ES2199448T3 - USE OF MIXTURES OF ELECTROLYTES AS SEQUESTRANTS. - Google Patents

Abstract

The invention relates to the use as sequestering agents for preparing bleaching agents, mixtures of electrolytes containing: a) phosphonates and b) at least one other electrolytic salt selected in the group comprising polyacrylates, silicates, carbonates and citrates. Preparations, preferably bleaching chloride solutions, which protect the tissue from yellowing, are also obtained together with chlorine resistant surfactants.

Description

Use of electrolyte mixtures such as kidnappers

Field of the Invention

The invention relates to the use of certain mixtures of electrolytes in the wash with aqueous bleaches.

State of the art

While they are used for textile washing soiled in many European states whole detergents powdery or liquid, which reach full power only at elevated temperatures, it is preferred, for example, by consumers in the United States and Spain cold wash, in which is added in addition to a detergent for the removal of particularly difficult spots a liquid bleach, preferably based on hypochlorite.

A great state of the art is known number of liquid bleach. This is recommended, for example, by EP-A0274885 (ICI) the use of mixtures of linear and branched amine oxides for obtaining viscous hypochlorite bleaches. According to the teaching of the EP-A 0145084 (Unilever) can be used for this purpose also mixtures of amine oxides with soaps, sarcosinates, taurids or sugar esters. Starting at EP-A 0137551 and EP-A publications 0447261 (Unilever) the use of amine oxides with soap or sarcosinate and other anionic surfactants, such as example, alkyl sulfates, alkyl ether sulfates, sulphonates of secondary alkane or alkylbenzenesulfonates as a component thickener for hypochlorite solutions. By EP-A1 0447261 further known compositions of aqueous bleaches with a sodium hypochlorite content and anionic surfactants. The hypochlorite concentration of these agents are, however, at 0.1 to 8% by weight of active chlorine In German patent DE-C1 4333100 ha proposed the applicant finally bleach bleach bleach to hypochlorite base, fatty alcohol ether sulfates, oxides of amine and aminoxydphosphonic acids. The use of silicates or Carbonates as a buffer in bleach bleach bleach can taken, for example, from US publications 4, 623,476 (Procter & Gamble) as well as EP-A1 0079102 and EP-A1 0137551 (Unilever).

Bleachers are put by the consumer high demands: they have to be compatible with textiles, that is to say by treatment with the chemical of aggressive hypochlorite itself have to remove stains without tissue attack How skin contact cannot be excluded with the bleach, the preparations also have to be the most dermatologically compatible as possible. A problem particular lies in the fact that hypochlorite solutions they also attack metals and metal traces can be deposited dissolved on the textile fibers during washing, which is finally reflects on a yellowing of the tissue. The agents of the market certainly try to avoid this redeposition by concomitant use of silicates, but in practice it is demonstrated This measure, however, is not always satisfactory.

The complex object of the invention consists, by consequently in counteracting the yellowing of clothes by the influence of heavy metal ions and make available sequestrants, which allow to obtain aqueous bleaches, particularly bleach bleach bleach, which are at the same time stable to chlorine, preservatives for textiles and most compatible with the possible skin, showing high viscosity and feasibly avoided with a high capacity of stain removal correspondingly the trace deposit Metallic on the fabric.

Description of the invention

The object of the invention is the use of mixtures of electrolytes, which contain

(a) phosphonates, chosen from phosphonates inorganic, which follow the formula (I),

HP (O) (OM1) 2 (I)

in which M means an alkali metal or alkaline earth, aluminum or zinc, and among organic phosphonates, following the formula (II),

R 1 P (O) (OR 2) 2 (II)

in which they mean R 1 and R 2 independently of each other hydrogen or hydrocarbon moieties linear or branched with 4 to 12 carbon atoms with the condition, that R1 and R2 cannot mean the same hydrogen time, and

(b) at least one other electrolytic salt, chosen of the group, which is formed by polyacrylates, silicates and carbonates,

for the reduction of metal deposits on the fabric during washing with aqueous bleaches with a alkaline hypochlorite content.

