EP0340589A1 - Detergents in the form of fusible shaped bodies - Google Patents

Abstract

Used as detergent which is in the form of fusible shaped bodies is a mixture of (A) 35 to 65% by weight of sodium metasilicate, (B) 4 to 25% by weight of at least one polyanionic builder substance from the class of polyphosphates, zeolites, of nitrilotriacetic acid, of (co)polymeric carboxylic acids and of polyphosphonic acids, each in the form of the sodium salts, (C) 10 to 30% by weight of a non-ionic surfactant and (D) 2 to 15% by weight of a water-soluble, wax-like compound from the class of polyethylene glycols with a molecular weight of at least 1,100 and the alkyl ethers thereof. For use in automatic washing machines, the shaped bodies are accommodated in a separate storage chamber and reduced in size, in an amount required for the particular washing process, by means of a programme-controlled, mechanically driven device.

Description

The invention relates to a detergent which is intended in particular for use in commercial laundries. These laundries usually use softened water, which is why the detergent content of builder salts that bind the hardness of lime is comparatively low compared to a household detergent, while the content of strongly alkaline builder salts, in particular metasilicates, is usually much higher. Due to the high level of alkalinity, powdery agents require special precautions when handling them and because they tend to clump together when exposed to moisture. Although it is known that such agents can also be stored and metered as liquid concentrates, so-called stock lyes, the technical systems required for this are not suitable for every location because of their increased expenditure and space requirements.

It was therefore the task of offering such an agent in a conveniently manageable, light and loss-free dosage form. The tablet, piece or block form is a suitable form. For this form of supply, it is additionally required that the agents be dissolved quickly and completely in the washing-up device of the washing machines in order to enable short work cycles. On the other hand, unlike powder compacts, pieces of this type must be sufficiently stable against mechanical stress and so compact that layer-by-layer, uniform dissolution without disintegration of the shaped body enables them becomes. Crumbling powder compacts often cause hard deposits in the induction boxes.

• A) 35 bis 65 Gew.-% Natriummetasilikat,
• B) 4 bis 25 Gew.-% mindestens eine polyanionische Buildersub­stanz aus der Klasse der Polyphosphate, Zeolithe, der Nitrilo­triessigsäure, der (co-)polymeren Carbonsäuren und der Poly­phosphonsäuren, jeweils in Form der Natriumsalze,
• C) 10 bis 30 Gew.-% eines nichtionischen Tensids,
• D) 2 bis 15 Gew.-% einer wasserlöslichen, wachsartigen Verbin­dung aus der Klasse der Polyethylenglykole mit einem Mole­kulargewicht von mindestens 1100 und deren Alkylether.

The object of the invention, with which these objects are achieved, is a detergent in the form of meltable molded articles containing (calculated as an anhydrous substance):

• A) 35 to 65% by weight sodium metasilicate,
• B) 4 to 25% by weight of at least one polyanionic builder from the class of the polyphosphates, zeolites, nitrilotriacetic acid, the (co) polymeric carboxylic acids and the polyphosphonic acids, in each case in the form of the sodium salts,
• C) 10 to 30% by weight of a nonionic surfactant,
• D) 2 to 15% by weight of a water-soluble, waxy compound from the class of polyethylene glycols with a molecular weight of at least 1100 and their alkyl ethers.

The sodium metasilicate (component A) with the composition Na₂O: SiO₂ = 1: 0.9 to 1: 1.1 is used as an anhydrous substance. The preferred amount is 40 to 60% by weight and in particular 45 to 55% by weight.

Component (B) consists of at least one polyanionic builder salt from the class of the polyphosphates, nitrilotriacetic acid, zeolite, polyphosphonic acids and (co) polymeric carboxylic acids in the form of the sodium salts. Their total amount is 4 to 25% by weight, preferably 5 to 20% by weight and in particular 7 to 15% by weight.

The most suitable polyphosphate is sodium tripolyphosphate (TPP), which can be present in proportions of 0 to 10% by weight, preferably 0 to 5% by weight. Of course, in cases where phosphate-free agents are mandatory are also suitable TPP-free agents. In these cases, component (B) advantageously consists of nitrilotriacetate (NTA) or zeolite or NTA-zeolite mixtures or of zeolite in a mixture with (co) polymeric carboxylic acids which act as so-called co-builders and threshold active ingredients. In combination with zeolite, polyphosphonates also have these properties.

NTA as a phosphate substitute can be used in amounts of 0 to 7, preferably 0 to 6 and in particular 0 to 5% by weight. These amounts refer to anhydrous trisodium salt.

Preferred phosphate substitutes are finely crystalline, synthetic, water-containing zeolites of the NaA type, which have a calcium binding capacity in the range from 100 to 200 mg CaO / g (according to the information in DE 22 24 837). Their particle size is usually in the range from 1 to 10 μm. The content of these zeolites is 0 to 15, preferably 0 to 10% by weight. Agents without phosphate or without NTA advantageously contain 5 to 10% by weight of zeolite.

The zeolite is preferably used together with polyanionic co-builders. These include compounds from the class of polyphosphonic acids and homo- or copolymeric polycarboxylic acids, derived from acrylic acid, methacrylic acid, maleic acid and olefinic unsaturated, copolymerizable compounds.

Suitable phosphonic acids or phosphonic acid salts 1-hydroxyethane-1,1-diphosphonate, ethylenediamine tetramethylene phosphonate (EDTMP) and diethylenetriamine pentamethylene phosphonate, mostly in the form of their sodium salts and their mixtures. The amounts are usually up to 2.0% by weight, based on the composition, preferably 0.2 to 1% by weight, based on the sodium salt. In the case of the diphosphonate, this amount refers to the tri sodium salt, in the case of tetraphosphonate on the hexasodium salt.

Further useful co-builders are homopolymers of acrylic acid and methacrylic acid, copolymers of acrylic acid with methacrylic acid and copolymers of acrylic acid, methacrylic acid or maleic acid with vinyl ethers, such as vinyl methyl ether or vinyl ethyl ether, furthermore with vinyl esters, such as vinyl acetate or vinyl propionate, acrylamide, methacrylamide and with ethylene, Propylene or styrene. In those copolymeric acids in which one of the components has no acid function, the proportion thereof in the interest of sufficient water solubility is not more than 70 mole percent, preferably less than 60 mole percent. Copolymers of acrylic acid or methacrylic acid with maleic acid, as are characterized, for example, in EP 25 551-B 1, have proven to be particularly suitable. These are copolymers which contain 40 to 90 percent by weight of acrylic acid. Copolymers in which 50 to 85% by weight of acrylic acid and 50 to 15% by weight of maleic acid are present are particularly preferred.

The (co) polymeric carboxylic acids mentioned can also be used without the use of zeolites. In such cases, their proportion can be up to 7% by weight, preferably up to 6% by weight, based on neutral reacting, i.e. H. in aqueous solution having a pH of 7 to 8 sodium salt. In zeolite-containing products, their proportion can be reduced, for example to proportions up to 6%, preferably 0.5 to 5% by weight and in particular 1 to 4% by weight.

Addition products of 2 to 20, preferably 3 to 15 moles of ethylene oxide (EO) with 1 mole of a compound having essentially 10 to 20 carbon atoms from the group of the alcohols can be used as nonionic surfactants (component C). Suitable nonionic surfactants are derived from primary alcohols, e.g. on coconut or tallow fatty alcohols, oleyl alcohol, oxo alcohols, or on secondary alcohols with 8 to 18, preferably 12 to 18 carbon atoms. Combinations of water-soluble nonionic surfactants (component C1) and water-insoluble or water-dispersible nonionic surfactants (component C2) are preferably used. Component C1 includes those with 6 to 15 EO and an HLB value of more than 11, component C2 includes those with 2 to 6 EO and an HLB value of 11 or less. The ratio of C1 to C2 can be 2: 1 to 1: 4, preferably 1: 1 to 1: 3.

The nonionic surfactants can also have propylene glycol ether groups (PO). These can be arranged at the end or distributed statistically with the EO groups. Preferred compounds of this class are those of the type R- (PO) _x - (EO) _y , in which R is the hydrophobic radical, x are numbers from 0.5 to 3 and y numbers from 3 to 20.

Other suitable nonionic surfactants are ethoxylates of alkylphenols, 1,2-diols, fatty acids and fatty acid amides and block polymers of polypropylene glycol and polyethylene glycol or alkoxylated alkylenediamines (Pluronics and Tetronics type). Furthermore, the above-described nonionic surfactants of the EO type can be partially replaced by alkyl polyglycosides. Suitable alkyl polyglycosides have, for example, a C₈₋₁₆ alkyl radical and an oligomeric glycoside radical with 1.5 to 6 glucose groups. Alkyl glycoside-type surfactants are preferably combined with nonionic ethoxylate surfactants, for example in a ratio of 5: 1 to 1: 5.

The content of the agents in nonionic surfactants or nonionic surfactant mixtures is 10 to 30% by weight, preferably 15 to 25% by weight and in particular 18 to 22% by weight.

The agents can optionally also contain anionic surfactants, which are referred to as component E. Soaps and surfactants of the sulfonate or sulfate type are suitable. Contents of up to 5% by weight, in some cases up to 10% by weight, of anionic surfactants increase the washing performance, but usually lead to an undesirable foam activity. This foam activity can be reduced by adding suitable foam inhibitors. Organopolysilixanes, in particular polydimethylsiloxanes and mixtures thereof with silica or silanized silica, hydrocarbon oils and waxes, microcrystalline waxes and bis-acylalkylenediamines derived from C₂ abgelalkylenediamines with long-chain acyl residues containing 14 to 22 carbon atoms (fatty acid residues) are suitable . Mixtures of such foam inhibitors are also advantageously used. The amount of such foam inhibitors in the compositions depends on the amount and the foam activity of the synthetic anionic surfactants and is up to 5% by weight, preferably 0.5 to 3% by weight, based on the anionic surfactant.

Suitable soaps are derived from natural or synthetic, saturated or monounsaturated fatty acids with 12 to 22 carbon atoms. Are particularly suitable from natural fatty acids such. B. coconut, palm kernel or tallow fatty acid derived soap mixtures. Preferred are those which are composed of 50 to 100% of saturated C₁₂₋₁₈ fatty acid soaps and 0 to 50% of oleic acid soap. Their proportion can be up to 10% by weight, preferably up to 4% by weight, based on sodium soaps.

Usable surfactants of the sulfonate type are linear alkylbenzenesulfonates (C₉₋₁₃-alkyl) and olefin sulfonates, ie mixtures of alkene and hydroxylalkanesulfonates as well as disulfonates, as can be obtained, for example, from C₁₂₋₁inen monoolefins with a terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent receives alkaline hydrolysis of the sulfonation products. Alkanesulfonates made from C₁₂₋₁₈ alkanes by sulfochlorination or sulfo-oxidation and subsequent hydrolysis or neutralization are available, and alphasulfonated hydrogenated coconut, palm kernel or tallow fatty acids and their methyl or ethyl esters and mixtures thereof. Among the surfactants containing sulfonate groups, preference is given to the alkylbenzenesulfonates, alpha-sulfofatty acid ester salts and the alpha-sulfofatty acid ester disalts. They are in the form of their sodium salts. Their proportion can be up to 5% by weight, in some cases up to 8% by weight. It is preferably at most 2% by weight.

The binders (component D) contain 2 to 15% by weight, preferably 2 to 10% by weight and in particular 3 to 8% by weight, of water-soluble, wax-like compounds from the class of polyethylene glycols with a molecular weight of at least 1100 and their alkyl ethers. The molecular weight of the polyglycol ether is preferably from 1300 to 40,000 and, if it has no alkyl groups, in particular from 1500 to 20,000. In the alkyl-substituted polyglycol ethers, the alkyl chain can have 6 to 24 C atoms, preferably 10 to 18 C atoms. Alkyl polyglycol ethers derived from C₁₄₋₁₈ alcohols or alcohol mixtures (for example tallow alcohol) which have 25 to 100, preferably 30 to 50, ethylene glycol ether groups have proven particularly suitable. Unsubstituted and alkyl-substituted polyethers can also be present in a mixture.

As further component F, the agents can also contain compounds containing active oxygen, such as sodium perborate as tetrahydrate or monohydrate or sodium percarbonate. These can be present in proportions of up to 30% by weight, preferably 5 to 25% by weight. The preferred oxygen carrier is sodium perborate monohydrate, the proportion of which can be up to 20% by weight, preferably 5 to 15% by weight. Surprisingly, it has been found that such per-compounds, which are normally unstable in highly alkaline mixtures, after incorporation into the inventive compounds Medium are extraordinarily stable and, for example, after 6 months of storage at 25 ° C., do not yet suffer any measurable loss of oxygen.

The detergents can also contain conventional detergent additives as further constituents, such as optical brighteners, graying inhibitors, disinfectant substances and colorants and fragrances. Suitable graying inhibitors are carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers such as methyl hydroxyethyl cellulose and mixtures of the cellulose ethers mentioned. The proportion of graying inhibitors is generally up to 3% by weight, usually 0.5 to 2% by weight. The proportion of the other additives is generally less than 1% by weight, usually less than 0.5% by weight.

The moldings or blocks can be produced in such a way that the surfactants and the polyethers (components C and D) are melted in heated kneading machines or pilier devices or are introduced in an already molten state, whereupon the other components are in fine powdered or granular form adds and homogenizes the plastic mixture. The grain size of the solid additives is not critical per se, which is why it is not necessary to grind these additives beforehand to a fineness of dust. In the interest of easy homogenizability and a reduction in the need for plasticizers, however, it has proven expedient if the solids have no significant proportions with a grain size above 1.6 mm, in particular no proportions above 1.2 mm. Average grain sizes from 0.05 to 0.8 mm are therefore well suited.

The temperature of the melt, depending on the melting range of components C and D, can be 40 ° to 100 ° C. In the interest of reducing the viscosity of the mixtures, however, minimum temperatures of 60 ° C., advantageously those of 75 ° to 90 ° C. prefers. The viscosity in this range should not exceed 50,000 mPa.s, or at least not significantly. If active oxygen-containing compounds are incorporated, the temperature should preferably not exceed 80 ° C. and the mixture should then be cooled and solidified as quickly as possible in order to avoid unnecessary loss of oxygen.

The homogenized melt can be pressed into strands while cooling, which can then be cut, as is customary in soap processing, and further deformed under pressure. However, they can also be advantageously poured into molds from which they can be easily ejected after cooling to temperatures below 40 ° C. This simple working method benefits from the fact that in many cases the moldings are sufficiently dimensionally stable even at this temperature.

The shape of the shaped body can be any, for. B. cylindrical, cuboid or of round or oval shape. Pieces formed by solidification advantageously have the shape of a truncated cone, truncated pyramid or a cuboid with a reduced base area up to hemispherical shapes for easier removal from the casting mold. With a formulation-dependent density of 1.3 to 1.7 g / cm³, the amount or size of the shaped body required for a washing process can be adjusted in a simple manner. The unit weight for a washing process in a commercial washing machine is of the order of 300 g. However, larger pieces can also be deposited in the induction devices and the amount to be dissolved or the desired alkali concentration can be regulated by determining the electrical conductivity. Since the pre-dosed shaped body does not tend to become stuck in the induction device with crust formation, several washing processes can be carried out manage with a single dose and rationalize the operation of the system.

The type of flushing can also be carried out in various ways and adapted to the properties of the moldings or the existing washing technology. In the case of moldings with a low dissolution rate, the entire water supply is passed through the induction chamber and then the wash liquor is circulated through the chamber until the desired concentration is reached. This concentration can be determined and programmed using the electrical conductivity of the wash liquor. A similar procedure can be followed if large moldings intended for multiple washing processes are used. For moldings with a high dissolving speed, a partial flow can be branched off from the water inlet and passed through the induction chamber. The rate of dissolution can then also be influenced via the temperature of the water supplied. Molded portions portioned for a wash cycle or existing product residues can be melted and flushed in very quickly by adding hot water from a mixer tap with steam supply. A conductivity check of the wash liquor concentration is not necessary.

A concept deviating from the dissolving chamber, which offers a number of advantages, is a device which is placed on the induction chamber or integrated therein and mechanically comminutes the detergent block to form a free-flowing powder. The grinder is e.g. B. electrically driven and supports the block in layers, e.g. B. by means of a rotating or vibrating grater. In this case, the mechanical dosing chamber advantageously has a capacity of several vertically stacked moldings which pass through the shredding area one after the other. The detergent dosing can be carried out via conductivity control in the washing liquor or, more simply, via the one switching duration of the grater can be controlled. At the same time the grinder is started, a water jet rinses the powder from the dispenser into the washing machine.

Examples

The meltable formulation components C and D given in the tables were combined in a heatable kneader and melted at temperatures between 80 and 100.degree. The solid constituents, which had a particle size of 0.05 to 0.5 mm, were then added and the melt was homogenized. If sodium perborate was added, the melt was previously cooled to 80 ° C. After complete homogenization, the molten mass was poured into cylindrical molds and quickly cooled to room temperature. Analytical tests showed that no separation or settling of individual grain fractions had taken place in the casting mold during cooling.

In the table mean:
STP = Na tripolyphosphate, anhydrous NTA = Nitrilotriacetate, trisodium salt Polycarboxylate Acrylic acid-maleic acid copolymer (MW 70,000), sodium salt Phosphonate = Ethylene diamine tetra (methylene phosphonate) hexasodium salt TA + 5 EO = Tallow alcohol 5-fold ethoxylated TA + 14 EO = Tallow alcohol ethoxylated 14 times OA 13/15 + 3 EO = Oxo alcohol C₁₃₋₁₅, 3 times ethoxylated OA 14/15 + 7 EO = Oxo alcohol C₁₄₋₁₅, 7-fold ethoxylated TA + 33 EO = Tallow alcohol, 33-fold ethoxylated (MW of the poly-EO residue = 1450) PE 4,000 = Polyethylene glycol, MW = 4,000 LAS = linear dodecylbenzenesulfonate (Na salt) Soap = Tallow / Coconut Soap (Na Salt) Cellulose ether Carboxymethyl cellulose-methyl hydroxyethyl cellulose mixture Defoamer = Polydimethylsiloxane-SiO₂ mixture Components 1 2nd 3rd 4th 5 6 7 A Na metasilicate 50.0 40.0 58.0 43.3 58.8 40.0 40.0 B STP 8.0 8.0 - 10.0 7.0 - - NTA 4.0 3.0 10.0 3.0 6.0 - 5.0 Zeolite NaA - - - - - 15.0 10.0 Polycarboxylate 4.0 4.0 - 1.5 - 5.0 5.0 Phosphonate 1.0 1.0 0.8 0.5 1.0 2.0 1.0 C. TA + 5 EO 11.0 15.0 7.5 - - 6.0 6.0 TA + 14 WO 11.0 15.0 7.5 - - 5.0 6.0 OA 13/15 + 3 EO - - - 11.0 5.0 - - OA 13/15 + 7 EO - - - - 5.0 - - OA 14/15 + 7 EO - - - 11.0 - - - D TA + 33 EO 8.0 11.0 4.0 12.0 3.8 5.0 10.0 PE 4,000 - - - - - 5.0 - E READ 0.8 - 2.0 0.5 1.0 - - Soap - 1.0 8.0 5.0 9.0 - 1.0 F NaBO₃-H₂O - - - - - 15.0 10.0 Cellulose ether 2.0 1.8 1.8 2.0 1.8 1.8 1.8 opt. Brightener 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Defoamer - - 0.2 - 0.2 - -

Claims (10)

1. Containing detergent in the form of fusible moldings (calculated as an anhydrous substance): A) 35 to 65% by weight sodium metasilicate, B) 4 to 25% by weight of at least one polyanionic builder from the class of the polyphosphates, zeolites, nitrilotriacetic acid, the (co) polymeric carboxylic acids and the polyphosphonic acids, in each case in the form of the sodium salts, C) 10 to 30% by weight of a nonionic surfactant, D) 2 to 15% by weight of a water-soluble, waxy compound from the class of polyethylene glycols with a molecular weight of at least 1100 and their alkyl ether. 2. Composition according to claim 1, containing 40 to 60 wt .-% of component (A) and 5 to 20 wt .-% of component (B). 3. Composition according to claim 1 or 2, wherein the content of sodium tripolyphosphate is up to 10 wt .-%, preferably up to 5 wt .-%. 4. Composition according to one or more of claims 1 to 3, wherein the content of zeolite is up to 15 wt .-% and in the absence of phosphate and / or nitrilotriacetate 5 to 10 wt .-%. 5. Composition according to one or more of claims 1 to 4, wherein the content of (co) polymeric carboxylic acids, based on sodium salt up to 7 wt .-%, preferably up to 6 wt .-% and in the presence of zeolite 0.5 is up to 5% by weight. 6. Composition according to one or more of claims 1 to 5, wherein the content of nonionic surfactants is 15 to 23 wt .-%, preferably 18 to 22 wt .-%. 7. Composition according to one or more of claims 1 to 6, wherein component (D) consists of polyethylene glycols with a molecular weight of 1300 to 40,000 and / or their alkyl ethers with 10 to 18 carbon atoms in the alkyl group, the content of which on average 2 to 10 wt .-%, preferably 3 to 8 wt .-%. 8. Composition according to one or more of claims 1 to 7, containing a component F which is composed of an active oxygen-containing compound, preferably sodium perborate monohydrate in proportions up to 30% by weight, preferably up to 20% by weight. 9. A process for the preparation of the compositions according to one or more of claims 1 to 8, characterized in that the powdery to granular constituents of the composition are distributed in a molten mixture of components (C) and (D) and the mixture is allowed to solidify with shaping . 10.Verfahren for dosing the agent according to one or more of the claims that the in a separate pantry housed in a shaped by means of a program-controlled, mechanically driven device in a quantity required for the respective washing process and the crushed portion in the wash liquor brings in.