EP0966514A1

EP0966514A1 - Aqueous bleaching agents

Info

Publication number: EP0966514A1
Application number: EP97953873A
Authority: EP
Inventors: Mercedes Mendoza; Jaume Josa
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 1997-01-13
Filing date: 1997-12-19
Publication date: 1999-12-29
Anticipated expiration: 2017-12-19
Also published as: BR9714282A; US6090770A; ES2197384T3; EP0966514B1; DE19700799C2; WO1998030671A1; PL334349A1; HUP0002817A3; DE19700799A1; HUP0002817A2

Abstract

The invention concerns novel aqueous bleaching agents containing - relative to the agents - between 1.0 and 10.0 wt % alkali hypochlorite, between 0.5 and 1.5 wt % alkali hydroxide, between 0.5 and 2.0 wt % silicates, between 0.01 and 1.0 wt % phosphonic acids and/or phosphonates, and between 0.01 and 1.0 wt % polyacrylic acid compounds as well as optionally other conventional additives and auxiliary materials. The agents can be formulated without turbidity and reliably protect the textiles treated therewith against encrustation and yellowing, even in the presence of water hardness and heavy metal ions.

Description

Aqueous bleach

Field of the Invention

The invention relates to new aqueous bleaching agents containing alkali hypochlorites, alkali metal hydroxides and a temporary inhibitor system and the use of the temporary mixture as incrustation and yellowing inhibitors for the production of aqueous bleaching agents.

State of the art

While heavily soiled textiles are used in many European countries to use powdered or liquid heavy-duty detergents that only reach their performance at higher temperatures, cold washing, for example, is preferred by consumers in the United States and Spain, where it is particularly difficult to remove a detergent and remove it Stains a liquid bleach, preferably based on hypochlorite.

A large number of liquid bleaching agents are known from the prior art. For example, EP-A 0274885 (101) recommends the use of mixtures of linear and branched amine oxides for the production of viscous hypochlorite bleaches. According to the teaching of EP-A 0145084 (Unilever), mixtures of amine oxides with soaps, sarcosinates, taurides or sugar esters can also be used for this purpose. From the documents EP-A 0137551 and EP-A 0447261 (Unilever) the use of amine oxides with soap or sarcosinate and other anionic surfactants, for example alkyl sulfates, alkyl ether sulfates, secondary alkane sulfonates or alkyl benzene sulfonates as a thickening component for hypochlorite solutions, is known. EP-A 0156438 reports on the use of alkylarylsulfonates as thickeners in aqueous bleaches which contain certain stilbene dyes as optical brighteners. ES-A 8801389 (Henkel Iberica) relates to bleaching agents based on aqueous hypochlorite solutions which, as surfactant components, predominantly contain alkyl ether sulfates and, in addition, small amounts of amine oxides. From EP-AI 0447261 aqueous bleaching compositions containing sodium hypochlorite and anionic surfactants are also known. However, the hypochlorite concentration of these agents is at 0.1 to 8 and preferably 0.5 to 5% by weight of active chlorine, in German patent DE-C1 4333100 the applicant has proposed aqueous bleaching and cleaning agents based on hypochlorites, fatty alcohol ether sulfates, amine oxides and amine oxide phosphonic acids.

International patent applications WO 94/10272, WO 95/03383, WO 95/08610 and WO 95/08611 (Procter & Gamble) relate to hypochlon-containing bleaches containing short-chain anionic surfactants such as e.g. Octyl sulfate. The European patent application EP-A 0688857 (Procter & Gamble) describes hypochlon-containing bleaching agents with a content of periodates and carbonates to adjust the pH. European patent application EP-A 0688345 (Procter & Gamble) discloses hypochlorite-based bleaches which contain small amounts of silicates and / or carbonates, polycarboxylates and radical scavengers. An alkaline hypochlorite-based bleach preparation containing carbonates and silicates for stabilizing perfume oils is also proposed in European patent application EP-A 0622451 (Procter & Gamble).

The bleaching agent of the type mentioned places high demands on the consumer: it must be compatible with textiles, i.e. treatment with the aggressive chemical hypochlorite means that the stains must be removed without attacking the tissue. Since skin contact with the bleaching agents is not excluded, the preparations must also be as dermatologically compatible as possible. In cases where hard water is used for the washing process, there is the problem of limescale deposits on the fibers and thus the risk of tissue incrustation, especially when the agents are left to act for a long time. Another problem is that hypochlorite solutions also attack metals and the dissolved metal traces can be deposited on the textile fibers during washing, which is ultimately reflected in the yellowing of the fabric.

Accordingly, the complex object of the invention was to provide storage-stable, haze-free aqueous bleaching agents which are chlorine-stable, gentle on textiles and as skin-friendly as possible, have a sufficiently high viscosity and, with high stain removal properties, reliably prevent the deposition of lime and metal traces on the fabric .

Description of the invention

The invention relates to aqueous bleaching agents containing - based on the agents -

1.0 to 10.0% by weight of alkali hypochlorite

0.5 to 1.5 wt .-% alkali hydroxide

0.5 to 2.0% by weight of silicates,

0.01 to 1.0% by weight of phosphonic acids and / or phosphonates and

0.01 to 1.0% by weight of polyacrylic acid compounds

and, if appropriate, other customary auxiliaries and additives.

Surprisingly, it was found that the addition of an inhibitor mixture consisting of defined amounts of silicates, phosphonic acids or phosphonates and polyacrylates to the alkaline hypochlorite solutions significantly reduced both the deposit of lime and metals on the fabric during washing and thus the incrustation and yellowing of the Counteracts fibers, as well as the formulation of turbidity-free and storage-stable preparations possible. The incrustation and corrosion protection of the new agents is particularly evident with long exposure times. The invention includes the knowledge that the use of mild, chlorine-stable surfactants such as preferably alkyl ether sulfates, amine oxides, alkyl and / or alkenyl oligoglycosides and fatty acid salts leads to a further improvement in cleaning performance and dermatological compatibility. Finally, the agents according to the invention have a sufficiently high viscosity so that metering by the consumer is possible without any problems.

Alkali hypochlorites and alkali hydroxides

Alkali hypochlorites are to be understood as lithium, potassium and in particular sodium hypochlorite. The hypochlorites can preferably be used in amounts of 3.0 to 7.0 and in particular 4 to 6% by weight, based on the composition. Alkali hydroxides are to be understood as sodium and / or potassium hydroxide, which - based on the agents - are preferably used in amounts of 0.7 to 1.2% by weight. Silicates

Silicates which come into consideration in the sense of the invention are understood to be salts and esters of orthosilicic acid Si (OH) and their self-condensation products. Accordingly, the following crystalline substances can be used as silicates:

(a) Neosilicates (island silicates) such as phenakite, olivine and zircon;

(b) Sorosilicates (group silicates) such as thortveitite and hemimorphite;

(c) cyclosilicates (ring silicates), such as, for example, benitoid, axinite, beryl, milarite, osumilite or eudialyth;

(d) inosilicates (chain and band silicates), such as metasilicates (e.g. diopside) or amphiboles (e.g. tremolite);

(e) phyllosilicates (leaf and layer silicates) such as talc, kaolinite or mica (e.g. muscovite);

(f) Tectosilicates (framework silicates) such as feldspars and zeolites as well as clathrasils or dodecasils (e.g. melanophlogite), thaumasite and neptunite.

In contrast to the ordered crystalline silicates, silicate glasses such as e.g. Soda or potash water glass used. These can be of natural origin (e.g. montmorillonite) or synthetic. In a further embodiment of the invention, aluminosilicates can also be used. Typical examples of alkali or alkaline earth silicates are sodium and / or potassium silicates with a modulus in the range from 1.0 to 3.0 and preferably 1.5 to 2.0. The amount of silicates used is usually based on the composition - In the range of 0.8 to 1, 2 wt .-%.

Phosphonic acids and phosphonates

For the purposes of the invention, phosphonic acids are understood to mean organic derivatives of the acid HP (0) (OH) ₂ ; Phosphonates are the salts and esters of these phosphonic acids. The organic phosphonic acids or phosphonates which are preferably considered in the context of the present invention are known chemical compounds which can be prepared, for example, by the Michaelis-Arbuzov reaction. For example, they follow formula (I)

O

II

R -P-OR ² (I)

I.

OR ² in R ¹ for an optionally functionalized alkyl and / or alkenyl radical having 1 to 22, preferably 2 to 18 and in particular 6 to 12 carbon atoms and R ² for hydrogen, an alkali and / or alkaline earth metal, ammonium, alkylammonium and / or alkanolammonium or an optionally functionalized alkyl and / or alkenyl radical having 1 to 22, preferably 2 to 18 and in particular 6 to 12 carbon atoms. Typical examples are optionally hydroxy-, nitrilo- and / or amino-substituted phosphonic acids such as ethylphosphonic acid, nitrilotris (methylenephosphonic acid), 1-amino- or 1-hydroxyalkane-1, 1-diphosphonic acids. In a preferred embodiment of the invention, amine oxide phosphonic acids are used which follow the formula (II)

0 CH ₃ H

II I I

HO-P- (CH ₂ ) _m (CH) _n -N-> 0 (II)

1 I

OR ³ H

in which R ^{3 represents} hydrogen, a (CH2) m (CHCH ₃ ) _n NH2θ group or an alkali metal, m represents numbers from 1 to 4 and n represents 0 or 1. Amine oxide phosphonic acids are builders or sequestering agents which are sold, for example, by Bozetto / IT under the SEQUION® brand. To their

Production starts from aminophosphonic acids, which are converted to amine oxide. For the purposes of the invention, both mono- and diamine oxides can be used in the form of the phosphonic acids or their salts, which follow the formula (II). Amine oxide phosphonic acids are preferably used in which R ^{3 is} hydrogen, m is 3 and n is 0 (amine oxide based on aminotrimethylenephosphonic acid). The amount of phosphonic acids or phosphonates used - based on the composition - is usually in the range from 0.3 to 0.7% by weight.

Polyacrylic acid compounds

Polyacrylic acid compounds are preferably to be understood as homopolymers of acrylic acid and methacrylic acid or their esters. In addition to the acids, esters of the acids can also be polymerized with alcohols having 1 to 4 carbon atoms. Polyacrylic acid compounds with a particularly advantageous stabilizing action are present as alkali salts and have an average molecular weight in the range from 1,000 to 10,000 and in particular 4,000 to 6,000 daltons. The preferred range of use is 0.02 to 0.05% by weight.

Alkyl ether sulfates

The agents according to the invention can contain, as further components, surfactants of the alkyl ether sulfate type, which are obtained by sulfating alkyl polyglycol ethers and subsequent neutralization. can hold. The alkyl ether sulfates which are suitable for the purposes of the invention follow the formula (III)

R ⁴ 0- (CH ₂ CH ₂ 0) nSθ3X (III)

in which R ^{4 represents} an alkyl radical having 12 to 18, in particular 12 to 14, carbon atoms, n represents numbers 2 to 5, in particular 2 to 3 and X represents sodium or potassium. Typical examples are the sodium salts of sulfates of Ci2 / i4 coconut alcohol + 2, + 2,3- and + 3-E0 adduct. The alkyl ether sulfates can have a conventional or narrow homolog distribution. The alkyl ether sulfates are preferably used in amounts of 1 to 8, preferably 1.5 to 6 and in particular 2 to 4% by weight, based on the composition.

Amine oxides

Amine oxides are also known substances, which are occasionally attributed to the cationic, but usually the nonionic surfactants. They are prepared from tertiary fatty amines, which usually have either one long and two short or two long and one short alkyl radical, and are oxidized in the presence of hydrogen peroxide. The amine oxides which are suitable as surfactant ingredients for the purposes of the invention follow the formula (IV)

IR ⁵ -N-> 0 (IV)

IR ⁷

in which R ^{5 represents} a linear or branched alkyl radical having 12 to 18 carbon atoms, and R ⁶ and R ⁷ independently of one another represent R ⁵ or an optionally hydroxy-substituted alkyl radical having 1 to 4 carbon atoms. Amine oxides of the formula (IV) in which R ⁵ and R ^{6 are} C12 / 14 or C12 / 18 coconut alkyl radicals and R ^{7 is} a methyl or a hydroxyethyl radical are preferably used. Also preferred are amine oxides of the formula (IV) in which R ^{5 is} a C12 / 14 or C12 / 18 cocoalkyl radical and R ⁶ and R ^{7 have} the meaning of a methyl or hydroxyethyl radical. The amine oxides are preferably used in amounts of 1.5 to 6, preferably 2 to 4,% by weight, based on the composition. Alkyl and / or alkenyl oligoglycosides

Alkyl and alkenyl oligoglycosides are known nonionic surfactants which follow the formula (V)

R80- [G] _P (V)

in which R ^{3 is} an alkyl and / or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms and p is a number from 1 to 10. The alkyl and / or alkenyl oligoglycosides, which are furthermore suitable as surfactant ingredients, can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. The preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides. The index number p in the general formula (V) indicates the degree of oligomerization (DP), ie the distribution of mono- and oligoglycosides, and stands for a number between 1 and 10. While p must always be an integer in a given compound and especially here can assume the values p = 1 to 6, the value p for a certain alkyl oligoglycoside is an analytically determined arithmetic parameter, which usually represents a fractional number. Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, those alkyl and / or alkenyl oligoglycosides are preferred whose degree of oligomerization is less than 1.7 and is in particular between 1.2 and 1.4. The alkyl or alkenyl radical R ⁸ can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms. Typical examples are butanol, capro alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as are obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis. Alkyl oligoglucosides of the chain length Cβ-Cio (DP = 1 to 3) are preferred, which are obtained as a preliminary step in the separation of technical Cβ-Ciβ-coconut fatty alcohol by distillation and can be contaminated with a proportion of less than 6% by weight of Ci2-alcohol and Alkyl oligoglucosides based on technical Cg / n oxo alcohols (DP = 1 to 3). The alkyl or alkenyl radical R ⁸ can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and the technical mixtures described above, which can be obtained as described above. Alkyl oligoglucosides based on hydrogenated Ci2 / 14 coconut alcohol with a DP of 1 to 3 are preferred. The glycosides are preferably used in amounts of 1.5 to 6, preferably 2 to 4% by weight, based on the composition. Fatty acid salts

The agents according to the invention can contain fatty acid salts of the formula (VI) as further surfactants,

R ⁹ CO-OX (VI)

in which R ⁹ CO is an acyl radical having 12 to 22 carbon atoms and X is an alkali metal. Typical examples are the sodium and / or potassium salts of lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoleic acid, behenic acid and technical mixtures as they occur in the pressure splitting of technical fats and oils. Salts of technical coconut or tallow fatty acids are preferably used. Since the recipes according to the invention are strongly alkaline, the fatty acids which are neutralized in situ when they are introduced into the mixture can also be used instead of the salts. Those agents according to the invention preferably contain, as an optional component, fatty acid salts in which a particular low foam level is desired. The soaps are preferably used in amounts of 1.5 to 6, preferably 2 to 4% by weight, based on the composition.

Industrial applicability

The agents according to the invention generally have a non-aqueous content of 5 to 35 and preferably 8 to 15% by weight and are suitable for the treatment of textile fabrics, such as, for example, yarns, fabric webs and in particular textiles. They are usually used at low temperatures, i.e. in the cold wash area (approx. 15 to 25 ° C). The agents are not only characterized by excellent stain removal, they also reliably prevent deposits of lime and metal on the fibers and thus also prevent encrustation and yellowing. Although the actual use of the agents is aimed at removing stains during washing, they are also fundamentally suitable for other purposes in which hypochlorite solutions are used, for example for cleaning and disinfecting hard surfaces.

Further auxiliaries and additives which may be used are, for example, other chlorine-stable surfactants or hydro tropes, such as, for example, alkyl sulfates, alkyl sulfonates, alkylbenzenesulfonates, xylene sulfonates, sarcosinates, taurides, isethionates, sulfosuccinates, betaines, sugar esters, fatty alcohol polyglycol ethers and fatty acid-N alkylglucamides. The sum of all surfactants, based on the preparations, preferably makes up 1 to 15 and preferably 5 to 10% by weight. The agents according to the invention generally have a pH in the range from 12.5 to 14. In addition, the agents can contain active chlorine-stable fragrances, optical brighteners, dyes and pigments in a total amount of 0.01 to 0.5% by weight, based on the agents. The fragrances known to be active chlorine-resistant include, for example, monocyclic and bicyclic monoterpene alcohols and their esters with acetic or propionic acid (for example isoborneal, dihydroterpene oil, isobornyl acetate, dihydroterpenyl acetate). The optical brighteners can be, for example, the potassium salt of 4,4'-bis (1, 2,3-triazolyl) - (2 -) - stilbin-2,2-suifonic acid, which is sold under the Phorwite® BHC brand 766 is distributed. Possible color pigments include green chlorophthalocyanines (Pigmosol® Green, Hostaphine® Green) or yellow Solar Yellow BG 300 (Sandoz). The agents according to the invention are produced by stirring. If necessary, the product obtained can be decanted or filtered to remove foreign bodies and / or agglomerates. The agents also have a viscosity above 100 mPas - measured at 20 ° C in a Brookfield viscometer.