It was surprisingly found that the addition of small amounts of the electrolyte mixtures cited to hypochlorite solutions significantly reduces the deposit of metals on the fabric during washing and counteracts yellowing of the fibers. The invention includes the knowledge, that the concomitant use of mild surfactants and stable against chlorine, as preferably alkyl ether sulfates,  aminoxides, alkyl- and / or alkenyl oligoglycosides and acid salts fatty leads to a further improvement of the stabilized against the yellowing, cleanliness and compatibility dermatological The agents finally show a viscosity sufficiently high, so that a dosage is possible by the consumer without problems.

Phosphonates

They are understood in the sense of the invention by the denomination phosphonates both inorganic phosphonates (also known as secondary phosphites) of the formula (I),

HP (O) (OM1) 2 (I)

in which M means an alkali metal or alkaline earth, aluminum or zinc, preferably sodium, as also organic phosphonates of the formula (II),

R 1 P (O) (OR 2) 2 (II)

in which they mean R 1 and R 2 independently hydrogen or linear hydrocarbon moieties or branched with 4 to 12 carbon atoms with the condition, which R 1 and R 2 cannot mean hydrogen at the same time. Typical examples for inorganic phosphonates are phosphonate sodium (= sodium phosphite), calcium phosphonate (= calcium phosphite) and zinc phosphonate (= zinc phosphite). Regarding obtaining and the properties of these compounds, see Holleman-Wiberg, Lehrbuch der Anorganischen Chemie, Walter de Gruyter, Berlin, Edition 81 to 90, 1976, pages 458 and 459. Examples of organic phosphonates are butyl phosphonate and 2-ethylhexyl phosphonate.

Alkaline hypochlorites

In the case of aqueous bleaches it is of bleach bleach bleach with a hypochlorite content alkaline. They are understood by alkaline hypochlorites hypochlorite of lithium, potassium and particularly sodium. Hypochlorites can be used in quantities of 1.5 to 10, preferably of 2 to 8 and particularly 4 to 6% by weight, referred to agents.

Electrolytic salts

Phosphonates are used in conjunction with al minus one other electrolytic salt. In this case it can be silicates or alkali and / or alkaline earth carbonates or their mixtures; Typical examples are sodium silicate, silicate potassium, sodium carbonate and potassium carbonate. In a way preferred embodiment of the invention are used as salts polyelectrolyte electrolytic polyacrylate type. I know they understand therefore not only acid homopolymers acrylic, but also methacrylic acid as well as its esters with linear or branched lower alcohols with 1 to 8 atoms carbon The denomination of polyacrylate species includes also the copolymers of the cited products. Molecular weight Polyacrylate medium can vary over a wide range and will between 300 and 5,000,000, preferably between 1,000 and 1,000,000, particularly between 50,000 and 500,000 and especially between 100,000 to 250,000 Dalton. Electrolytic salts support the sequestering effect of phosphonates and guarantee that Preparations show an alkaline pH value constantly elevated in the range of 10 to 14. Phosphonates and salts electrolytes can be used in the weight ratio of 95: 5 until 5:95, preferably from 80:20 to 20:80 and particularly from 60:40 to 40:60. The quantity of mixtures used electrolytic, containing phosphonates and electrolytic salts, it can amount to 0.01 to 5, preferably 0.1 to 2 and particularly 0.5 to 1% by weight, based on Agents

Chlorine stable surfactants (a) Alkyl ether sulfates

Alkyl ether sulfates represent surfactants known anionics, which are obtained by sulfation of nonionic surfactants of the type of alkyl polyglycol ethers and Next neutralization. Alkyl ether sulfates, which enter consideration in the sense of the agents according to the invention follow to the formula (III),

R 3 O- (CH 2 CH 2 O) q SO 3 X (III)

in which R 3 means an alkyl moiety with 12 to 18, particularly with 12 to 14 carbon atoms, q numbers from 2 to 5, particularly from 2 to 3 and X sodium or potassium. The Typical examples are the sodium sulfate salts of the adduct of coconut alcohol-2-, -2,3- and -3-EO with 12 to 14 carbon atoms. Alkyl ether sulfates may show a conventional or narrowed homolog distribution. Preference is given to using alkyl ether sulfates in amounts of 1 to 8, preferably 1.5 to 6 and particularly from 2 to 4% by weight, based on Agents

(b) Amino acids

Amino acids also represent products known, which are occasionally assigned to surfactants cationic, generally, however, non-ionic. For your obtaining part of the tertiary fatty amines, which show usually a long and two short or two long alkyl moiety and one short, and they oxidize in the presence of hydrogen peroxide. The amino acids, which come into consideration in the sense of invention, follow the formula (IV),

       \ dotable {\ tabskip \ tabcolsep # \ hfil \ + # \ hfil \ + # \ hfil \ tabskip0ptplus1fil \ dddarstrut \ cr} {
 \ + R ^ {5} \ + \ cr \ + \ hskip0,1mm | \ + \ cr
R 4 - \ hskip-3mm \ + N-> O
\ + \ hskip6cm (IV) \ cr \ + \ hskip0,1mm | \ + \ cr \ +
R 6 \ + \ cr}
    

in which R 4 means an alkyl moiety linear or branched with 12 to 18 carbon atoms as well as R 5 and R 6 independently from each other R 4 or an alkyl moiety, if necessary, hydroxysubstituted with 1 to 4 carbon atoms. Preferably, amino acids of the formula (IV) are used in the which means R 4 and R 5 cocoalkyl moieties with 12 to 14 carbon atoms or with 12 to 18 carbon atoms and R 6 a methyl- or hydroxyethyl moiety. Aminoxides of the formula (IV), in which R 4 means a cocoalkyl moiety with 12 to 14 carbon atoms or with 12 to 18 carbon atoms and  R 5 and R 6 have the meaning of a methyl moiety- or of hydroxyethyl. Aminoxides are commonly used in amounts from 0.5 to 5, preferably from 1 to 1 4% by weight, referred to agents.

(c) Alkyl- and / or alkenyl oligoglycosides

Alkyl- and alkenyl oligoglycosides represent known nonionic surfactants, which follow the formula (V),

R 7 O- [G] p (V)

in which R 7 means an alkyl moiety and / or alkenyl with 4 to 22 carbon atoms, G a sugar moiety with 5 or 6 carbon atoms and p the numbers from 1 to 10. They can be obtained  according to the procedures of the chemical preparation organic Representing the numerous publications refers here to publications EP-A1 0301298 and WO 90/03977. The alkyl- and / or alkenyl oligoglycosides can derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. Preferred rent- and / or alkenyl oligoglycosides are, therefore, alkyl- and / or alkenyl oligoglycosides. The index number p in the general formula (V) indicates the degree of oligomerization (DP), that is, the distribution of mono- and oligoglycosides and means a number between 1 and 10. While p has to be in a given compound always of integers and you can adapt in this case the values of p = 1 to 6, is the p-value for a given alkyl oligoglycoside a calculative and analytically determined magnitude, which represents Often a fractional number. Preferably alkyl- and / or alkenyl oligoglycosides with an average degree of oligomerization p from 1.1 to 3.0. From the technical point of view of application, Prefer those alkyl- and / or alkenyl oligoglycosides, the degree of which oligomerization is less than 1.7 and is particularly between 1.2 and 1.4. The alkyl- or alkenyl R7 moiety can be derived from primary alcohols with 4 to 11, preferably with 8 at 10 carbon atoms. Typical examples are butanol, capronalcohol, caprilalcohol, caprinalcohol and undecilalcohol as well as their technical mixtures, as obtained, for example, in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from the Roelen oxosynthesis. Alkyl oligoglycosides with a chain length of 8 to 10 carbon atoms (DP = 1 to 3), which is produced as head in the disintegration by distillation of technical coconut fat alcohol with 8 to 18 carbon atoms and that may be impurified with a percentage lower than 6% by weight of alcohol with 12 carbon atoms as well as alkyl oligoglucosides based on technical oxoalcohols with 9 to 11 carbon atoms (DP = 1 to 3). The alkyl or alkenyl moiety R 7 can also be derived from primary alcohols with 12 to 22, preferably with 12 to 14 carbon atoms. The examples Typical are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleilalcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroselinyl alcohol, araquila alcohol, gadoleilalcohol, behenilalcohol, erucilalcohol, brasidilalcohol as well as its technical mixtures, which can be obtained as described previously. Alkyl oligoglycosides based on cocoalcohol with 12 to 14 carbon atoms hardened with a DP of 1 to 3. Preferably glycosides are used in amounts of a 1.5 to 6, preferably 2 to 4% by weight, referred to agents.

