in a first embodiment to a liquid at room temperature aid for the treatment or finishing of textile fiber material and / or textile products comprising a blend of at least one or more, liquid at room temperature peroxide and at least one or more liquid at room temperature surfactants. Particularly preferably, the auxiliary consists only of peroxide activator and surfactant.

The auxiliaries according to the invention are homogeneous and storage-stable. They can therefore be used particularly well with dosing systems for liquid substances in the finishing or treatment processes.

The aids according to the invention ensure that the peroxide activator distributes itself homogeneously in the liquor sufficiently quickly. In this case, the surfactant admixed with the peroxide activator ensures a faster distribution process of the only slightly water-soluble peroxide activator.

It has been found that mixtures of peroxide-activating components, surfactants and optionally solubilizers form liquids which, despite their low viscosity, neither separate nor lose activity or undergo hydrolysis even after prolonged storage.

It has furthermore been found that the blends according to the invention in combination with hydrogen peroxide and an alkali source have wetting and, at the same time, whitening-increasing effects.

The formulations of the invention are liquid at room temperature (25 ° C) and low in viscosity. Low viscosity for the purposes of the present invention means that the formulations according to the invention have a viscosity of up to 200 mPas at 25 ° C.

Peroxide activators for the purposes of the present invention are reactive acyl compounds which form bleach-active species with bleaching agents such as hydrogen peroxide in the bleaching liquor at pH> 7 peroxide anions. In particular, acetylated compounds are effective in the peroxide activators. Particularly preferred peroxide activators include, for example, ethylene glycol diacetate, N-acetylcaprolactam, triacetin or tributylacetyl citrate, and mixtures thereof.

Surfactants in the sense of the present invention comprise amphiphilic compounds having at least one hydrophobic and one hydrophilic moiety. The surfactants are preferably selected from one or more nonionic surfactants.

Advantageously, the weight ratio in the inventive mixture of peroxide activator to surfactant from 9.5 to 0.5 to 0.5 to 9.5, more preferably 9 to 1 to 5 to 5 proves.

An essential preferred element of the invention is the treatment or refinement of textile fiber material and / or textile products with the aid of a liquid auxiliary which, in addition to liquid peroxide activator and wetting surfactant, also contains or consists of solubilizers. The auxiliary according to the invention particularly preferably contains up to 20% by weight of the solubilizers. Solubilizers for the purposes of the present invention include chemicals which allow a mixture of surfactant with bleach activator, which do not form a homogeneous mixture without the addition of solubilizers. Examples of such solubilizers are glycol ethers such as butyl diglycol, butyl triglycol or alcohols such as methanol, ethanol or ketones such as acetone, butanone or esters such as glycol esters.

The formulations according to the invention preferably contain less than 1% by weight of water, since peroxide activators can hydrolyze in the presence of water.

The preferred field of application of the present invention is the bleaching and whitening of textile fiber materials. In addition to the auxiliaries according to the invention, the treatment liquor furthermore contains hydrogen peroxide and, if appropriate, an alkali donor such as, for example, inorganic carbonates or phosphates.

In the process according to the invention, the auxiliary is used at 0.5 to 10% by weight, preferably at 2 to 6% by weight, based on the weight of the product. This will ensure that there is minimum wetting and sufficient peroxide activator. The textile substrate is treated batchwise or continuously in aqueous liquor. The pH of the treatment liquor is in particular in the range of 4 to 11, preferably 6 to 9.5.

It has proved to be advantageous if the weight ratio of the auxiliaries according to the invention to hydrogen peroxide (35% strength by weight in water) in the treatment liquor is 0.5 to 10 to 1, particularly preferably 0.75 to 1.5 to 1.

The process according to the invention preferably carries out the treatment at 20 to 130.degree.

As a textile fiber material are preferably cellulosic fibers such as linen, hemp, cotton, jute; Regenerated cellulose fibers such as viscose, viscose acetate; animal fibers such as wool and silk; Chemical fibers such as polyamide, polyacrylonitrile, polyester, elastomers and fiber blends such as cotton / spandex or cotton / polyamide used.

