CZ248299A3 - Aqueous bleaching preparations - Google Patents

Abstract

Aqueous bleaching compositions containing, based on the composition as a whole, 1.0 to 10.0% by weight of alkaline hypochlorite, 0.5 to 1.5% by weight of alkali hydroxide, 0.5 to 2.0 % by weight of silicate, 0.01 to 1.0% by weight phosphoric and / or phosphonate acids, 0.01 to 1.0% % by weight of polyalaylic acid compounds and optionally other conventional auxiliaries and additives. Resources can be formulated so that it does not form a haze and reliably protect the treated fabric even in the presence of water hardness and heavy metal ions against incrustation and yellowing.

Description

Technical field

The present invention relates to novel aqueous bleaching compositions comprising alkali hypochlorites, alkali metal hydroxides and a ternary inhibition system, and to the use of the ternary mixture as incrustation and yellowing inhibitors for the manufacture of aqueous bleaching compositions.

Technical field

While washing heavily soiled fabrics in many European countries uses powder or liquid complete detergents that only achieve their washing effect at higher temperatures, consumers in the United States and Spain, for example, prefer cold washing to add to the detergent for removal particularly difficult to remove stains, a liquid bleaching agent, preferably based on hypochlorite.

A large number of liquid bleaching agents are known in the art. For example, it is recommended in EP-A 0274885 (ICI) to use mixtures of straight and branched amine oxides for the production of viscous hypochlorite bleaching compositions. According to EP-A 0145084 (Unilever), mixtures of amine oxides with soaps, sarcosinates, taurides or sugar esters can also be used for this purpose. EP-A 0137551 and EPA 0447261 (Unilever) disclose the use of amine oxides with soaps or sarcosinate and other anionic surfactants, for example alkyl sulfates, alkyl ether sulfates, secondary alkanesulfonates or alkylbenzenesulfonates as thickeners for hypochlorite solutions. The use of alkylarylsulfonates as thickeners in aqueous bleaching compositions containing certain stilbene dyes as optical brighteners is described in EP-A 0156438.

2 A 8801389 (Henkel Ibérica) are bleaching agents based on aqueous hypochlorite compositions which contain, as surfactant components, predominantly alkyl ether sulfates and, in addition, small proportions of amine oxides. Further, EPA1 0447261 discloses aqueous bleaching compositions comprising sodium hypochlorite and anionic surfactants. However, the concentration of hypochlorite in these compositions is 0.1 to 8 and preferably 0.5 to 5% by weight of active chlorine. In German patent DE-C1 4333100, the applicant proposed aqueous bleaching and cleaning compositions 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) are concerned with hypochlorite-containing bleaching compositions containing short-chain anionic surfactants, such as octyl sulfate. European patent application EP-A 0688857 (Procter & Gamble) describes hypochlorite bleaching compositions containing periodates and carbonates for pH adjustment. European Patent Application EP-A 0688345 (Procter & Gamble) discloses hypochlorite-based bleaching compositions containing small amounts of silicates and / or carbonates, polycarboxylates and a radical scavenger. An alkali hypochlorite bleaching agent containing carbonates and silicates for stabilizing perfume oils is also proposed in European patent application EP-A 0622451 (Procter & Gamble).

Bleaching agents of this type are subject to high demands from the consumer: they must be well tolerated by textiles, that is, the aggressive chemical hypochlorite itself must remove stains in its action without attacking the fabric. Furthermore, since skin contact with bleaching agents is not excluded, the compositions must furthermore be as dermatologically acceptable as possible. If hard water is used for washing, the problem of limestone deposition on the fibers, and thus the risk of tissue incrustation, arises especially during prolonged exposure to the composition. Another problem is that hypochlorite solutions attack •

- 3 also metals and dissolved metal traces can be deposited on textile fibers during washing, which ultimately translates into yellowing of the fabrics.

The present invention is therefore intended to meet the complex object of preparation for the storage of stable, bleach-free, aqueous bleaching compositions that are stable to chlorine, save textiles and are preferably skin-tolerant, have sufficiently high viscosity and reliably prevent limestone and metal traces on fabric.

SUMMARY OF THE INVENTION

The present invention relates to aqueous bleaching compositions which comprise, based on the composition as a whole

1.0 to 10.0 % by weight of alkali hypochlorite 0.5 to 1.5 % alkali hydroxide 0.5 to 2,0 % silicates 0.01 to 1.0 % by weight of phosphonic acids and / or phosphonates 0.01 to 1.0 % by weight of polyacrylic compounds acid

and optionally other conventional excipients and additives.

Surprisingly, it has been found that the addition of a mixture of inhibitors composed of defined amounts of silicates, phosphonic acids and / or phosphonates and polyacrylates to alkaline hypochlorite solutions significantly reduces both the deposition of limestone and metals on the fabric during washing, thereby creating crust and yellowing of the fibers, that do not produce haze and are stable when stored. Protection against incrustation and corrosion of new agents is particularly pronounced at long exposure times. The invention utilizes the knowledge that:

The use of fine chlorine-stable surfactants such as, preferably, alkyl ether sulfates, amine oxides, alkyl- and / or alkenyl oligo-glycosides and fatty acid salts leads to a further improvement in cleaning performance and dermatological tolerance. Finally, the compositions of the invention exhibit a sufficiently high viscosity such that dosing at the consumer is problem-free.

Alkaline hypochlorites and alkali hydroxides

Alkali hypochlorites are particularly understood to be lithium hypochlorite, potassium potassium and especially sodium hypochlorite. The hypochlorites may preferably be present in an amount of from 3.0 to 7.0, and in particular from 4 to 6% by weight of the composition as a whole. The term alkali hydroxides refers to sodium hydroxide and / or potassium hydroxide, which are preferably used in an amount of from 0.7 to 1.2% by weight of the composition as a whole.

Silicates

Suitable silicates for the purposes of the invention are the salts and esters of silicic acid Si (OH) ₄ and its own condensation products. Thus, for example, the following crystalline substances can be used as silicates:

(a) non-silicates (islet silicates) such as fenakite, olivine and zirconium;

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

(c) cyclosilicates (ring silicates) such as benitoid, axinite, beryl, milarit, osumilit or audialyt;

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

· · · · · · * * * * * * * * * * * * * * * * * * * * * * *

(E) phyllosilicates (foliate and layered silicates) such as talc, kaolinite or mica (eg muscovite);

(f) tectosilicates (silicates with skeleton) such as feldspar and zeolites and klatrasils or dodecasils (for example melanoflogite), thaumasite and neptunite.

As opposed to ordered crystalline silicates, for example, silicate glasses such as sodium or potassium water glass are used. These may be of natural origin (for example montmorillonite) or may be made synthetically. Aluminosilicates can also be used in other embodiments of the invention. Typical examples of alkaline or alkaline earth silicates are sodium and / or potassium silicates with a modulus in the range of 1.0 to 3.0, and preferably 1.5 to 2.0. The amount of silicate used is usually - based on the composition - in the range of 0.8 to 1.2% by weight.

Phosphonic acids and phosphonates

For the purposes of the invention, phosphonic acids are organic derivatives of HP (O) (OH) ₂ ; phosphonates are salts and esters of these phosphonic acids. The organic phosphonic acids or phosphonates which are preferably within the scope of the present invention are known chemical compounds which can be prepared, for example, by the Michaelis-Arbuzov reaction. For example, they have formula (I)

O

R ¹ -P-OR ²

I ₂

OR ² wherein R ¹ represents an optionally functionalized alkyl and / or alkenyl radical having 1 to 22, preferably 2 to 18 and especially 6 to 12?

- 6 carbon atoms and R ² represents a hydrogen atom, an alkali metal and / or alkaline earth metal, an ammonium group, alkylammonium and / or alkanolammonium or an optionally functionalized alkyl and / or alkenyl radical having 1-22, preferably 2-18 and especially 6 up to 12 carbon atoms. Typical examples are hydroxy, nitrilo and / or amino groups of optionally substituted phosphonic acids such as ethylphosphonic acid, nitrilotris (methylenephosphonic acid), 1-amino- or 1-hydroxyalkylene-1,1-diphosphonic acid. In a preferred embodiment of the invention amine phosphine acids of formula (II) are used.

CH ₃ H

II I I

Ho-P- (CH ₂ ) _m (CH) _m -N-> O (II)

I 3 I

OR ³ H where R ³ represents a hydrogen atom, (CH 2) _m (CHCH ₃ ) _n NH ₂ O or an alkali metal, m represents a number from 1 to 4 and _n is 0 or 1. Aminooxide phosphonic acids are builders or sequestering agents which are supplied for example by Bozetto / IT under the SEQUION® brand. They are prepared from aminophosphonic acids, which are converted to amine oxide. For the purposes of the invention, both mono- and diamine oxides in the form of phosphonic acids or their salts which comply with formula (II) can be used. Preference is given to using amine oxide phosphonic acids in which R ³ represents a hydrogen atom, m is 3 and n is 0 (aminotrimethylphosphonic acid amine oxide). The amount of phosphonic acids or phosphonates used is generally in the range from 0.3 to 0.7% by weight of the composition as a whole.