Another object of the invention relates to the use of mixtures consisting of

(a) silicates,

(b) phosphonic acids and / or phosphonates and

(c) Polyacrylic acid compounds

as incrustation and yellowing inhibitors for the production of aqueous bleaching agents. The mixtures can contain the components in the weight ratio (a): (b): (c) from (10 to 50): (5 to 25): (10 to 50) under the conditions that the quantities add up to 100 parts by weight.

Examples

To investigate the bleaching effect, soiled tissue was treated with various bleaching solutions. The turbidity of the formulations was checked visually after storage for 1 or 4 weeks at 20 ° C. The incrustation of the tissue was determined by ashing, while the yellowing of the tissue was determined photometrically, the initial value of the soiled tissue serving as the standard (100%). The measurements were carried out in a liquor with a metal ion content of 300 ppb Fe and 100 ppb Mn; the water hardness was 300 ppm CaC0 ₃ . The liquor ratio (tissue: water) was 1:50, the exposure time was 30 minutes at a temperature of 40 ° C. The results are summarized in Table 1; the quantities are understood as% by weight. Preparations 1 and 2 are according to the invention, and mixtures V1 to V3 are used for comparison.

Table 1 Bleaching effect

*) Module 2.0, **) Sequion® ***). Norasol® LMW 45 N (sodium salt, MW = 4,500, from NorsoHaas)

It can be seen that the preparations according to the invention are free from haze even after storage and, compared to the products of the prior art, lead to less limescale and yellowing of the treated textiles.

Claims

claims

1. Aqueous bleaching agents containing - based on the agents -

1.0 to 10.0% by weight of alkali hypochlorite,

0.5 to 1.5% by weight of alkali hydroxide,

0.5 to 2.0% by weight of silicates,

0.01 to 1.0% by weight of phosphonic acids and / or phosphonates and

0.01 to 1.0% by weight of polyacrylic acid compounds

and, if appropriate, other customary auxiliaries and additives.

according to claim 1, characterized in that they contain sodium hypochlorite.

3. Composition according to claims 1 and 2, characterized in that they contain sodium hydroxide.

4. Composition according to claims 1 to 3, characterized in that they contain sodium, potassium and / or aluminosilicates.

5. Composition according to claims 1 to 4, characterized in that they contain phosphonic acids or phosphonates of the formula (I),

R ¹ -P-OR ² (I)

I OR ²

in which R ^{1 represents} an optionally functionalized alkyl and / or alkenyl radical with 1 to 22 carbon atoms and R ^{2 represents} hydrogen, an alkali and / or alkaline earth metal, ammonium, alkylammonium and / or alkanolammonium or an optionally functionalized alkyl and / or alkenyl radical having 1 to 22 carbon atoms.

according to Claims 1 to 5, characterized in that they contain amine oxidephosphonic acids of the formula (II),

n 0 CH ₃ H

II I I

HO-P- (CH ₂ ) m (CH) _n -N-> 0 (II)

1 I

OR ³ H

in which R ^{3 represents} hydrogen, a (CH2) m (CHCH ₃ ) _n NH2θ group or an alkali metal, m represents numbers from 1 to 4 and n represents 0 or 1.

7. Compositions according to claims 1 to 6, characterized in that they further contain alkyl ether sulfates, amine oxides and / or alkyl and / or alkenyl oligoglycosides as surfactants.

8. Composition according to claims 1 to 7, characterized in that they further contain fatty acid salts.

9. Agent according to claims 7 and 8, characterized in that they contain the surfactants and fatty acid salts - based on the agent - together in amounts of 1 to 15 wt .-%.

10. Use of mixtures consisting of

(a) silicates,

(b) phosphonic acids and / or phosphonates and

(c) Polyacrylic acid compounds

as incrustation and yellowing inhibitors for the production of aqueous bleaching agents.