The material to be treated can be present in various presentations, for example flake, roving, roving, yarn, twisted yarn, knitted fabric, knitted fabric, fleece, woven fabric or as a ready-made textile.

In the case of processes and corresponding components not according to the invention, additional metering units for the chemical dosage must be made available. In the case of non-inventive bleaching processes and corresponding pH values of 12 to 14, the risk of damage to alkali-sensitive substrates and possibly significantly worse brightening results is given.

Production of the Aids According to the Invention

The individual components were added successively, examples according to the invention are marked as M1 to M15. The comparative components used were the unblended individual components which are identified by K1 to K12.

All of the formulations according to the invention were blends which were liquid at room temperature.

Table 1 below shows the weight proportions of the components used.

storage stability

To determine the storage stability, the mixtures according to the invention were stored at room temperature and at 37 ° C. and then evaluated with regard to the occurrence of phase separation, turbidity and sediment. Examples M1 to M11 were stable for 3 months. Mixture M12 and M14 showed a phase separation or a sediment. A further formulation was ever prepared for comparison with Example M12 and M14. Example M13 corresponded to Example M12, but instead of 35 parts of component K6 thereof 31 parts and instead 4 parts of the solubilizer K11 were used. Example 15 corresponded to Example 14 but instead of 35 parts of component K8, only 15 parts and 20 parts of the solubilizer K12 were used.

The storage stability test of Examples K13 and K15 gave stable mixtures after 3 months at 37 ° C. and at room temperature.

Distribution in the fleet

Each 1 liter of solution was prepared with 4 g / L of the stable mixture according to the invention or the components K1 to K4. Thereafter, the solutions were stirred for 1 minute. After a service life of 2 minutes, the fleet was assessed visually.

It was found that the mixtures according to the invention were either finely dispersed or completely homogeneous in the solution. In the comparative experiments with the components K1 to K4, a sedimentation of the activator took place in each case.

Chemical stability

The mixtures according to the invention were tested both after preparation and after a storage time of 3 months. A loss of activity was not detectable.

net assets

The determination of the wetting times of the blends according to the invention is carried out according to DIN ISO 8022 Determination of the immersion wetting power. The result of the examinations is given as the net time in seconds.

The determination of the immersion wetting power takes place at room temperature and 4 g / L of the blend according to the invention or of the comparison substance are used. The data obtained are shown in Table 2. <u> Table 2: </ u> Component mixture M1 M2 M3 M5 M8 M9 M10 K1 K2 K3 K4 Net time [s] 10 6 228 9 10 78 4 > 300 > 300 > 300 > 300

Bleach on cotton

Commercially available cotton tricot raw material was treated at 60 ° C. at a liquor ratio of 1 to 10 with 4 g / L of inventive blend, 4 mL / L hydrogen peroxide 35% and 2 g / L sodium carbonate for pH adjustment for 60 minutes. The blank values were carried out without blending according to the invention, but with 4 g / L of the components K7 to K10. Subsequently, the Fleet drained, the goods rinsed and dried. After drying, the colorimetric determination of the whiteness according to Berger. The values are shown in Table 3. <u> Table 3: </ u> Component mixture M1 M2 M5 M7 M9 M11 K7 K8 K9 K10 Whiteness Berger 68 57 62 68 70 68 51 48 50 50

Depending on the mixture, whiteness increases of up to 22 points were achieved for the adjuvants according to the invention in comparison with surfactants without activating substance.

Bleach on linen

Linen roving was treated at 60 ° C at a liquor ratio of 1 to 10 with 4 g / L inventive mixture, 4 mL / L hydrogen peroxide 35% and 2 g / L sodium carbonate for pH adjustment for 60 minutes. The comparative value was determined without blending according to the invention, but with 4 g / L of the components K. The liquor was then drained off, the goods were rinsed and dried. After drying, the colorimetric determination of the whiteness according to Stansby was carried out. The values obtained are shown in Table 4. <u> Table 4: </ u> Component mixture M1 M4 M7 M8 K5 K6 K7 K9 Whiteness Stansby 47 44 45 49 39 40 40 39

The results obtained from the comparative experiments were clearly superior to the values obtained with the addition of the blends according to the invention.

Industrial laundering of made-up cotton (BW) BW woven fabric

White table linen made of 100% cotton (tablecloths, napkins) was applied on a washer-extractor together with standard dirt cloth EMPA Art. 111 (BW fabric with blood stain) and EMPA Art. 114 (BW fabric with red wine stain) at 60 ° C with a liquor ratio of 1 to 5 with 2 g / L mixture according to the invention (Table 5), 2 mL / L hydrogen peroxide 35% and 2 g / L sodium metasilicate for pH adjustment for 15 minutes. The comparative value was determined without blending according to the invention, but with 2 g / L of the components K. The liquor was then drained off, the goods were rinsed and dried. After drying, the colorimetric determination of the degree of whiteness of the dirt was made according to Berger. The values obtained are shown in Table 5. <u> Table 5: </ u> Component mixture M 1 M 7 M 8 K 1 K 9 K 10 Whiteness Berger blood 10 12 21 2 6 4 Whiteness Berger red wine 32 56 54 14 2 8th

The results obtained from the comparative experiments were clearly superior to the values obtained with the addition of the blends according to the invention.

Claims (16)

At room temperature liquid, bleach-free and alkali-free adjuvant for the industrial treatment or finishing of textile fiber material and / or textile products containing a blend of at least one or more at room temperature liquid peroxide activators in an amount of at least 35 wt .-% and at least one or more , at room temperature liquid surfactants. Auxiliary agent according to claim 1, characterized in that the amount of peroxide activators is at least 50 wt .-%. Auxiliaries according to claim 1 or 2, characterized in that the peroxide activator is selected from ethylene glycol diacetate, N-acetylcaprolactam, triacetin or tributylacetyl citrate and mixtures thereof. Auxiliary agent according to any one of claims 1 to 3, characterized in that the surfactant is selected from one or more nonionic surfactants. Auxiliaries according to one of claims 1 to 4, characterized in that the weight ratio of peroxide activator to surfactant is 9.5 to 0.5 to 3.5 to 6.5, in particular 5 to 5 to 9 to 1. Aid according to one of claims 1 to 4, characterized in that the admixture further includes a solubilizer. Auxiliary agent according to claim 6, characterized in that the blend contains up to 20 wt.% Of the solubilizers. Auxiliary agent according to one of claims 1 to 7, characterized in that the mixture contains up to 1 wt.% Water. Process for the finishing or treatment of textile products, comprising the use of a liquid at room temperature aid containing a mixture of at least one or more at room temperature liquid peroxide activators and at least one or more liquid at room temperature surfactants. A method according to claim 9, characterized in that one uses 0.5 to 10 wt.%, In particular 2 to 6 wt.% Of the auxiliary, based on the substrate. A method according to claim 9 or 10, characterized in that adjusting a pH of the treatment liquor in a range of 4 to 11, preferably 6 to 9.5. Method according to one of claims 9 to 11, characterized in that one sets the weight ratio of the auxiliary to hydrogen peroxide (35 wt .-%) in the treatment liquor 0.5 to 10 to 1, in particular 0.75 to 1.5 to 1 , Method according to one of claims 9 to 12, characterized in that one carries out the finishing or treatment at a temperature in the range of 20 to 130 ° C. Method according to one of claims 9 to 13, characterized in that one cellulosic fibers, bast fibers or cotton; Regengeratz cellulose fibers, in particular viscose, viscose acetate; animal fibers, in particular wool and silk; Man-made fibers, in particular polyamide, polyacrylonitrile, polyester, elastomers and fiber blends, in particular cotton / spandex or cotton / polyamide, are finished or treated. Method according to one of claims 9 to 14, characterized in that the bast fibers used are linen, hemp or jute. Method according to one of claims 9 to 15, characterized in that bleaching textile products.