«& · 4 · · * · 4 ·» ·· ·

Polvacrylic acid compounds

The term polyacrylic acid compounds preferably means homopolymers of acrylic and / or methacrylic acid or esters thereof. In addition to these acids, they can also polymerize esters of acids with C1-C4 alcohols. The polyacrylic acid compounds having a particularly advantageous stabilizing effect are used in the form of alkali salts and have an average molecular weight of 1000 to 10,000 and in particular 4000 to 6000 Daltons. The preferred range of use is 0.02 to 0.05% by weight.

Alkylethersulfátv

The compositions of the invention may contain as additional components surfactants of the alkyl ether sulfate type, which may be obtained by sulfaltation of alkyl polyglycol ethers and subsequent neutralization. The alkyl ether sulfates which can be used according to the invention comply with formula (III)

R ⁴ O- (CH ₂ CH ₂ O) _m SO ₃ X (III) wherein R ⁴ represents an alkyl radical having 12 to 18, in particular 12 to 14 carbon atoms, n is 2 to 5, especially 2 to 3, and X is sodium or potassium. Typical examples are the sodium salts of sulfated adduct of C _2/14 coconut alcohol +2, +3 and + 2.3 ethylene oxide groups. Alkyl ether sulfates may have a conventional or narrowed homolog distribution. The alkyl ether sulfates are preferably used in an amount of from 1 to 8, preferably from 1.5 to 6, and in particular from 2 to 4% by weight of the composition as a whole.

Aminoxides

Known substances are present as amine oxides, which optionally belong to cationic, but generally nonionic, surfactants. With them

The production is based on tertiary fatty amines which generally contain either one long and two short alkyl radicals or two long and one short alkyl radicals which are oxidized in the presence of hydrogen peroxide. Amine oxides of formula (IV) may be used as a surfactant component within the meaning of the present invention.

R ⁶

AND

R ⁵ -N-> O (IV) wherein R ⁵ is a straight or branched C 12 -C 18 alkyl radical and R ⁶ and R ⁷ are independently R ⁵ or an optionally substituted C 1 -C 4 alkyl radical. Preferable to use amine oxides of formula (IV) in which R ⁵ and R ⁶ represent C12 / 14 or C12 / 18 coconut alkyl radicals and R ⁷ is methyl or a hydroxyethyl radical. Equally preferred are amine oxides of formula (IV) wherein R ⁵ is C 12/14 or C 12/18, respectively, a coconut alkyl radical and R ⁶ and R ⁷ are a methyl or hydroxyethyl radical. The amine oxides are preferably used in amounts of from 1.5 to 6, preferably from 2 to 4% by weight of the composition as a whole.

Alkyl- and / or alkenyloligoglycosides

Alkyl- and alkenyloligoglycosides are known nonionic surfactants of formula (V)

R ⁸ O- [G] _p (V) in which ^R represents an alkyl or alkenyl radical having 4 to 22 carbon atoms, G is a sugar radical having 5 or 6 carbon atoms, • · ·

9 and p is a number from 1 to 10. The alkyl and / or alkenyl oligoglycosides which are further suitable as surfactants may be derived from aldoses or ketoses having 5 or 6 carbon atoms, preferably glucose. Thus preferred alkyl- and / or alkenyloligoglycosides are alkyl- and / or alkenyloligoglucosides. The index p in the general formula (V) indicates the degree of oligomerization (DP), i. The distribution of mono- and oligoglycosides is between 1 and 10. While p must be an integer in a given compound and may in particular have values of p = 1 to 6, the p value for an alkyloligoglycoside is an analytically calculated calculated value, which is usually a fraction. Preference is given to using alkyl- and / or alkenyloligoglycosides having a mean degree of oligomerization of p from 1.1 to 3.0. Technically preferred are those alkyl- and / or alkenyloligoglycosides whose degree of oligomerization is less than 1.7, and in particular is between 1.2 and 1.4. The alkyl or alkenyl radical R @ ⁸ may be derived from primary alcohols having from 4 to 11, preferably from 8 to 10, carbon atoms. Typical examples are butanol, capro alcohol, caprylalcohol, caprinal alcohol and undecyl alcohol and technical mixtures thereof, which can be obtained, for example, by hydrogenation of industrial fatty acid methyl esters or during the hydrogenation of aldehydes in Roelen oxosynthesis. Preferred are C ₈ -C 10 alkyl oligoglucosides (DP value of 1 to 3) which are obtained as a support for the distillation separation of C ₈ -C ₁₈ technical coconut fatty alcohol and which may contain less than 6% by weight of C12 as impurities alcohol and alkyl oligoglucosides based on C _9/11 -oxoalcohol (DP = 1 to 3). The alkyl or alkenyl radical R @ ⁸ may 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, erukyl alcohol, brasidyl alcohol, and technical mixtures thereof as described above. Preferred are:

The C12 / 14 Coconut Alcohol Alkyl Ligoglucosides having a DP value of 1 to 3. The glycosides are preferably used in an amount of 1.5 to 6, preferably 2 to 4% by weight of the composition as a whole.

Salts of fatty acids

The compositions of the invention may contain, as further surfactants, fatty acid salts of formula (VI)

R ⁹ CO-OX (VI) wherein R ⁹ CO is a C 12 -C 22 acyl radical and X is an alkali metal. Typical examples are the sodium and / or potassium salts of lauric, myristic, palmitic, palmoleic, stearic, isostearic, oleic, eladinic, petroselinic, linoleic, linolenic, elaostearic, arachic, gadoleic, behenic and erucic acids and technical mixtures thereof, e.g. by pressure fission of technical fats and oils. Preferably, salts of technical acids of coconut or tallow fat are used. Since the pH of the formulations of the invention is set to a strongly alkaline range, fatty acids can also be used instead of salts, which are neutralized when added to the mixture in situ. The compositions according to the invention preferably contain, as an optional component, salts of fatty acids in which low foam formation is particularly desirable. Preferably, the soaps are used in an amount of from 1.5 to 6, preferably 2 to 4% by weight of the composition as a whole.

Industrial applicability

The compositions according to the invention generally have a non-aqueous component content of from 5 to 35, preferably from 8 to 15% by weight, and are suitable for the treatment of textile surfaces, such as yarns, fabric strips and especially textiles.

• · · · · · · · · · · · · · · ·

Usually, the composition is used at lower temperatures, i.e.. in the cold wash temperature range (about 15-25 ° C). The compositions not only have excellent stain removal properties, but reliably prevent the formation of traces of limestone and metals on the fibers, preventing incrustation and yellowing. Although the actual use of the compositions is intended to remove stains from washing, they are basically also useful for other purposes where hypochlorites are used, for example for cleaning and disinfecting solid surfaces.

Further auxiliaries which may be mentioned are, for example, other chlorine-stable surfactants, for example hydrotropes, such as alkyl sulfates, alkylsulfonates, alkylbenzenesulfonates, xylolsulfonates, sarcosinates, taurides, isethionates, sulfosuccinates, betaines, sugar esters of alkyl alcohol polyglycol ethers of fatty alcohol polyglycol ethers of fatty acids. Preferably, the total amount of all surfactants is 1 to 15, more preferably 5 to 10% by weight of the composition as a whole. The compositions of the invention generally have a pH in the range of 12.5 to 14.

In addition, the compositions may contain perfumes, optical brighteners, dyes, and chlorine-resistant pigments in an amount of from 0.01 to 0.5% by weight based on the composition as a whole. Known active chlorine-resistant perfumes include, for example, monocyclic and bicyclic monoterpenic alcohols and their esters with acetic or propionic acid (e.g. isoborneal, dihydroterpene oil, isobornylacetate, dihydroterpenylacetate). In the case of optical brighteners, for example, the potassium salt of 4,4'-bis- (1,2,3-triazolyl) (2 -) - stilbine-2,2-sulfonic acid, which is available as Phorwite® BHC 766, may be used. Suitable coloring pigments are, inter alia, green chlorophthalocyanines (Pigmosol (R) Green, Hostaphine (R) Green) or Solar Yellow BG 300 (Sandoz). The compositions according to the invention are prepared by mixing with one another. The product obtained may be decanted to separate foreign bodies and / or agglomerates, or

- 12 filtered. The compositions, when measured with a Brookfield viscometer, have a viscosity of greater than 100 mPas measured at 20 ° C.

Another object of the invention is the use of mixtures composed of

(a) silicates,

(b) phosphonic acids and / or phosphonates, and

c) polyacrylic acid compounds as inhibitors of incrustation and yellowing in the manufacture of aqueous bleaching compositions. The compositions may contain the individual components in a weight ratio of a): b): c) (10 to 50): (5 to 25): (10 to 50), provided that these amounts comprise a total of 100 parts by weight.

DETAILED DESCRIPTION OF THE INVENTION

To investigate the bleaching effects, the soiled fabric was treated with various bleach solution solutions. The turbidity of the mixtures was visually monitored after storage for one or four weeks at 20 ° C. The incrustation of the fabric was determined by ashing, the yellowing of the fabric was determined photometrically, the starting value for the soiled fabric always serving as a standard (100%). The measurements were performed in a bath containing metal ions of 300 ppb Fe and 100 ppb Mn; the water hardness was 300 ppm CaCO3. The fabric: water ratio was approximately 1:50, the treatment time was 30 min at 40 ° C. The results are summarized in Table 1; quantities are in percent by weight. Formulations 1 and 2 are according to the invention, mixtures V1 to V3 serve for comparison.

• ·

- 13 Table 1

Bleaching effect

Ingredients 1 2 V1 V2 V3 Sodium hypochlorite 5.0 5.0 5.0 5.0 5.0 Sodium hydroxide 0.9 0.95 1.0 0.9 0.5 Sodium silicate * 0.95 0.95 1.0 - 0.8 Sodium carbonate - - 0.5 1,2 1,2 Acid aminoxidphosphonová 0.1 0.1 - 0.1 - *** Polyacrylate 0.05 0.05 0.05 0.05 0.05 Appearance after 1 week pure pure pure pure cloudy Appearance after 4 weeks pure pure cloudy cloudy cloudy Incrustation (rel.%) 105 103 113 115 118 Yellowing (rel.%) 28 32 54 56 54

*) Module 2.0, **) Sequion®, ***) Norasol® KMW 45N (sodium salt, 5 molecular weight = 4500, by NorsoHaas)

It has been shown that the compositions according to the invention do not produce haze even after storage and, in comparison with the prior art products, result in reduced limestone deposition and less yellowing of the treated fabrics.

Represented by:

Claims (10)

PATENT CLAIMS 1 2 R ¹ -P-OR ² (I) I ₂ OR ² wherein R ¹ represents an optionally functionalized alkyl and / or alkenyl radical of 1 to 22 and R ² represents a hydrogen atom, an alkali metal and / or an alkaline earth metal, an ammonium group, an alkylammonium and / or alkanolammonium group or an optionally functionalized alkyl- and / or or an alkenyl radical having 1 to 22 carbon atoms. Aqueous bleaching compositions, characterized in that they contain, based on the composition as a whole Compositions according to claim 1, characterized in that They contain sodium hypochlorite. Compositions according to claim 1 or 2, characterized in that they contain sodium hydroxide. 20 May Compositions according to one of Claims 1 to 3, characterized in that they contain sodium, potassium and / or aluminosilicates. Compositions according to any one of claims 1 to 4, 25 characterized in that they contain phosphonic acids or phosphonates of the general formula (I) - 15 o 5 1.0 to 10.0 % by weight of alkali hypochlorite 0.5 to 1.5 % alkali hydroxide 0.5 to 2,0 % silicate 0.01 to 1.0 % by weight of phosphonic acids and / or phosphonates 10 0.01 to 1.0 % by weight of polyacrylic compounds acids and optionally other customary auxiliaries and additives. Compositions as claimed in any one of claims 1 to 5, characterized in that they contain amine oxide phosphonic acids of the formula (II) CH ₃ H II I I Ho-P- (CH ₂ ) m (CH) _m -N-> O (II) I ₃ I OR ³ H wherein R ³ represents a hydrogen atom, a (CH ₂ ) _m (CHCH 3) _n NH ₂ O or an alkali metal, m represents a number from 1 to 4 and _n is 0 or 1. Compositions according to any one of claims 1 to 6, characterized in that they additionally contain as surfactants alkyl ether sulphates, amine oxides and / or alkyl and / or alkenyl oligoglycosides. 8. Compositions according to characterized fatty acids. 8. The method of claim 1, further comprising salts 9. The composition according to any one of the preceding claims wherein the total amount of fatty acids is 1 based on the composition as a whole. of claims 7 and 8, containing surfactants and salts of up to 15% by weight 10. Use of mixtures composed of (a) silicates, (b) phosphonic acids and / or phosphonates; and c) polyacrylic acid compounds as incrustation and yellowing inhibitors for the manufacture of aqueous bleaching compositions. Represented by: