CA2143609A1 - A dishwashing detergent containing a selected builder system - Google Patents
A dishwashing detergent containing a selected builder systemInfo
- Publication number
- CA2143609A1 CA2143609A1 CA002143609A CA2143609A CA2143609A1 CA 2143609 A1 CA2143609 A1 CA 2143609A1 CA 002143609 A CA002143609 A CA 002143609A CA 2143609 A CA2143609 A CA 2143609A CA 2143609 A1 CA2143609 A1 CA 2143609A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- detergent
- alkali metal
- mole
- builder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Abandoned
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
- C11D3/223—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin oxidised
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
- C11D17/0091—Dishwashing tablets
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
- C11D17/065—High-density particulate detergent compositions
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
- Washing And Drying Of Tableware (AREA)
Abstract
Solid, weakly alkaline, phosphate- and chlorine-free products for dish-washing machines contain organic water-soluble builders, alkali carbonate, oxygen-based bleaching agents, surfactants and if required further usual components. In order to avoid the inconvenient formation of lime deposits in the dish-washing machines used, and in particular on the washed dishes, washing products are disclosed which contain oxidation products of polyglucosanes and/or their soluble salts as builder compo-nents.
Description
`` 2143~9 ._ TRANSLATION
A dishwashing detergent containing a selected builder system This invention relates to a solid dishwashing detergent for use in dishwashing machines.
In addition to surfactants, machine dishwashing detergents of the latest phosphate-free generation contain oxygen-based oxidizing agents and a relatively complex builder combination of alkali metal carbonates and organic complexing agents. The organic complexing agents hitherto used include organophosphonic acids, hydroxycarboxylic acids, aminocarboxylic acids and, in particular, polymeric polycarboxylic acids, which are often used in admixture with low molecular weight poly-hydroxypolycarboxylic acids, for example citric acid, or water-soluble salts thereof. In general, alkali metal silicate is additionally present as a further builder component. Detergents with this composition are often attended by the disadvantage that they form lime bloom both in the dishwashing machine and in particular on its clean contents, particularly where the water used is relatively hard.
It has now surprisingly been found that the bloom formed by the dishwashing detergent in conjunction with the hardness constituents of water can be inhibited by using a builder combination containing certain oxidation products of polyglucosans.
Accordingly, the present invention relates to a solid, low-alkali, phosphate- and chlorine-free machine dishwashing detergent containing organic water-soluble builder, alkali metal carbonate, oxygen-based bleaching agent, surfactant and if desired other typical constitu-ents, characterized in that it contains oxidation prod-ucts of polyglucosans and/or soluble salts thereof as the 21~350~
Wo 94/05762 2 PCT/EP93/022S2 builder component.
In the context of the present invention, oxidation products of polyglucosans are understood to be polymers of monosaccharides which consist at least partly of oxidized anhydroglucose units with one, two or three carboxyl groups per unit. These oxidized anhydroglucose units correspond to the following structural formulae I, II or III:
~ (I) J\~O H
OH
cH2oH
_ (II) COOH COOH
,COOH
~
(III) COOH COOH
Extensive knowledge exists on the production of such polysaccharide derivatives by oxidative treatment of, for example, cellulose, starch and dextrins, cf. for example Houben-Weyl "Methoden der organischen Chemie~, Thieme-Verlag, Stuttgart (1987), Vol. E 20, Makromolekulare Stoffe, sub-chapter entitled "Polysaccharide Derivatives"
edited by Dr. K. Engelskirchen, loc. cit., pages 2042 et seq., more particularly pages 2124 et seq. (oxidation products of cellulose) and pages 2166 et seq. (oxidized starches); and "Cellulose Chemistry and Its Applications"
(1983), John Wiley & Sons, Chichester, GB, more particu-21~3609 larly T.P. Nevell, "Oxidation of Cellulose" (Chapter 10), and the extensive literature cited therein, loc. cit.
pages 262 to 265; and European patent applications EP 425 369, EP 455 522 and EP 472 042.
Broadly summarized, it may be said that a large number of oxidizing agents are used for the oxidation of polyglucosans, including for example (atmospheric) oxygen, hydrogen peroxide, sodium hypochlorite or bro-mite, periodic acid and periodates, lead(IV) acetate, nitrogen dioxide and cerium(IV) salts. These oxidizing agents react very differently with the anhydroglucose units, cf. for example the formula schemes in Houben-Weyl, loc. cit., page 2124. It is known that, when cellulose is exposed to the action of nitrogen dioxide, oxidation of the primary alcohol group to the carboxy group is by far the predominant reaction. The oxidizing agent may be used in gaseous form or in the form of a solution in an inert organic solvent, cf. also Houben-Weyl, loc. cit., page 2125 and the primary literature cited in this connection. Even where starch is used as the starting material, largely selective oxidations of the primary alcohol group of the anhydroglucose unit to the carboxy group can be achieved. The teaching accord-ing to the present invention is based on this knowledge of the prior art.
For example, monocarboxyl starches with a freely selectable degree of reaction of the primary alcohol groups can be obtained by selective oxidation with nitro-gen dioxide at low temperatures, even in the absence of auxiliaries, for example solvents or catalysts. Substan-tially quantitative and largely selective reaction of the structural elements of the starch molecule is also possible.
However, a quantitative reaction such as this is not necessary for the purpose according to the invention of `` 2143609 using derivatives of natural substances of the type in question as builders in the detergents mentioned. In-stead, what is crucial is the interplay between the fol-lowing two parameters: adequate conversion of the primary alcohol groups into carboxy groups and, on the other hand, regulation of the average molecular weight of the natural polyglucosan molecule to sufficiently degraded fragments. The first of these two parameters would appear to be of functional significance to the inter-action, for example with the hardness constituents, whilethe sufficiently limited average molecular weight of the modified polyglucosan units can be important inter alia for the sufficient solubility of the builder under in-use conditions.
The following observations apply to these two parameters:
The preferred lower limit to the content of oxidized anhydroglucose units corresponding to formula I, II
and/or III in the polyglucosan derivatives is at around 25 mole-% and preferably at at least around 35 mole-% to 40 mole-%. The substantially quantitative conversion of one, two or three alcohol groups into carboxy groups is possible so that the upper limit to the corresponding content of oxidized anhydroglucose units is at 95 mole-%
to around 100 mole-%. Corresponding oxidation products characterized by contents of around 35 mole-% to 80 mole-% of oxidized anhydroglucose units can be particularly suitable for practical application, their content in one important embodiment being in the range from about 40 mole-% to 60 mole-%.
It has been found, particularly in the field of starch derivatization in accordance with the invention, that, in the oxidative treatment of dry starch which normally contains limited quantities of water with NO2 and, optionally, conversion of the oxidation products Wo 94/~5762 5 PCT/EP93/02252 into water-soluble salts, the largely selective oxidation of the primary alcohol groups is accompanied by a reduc-tion in the molecular weight of the starch molecule to such an extent that the derivatized polyglucosans obtain-ed are particularly suitable for use as builders and formaqueous solutions having viscosities in the range men-tioned above.
On a statistical average, at least 15 mole-% of the oxidized polyglucosans to be used in accordance with the invention preferably consist of anhydroglucose units corresponding to formula I, the oxidized polyglucosans having average molecular weights below 15,000.
The builder component corresponding to the defini-tion according to the invention is used in the dishwash-ing detergents in quantities of preferably 5 to 60% byweight and, more preferably, 10 to 40% by weight, based on the total weight of the detergent. In many cases, quantities of 15% by weight to 30% by weight can be useful. The builder component may be used both in the form of the free carboxylic acid and in the neutralized form, more particularly in the form of the alkali metal salts. Where the free carboxylic acid is used, the alkali metal salts are generally formed under in-use conditions.
The composition of the detergents may otherwise be selected virtually as required within the limits of known formulations.
Machine dishwashing detergents according to the invention contain as their principle components surfac-tants, the builder component according to the invention, peroxy bleaching agents and other typical ingredients of dishwashing detergents, such as enzymes, dyes and fra-grances, alkalizing agents, such as soluble alkali metal silicates, and optionally neutral salts and water.
Among the compounds yielding H2O2 in water which -~ 21~36~9 serve as bleaching agents, sodium perborate tetrahydrate (NaBO2-H2O2-3H2O) and sodium perborate monohydrate (NaBO2-H2O2) are particularly important. Other useful bleaching agents are, for example, peroxycarbonate (Na2CO3 1.5H2O2) or peracidic salts of organic acids, such as perbenzoates or salts of diperdodecanedioic acid.
Suitable bleach activators for these oxidizing agents are, in particular, the N-acyl and O-acyl compounds which form organic peracids with H2O2, preferably N,N'-tetraacy-lated diamines, such as N,N,N',N'-tetraacetyl ethylenedi-amine. The content of oxygen-based oxidizing agents in the dishwashing detergents is preferably between about 5%
by weight and 15% by weight, more particularly in com-bination with 1% by weight to 10% by weight and, more particularly, 2% by weight to 5% by weight of a bleach activator.
The total surfactant content of the detergents is generally between 0.5% by weight and 5% by weight and may advantageously be between 0.8 and 3% by weight. Typical surfactants for detergents belong to the groups of anionic, nonionic and/or zwitterionic surfactants, the use of anionic and/or nonionic surfactants being prefer-red. Suitable anionic surfactants are, in particular, sulfonates and sulfates and also soaps of preferably natural fatty acids or fatty acid mixtures. Suitable surfactants of the sulfonate type are, for example, C9l3 alkyl benzene sulfonates, olefin sulfonates, esters of ~-sulfofatty acids or ~-sulfofatty acid disalts. Suitable surfactants of the sulfate type are the sulfuric acid monoesters of primary alcohols of natural or synthetic origin, i.e. of Cl2l8 fatty alcohols or of Cl020 oxoal-cohols, and those of secondary alcohols with the same chain length. The sulfuric acid monoesters of alcohols reacted with 1 to 6 moles of ethylene oxide (EO) are also suitable.
21~3609 Suitable nonionic surfactants are, above all, addition products of, preferably, 2 to 20 moles of EO
with 1 mole of an aliphatic compound essentially contain-ing 10 to 20 carbon atoms from the group of alcohols, carboxylic acids, fatty amines, carboxylic acid amides and alkane sulfonamides. In addition to water-soluble nonionic surfactants, however, water-insoluble or sub-stantially water-insoluble polyglycol ethers containing 2 to 7 ethylene glycol ether units in the molecule are also important, particularly when they are used together with water-soluble nonionic or anionic surfactants. In addition, alkyl polyglycosides corresponding to the general formula R-0-(G)x, where R is a primary, linear or branched aliphatic radical containing 8 to 22 and prefer-ably 12 to 18 carbon atoms, G is a glycose unit contain-ing 5 or 6 carbon atoms and the degree of oligomerization x is between 1 and 10, may also be used as nonionic surfactants.
In one preferred embodiment, the dishwashing deter-gents according to the invention contain no more than 10%
by weight of water-soluble organic complexing agents or cobuilders from the group of synthetic polymeric poly-carboxylates, which are understood to be the salts of polymerization products of unsaturated carboxylic acids and which include, for example, polyacrylates, polymeth-acrylates, polymaleates or copolymers of acrylic acid with maleic acid or maleic anhydride. Substances such as these are preferably absent altogether from the deter-gents according to the invention. In another preferred embodiment of the detergents according to the invention, other complexing agents, such as citric acid or alkali metal citrates and/or the salts of nitrilotriacetic acid, are absent or are present at most in quantities of not more than 30% by weight and, in particular, not more than 10% by weight.
~ 2143~0~
Wo 94/05762 8 PCT/EP93/02252 Besides alkali metal carbonates, alkalizing agents typically used in solid dishwashing detergents are alkali metal silicates, preferably sodium silicates, more particularly amorphous sodium silicates with a molar ratio of Na20 to SiO2 of 1:1.5 to 1:2.5. Amorphous alkali metal silicates such as these are commercially available, for example, under the name of Portil~. The content of alkali metal silicates in the detergents according to the invention may be up to 30% by weight, based on anhydrous substance. Contents of amorphous sodium silicate below 20% by weight and, more particularly, between 5% by weight and 15% by weight are preferred. Alkali metal carbonate is preferably present in quantities of 10% by weight to 60% by weight and, more preferably, in quanti-ties of 20% by weight to 40% by weight in the detergents according to the invention, the carbonate being at least partly replaceable by hydrogen carbonate of which the content is then preferably 30% by weight to 50% by weight, based on the detergent as a whole.
The other detergent ingredients mentioned above, which normally are present in only small quantities, may make up in particular as much as 20% by weight and preferably make up from 5 to 10% by weight. These minor components include, for example, other organic builder components, foam inhibitors and enzymes of the protease, amylase, lipase and/or cellulase type and also water which is not bound as water of crystallization or associ-ated with the constituents in similarly solid form. The enzymes may be adsorbed onto supports and/or encapsulated in shell-forming substances in the usual way and are preferably used in total quantities of not more than 5%
by weight and, more particularly, between 2 and 4% by weight. Suitable non-surface-active and preferred foam inhibitors are organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica. The foam-214360~
inhibiting use of long-chain soaps is also possible.
Mixtures of various foam inhibitors, for example mixtures of silicones and paraffins or waxes, may also be used.
These foam inhibitors are preferably fixed to a granular water-soluble or water-dispersible support.
The solid, pourable dishwashing detergents according to the invention are preferably present as powder-form, granular or tablet-like preparations which may be pro-duced by methods known per se, for example by mixing, granulation, roller compacting and/or spray drying.
To produce the detergents according to the invention in tablet form, all the constituents are preferably mixed together in a mixer and the resulting mixture is tablet-ted in conventional tablet presses, for example eccentric presses or rotary presses, under pressures of 200-105 Pa to 1,500 105 Pa. Breaking-resistant tablets which still dissolve sufficiently quickly under in-use conditions with flexural strengths of normally more than 150 N are readily obtained in this way. A tablet produced in this way preferably weighs between 50 g and 40 g and more preferably between 20 g and 30 g for a diameter of 35 mm to 40 mm.
The production of the machine dishwashing detergents in accordance with the invention in the form of dust-free, storable free-flowing powders and/or granules with high apparent densities of preferably 750 to 1,000 g/l is characterized in that, in a first process step, the builder component is mixed with at least part of the liquid components to form a premix of increased apparent density, after which the other constituents of the machine dishwashing detergent are combined with the premix, if desired after intermediate drying.
The surfactant compounds liquid under normal condi-tions, i.e. in particular the corresponding nonionic surfactants, and optionally other liquid components of 21s36ns -the formulation as a whole are used as the liquid phase in the first stage of the process. The other liquid com-ponents in question are the fragrances dissolved in carrier liquids and/or limited quantities of water or aqueous solutions of mixture components of the dishwash-ing detergent to be produced.
In the first stage of the mixing process according to the invention, the builder - generally in admixture with at least one other component of the dishwashing detergent - is impregnated with the liquid components.
For example, the builder component in admixture with perborate may be impregnated and thoroughly mixed with the liquid nonionic surfactants and the solution of fragrances in the first stage. The remaining components are then added and the mixture as a whole is compounded and homogenized in the mixer. In general, there is no need at this stage to use additional quantities of liquid, i.e. additional water. The mixture obtained is a free-flowing powder which does not emit any dust and which has the required high apparent densities, for example of 800 to 900 g/l.
In another embodiment, importance is attached to relatively intensive agglomeration to form heavy agglom-erate particles. To this end, it may be useful or neces-sary to use relatively large quantities of liquid so thatalready relatively large quantities of the components to be combined may be premixed together with the builder component. For example, the builder component may be mixed with alkali metal carbonate and at least part of the fine-particle solid alkali metal silicate and com-pactingly agglomerated by addition of limited quantities of water and/or aqueous alkali metal silicate solutions.
If, for example, a Lodige plowhsare mixer with a circular blade is used, heavy granules with apparent densities of up to 950 g/l are obtained where the procedure described 21436~9 -in detail in the following Examples is adopted.
If, in this granulation process, water is used as an auxiliary liquid in such quantities that the residual moisture content of the end product exceeds about 4 to 7%
by weight, it can be useful to subject the pregranules formed to intermediate drying. For example, fluidized-bed drying is suitable for this purpose. In general, drying such as this with material temperatures of the order of 80C for a limited period (for example 10 to 15 minutes) is sufficient to establish the required residual moisture content of around 4 to 7% by weight in the product.
The pregranules are then mixed with the missing components of the dishwashing detergent to form the end product. In all the cases illustrated herein, the mixing time is of the order of a few minutes, for example from 1 to 5 minutes, both in the preliminary stage of compact-ing mixing under the influence of liquid components and in the subsequent final mixing with the other components.
In one particular embodiment, it can be useful in the production of fine granules to achieve further stabilization and equalization by dusting the surface of the granules formed with a powder, small quantities of waterglass powder or powder-form alkali metal carbonate being particularly suitable for this purpose.
E x a m p l e s Example 1:
Preparation of the oxidized polyglucosans 275.2 g of potato starch (1.6 moles, based on one anhydroglucose unit) with a moisture content of around 6%
by weight were suspended in 825 g of carbon tetrachloride and the resulting suspension was transferred to a 2 liter stirred autoclave. After the autoclave had been evacu-_ ated and purged with nitrogen, 73.6 g of condenseddinitrogen tetroxide (0.8 mole) were added. The reaction mixture was heated to 50C over a period of 30 minutes.
The internal pressure in the autoclave was 0.5 bar (adjusted with nitrogen). By introducing oxygen under pressure, an internal pressure of 2 bar was maintained for the first hour of the reaction, being increased to 6 bar over the next hour. After a reaction time of 4.5 hours, there was no further consumption of oxygen (re-flected in the fall in pressure). The autoclave wascooled to room temperature, vented and 1 liter of demin-eralized water added to the reaction mixture. The suspension of the oxidation product was filtered through a glass filter nutsche. The product was washed first with acetone and then with water until the washing liquid showed a neutral reaction, freed from water with acetone and dried (70C, vacuum drying cabinet). 256 g of a white powder-form polycarboxylate Bl with an acid value of 324, corresponding to an average content of around 1 carboxyl group per anhydroglucose unit, were obtained.
The product had a reduced viscosity (~red) of 3 ml/g, as measured on a 2% by weight solution of the sodium salt in 1 N aqueous sodium nitrate solution at 20C.
ExamPle 2 The raw materials listed in Table 1 below were mixed in the quantities shown (% by weight, based on the final detergent) in a Lodige mixer with a circular blade.
Detergents Dl to D6 according to the invention were obtained using the polycarboxylate Bl produced in accord-ance with Example 1, detergents Cl and C2 being intended for comparison.
Table 1:
Composition of the detergents (% by weight) Bl 30 30 8 10 30 30 - -Na citratea) - -3 0 3 0 - -3 0 3 0 Polycarboxylateb) 8 - - - 10 - 8 10 Na disilicate 20 20 20 - - - 20 Na carbonate 30 38 30 13 13 13 30 13 Na hydrogen carbonate - - - 36 36 46 - 36 Na perborate ) 7 7 7 5 5 5 7 5 Nonionic surfactant ) 2 2 2 1 1 1 2 Enzymee) 1 1 1 3 3 3 1 3 a) Trisodium citrate dihydrate b) Na Poly(acrylate/maleate) (Sokalan~ CP 5, a product of BASf) C ) Monohydrate d) Plurafac~ LF 403 (a product of BASF) e) 1:1 mixture of protease (BLAP~ 140, a product of Biozym) and amylase granules (Termamyl~ 60 T, a product of Novo) Example 3 The detergents according to Example 2 were perform-ance-tested in the wash cycle of a dishwashing machine (Miele G531; program Universal 55) in quantities of 20 g ` ` 214~609 -in 7 liters of water with a hardness of 16dH (soils as described in Th. Altenschopfer, SOFW 98 (1972) 763-765:
tea, milk, minced meat, pudding, grease stick, starch, oatflakes). Detergents Dl to D6 according to the inven-tion showed superior performance, particularly in theremoval of the starch and oatflake soils, and were comparable in performance with comparison detergents C1 and C2 in regard to the removal of the other soils.
The detergents according to Example 2 were tested for bloom formation over ten rinse cycles in a Bosch S
712 dishwashing machine (detergent dosage 20 g in 6.2 liters of water with a hardness of 16dH, operating temperature 50C) with addition of 50 g of pumpable soils (mixture of ketchup, gravy, mustard, potato starch, egg yolk, milk, margarine). On a scale of 1 (= no bloom) to 10 (= very heavy bloom), detergents D1 to D3 according to the invention achieved the scores shown in Table 2 below for bloom formation in the machine (score A) and for bloom formation on the machine load (china/glass/
cutlery; score B). In every case, these scores were significantly better than the scores achieved by com-parison detergent Cl. Similarly, the scores achieved by detergents D4 to D6 were significantly better than the scores of the similarly formulated comparison detergent C2.
21~3609 Table 2:
Bloom formation using the detergents Detergent Bloom A Bloom B
Dl n.d. 6.5 D2 6.0 4.5 D3 5.0 3.5 D4 3.5 4.0 D5 5.5 4.5 D6 3.0 3.0 Cl 6.5 7.0 C2 6.0 5.8 n.d.: not determined
A dishwashing detergent containing a selected builder system This invention relates to a solid dishwashing detergent for use in dishwashing machines.
In addition to surfactants, machine dishwashing detergents of the latest phosphate-free generation contain oxygen-based oxidizing agents and a relatively complex builder combination of alkali metal carbonates and organic complexing agents. The organic complexing agents hitherto used include organophosphonic acids, hydroxycarboxylic acids, aminocarboxylic acids and, in particular, polymeric polycarboxylic acids, which are often used in admixture with low molecular weight poly-hydroxypolycarboxylic acids, for example citric acid, or water-soluble salts thereof. In general, alkali metal silicate is additionally present as a further builder component. Detergents with this composition are often attended by the disadvantage that they form lime bloom both in the dishwashing machine and in particular on its clean contents, particularly where the water used is relatively hard.
It has now surprisingly been found that the bloom formed by the dishwashing detergent in conjunction with the hardness constituents of water can be inhibited by using a builder combination containing certain oxidation products of polyglucosans.
Accordingly, the present invention relates to a solid, low-alkali, phosphate- and chlorine-free machine dishwashing detergent containing organic water-soluble builder, alkali metal carbonate, oxygen-based bleaching agent, surfactant and if desired other typical constitu-ents, characterized in that it contains oxidation prod-ucts of polyglucosans and/or soluble salts thereof as the 21~350~
Wo 94/05762 2 PCT/EP93/022S2 builder component.
In the context of the present invention, oxidation products of polyglucosans are understood to be polymers of monosaccharides which consist at least partly of oxidized anhydroglucose units with one, two or three carboxyl groups per unit. These oxidized anhydroglucose units correspond to the following structural formulae I, II or III:
~ (I) J\~O H
OH
cH2oH
_ (II) COOH COOH
,COOH
~
(III) COOH COOH
Extensive knowledge exists on the production of such polysaccharide derivatives by oxidative treatment of, for example, cellulose, starch and dextrins, cf. for example Houben-Weyl "Methoden der organischen Chemie~, Thieme-Verlag, Stuttgart (1987), Vol. E 20, Makromolekulare Stoffe, sub-chapter entitled "Polysaccharide Derivatives"
edited by Dr. K. Engelskirchen, loc. cit., pages 2042 et seq., more particularly pages 2124 et seq. (oxidation products of cellulose) and pages 2166 et seq. (oxidized starches); and "Cellulose Chemistry and Its Applications"
(1983), John Wiley & Sons, Chichester, GB, more particu-21~3609 larly T.P. Nevell, "Oxidation of Cellulose" (Chapter 10), and the extensive literature cited therein, loc. cit.
pages 262 to 265; and European patent applications EP 425 369, EP 455 522 and EP 472 042.
Broadly summarized, it may be said that a large number of oxidizing agents are used for the oxidation of polyglucosans, including for example (atmospheric) oxygen, hydrogen peroxide, sodium hypochlorite or bro-mite, periodic acid and periodates, lead(IV) acetate, nitrogen dioxide and cerium(IV) salts. These oxidizing agents react very differently with the anhydroglucose units, cf. for example the formula schemes in Houben-Weyl, loc. cit., page 2124. It is known that, when cellulose is exposed to the action of nitrogen dioxide, oxidation of the primary alcohol group to the carboxy group is by far the predominant reaction. The oxidizing agent may be used in gaseous form or in the form of a solution in an inert organic solvent, cf. also Houben-Weyl, loc. cit., page 2125 and the primary literature cited in this connection. Even where starch is used as the starting material, largely selective oxidations of the primary alcohol group of the anhydroglucose unit to the carboxy group can be achieved. The teaching accord-ing to the present invention is based on this knowledge of the prior art.
For example, monocarboxyl starches with a freely selectable degree of reaction of the primary alcohol groups can be obtained by selective oxidation with nitro-gen dioxide at low temperatures, even in the absence of auxiliaries, for example solvents or catalysts. Substan-tially quantitative and largely selective reaction of the structural elements of the starch molecule is also possible.
However, a quantitative reaction such as this is not necessary for the purpose according to the invention of `` 2143609 using derivatives of natural substances of the type in question as builders in the detergents mentioned. In-stead, what is crucial is the interplay between the fol-lowing two parameters: adequate conversion of the primary alcohol groups into carboxy groups and, on the other hand, regulation of the average molecular weight of the natural polyglucosan molecule to sufficiently degraded fragments. The first of these two parameters would appear to be of functional significance to the inter-action, for example with the hardness constituents, whilethe sufficiently limited average molecular weight of the modified polyglucosan units can be important inter alia for the sufficient solubility of the builder under in-use conditions.
The following observations apply to these two parameters:
The preferred lower limit to the content of oxidized anhydroglucose units corresponding to formula I, II
and/or III in the polyglucosan derivatives is at around 25 mole-% and preferably at at least around 35 mole-% to 40 mole-%. The substantially quantitative conversion of one, two or three alcohol groups into carboxy groups is possible so that the upper limit to the corresponding content of oxidized anhydroglucose units is at 95 mole-%
to around 100 mole-%. Corresponding oxidation products characterized by contents of around 35 mole-% to 80 mole-% of oxidized anhydroglucose units can be particularly suitable for practical application, their content in one important embodiment being in the range from about 40 mole-% to 60 mole-%.
It has been found, particularly in the field of starch derivatization in accordance with the invention, that, in the oxidative treatment of dry starch which normally contains limited quantities of water with NO2 and, optionally, conversion of the oxidation products Wo 94/~5762 5 PCT/EP93/02252 into water-soluble salts, the largely selective oxidation of the primary alcohol groups is accompanied by a reduc-tion in the molecular weight of the starch molecule to such an extent that the derivatized polyglucosans obtain-ed are particularly suitable for use as builders and formaqueous solutions having viscosities in the range men-tioned above.
On a statistical average, at least 15 mole-% of the oxidized polyglucosans to be used in accordance with the invention preferably consist of anhydroglucose units corresponding to formula I, the oxidized polyglucosans having average molecular weights below 15,000.
The builder component corresponding to the defini-tion according to the invention is used in the dishwash-ing detergents in quantities of preferably 5 to 60% byweight and, more preferably, 10 to 40% by weight, based on the total weight of the detergent. In many cases, quantities of 15% by weight to 30% by weight can be useful. The builder component may be used both in the form of the free carboxylic acid and in the neutralized form, more particularly in the form of the alkali metal salts. Where the free carboxylic acid is used, the alkali metal salts are generally formed under in-use conditions.
The composition of the detergents may otherwise be selected virtually as required within the limits of known formulations.
Machine dishwashing detergents according to the invention contain as their principle components surfac-tants, the builder component according to the invention, peroxy bleaching agents and other typical ingredients of dishwashing detergents, such as enzymes, dyes and fra-grances, alkalizing agents, such as soluble alkali metal silicates, and optionally neutral salts and water.
Among the compounds yielding H2O2 in water which -~ 21~36~9 serve as bleaching agents, sodium perborate tetrahydrate (NaBO2-H2O2-3H2O) and sodium perborate monohydrate (NaBO2-H2O2) are particularly important. Other useful bleaching agents are, for example, peroxycarbonate (Na2CO3 1.5H2O2) or peracidic salts of organic acids, such as perbenzoates or salts of diperdodecanedioic acid.
Suitable bleach activators for these oxidizing agents are, in particular, the N-acyl and O-acyl compounds which form organic peracids with H2O2, preferably N,N'-tetraacy-lated diamines, such as N,N,N',N'-tetraacetyl ethylenedi-amine. The content of oxygen-based oxidizing agents in the dishwashing detergents is preferably between about 5%
by weight and 15% by weight, more particularly in com-bination with 1% by weight to 10% by weight and, more particularly, 2% by weight to 5% by weight of a bleach activator.
The total surfactant content of the detergents is generally between 0.5% by weight and 5% by weight and may advantageously be between 0.8 and 3% by weight. Typical surfactants for detergents belong to the groups of anionic, nonionic and/or zwitterionic surfactants, the use of anionic and/or nonionic surfactants being prefer-red. Suitable anionic surfactants are, in particular, sulfonates and sulfates and also soaps of preferably natural fatty acids or fatty acid mixtures. Suitable surfactants of the sulfonate type are, for example, C9l3 alkyl benzene sulfonates, olefin sulfonates, esters of ~-sulfofatty acids or ~-sulfofatty acid disalts. Suitable surfactants of the sulfate type are the sulfuric acid monoesters of primary alcohols of natural or synthetic origin, i.e. of Cl2l8 fatty alcohols or of Cl020 oxoal-cohols, and those of secondary alcohols with the same chain length. The sulfuric acid monoesters of alcohols reacted with 1 to 6 moles of ethylene oxide (EO) are also suitable.
21~3609 Suitable nonionic surfactants are, above all, addition products of, preferably, 2 to 20 moles of EO
with 1 mole of an aliphatic compound essentially contain-ing 10 to 20 carbon atoms from the group of alcohols, carboxylic acids, fatty amines, carboxylic acid amides and alkane sulfonamides. In addition to water-soluble nonionic surfactants, however, water-insoluble or sub-stantially water-insoluble polyglycol ethers containing 2 to 7 ethylene glycol ether units in the molecule are also important, particularly when they are used together with water-soluble nonionic or anionic surfactants. In addition, alkyl polyglycosides corresponding to the general formula R-0-(G)x, where R is a primary, linear or branched aliphatic radical containing 8 to 22 and prefer-ably 12 to 18 carbon atoms, G is a glycose unit contain-ing 5 or 6 carbon atoms and the degree of oligomerization x is between 1 and 10, may also be used as nonionic surfactants.
In one preferred embodiment, the dishwashing deter-gents according to the invention contain no more than 10%
by weight of water-soluble organic complexing agents or cobuilders from the group of synthetic polymeric poly-carboxylates, which are understood to be the salts of polymerization products of unsaturated carboxylic acids and which include, for example, polyacrylates, polymeth-acrylates, polymaleates or copolymers of acrylic acid with maleic acid or maleic anhydride. Substances such as these are preferably absent altogether from the deter-gents according to the invention. In another preferred embodiment of the detergents according to the invention, other complexing agents, such as citric acid or alkali metal citrates and/or the salts of nitrilotriacetic acid, are absent or are present at most in quantities of not more than 30% by weight and, in particular, not more than 10% by weight.
~ 2143~0~
Wo 94/05762 8 PCT/EP93/02252 Besides alkali metal carbonates, alkalizing agents typically used in solid dishwashing detergents are alkali metal silicates, preferably sodium silicates, more particularly amorphous sodium silicates with a molar ratio of Na20 to SiO2 of 1:1.5 to 1:2.5. Amorphous alkali metal silicates such as these are commercially available, for example, under the name of Portil~. The content of alkali metal silicates in the detergents according to the invention may be up to 30% by weight, based on anhydrous substance. Contents of amorphous sodium silicate below 20% by weight and, more particularly, between 5% by weight and 15% by weight are preferred. Alkali metal carbonate is preferably present in quantities of 10% by weight to 60% by weight and, more preferably, in quanti-ties of 20% by weight to 40% by weight in the detergents according to the invention, the carbonate being at least partly replaceable by hydrogen carbonate of which the content is then preferably 30% by weight to 50% by weight, based on the detergent as a whole.
The other detergent ingredients mentioned above, which normally are present in only small quantities, may make up in particular as much as 20% by weight and preferably make up from 5 to 10% by weight. These minor components include, for example, other organic builder components, foam inhibitors and enzymes of the protease, amylase, lipase and/or cellulase type and also water which is not bound as water of crystallization or associ-ated with the constituents in similarly solid form. The enzymes may be adsorbed onto supports and/or encapsulated in shell-forming substances in the usual way and are preferably used in total quantities of not more than 5%
by weight and, more particularly, between 2 and 4% by weight. Suitable non-surface-active and preferred foam inhibitors are organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica. The foam-214360~
inhibiting use of long-chain soaps is also possible.
Mixtures of various foam inhibitors, for example mixtures of silicones and paraffins or waxes, may also be used.
These foam inhibitors are preferably fixed to a granular water-soluble or water-dispersible support.
The solid, pourable dishwashing detergents according to the invention are preferably present as powder-form, granular or tablet-like preparations which may be pro-duced by methods known per se, for example by mixing, granulation, roller compacting and/or spray drying.
To produce the detergents according to the invention in tablet form, all the constituents are preferably mixed together in a mixer and the resulting mixture is tablet-ted in conventional tablet presses, for example eccentric presses or rotary presses, under pressures of 200-105 Pa to 1,500 105 Pa. Breaking-resistant tablets which still dissolve sufficiently quickly under in-use conditions with flexural strengths of normally more than 150 N are readily obtained in this way. A tablet produced in this way preferably weighs between 50 g and 40 g and more preferably between 20 g and 30 g for a diameter of 35 mm to 40 mm.
The production of the machine dishwashing detergents in accordance with the invention in the form of dust-free, storable free-flowing powders and/or granules with high apparent densities of preferably 750 to 1,000 g/l is characterized in that, in a first process step, the builder component is mixed with at least part of the liquid components to form a premix of increased apparent density, after which the other constituents of the machine dishwashing detergent are combined with the premix, if desired after intermediate drying.
The surfactant compounds liquid under normal condi-tions, i.e. in particular the corresponding nonionic surfactants, and optionally other liquid components of 21s36ns -the formulation as a whole are used as the liquid phase in the first stage of the process. The other liquid com-ponents in question are the fragrances dissolved in carrier liquids and/or limited quantities of water or aqueous solutions of mixture components of the dishwash-ing detergent to be produced.
In the first stage of the mixing process according to the invention, the builder - generally in admixture with at least one other component of the dishwashing detergent - is impregnated with the liquid components.
For example, the builder component in admixture with perborate may be impregnated and thoroughly mixed with the liquid nonionic surfactants and the solution of fragrances in the first stage. The remaining components are then added and the mixture as a whole is compounded and homogenized in the mixer. In general, there is no need at this stage to use additional quantities of liquid, i.e. additional water. The mixture obtained is a free-flowing powder which does not emit any dust and which has the required high apparent densities, for example of 800 to 900 g/l.
In another embodiment, importance is attached to relatively intensive agglomeration to form heavy agglom-erate particles. To this end, it may be useful or neces-sary to use relatively large quantities of liquid so thatalready relatively large quantities of the components to be combined may be premixed together with the builder component. For example, the builder component may be mixed with alkali metal carbonate and at least part of the fine-particle solid alkali metal silicate and com-pactingly agglomerated by addition of limited quantities of water and/or aqueous alkali metal silicate solutions.
If, for example, a Lodige plowhsare mixer with a circular blade is used, heavy granules with apparent densities of up to 950 g/l are obtained where the procedure described 21436~9 -in detail in the following Examples is adopted.
If, in this granulation process, water is used as an auxiliary liquid in such quantities that the residual moisture content of the end product exceeds about 4 to 7%
by weight, it can be useful to subject the pregranules formed to intermediate drying. For example, fluidized-bed drying is suitable for this purpose. In general, drying such as this with material temperatures of the order of 80C for a limited period (for example 10 to 15 minutes) is sufficient to establish the required residual moisture content of around 4 to 7% by weight in the product.
The pregranules are then mixed with the missing components of the dishwashing detergent to form the end product. In all the cases illustrated herein, the mixing time is of the order of a few minutes, for example from 1 to 5 minutes, both in the preliminary stage of compact-ing mixing under the influence of liquid components and in the subsequent final mixing with the other components.
In one particular embodiment, it can be useful in the production of fine granules to achieve further stabilization and equalization by dusting the surface of the granules formed with a powder, small quantities of waterglass powder or powder-form alkali metal carbonate being particularly suitable for this purpose.
E x a m p l e s Example 1:
Preparation of the oxidized polyglucosans 275.2 g of potato starch (1.6 moles, based on one anhydroglucose unit) with a moisture content of around 6%
by weight were suspended in 825 g of carbon tetrachloride and the resulting suspension was transferred to a 2 liter stirred autoclave. After the autoclave had been evacu-_ ated and purged with nitrogen, 73.6 g of condenseddinitrogen tetroxide (0.8 mole) were added. The reaction mixture was heated to 50C over a period of 30 minutes.
The internal pressure in the autoclave was 0.5 bar (adjusted with nitrogen). By introducing oxygen under pressure, an internal pressure of 2 bar was maintained for the first hour of the reaction, being increased to 6 bar over the next hour. After a reaction time of 4.5 hours, there was no further consumption of oxygen (re-flected in the fall in pressure). The autoclave wascooled to room temperature, vented and 1 liter of demin-eralized water added to the reaction mixture. The suspension of the oxidation product was filtered through a glass filter nutsche. The product was washed first with acetone and then with water until the washing liquid showed a neutral reaction, freed from water with acetone and dried (70C, vacuum drying cabinet). 256 g of a white powder-form polycarboxylate Bl with an acid value of 324, corresponding to an average content of around 1 carboxyl group per anhydroglucose unit, were obtained.
The product had a reduced viscosity (~red) of 3 ml/g, as measured on a 2% by weight solution of the sodium salt in 1 N aqueous sodium nitrate solution at 20C.
ExamPle 2 The raw materials listed in Table 1 below were mixed in the quantities shown (% by weight, based on the final detergent) in a Lodige mixer with a circular blade.
Detergents Dl to D6 according to the invention were obtained using the polycarboxylate Bl produced in accord-ance with Example 1, detergents Cl and C2 being intended for comparison.
Table 1:
Composition of the detergents (% by weight) Bl 30 30 8 10 30 30 - -Na citratea) - -3 0 3 0 - -3 0 3 0 Polycarboxylateb) 8 - - - 10 - 8 10 Na disilicate 20 20 20 - - - 20 Na carbonate 30 38 30 13 13 13 30 13 Na hydrogen carbonate - - - 36 36 46 - 36 Na perborate ) 7 7 7 5 5 5 7 5 Nonionic surfactant ) 2 2 2 1 1 1 2 Enzymee) 1 1 1 3 3 3 1 3 a) Trisodium citrate dihydrate b) Na Poly(acrylate/maleate) (Sokalan~ CP 5, a product of BASf) C ) Monohydrate d) Plurafac~ LF 403 (a product of BASF) e) 1:1 mixture of protease (BLAP~ 140, a product of Biozym) and amylase granules (Termamyl~ 60 T, a product of Novo) Example 3 The detergents according to Example 2 were perform-ance-tested in the wash cycle of a dishwashing machine (Miele G531; program Universal 55) in quantities of 20 g ` ` 214~609 -in 7 liters of water with a hardness of 16dH (soils as described in Th. Altenschopfer, SOFW 98 (1972) 763-765:
tea, milk, minced meat, pudding, grease stick, starch, oatflakes). Detergents Dl to D6 according to the inven-tion showed superior performance, particularly in theremoval of the starch and oatflake soils, and were comparable in performance with comparison detergents C1 and C2 in regard to the removal of the other soils.
The detergents according to Example 2 were tested for bloom formation over ten rinse cycles in a Bosch S
712 dishwashing machine (detergent dosage 20 g in 6.2 liters of water with a hardness of 16dH, operating temperature 50C) with addition of 50 g of pumpable soils (mixture of ketchup, gravy, mustard, potato starch, egg yolk, milk, margarine). On a scale of 1 (= no bloom) to 10 (= very heavy bloom), detergents D1 to D3 according to the invention achieved the scores shown in Table 2 below for bloom formation in the machine (score A) and for bloom formation on the machine load (china/glass/
cutlery; score B). In every case, these scores were significantly better than the scores achieved by com-parison detergent Cl. Similarly, the scores achieved by detergents D4 to D6 were significantly better than the scores of the similarly formulated comparison detergent C2.
21~3609 Table 2:
Bloom formation using the detergents Detergent Bloom A Bloom B
Dl n.d. 6.5 D2 6.0 4.5 D3 5.0 3.5 D4 3.5 4.0 D5 5.5 4.5 D6 3.0 3.0 Cl 6.5 7.0 C2 6.0 5.8 n.d.: not determined
Claims (12)
1. A solid, low-alkali, phosphate- and chlorine-free machine dishwashing detergent containing organic water-soluble builder, alkali metal carbonate, oxygen-based bleaching agent, surfactant and if desired other typical constituents, characterized in that it contains 10% by weight to 60% by weight of alkali metal carbonate and, as builder, 5% by weight to 60% by weight of a polymer of anhydroglucose units which consists at least partly of oxidized anhydroglucose units with the following struc-tural formulae I, II and/or III:
(I) (II) (III) containing one, two or three carboxyl groups and/or soluble salts thereof per unit.
(I) (II) (III) containing one, two or three carboxyl groups and/or soluble salts thereof per unit.
2. A detergent as claimed in claim 1, characterized in that the content of oxidized anhydroglucose units corre-sponding to formulae I, II and/or III in the polyglucosan derivatives is at least 25 mole-%, preferably at least 35 mole-% and more preferably at least 40 mole-%, the upper limit to the content of these oxidized anhydroglucose units being at around 100 mole-% and, more particularly, 95 mole-%.
3. A detergent as claimed in claim 1 or 2, charac-terized in that it contains as builder oxidation products of polyglucosans of which - on a statistical average - at least 15 mole-% consist of oxidized anhydroglucose units corresponding to formula I and which have average molecu-lar weights below 15,000 and/or soluble salts thereof.
4. A detergent as claimed in any of claims 1 to 3, characterized in that it contains builders based on the selectively oxidized polyglucosans in quantities of 10%
by weight to 40% by weight, based on the total weight of the detergent.
by weight to 40% by weight, based on the total weight of the detergent.
5. A detergent as claimed in claim 4, characterized in that it contains no more than 10% by weight of water-soluble organic complexing agents from the group of synthetic polymeric carboxylates and, preferably, is at least substantially free therefrom.
6. A detergent as claimed in any of claims 1 to 5, characterized in that it contains other complexing agents, such as citric acid or alkali metal citrates and/or the salts of nitrilotriacetic acid, at most in quantities of not more than 30% by weight and, more particularly, not more than 10% by weight, if at all.
7. A detergent as claimed in any of claims 1 to 6, characterized in that it contains 15% by weight to 30% by weight of oxidation products of polyglucosans, 20% by weight to 40% by weight of alkali metal carbonate and/or hydrogen carbonate, 5% by weight to 15% by weight of alkali metal perborate and/or percarbonate, 2% by weight to 10% by weight of bleach activator, 0.5% by weight to 5% by weight and, more particularly, 0.8 to 3% by weight of surfactant, more particularly nonionic surfactant, up to 30% by weight and, more particularly, 5% by weight to 20% by weight of alkali metal silicate, not more than 5% by weight and, more particularly, 2% by weight to 4% by weight of enzyme, not more than 5% by weight and, more particularly, 0.5%
by weight to 2% by weight of fragrance.
by weight to 2% by weight of fragrance.
8. A powder-form or granular detergent as claimed in any of claims 1 to 7, characterized in that it has an apparent density of 750 g/l to 1,000 g/l.
9. A process for the production of a tablet-form detergent with the composition according to any of claims 1 to 7, characterized in that all its constituents are mixed in a mixer and the resulting mixture is tabletted in a tablet press under pressures of 200-105 Pa to 1,500?10 5 Pa.
10. A process for the production of the detergents claimed in claim 8 in powder form and/or granular form with apparent densities of 750 to 1,000 g/l, charac-terized in that, in a first process step, the builder component is mixed with at least part of the liquid mixture components, an increase in apparent density being obtained, surplus moisture, if any, is removed and the premix is subsequently combined with the other components of the dishwashing detergent.
11. A process as claimed in claim 10, characterized in that liquid surfactant compounds, more particularly corresponding nonionic surfactants, solutions of fragran-ces in carrier liquids and/or water or aqueous solutions of mixture components, more particularly aqueous alkali metal silicate solutions, are used as the liquid phase in the first stage of the process.
12. A process as claimed in claim 10 or 11, charac-terized in that, where the mixture of active substances is granulated, the granules obtained are powdered and spheronized in a final step with powder-form alkali metal silicate and/or alkali metal carbonate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4228786.3 | 1992-08-29 | ||
| DE4228786A DE4228786A1 (en) | 1992-08-29 | 1992-08-29 | Dishwashing liquid with selected builder system |
| PCT/EP1993/002252 WO1994005762A1 (en) | 1992-08-29 | 1993-08-21 | Dish-washing products with selected builder system |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2143609A1 true CA2143609A1 (en) | 1994-03-17 |
Family
ID=6466721
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002143609A Abandoned CA2143609A1 (en) | 1992-08-29 | 1993-08-21 | A dishwashing detergent containing a selected builder system |
Country Status (7)
| Country | Link |
|---|---|
| EP (1) | EP0656937B1 (en) |
| JP (1) | JPH08500626A (en) |
| AT (1) | ATE154071T1 (en) |
| CA (1) | CA2143609A1 (en) |
| DE (2) | DE4228786A1 (en) |
| ES (1) | ES2102055T3 (en) |
| WO (1) | WO1994005762A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020011764A1 (en) * | 2018-07-09 | 2020-01-16 | Koninklijke Coöperatie Cosun U.A. | Antiscalant composition comprising a uronic acid polysaccharide |
Families Citing this family (39)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5898025A (en) * | 1992-09-25 | 1999-04-27 | Henkel Kommanditgesellschaft Auf Aktien | Mildly alkaline dishwashing detergents |
| DE4232170C2 (en) | 1992-09-25 | 1999-09-16 | Henkel Kgaa | Weakly alkaline dish detergent |
| DE4330339A1 (en) * | 1993-09-08 | 1995-03-09 | Henkel Kgaa | Carbohydrate-based scale inhibitor |
| DE4408718A1 (en) * | 1994-03-15 | 1995-09-21 | Henkel Kgaa | Breakage and storage stable, polyfunctional cleaning tablets, process for their preparation and their use |
| US5437810A (en) * | 1994-04-26 | 1995-08-01 | Colgate-Palmolive Co. | Aqueous liquid detergent compositions containing oxidized polysaccharides |
| DE4439678A1 (en) * | 1994-11-07 | 1996-05-09 | Henkel Kgaa | Rinse aid with polyglucosan oxidation products |
| DE4439681A1 (en) * | 1994-11-07 | 1996-05-09 | Henkel Kgaa | Use of polyglucosan oxidation products as a builder in cleaning agents for hard surfaces |
| DE19507532C2 (en) * | 1995-03-03 | 2000-01-05 | Henkel Ecolab Gmbh & Co Ohg | Pasty detergent |
| US6008345A (en) * | 1995-06-30 | 1999-12-28 | Lion Corporation | Process for making polycarboxylic acid derived from polysaccharide composed of anhydrous glucose units and salts thereof |
| DE19600018A1 (en) * | 1996-01-03 | 1997-07-10 | Henkel Kgaa | Detergent with certain oxidized oligosaccharides |
| US6235695B1 (en) * | 1996-04-01 | 2001-05-22 | Henkel Kommanditgesellschaft Auf Aktien | Cleaning agent with oligoammine activator complexes for peroxide compounds |
| DE19620411A1 (en) | 1996-04-01 | 1997-10-02 | Henkel Kgaa | Transition metal amine complexes as activators for peroxygen compounds |
| DE19617215A1 (en) | 1996-04-30 | 1997-11-06 | Henkel Ecolab Gmbh & Co Ohg | Compact cleaner for commercial dishwashers |
| CA2266068A1 (en) | 1996-09-24 | 1998-04-02 | Henkel-Ecolab Gmbh & Co. Ohg | A surfactant-containing compact detergent |
| DE19649375A1 (en) | 1996-11-29 | 1998-06-04 | Henkel Kgaa | Acetonitrile derivatives as bleach activators in detergents |
| DE19732750A1 (en) | 1997-07-30 | 1999-02-04 | Henkel Kgaa | Cleaning agent containing glucanase for hard surfaces |
| DE19732751A1 (en) | 1997-07-30 | 1999-02-04 | Henkel Kgaa | New Bacillus beta glucanase |
| DE19732749A1 (en) | 1997-07-30 | 1999-02-04 | Henkel Kgaa | Detergent containing glucanase |
| DE19741874A1 (en) | 1997-09-23 | 1999-04-01 | Henkel Ecolab Gmbh & Co Ohg | Alcoholic cleaner |
| DE19752601C1 (en) * | 1997-11-28 | 1998-12-10 | Henkel Kgaa | Production of dishwasher detergent tablet with good breaking strength |
| DE19819187A1 (en) | 1998-04-30 | 1999-11-11 | Henkel Kgaa | Solid dishwasher detergent with phosphate and crystalline layered silicates |
| EP1004661A1 (en) * | 1998-11-11 | 2000-05-31 | DALLI-WERKE WÄSCHE- und KÖRPERPFLEGE GmbH & Co. KG | High density granule, method for production thereof, and its use as disintegrant in tablets |
| DE19908051A1 (en) | 1999-02-25 | 2000-08-31 | Henkel Kgaa | Process for the preparation of compounded acetonitrile derivatives |
| DE19925274A1 (en) | 1999-06-02 | 2000-12-07 | Henkel Ecolab Gmbh & Co Ohg | Mop detergent |
| DE19936612A1 (en) * | 1999-08-04 | 2001-02-08 | Henkel Kgaa | Low dose, soluble builder |
| DE19936726A1 (en) * | 1999-08-06 | 2001-02-08 | Henkel Kgaa | Process for the preparation of preparations containing cobuilder |
| DE19940548A1 (en) * | 1999-08-26 | 2001-03-01 | Henkel Kgaa | Detergent tablets |
| DE19962343A1 (en) | 1999-12-23 | 2001-07-05 | Henkel Ecolab Gmbh & Co Ohg | Disinfectant washing of delicate textiles with peracids |
| DE19962344A1 (en) | 1999-12-23 | 2001-07-12 | Henkel Ecolab Gmbh & Co Ohg | Methods and agents for cleaning and disinfecting sensitive medical devices |
| DE19962342A1 (en) | 1999-12-23 | 2001-07-12 | Henkel Ecolab Gmbh & Co Ohg | Peracids with good adhesion to surfaces |
| DE10022419A1 (en) | 2000-05-09 | 2001-11-22 | Henkel Ecolab Gmbh & Co Ohg | Surfactant composition used for removing residues containing silicone from surfaces contains hydrophilic polyethylene oxide monoalk(en)yl ether, N,N-bis(ethoxylated)-N-alk(en)yl amine and/or alkyl sulfonate and other surfactant |
| JP2009263641A (en) * | 2008-03-31 | 2009-11-12 | Kao Corp | Method for producing polyuronate |
| JP5544107B2 (en) * | 2008-03-31 | 2014-07-09 | 花王株式会社 | Polymer builder |
| WO2009122953A1 (en) * | 2008-03-31 | 2009-10-08 | 花王株式会社 | Method for manufacturing polyuronate |
| DE102015109019A1 (en) | 2015-06-08 | 2016-12-08 | Budich International Gmbh | Cleaning device for commercial cooking appliances |
| DE102015109017A1 (en) | 2015-06-08 | 2016-12-08 | Budich International Gmbh | Detergents for cleaning commercial cooking appliances |
| WO2017157781A1 (en) | 2016-03-14 | 2017-09-21 | Henkel Ag & Co. Kgaa | Method for controlling malodors, in particular in dish washing machines, using bacterial spores capable of inhibiting or preventing the production of malodor |
| WO2017157775A1 (en) | 2016-03-14 | 2017-09-21 | Henkel Ag & Co. Kgaa | Method for controlling malodors, in particular in dish washing machines, using bacterial spores capable of inhibiting or preventing the production of malodor |
| CN114341327A (en) * | 2019-09-30 | 2022-04-12 | 埃科莱布美国股份有限公司 | Ware washing liquid containing oxidized starch |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3629121A (en) * | 1969-12-15 | 1971-12-21 | Ibrahim A Eldib | Carboxylated starches as detergent builders |
| DE4010524A1 (en) * | 1990-04-02 | 1991-10-10 | Henkel Kgaa | STABLE, BIFUNCTIONAL, PHOSPHATE-FREE DETERGENT TABLETS FOR THE MACHINE DISHWASHER |
| EP0554256B1 (en) * | 1990-07-10 | 1995-04-12 | The Procter & Gamble Company | Process for making a high bulk density detergent composition |
| IT1249883B (en) * | 1990-08-13 | 1995-03-30 | Ferruzzi Ricerca & Tec | CALCIUM SEQUESTRING AGENTS BASED ON OXIDIZED CARBOHYDRATES AND THEIR USE AS BUILDER FOR DETERGENTS |
| FR2675514A1 (en) * | 1991-04-22 | 1992-10-23 | Roquette Freres | WASHING PRODUCT WITH REDUCED OR ZERO CONTENT. |
| DE4134914A1 (en) * | 1991-10-23 | 1993-04-29 | Henkel Kgaa | DETERGENT AND CLEANING AGENT WITH SELECTED BUILDER SYSTEMS |
| EP0542496B1 (en) * | 1991-11-14 | 1998-05-20 | The Procter & Gamble Company | C6/C2-C3 Oxidized starch as detergent ingredient |
-
1992
- 1992-08-29 DE DE4228786A patent/DE4228786A1/en not_active Withdrawn
-
1993
- 1993-08-21 DE DE59306692T patent/DE59306692D1/en not_active Expired - Lifetime
- 1993-08-21 WO PCT/EP1993/002252 patent/WO1994005762A1/en active IP Right Grant
- 1993-08-21 ES ES93919136T patent/ES2102055T3/en not_active Expired - Lifetime
- 1993-08-21 EP EP93919136A patent/EP0656937B1/en not_active Expired - Lifetime
- 1993-08-21 JP JP6506814A patent/JPH08500626A/en active Pending
- 1993-08-21 CA CA002143609A patent/CA2143609A1/en not_active Abandoned
- 1993-08-21 AT AT93919136T patent/ATE154071T1/en not_active IP Right Cessation
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020011764A1 (en) * | 2018-07-09 | 2020-01-16 | Koninklijke Coöperatie Cosun U.A. | Antiscalant composition comprising a uronic acid polysaccharide |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2102055T3 (en) | 1997-07-16 |
| DE59306692D1 (en) | 1997-07-10 |
| DE4228786A1 (en) | 1994-03-03 |
| JPH08500626A (en) | 1996-01-23 |
| EP0656937A1 (en) | 1995-06-14 |
| ATE154071T1 (en) | 1997-06-15 |
| EP0656937B1 (en) | 1997-06-04 |
| WO1994005762A1 (en) | 1994-03-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2143609A1 (en) | A dishwashing detergent containing a selected builder system | |
| US5501814A (en) | Detergents and cleaning preparations containing selected builder systems | |
| EP0245551B1 (en) | Detergent granules | |
| JP2745400B2 (en) | Spherical co-granules based on hydrated alkali metal silicates and alkali metal carbonates | |
| EP0126551B1 (en) | Detergent compositions | |
| JPH09507205A (en) | Silicate builders and their use in laundry or cleaning agents and multicomponent mixtures for use in the field | |
| EP0770121B1 (en) | Washing process and composition | |
| EP0267042A2 (en) | Detergent granules and a process for their preparation | |
| US6528474B1 (en) | Method of manufacturing a detergent with soluble builder | |
| JPH03210399A (en) | Chlorine-free liquid compound for automatic dish washer | |
| JPH07501036A (en) | Liquid or paste detergents or cleaning agents | |
| CA2166277A1 (en) | Dishwashing detergents containing a biologically degradable builder component | |
| JPH01146996A (en) | Phosphorus free washing bleaching agent composition | |
| JPH07501564A (en) | Surfactant mixture in powder form | |
| JPH10508042A (en) | Low film-forming dishwashing detergent | |
| CA2166186A1 (en) | Dishwashing detergents containing a biologically degradable builder component | |
| JPH05271696A (en) | Activator for oxygen bleaching agent, and bleaching agent composition | |
| JP2002517552A (en) | Detergent containing amylase and percarboxylic acid | |
| JPH10279991A (en) | Detergent composition for automatic dishwasher | |
| JPH03502108A (en) | Zeolites in liquid cleaning compositions | |
| EP0783561A1 (en) | Silicates granules and method for manufacturing the same | |
| JP2000351991A (en) | Detergent composition | |
| JP2003193091A (en) | Water-containing inorganic particle and detergent composition containing the same | |
| WO1995012651A1 (en) | Spray drying process for making a low or nil phosphate automatic dishwashing detergent composition | |
| US20040259756A1 (en) | Process for preparing and using active shaped bodies |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |