EP2132288B1 - Detergent composition containing bleaching agent - Google Patents

Description

The present patent application relates to detergents or cleaners containing peracid particles and corrosion inhibitor.

Phthalimidoperoxoalkanoic acids such as 6-phthalimidoperoxohexanoic acid (PAP) are highly efficient bleaches. Their use in solid as well as liquid detergents or cleaning agents has been variously proposed.

When using phthalimidoperoxoalkansäurehaltiger detergent formulations can be found in commercial washing machines, however, after about at least 50 wash cycles traces of corrosion, which are often found on the brackets of the heating elements and the heating elements themselves, and largely independent of whether it is nickel-plated material. In the case of nickel-plated heating elements in particular, it may happen that the Ni layer of the nickel-plated heating elements is first removed directly at the point of contact with the holder made of Cr steel or stainless steel such as Nirosta® 4301. There may be a brownish "yard" around this spot, which is presumably rust. Likewise, rust often occurs at the Heizstabhalterung in the immediate vicinity of the contact point. The heating element itself may be coated with small, brownish discolorations, which, however, are usually not nearly as pronounced elsewhere as at the point of contact with the holder. When such corrosion phenomena occur, a premature failure of the heating element must be expected. Correspondingly, the same corrosion effect also results in dishwashers.

In EDX measurements on steel pieces treated with phthalimidoperoxoalkanoic acid-free and for comparison with phthalimidoperoxoalkansäurehaltiger wash liquor, nitrogen can be detected on the metal surface after treatment with phthalimidoperoxoalkansäurehaltiger liquor. This leads to the conclusion that phthalimidoperoxoalkanoic acids have an affinity for the metal surface and adsorb onto it.

The corrosion potential between nickel and steel in a phthalimidoperoxoalkansäurehaltigen wash liquor is time-dependent. This temporal change in potential may be due to degradation of the phthalimidoperoxoalkanoic acid.

Without wishing to be bound by this theory, this adsorption of the phthalimidoperoxoalkanoic acid on the metal surface may be the cause of the corrosive action, since in this case the oxidizing agent phthalimidoperoxoalkanoic acid is present directly at the surface of the cathode in a high concentration.

Surprisingly, it has been found that this problem can not be solved by the use of any known corrosion inhibitors.

The present invention, which seeks to remedy this, is a bleach-containing washing or cleaning agent containing a particulate Phthalimidoperoxoalkansäure and Zn ions, In addition, it may be an active ingredient selected from the group comprising benzotriazole, nitrate ions, phosphonocarboxylic acids, phosphonic acids, phosphates, Polyaspartic acids, fatty amines, surfactants with nitrogen-containing head groups and mixtures thereof. Instead of the abovementioned acids or in addition to these, their salts, in particular ammonium, alkylammonium, hydroxyalkylammonium and / or alkali metal salts may also have.

Zn ions are introduced in the form of water-soluble Zn salts, for example zinc acetate, zinc nitrate and / or zinc sulfate. These are combined in preferred embodiments of the invention with at least one other of said active ingredients, wherein in the case of said acids, the combination can also be realized by the use of the corresponding zinc salts. The concentration of the zinc salt in the washing or cleaning liquor is preferably in the range from 1 ppm to 500 ppm, in particular from 10 ppm to 200 ppm. An agent according to the invention preferably contains 0.05% by weight to 4% by weight, in particular 0.2% by weight to 2% by weight, of zinc salt.

For example, nitrate can be introduced into the agent according to the invention via said zinc nitrate or as an alkali metal salt, for example sodium nitrate.

Phosphonocarboxylic acids may have one or more carboxylic acid functionalities. Moreover, they may include other functionalities, such as N-oxide, amino and / or hydroxyl groups. Preferred phosphonocarboxylic acids include 2-hydroxyphosphonoacetic acid and 2-phosphonobutane-1,2,4-tricarboxylic acid. In agents according to the invention are preferably up to 10 wt .-%, in particular 2 wt .-% to 4 wt .-% phosphonocarboxylic acid.

The usable phosphonic acids may also contain other functionalities, such as N-oxide, amino and / or hydroxyl groups. The preferred phosphonic acids include (1-hydroxyethylidene) diphosphonic acid, amino tri (methylenephosphonic acid), ethylenediamine tetra (methylenephosphonic acid) and / or diethylenetriamine penta (methylenephosphonic acid) and the N-oxides of said nitrogen-containing compounds. In agents according to the invention are preferably up to 10 wt .-%, in particular 2 wt .-% to 4 wt .-% of phosphonic acid. Suitable phosphonic acids, mixtures of phosphonic acids and / or salts thereof are commercially available, for example under the name Cublen® MA from Zschimmer & Schwarz (Germany) or under the name Aquacid® 1084 EX from Aquapharm Chemical (India).

The preferred phosphates include orthophosphate, pyrophosphate, triphosphate and polyphosphates. They have customary countercations, preferably alkali metal ions such as sodium and / or potassium. Phosphates are preferably present in agents according to the invention in amounts of up to 40% by weight, in particular from 2% by weight to 20% by weight. Polyaspartic acid is commercially available, for example, under the name Baypure® CX.

Fatty amines are nitrogen analogs of fatty alcohols. They are produced industrially by ammonolysis of fatty alcohols or fatty acids via the fatty acid nitrile stage. Depending on the choice of reaction conditions, the hydrogenation of the fatty acid nitriles leads to the primary fatty amine or to symmetrical secondary and tertiary fatty amines.

Among the surfactants having nitrogen-containing head groups, trimethyl fatty alkyl ammonium compounds and the alkyl sarcosinates are particularly preferred.

In solid compositions according to the invention, in addition to the substance classes mentioned, the use of mercapto compounds such as mercaptobenzothiazole is also suitable. In liquid compositions, these can be used if the composition consists of several separately stored sub-compositions and they are present in a partial composition which is free of phthalimidoperoxoalkanoic acid.

It corresponds to particularly preferred embodiments, when the agent according to the invention 0.05 wt .-% to 10 wt .-%, preferably 0.1 wt .-% to 5 wt .-%, advantageously 0.2 wt .-% to 4 wt %, in particular 0.3 wt .-% to 3 wt .-% of said active ingredient, wherein the indication wt .-% based on the total mean.

The concentration of said active substance in the wash liquor is preferably at least 2 ppm, advantageously in the range from 5 ppm to 300 ppm, more advantageously in the range from 10 ppm to 250 ppm, in particular in the range from 20 ppm to 200 ppm.

In addition to the ions, an agent according to the invention may additionally contain polycarboxylate in preferred embodiments. Polycarboxylates are preferably present in amounts of from 0.5% to 15% by weight, more preferably from 1% to 10% by weight, advantageously 2% Wt .-% to 8 wt .-%, in particular 3 wt .-% to 6 wt .-% in the agent, wt .-% based on the total agent.

The concentrations of the polycarboxlates in the wash liquor is preferably at least 40 ppm, advantageously in the range of 50 ppm to 500 ppm, more advantageously in the range of 100 ppm to 400 ppm, in particular in the range of 150 ppm to 300 ppm

Suitable polycarboxylates are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a weight-average molar mass M _{w of} from 500 to 70,000 g / mol, with particular preference being given to those polycarboxylates which have a low molecular weight M _w , preferably less than 40,000 g / mol.

According to a preferred embodiment of the invention, preference is given to those polycarboxylates which have weight-average molecular weights M _w in the range of less than 40 000 g / mol, advantageously less than 30 000 g / mol, preferably less than 20000, preferably in the range from 1000 to 15 000 g / mol, in particular in the range from 2000 to 10,000 g / mol.

For the purposes of this document, the molecular weights stated for the polycarboxylates are weight-average molar masses M _{w of} the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

The term polycarboxylates also includes copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Suitable are e.g. Copolymers of acrylic acid with maleic acid containing from 50 to 90% by weight of acrylic acid and from 50 to 10% by weight of maleic acid.

In order to improve the solubility in water, the polycarboxylates may also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomer.

It is also possible to use biodegradable polymers of more than two different monomer units which contain, as monomers, salts of acrylic acid and maleic acid and, for example, vinyl alcohol or vinyl alcohol derivatives or, as monomers, salts of acrylic acid and 2-alkylallyl sulphonic acid and, for example, sugar derivatives.

It is particularly preferred if the polycarboxylates polyacrylates (ie homopolymers and / or copolymers of acrylic acid) are included in the composition according to the invention, preferably those having weight average molecular weights M _w in the range less than 40,000 g / mol, advantageously less than 30,000 g / mol, preferably less than 20,000 , preferably in the range from 1000 to 15000 g / mol, in particular in the range from 2000 to 10000 g / mol, the molar masses being determined by gel permeation chromatography as indicated above. This corresponds to a particularly preferred embodiment. Suitable polyacrylates are commercially available, for example Sokalan® PA 25 Cl or Sokalan® PA 30 CI, both of which are commercial products of BASF AG.

The content of phthalimidoperoxoalkanoic acid in the compositions according to the invention is preferably 0.5% by weight to 25% by weight, in particular 1% by weight to 20% by weight and particularly preferably 1.5% to 15% by weight, Wt .-% based on the total agent.

The concentration of phthalimidoperoxoalkanoic acid in the wash liquor is preferably at least 5 ppm, but is advantageously in the range of 10 ppm to 400 ppm, preferably in the range of 20 ppm to 300 ppm, in particular in the range of 30 ppm to 200 ppm.

The phthalimidoperoxoalkanoic acid may have been formulated in a known manner using inert carrier materials in particulate form; preferably it is used in coated form. For example, 4-phthalimidoperoxobutanoic acid, 5-phthalimidoperoxopentanoic acid, 6-phthalimidoperoxohexanoic acid, 7-phthalimidoperoxoheptanoic acid, N, N'-terephthaloyl-di-6-amino-peroxohexanoic acid and mixtures of these come into consideration. Preferred phthalimidoperoxoalkanoic acids include 6-phthalimidoperoxohexanoic acid (PAP).

If desired, the phthalimidoperoxoalkanoic acid particles present in the composition of the invention may be coated. It is important that the coating material releases the coated peroxycarboxylic acid under the conditions of use of the composition (at a higher temperature, by dilution with water-changing pH, or the like). A preferred coating material is one which consists, at least in part, of saturated fatty acid. The chain length of the fatty acid is preferably greater than C ₁₂ , particularly preferred is stearic acid. Another preferred coating material is paraffin.

A coating material, if present, is preferably applied to the particulate peroxycarboxylic acid in amounts such that the coated peroxycarboxylic acid particles consist of 1% to 50% by weight of the coating material. The diameters of the coated Peroxocarbonsäureteilchen are preferably in the range of 100 microns to 4000 microns; Therefore, it starts from correspondingly finely divided Peroxocarbonsäurematerial and covers it with the wrapping material. Preferably, the procedure is to spray a fluidized bed of the peroxycarboxylic acid particles to be coated with a solution or slurry, preferably an aqueous solution, or a melt of the coating material, if present Solvent or suspending agent, preferably water, removed by evaporation or solidifies the molten cladding material by cooling and discharges the enveloped peroxycarboxylic in basically conventional manner from the fluidized bed. In the case of the mentioned coating with fatty acids and / or paraffin, a melt coating is preferred.

In addition to the active substances mentioned and the peroxycarboxylic acid particles, a washing or cleaning agent according to the invention may contain all ingredients customary in such agents, for example surfactant, builder, enzymes and other auxiliaries, such as soil repellants, thickeners, dyes and fragrances or the like.

In a preferred embodiment, it contains nonionic surfactants and optionally anionic surfactants, cationic surfactants and / or amphoteric surfactants.

Surfactants of the sulfonate type, alk (en) ylsulfates, alkoxylated alk (en) ylsulfates, ester sulfonates and / or soaps are preferably used as anionic surfactants.

As surfactants of the sulfonate type are preferably C ₉ -C ₁₃ alkylbenzenesulfonates, olefinsulfonates, ie mixtures of alkene and Hydroxyalkansulfonaten and disulfonates, such as those from C ₁₂ -C ₁₈ monoolefins having terminal or internal double bond by sulfonation with gaseous Sulfur trioxide and subsequent alkaline or acid hydrolysis of the sulfonation obtained.

Alk (en) ylsulfates are the alkali metal salts and, in particular, the sodium salts of the sulfuric monoesters of C ₁₀ -C ₁₈ fatty alcohols, for example of coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or of C ₈ -C ₂₀ -oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, straight-chain alkyl radical produced on a petrochemical basis. Of washing-technical interest, C ₁₂ -C ₁₆ -alkyl sulfates and C ₁₂ -C ₁₅ -alkyl sulfates and C ₁₄ -C ₁₅ -alkyl sulfates and C ₁₄ -C ₁₆ -alkyl sulfates are particularly preferred. 2,3-alkyl sulfates, which may for example be obtained as commercial products from Shell Oil Company under the name DAN ^®, are suitable anionic surfactants.

Also, the sulfuric acid monoesters of the straight-chain or branched C ₇ -C ₂₁ -alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C ₉ -C ₁₁ -alcohols having on average 3.5 mol of ethylene oxide (EO) or C ₁₂ -C ₁₈ Fatty alcohols containing 1 to 4 EO are suitable. Due to their high foaming behavior, they are usually used in detergents only in relatively small amounts, for example in amounts of from 0 to 5% by weight.

Also suitable are the esters of α-sulfo fatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids.

As further anionic surfactants are particularly soaps into consideration. Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural fatty acids, for. Coconut, palm kernel or tallow fatty acids, derived soap mixtures. In particular, those soap mixtures are preferred which are composed of 50 to 100 wt .-% of saturated C ₁₂ -C ₂₄ fatty acid soaps and 0 to 50 wt .-% of Olsäureseife.

Another class of anionic surfactants is the class of ether carboxylic acids obtainable by the reaction of fatty alcohol ethoxylates with sodium chloroacetate in the presence of basic catalysts. They have the general formula: RO- (CH ₂ -CH ₂ -O) _p -CH ₂ -COOH with R = C ₁ -C ₁₈ and p = 0.1 to 20. Ethercarboxylic acids are water hardness insensitive and have excellent surfactant properties.

Cationic surfactants contain the surface activity of the high molecular weight hydrophobic residue upon dissociation in aqueous solution in the cation. The most important representatives of the cationic surfactants are the quaternary ammonium compounds of the general formula: (R ¹ R ² R ³ R ⁴ N ⁺ ) X ^- . Where R _{1 is} C ₁ -C ₈ -alk (en) yl, R ² to R ⁴ are each independently C _n H _{2n + 1-px} - (Y ¹ (CO) R ⁵ ) _p - (Y ² H) _x , where n stands for integers without 0 and p and x stand for integers or 0. Y ¹ and Y ² are each independently O, N or NH. R ⁵ denotes a C ₃ -C ₂₃ -alk (en) yl chain. X is a counterion, which is preferably selected from the group of alkyl sulfates and alkyl carbonates. Particularly preferred are cationic surfactants in which the nitrogen group is substituted with two-long acyl and two short alk (en) yl radicals.

Amphoteric or ampholytic surfactants have a plurality of functional groups which can ionize in aqueous solution and thereby - depending on the conditions of the medium - give the compounds anionic or cationic character. Near the isoelectric point, the amphoteric surfactants form internal salts, rendering them difficult or insoluble in water. Amphoteric surfactants are subdivided into ampholytes and betaines, the latter being present in solution as zwitterions. Ampholytes are amphoteric electrolytes, ie, compounds that have both acidic and basic hydrophilic groups and thus behave acidic or basic depending on the condition. Betaines are compounds with the atomic group R ₃ N ⁺ -CH ₂ -COO ^- which show typical properties of zwitterions.

The nonionic surfactants used are preferably alkoxylated and / or propoxylated, in particular primary, alcohols having preferably 8 to 18 C atoms and on average 1 to 12 moles of ethylene oxide (EO) and / or 1 to 10 moles of propylene oxide (PO) per mole of alcohol. Particular preference is given to C ₈ -C ₁₆ -alcohol alkoxylates, advantageously ethoxylated and / or propoxylated C ₁₀ -C ₁₅ -alcohol alkoxylates, in particular C ₁₂ -C ₁₄ -alcohol alkoxylates, having a degree of ethoxylation of between 2 and 10, preferably between 3 and 8, and / or a degree of propoxylation between 1 and 6, preferably between 1.5 and 5. The stated degrees of ethoxylation and propoxylation represent statistical averages that can be a whole or a fractional number for a particular product. Preferred alcohol ethoxylates and propoxylates have a narrow homolog distribution (narrow range ethoxylates / propoxylates, NRE / NRP). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO can also be used. Examples include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.

In addition, as further nonionic surfactants and alkyl glycosides of the general formula RO (G) _x , z. B. as compounds, especially with anionic surfactants, are used, in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol that represents a glycose unit having 5 or 6 C atoms, preferably glucose. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.1 to 1.4.

Another class of preferred nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl ester. Particularly preferred are C ₁₂ -C ₁₈ fatty acid methyl esters having an average of 3 to 15 EO, in particular having an average of 5 to 12 EO.

Nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethyl-amine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.

Other suitable surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated by a so-called "spacer". This spacer is typically a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, however, the term gemini surfactants is understood to mean not only dimeric but also trimeric surfactants.

Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers or dimer alcohol bis- and trimer tris sulfates and ether sulfates. End-capped dimeric and trimeric mixed ethers are characterized in particular by their bi- and multi-functionality. So have the said end-capped surfactants good wetting properties and are low in foam, so that they are particularly suitable for use in machine washing or cleaning processes. However, it is also possible to use gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides.

The amount of surfactants present in the agents according to the invention is preferably 0.1% by weight to 50% by weight, in particular 10% by weight to 40% by weight, and particularly preferably 20% by weight to 70% by weight. -%. Preference is given to using mixtures of anionic and nonionic surfactants.

Suitable enzymes are, in particular, those from the class of the hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases in the wash contribute to the removal of stains such as proteinaceous, greasy or starchy stains, and graying. Cellulases and other glycosyl hydrolases can contribute to color retention and increase the softness of the fabric by removing pilling and microfibrils. It is also possible to use oxidoreductases for bleaching or inhibiting color transfer.

Particularly suitable are enzymatic agents obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens. Preferably, subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used. In this case, enzyme mixtures, for example from protease and amylase or protease and lipase or lipolytic enzymes or protease and cellulase or from cellulase and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest. Examples of such lipolytic enzymes are the known cutinases. Peroxidases or oxidases have also proved suitable in some cases. Suitable amylases include in particular α-amylases, iso-amylases, pullulanases and pectinases. As cellulases are preferably cellobiohydrolases, endoglucanases and β-glucosidases, which are also called cellobiases, or mixtures thereof used. Since the different cellulase types differ by their CMCase and avicelase activities, targeted mixtures of the cellulases can be used to set the desired activities.

The proportion of enzymes or enzyme mixtures may be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 3% by weight. They are preferably used in preparations according to the invention in particulate form.

Further detergent ingredients may be builders, cobuilders, soil repellents, alkaline salts and foam inhibitors, complexing agents, enzyme stabilizers, grayness inhibitors, optical brighteners and UV absorbers.

As a builder, for example, fine crystalline, synthetic and bound water-containing zeolite can be used, preferably zeolite A and / or P. As zeolite P zeolite MAP ^® (commercial product from Crosfield) is particularly preferred. Also suitable however are zeolite X and mixtures of A, X and / or P. Of particular interest is a co-crystallized sodium / potassium aluminum silicate of zeolite A and zeolite X, which as VEGOBOND AX ^® (a product of Condea) commercially available is. The zeolite may preferably be used as a spray-dried powder. In the event that the zeolite is used as a suspension, it may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3 wt .-%, based on zeolite, of ethoxylated C ₁₂ -C ₁₈ fatty alcohols having 2 to 5 ethylene oxide groups , C ₁₂ -C ₁₄ fatty alcohols having 4 to 5 ethylene oxide groups or ethoxylated isotridecanols. Suitable zeolites have an average particle size of less than 10 μm (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water. In addition, phosphates can also be used as builders.

Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the general formula NaMSi _x O _{2x + 1} y H ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 is up to 20 and preferred values for x are 2, 3 or 4. Preferred crystalline layered silicates of the formula given are those in which M is sodium and x assumes the values 2 or 3. In particular, both β- and δ-sodium disilicates Na ₂ Si ₂ O ₅ y H ₂ O are preferred.

The preferred builder substances also include amorphous sodium silicates with a Na ₂ O: SiO ₂ modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2, 6, which are delay-delayed and have secondary washing properties. The dissolution delay over conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by over-drying. In the context of this invention, the term "amorphous" is also understood to mean "X-ray amorphous". This means that in X-ray diffraction experiments the silicates do not give sharp X-ray reflections typical of crystalline substances, but at most one or more maxima of the scattered X-rays which are several angstroms in width of the diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, with values of up to max. 50 nm and in particular up to max. 20 nm are preferred. Particularly preferred densified / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.

Suitable organic builder substances which are useful as co-builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA) and their derivatives and mixtures thereof. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures thereof.

The acids themselves can also be used. In addition to their builder effect, the acids also typically have the property of an acidifying component and thus also serve to set a lower and milder pH of detergents or cleaners. In particular, citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here. Further useable acidulants are known pH regulators, such as sodium bicarbonate and sodium hydrogen sulfate.

Other suitable builders are polymeric polycarboxylates, for example the alkali metal salts of polyacrylic acid or of polymethacrylic acid, for example those having a relative molecular weight of 500 to 70,000 g / mol.

For the purposes of this document, the molecular weights given for polymeric polycarboxylates are, for the purposes of this document, weight-average molar masses M _{w of} the particular acid form, which were determined in principle by gel permeation chromatography (GPC), using a UV detector. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.

Polymers suitable as builders are, in particular, polyacrylates, which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molecular weights of from 2,000 to 10,000 g / mol, and particularly preferably from 3,000 to 5,000 g / mol, may again be preferred from this group.

Suitable polymers may also include substances consisting partly or wholly of units of vinyl alcohol or its derivatives.

Also suitable as builders are copolymeric polycarboxylates, in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid. Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable. Their relative molecular weight, based on free acids, is generally from 2,000 to 70,000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol. The (co) polymeric polycarboxylates can be used either as an aqueous solution or, preferably, as a powder.

To improve the water solubility, the polymers may also contain allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid as a monomer.

Also particularly preferred are biodegradable polymers of more than two different monomer units, for example those containing as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.

Further copolymers which are suitable as builders are those which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.

Further suitable builder substances are polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups. Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.

Further suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches. The hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes. Preferably, it is hydrolysis products having average molecular weights in the range of 400 to 500 000 g / mol. In this case, a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is. Both maltodextrins with a DE of between 3 and 20 and dry glucose syrups with a DE of between 20 and 37 and also yellow dextrins and white dextrins with relatively high molecular weights in the range from 2 000 to 30 000 g / mol are useful.

The oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function. These are at C ₆ and / or under ring opening C ₂ / C _{3 of} the saccharide ring oxidized products. A product oxidized to C _{6 of} the saccharide ring may be particularly advantageous.

Oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable co-builders. In this case, ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts. Also preferred in this context are glycerol disuccinates and glycerol trisuccinates. Suitable amounts are in zeolithhaltigen and / or silicate-containing formulations at 3 to 15 wt .-%.

Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.

In addition, the compositions may also contain components which positively influence the oil and grease washability from textiles, so-called soil repellents. This effect is particularly evident when a textile is dirty, which has been previously washed several times with a detergent according to the invention, which contains this oil and fat dissolving component. The preferred oil and fat dissolving components include, for example, nonionic cellulose ethers such as methylcellulose and methylhydroxypropylcellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic cellulose ether, and polymers of phthalic acid and / or terephthalic acid or derivatives thereof known from the prior art, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic and terephthalic acid polymers.

When used in automatic washing processes, it may be advantageous to add conventional foam inhibitors to the compositions. As foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C ₁₈ -C ₂₄ fatty acids. Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silica or bistearylethylenediamide. It is also advantageous to use mixtures of different foam inhibitors, for example those of silicones, paraffins or waxes.

An agent according to the invention can be solid or liquid. Liquid agents are preferably hydrous. The pH of liquid compositions according to the invention is preferably between 2 and 6, in particular between 3 and 5.5 and more preferably between 3.5 and 5. If desired, water in such compositions according to the invention can be present in amounts of up to 90% by weight, in particular 20 wt .-% to 75 wt .-%, be included; if necessary, however, these areas can also be exceeded or fallen short of. Preferred liquid agents have densities of 0.5 to 2.0 g / cm ³ , in particular 0.7 to 1.5 g / cm ³ , on. The difference in density between the phthalimidoperoxoalkanoic acid particles and the liquid phase of the composition is preferably not more than 10% of the density of either, and is particularly so low that the phthalimidoperoxoalkanoic acid particles, and preferably also any other solid particles contained in the agents, float in the liquid phase.

Polydiols, ethers, alcohols, ketones, amides and / or esters, in amounts of up to 80% by weight, preferably 0.1 to 70% by weight, in particular 0.1, can preferably be used as organic solvents, especially in liquid agents according to the invention to 60 wt .-%, can be used. Preference is given to low molecular weight polar substances, such as, for example, methanol, ethanol, propylene carbonate, acetone, acetonylacetone, diacetone alcohol, ethyl acetate, 2-propanol, ethylene glycol, propylene glycol, glycerol, diethylene glycol, dipropylene glycol monomethyl ether and dimethylformamide or mixtures thereof.

Grayness inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing the dirt from being rebuilt. Water-soluble colloids of mostly organic nature are suitable for this purpose, for example the water-soluble salts of (co) polymeric carboxylic acids, glue, gelatin, salts of ethercarboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, soluble starch preparations and other than the above-mentioned starch products can be used, for. Degraded starch, aldehyde levels, etc. Also, polyvinylpyrrolidone is useful. However, preference is given to cellulose ethers, such as carboxymethylcellulose (sodium salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, and polyvinylpyrrolidone, for example, in amounts of from 0.1 to 5% by weight, based on the compositions, used.

The funds can optical brighteners such. B. derivatives of Diaminostilbendisulfonsäure or their alkali metal salts. Suitable z. B. salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or compounds of similar structure, instead of the morpholino group a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyrene type may be present, e.g. the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4- (4-chlorostyryl) -4 '- (2- sulfostyryl). Mixtures of the aforementioned brightener can be used.

In addition, UV absorbers can also be used. These are compounds with pronounced ultraviolet radiation absorbability, which are used as light stabilizers (UV stabilizers) for both Improve the light resistance of dyes and pigments as well as textile fibers and also protect the skin of the wearer of textile products from the textile through the urgent UV radiation. In general, the compounds which are active by radiationless deactivation are derivatives of benzophenone whose substituents, such as hydroxyl and / or alkoxy groups, are usually in the 2- and / or 4-position. Furthermore, substituted benzotriazoles are also suitable, furthermore in the 3-position phenyl-substituted acrylates (cinnamic acid derivatives), optionally with cyano groups in the 2-position, salicylates, organic nickel complexes and natural products such as umbelliferone and the body's own urocanic acid. In a preferred embodiment, the UV absorbers absorb UV-A and UV-B radiation and optionally UV-C radiation and radiate back with wavelengths of blue light, so that they additionally have the effect of an optical brightener. Preferred UV absorbers are also triazine derivatives, eg. B. hydroxyaryl-1,3,5-triazine, sulfonated 1,3,5-triazine, o-hydroxyphenylbenzotriazole and 2-aryl-2H-benzotriazole and bis (anilinotriazinylamino) stilbene disulfonic acid and derivatives thereof. As UV absorbers, it is also possible to use pigments which absorb ultraviolet radiation, such as titanium dioxide.

Liquid agents according to the invention may, if desired, contain customary thickeners and anti-settling agents and also viscosity regulators such as polyacrylates, polycarboxylic acids, polysaccharides and their derivatives, polyurethanes, polyvinylpyrrolidones, castor oil derivatives, polyamine derivatives such as quaternized and / or ethoxylated hexamethylenediamines and any desired mixtures thereof. Preferred liquid agents contain xanthan gum as thickening agents and have a viscosity between 100 and 10,000 mPa.s when measured with a Brookfield viscometer at a temperature of 20 ° C. and a shear rate of 20 min ^-1 .

Liquid agents according to the invention can also consist of at least two, preferably exactly two, separate subcomponents which are present in a multichamber container separated from each other, wherein in one chamber a hydrous dispersion of the particulate phthalimidoperoxoalkanoic acid containing an active ingredient selected from the group comprising Zn ions, Phosphonocarboxylic acids, phosphonic acids, phosphates, polyaspartic acids, fatty amines, surfactants containing nitrogen-containing head groups and mixtures thereof, contains, and located in the second chamber or the other chambers, the remaining ingredients of the finished detergent or cleaning composition. The corrosion inhibitor actives may, in principle, also be contained in the second chamber, i. not in the same chamber in which the dispersion of the particulate phthalimidoperoxoalkanoic acid is contained.

The compositions may contain other typical detergent and cleaner components such as perfumes and / or dyes, preference being given to those dyes which have no or negligible coloring action on the textiles to be washed. Preferred amount ranges of the totality The dyes used are less than 1 wt .-%, preferably less than 0.1 wt .-%, based on the agent. The agents may optionally also white pigments such. B. TiO ₂ included.

Another object of the invention is the use of a hydrous dispersion of a particulate Phthalimidoperoxoalkansäure, the Zn ions optionally additionally contains polycarboxylate, for the preparation of particular liquid detergents or cleaning agents.

Another object of the invention is the use of Zn ions, optionally in admixture with additionally polycarboxylate, for suppressing corrosion phenomena on machine parts in textile washing in an automatic washing machine using phthalimidoperoxoalkansäurehaltiger detergent.

Examples Example 1: Means E1 and E2 are not covered by the claims.

The liquid detergent E1 was a perfume-containing and surfactant-containing liquid detergent which had been adjusted to a pH of 5.0 and had a total surfactant content (anionic and nonionic surfactant) of about 27% by weight. E1 also contained 2.5 wt .-% PAP granules (Eureco®, Solvay) and 2 wt .-% hydroxyphosphono-acetic acid (BioLab Water Additives), wt .-% each based on the total agent. In addition to water, it also contained sodium sulfate, sodium citrate and complexing agents as well as foam inhibitor and thickener. Apart from the PAP granules, no further bleaching agents were included.

The liquid detergent E2 was a fragrance and surfactant-containing liquid detergent, which was adjusted to a pH of 5.0, and a surfactant content (anionic and nonionic surfactant) of about 27 wt .-% total had. E2 also contained 2.5% by weight of PAP granules (Eureco®, Solvay) and 0.6% by weight of a phosphonic acid (Aquacid 1084 EX, Aquapharm Chemical, India) and 3% by weight of polyacrylic acid sodium salt M _w 4000 g / mol (Sokalan PA 25 CL, BASF), wt .-% in each case based on the total agent. In addition to water, it also contained sodium sulfate, sodium citrate and complexing agents as well as foam inhibitor and thickener. Apart from the PAP granules, no further bleaching agents were included.

Example 2: Comparative Examples V1 and V2

The agent V1 corresponded to the agent E1 with the difference that V1 contained no phosphonic acid. The mean V2 corresponded to the mean E2 with the difference that V2 contained neither phosphonic acid nor polyacrylate. These missing ingredients were replaced by water.

Example 3: Comparative Example 3

The agent V3 corresponded to the agent V2 with the difference that V3 did not contain PAP granules. This ingredient has been replaced by water.

Example 4: Conducting the corrosion tests

• Praxisversuch: In einer Waschmaschine des Herstellers BSH wurden 50 Waschzyklen eines 60°C Buntwaschprogramms mit 3,5 kg Füllwäsche durchfahren, anschließend wurde der Heizstab und dessen Halterung ausgebaut und visuell auf Korrosionsspuren hin untersucht. Der Heizstab besteht aus Edelstahl Nirosta® 4301, der mit einer Ni-Schicht überzogen ist, die Halterung besteht ebenfalls aus Nirosta® 4301.

Corrosion tests were carried out with the products V1, V2, V3, E1 and E2 described above in a dosage of 80 g / 15 l of water in the following ways:

• Practical experiment: In a washing machine of the manufacturer BSH, 50 washing cycles of a 60 ° C wash program with 3.5 kg filling laundry were passed through, then the heating rod and its holder were removed and visually inspected for signs of corrosion. The heating element is made made of stainless steel Nirosta® 4301, which is coated with a Ni-layer, the holder is also made of Nirosta® 4301.

Model test: In a 17 l stainless steel vessel with stirrer was a equipped with a control rod of the manufacturer BSH (the heating rod is made of stainless steel Nirosta® 4301, which is coated with a Ni-layer, the holder is made according to an XPS analysis made of a Ni-free Cr stainless steel.) with the corresponding bracket horizontally mounted near the ground. This vessel was charged 50 times, each time for 1 hour, with each fresh wash of the products to be tested. The temperature was raised with the heating rod to 70 ° C and kept constant. Subsequently, the heating rod was removed with the brackets and visually inspected for traces of corrosion.

The pH of the wash liquors was 7.0 each.

Results:

When using the comparative formulations V1 or V2 showed in the model experiment after 10 washing cycles recognizable traces of corrosion in the form of a brown court to the Ni-stainless steel contact point on the Heizstabhalterung. After 50 wash cycles, the Ni layer of the heating element in the area of the heating element holder had been removed in the practical test and in the model experiment, and the holder had been significantly rusted. In addition, minor rust marks were visible at other locations of the heating element. The model test showed a clear brown color and roughness around the Ni-stainless steel contact point.

When using the comparative formulation V3 no corrosion was detected. In practical tests and in a pilot experiment, the heating element was essentially still bright after 50 washing cycles.

When using the formulations E1 or E2, the Ni stainless steel contact point was completely free of traces of corrosion after 50 cycles in the model test and in practical application.

Claims (15)

1. A bleach-containing washing or cleaning agent containing a particulate phthalimidoperoxyalkanoic acid, characterised in that it comprises Zn ions.
2. An agent according to claim 1, characterised in that it additionally comprises an active ingredient selected from the group comprising benzotriazole, nitrate ions, phosphonocarboxylic acids, phosphonic acids, phosphates, polyaspartic acids, fatty amines, surfactants with nitrogenous head groups and mixtures thereof.
3. An agent according to claim 1 or claim 2, characterised in that it contains 0.5 wt.% to 25 wt.%, in particular 1 wt.% to 20 wt.% of phthalimidoperoxyalkanoic acid.
4. An agent according to any one of claims 1 to 3, characterised in that the phthalimidoperoxyalkanoic acid is 6-phthalimidoperoxyhexanoic acid (PAP).
5. An agent according to any one of claims 1 to 4, characterised in that it contains 0.05 wt.% to 4 wt.%, in particular 0.2 wt.% to 2 wt.% of zinc salt.
6. An agent according to any one of claims 1 to 5, characterised in that it contains up to 10 wt.%, in particular 2 wt.% to 4 wt.% of phosphonocarboxylic acid.
7. An agent according to any one of claims 1 to 6, characterised in that it contains up to 10 wt.%, in particular 2 wt.% to 4 wt.% of phosphonic acid.
8. An agent according to any one of claims 1 to 7, characterised in that it additionally contains 0.5 wt.% to 15 wt.%, preferably 1 wt.% to 10 wt.%, advantageously 2 wt.% to 8 wt.%, in particular 3 wt.% to 6 wt.% of polycarboxylate.
9. An agent according to claim 8, characterised in that it contains polyacrylates as the polycarboxylates, preferably those having weight-average molar masses M_w in the range of less than 40000 g/mol, advantageously of less than 30000 g/mol, preferably of less than 20000, preferably in the range from 1000 to 15000 g/mol, in particular in the range from 2000 to 10000 g/mol, the molar masses being determined by gel permeation chromatography.
10. An agent according to any one of claims 1 to 9, characterised in that it contains a mixture of anionic and nonionic surfactants and/or that it contains 0.1 wt.% to 50 wt.%, in particular 10 wt.% to 40 wt.% of surfactant.
11. An agent according to any one of claims 1 to 10, characterised in that it is liquid and has a pH value in the range from 2 and 6, in particular from 3 to 5.5.
12. An agent according to claim 11, characterised in that the densities of the phthalimidoperoxyalkanoic acid particles and of the liquid phase of the agent differ from one another by no more than 10%.
13. An agent according to any one of claims 1 to 12, characterised in that it is liquid and consists of at least two, preferably of exactly two, sub-compositions kept separately from one another, which are present separately from one another in a multi-chamber container, a hydrous dispersion of the particulate phthalimidoperoxyalkanoic acid which comprises Zn ions being present in one chamber, while the remaining ingredients of the finished washing or cleaning agent composition are present in the second chamber or the further chambers.
14. Use of a hydrous dispersion of a particulate phthalimidoperoxyalkanoic acid, which comprises Zn ions, for producing in particular liquid washing or cleaning agents.
15. Use of Zn ions for suppressing corrosion phenomena on machine parts in textile washing in an automatic washing machine using washing agents containing phthalimidoperoxyalkanoic acid.