       \ newpage
    

(d) Fatty acid salts

As other surfactants may contain the agents according to the invention fatty acid salts of the formula (SAW),

R 8 CO-OX (VI)

in which R 8 CO means an acyl moiety with 12 to 22 carbon atoms and X 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, elaidinic acid, petroselinic acid, linoleic acid, linoleic acid, elaeoestearic acid, araicic acid , gadoleic acid, behenic acid and erucic acid as well as their technical mixtures, as they occur in the pressure dissociation of technical fats and oils. Preferably coconut fatty acid and tallow technical salts are used. As the recipes according to the invention are adjusted strongly alkaline, fatty acids, which are neutralized in the feed in the mixture in situ , can also be used instead of the salts. Preferably those agents according to the invention contain as an optional component salts of fatty acids, in which a particular foam poverty is desired. Preferably the soaps are used in amounts of 1.5 to 6, preferably 2 to 4% by weight, based on the agents.

Commercial use

The bleaching agents obtainable with employment according to the invention of electrolyte mixtures generally show a non-aqueous percentage from 5 to 35 and preferably from 8 up to 15% by weight and preferably used for treatment of textile surface formations, such as threads, cloth tapes and particularly textiles. It usually takes carried out its application at low temperatures, that is in the cold wash interval (approximately 15 to 25 ° C). Agents stand out not only for excellent removal of stains, but do not prevent the deposit of metallic traces on the fibers and therefore prevent also the yellowing Although the employment itself of the agents is directed  to stain removal during washing, they basically serve also for other purposes, in which solutions are used of hypochlorite, such as for cleaning and hard surface disinfection.

Like other auxiliary products and additives for example, other stable surfactants are considered chlorine or hydrotropic, such as perhaps alkyl sulfates, alkyl sulfonates, alkyl benzenesulfonates, xylene sulfonates, sarcosinates, taurides, isethionates, sulfosuccinates, betaines, sugar esters, polyglycol ethers of fatty alcohols and N-alkylglucamides of fatty acids. Preferably the sum of all surfactants amounts to a maximum of one 10 to 15% by weight of the total amount of Products contained in the recipe. The agents according to the invention may contain alkali metal compounds, preferably sodium hydroxide or potassium hydroxide, with whose help you can adjust the pH value of the recipes to an optimum value of 10 to 14, preferably from 12.5 to 13.5.

Agents may also contain products. stable aromatics against active chlorine, optical brighteners, dyes and pigments in amounts of a total of 0.01 to 0.5% by weight, based on agents. To aromatic products  known against active chlorine belong, for example, monocyclic and bicyclic monoterpenal alcohols as well as their esters with acetic or propionic acid (for example isoborneal, dihydroterpene, isobonylacetate and dihydroterpenylacetate). Others aromatic products, which come into consideration for this purpose, they are cited, for example, in publications EP-A1 0622451 (Procter & Gamble) as well as JP-A Sho 62/89800 (Raison). In the case of optical brighteners can be, for example, salt acid potassium 4,4'-bis- (1,2,3-triazolyl) - (2 -) - stinbin-2,  2-sulfonic, which is marketed under the brand Phorwite® BHC 766. As dye pigments enter consideration, among others, green chlorophthalocyanines (Pigmosol® Green, Hostaphine® Green) or Solar Yellow BG 300 (Sandoz) yellow. Obtaining the agents is carried out by stirring. In if necessary, the product obtained can be decanted or filtered to the separation of foreign bodies and / or agglomerates. The agents they also show a viscosity above 100 mPas, determined at 20 ° C in a Brookfield viscometer.

Examples

For the investigation of the bleaching effect, treated soiled tissue with different bleach bleach chlorine. The yellowing of the tissue was determined in a way photometric, serving the starting value of the soiled tissue as  normalized (100%). The measurements were carried out in a bath with a metal ion content of a 300 ppb of Fe and a 100 ppb of Mn; water hardness amounted to 1000 ppm of CaCl2, the hydrogencarbonate content at 0.013% by weight. The proportion of the bath (fabric: water) stood at 1:50, the time of action amounted to 30 minutes at a temperature of 40 ° C. The results are summarized in table 1; the indications are They understand as% by weight. Examples 1 to 6 are according to the invention, Examples V1 and V2 are for comparison.

TABLE 1 Whitening effect

Composition one two 3 4 5 6 V1 V2 Sodium hypochlorite 5.0 Hydroxide sodium 0.5 2-ethylhexyl phosphonate 0.1 0.1 0.1 0.1 - - - 0.2 Phosphite sodium - - - - 0.1 - - - Phosphite calcic - - - - - 0.1 - - Polyacrylate * 0.1 - - - - - - - Silicate sodium ** - 0.1 - 0.1 0.1 0.1 0.2 - Carbonate sodium - - 0.1 0.1 - - - - Yellowing [% -rel] 85 85 85 83 88 89 101 92 *) Acid polyacrylic, approximately 15,000 Dalton **) Module 2.0

Claims (8)

1. Use of electrolytic mixtures, which they contain

(to)

phosphonates, chosen among inorganic phosphonates, which follow the formula (I),

HP (O) (OM1) 2 (I) in which M means an alkali metal or alkaline earth, aluminum or zinc, and among organic phosphonates, following the formula (II), R 1 P (O) (OR 2) 2 (II) in which they mean R 1 and R 2 independently of each other hydrogen or hydrocarbon moieties linear or branched with 4 to 12 carbon atoms with the condition, that R1 and R2 cannot mean the same hydrogen time.,

(b)

at least one other hydrolytic salt, chosen from the group, which includes polyacrylates, silicates and carbonates,

for the reduction of the metal deposit on the fabric during washing with aqueous bleaches with a alkaline hypochlorite content. 2. Use according to claim 1, characterized in that they are used as electrolytic salts of polyacrylate homo- or copolymers of acrylic acid, methacrylic acid as well as their esters with linear or branched lower alcohols with 1 to 8 carbon atoms. 3. Use according to claim 2, characterized in that polyacrylates with an average molecular weight of 300 and 5,000,000 Daltons are used. 4. Use according to claims 1 to 3, characterized in that sodium silicate, potassium silicate, sodium carbonate, potassium carbonate or mixtures thereof are used as electrolytic salts. 5. Use according to claims 1 to 4, characterized in that phosphonates and electrolytic salts are used in the weight ratio of 95; 5 to 5:95. 6. Use according to claims 1 to 5, characterized in that the electrolytic mixtures are used in amounts of 0.01 to 5% by weight, based on aqueous bleaches. 7. Use according to claims 1 to 6, characterized in that the electrolytic mixtures are used in conjunction with chlorine stable surfactants, which are chosen from the group, which is formed by alkyl ether sulfates, aminoxides, alkyl- and / or alkenyl oligoglycosides and / or acid salts fatty 8. Use according to claims 1 to 7, characterized in that the electrolytic mixtures are used together with chlorine-stable aromatic products.