CA2165285A1 - Dishwashing detergents with a reduced tendency towards bloom formation - Google Patents
Dishwashing detergents with a reduced tendency towards bloom formationInfo
- Publication number
- CA2165285A1 CA2165285A1 CA002165285A CA2165285A CA2165285A1 CA 2165285 A1 CA2165285 A1 CA 2165285A1 CA 002165285 A CA002165285 A CA 002165285A CA 2165285 A CA2165285 A CA 2165285A CA 2165285 A1 CA2165285 A1 CA 2165285A1
- Authority
- CA
- Canada
- Prior art keywords
- weight
- detergent
- salts
- terized
- charac
- 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
- 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
-
- 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
- C11D3/26—Organic compounds containing nitrogen
- C11D3/33—Amino carboxylic acids
Abstract
The invention pertains to automatic dish-washing detergents containing as good biodegradable alkali carriers. amino acids and their salts, especially short-chain .alpha.-amino acids, primarily glycine or glycinate. These dish-washing detergents containing amino acids show markedly better properties of inhibiting calcium buildup than conventional dish-washing detergents based on carbonate and/or hydrocarbonate.
Description
TRANSLATION
-Dishwashing detergents with a reduced tendency toward~ bloom formation This invention relates to dishwashing detergents for dishwashing machines, more particularly low-alkali dishwashing detergents with an in-use pH value of 9 to 11, which contain amino acids, preferably lower ~-amino acids, as alkali carriers.
Low-alkali machine dishwashing detergents of the latest generation contain alkali carriers, for example soda, hydrogen carbonate or disilicate, in addition to water-soluble builders, oxygen-based bleaching agents, surfactants and enzymes.
Their in-use pH value is generally between 10 and 11. Unfortunately, the formulations involved have the disadvantage that lime coatings build up on the articles washed in the machine in the main wash and final rinse cycles at residual water hardness values of 4dH and higher. The partial replacement of carbonate by hydrogen carbonate can reduce the in-use pH value to 9-10 which increases the complexing effect of certain builder ~ components s-o that the tendency-to form lime coatings can be reduced. Where very hard water (above 16dH is used, however, the inhibiting effect on the formation of lime coatings is not entirely satisfactory, even at a reduced in-use pH value.
Accordingly, the problem addressed by the present invention was to provide an alkali carrier system which would not have any of the above-described disadvantages of increased lime coating formation and which would be compatible with the builder components typically used in machine dishwashing detergents. At the same time, the alkali carriers would be readily biodegradable substan-ces. It has now been found that amino acids, more ~ - , WO 94/29420 2 21652~ PCT/EP94/01830 particularly lower ~-amino acids, meet the requirements ~ the new alkali carriers are expected to satisfy to a particular degree.
DE-OS8 19 42 236 and 19 64 792 disclose laundry detergents in which protein-dissolving enzymes are completely or partly replaced by sulfur-free amino acids.
However, there are no references to the fact that amino acids can be used as a replacement for conventional alkali carriers in machine dishwashing detergents.
The use of substituted ~-alanine derivatives as builders in machine dishwashing detergents is claimed in DB-O~ 40 36 695.
The present invention relates to a machine dishwash-ing detergent of which a 1% by weight aqueous solution has a pH value of 8 to 12 and preferably 9 to 11 and which contains water-soluble builder components and oxygen-based bleaching agents, characterized in that it contains one or more amino acids or alkali metal or ammonium salts thereof as alkali carriers in a quantity of 0.5 to 60% by weight and preferably 10 to 50% by weight, based on the detergent as a whole.
Amino acids in the context of the invention are - ~ amino acids of which the amino function is not substitu-ted, i.e. of which the amino functions carry only hydro-gens.
Suitable amino acids are synthetic or naturally occurring amino acids obtainable, for example, by hydro-lysis from vegetable or animal proteins, such as col-lagen, keratin, casein, elastin, soya protein, wheat gluten or almond protein.
Preferred amino acids are ~-amino acids, for example serine, threonine, ornithine, arginine, lysine, aspara-gine, glucamine, phenyl alanine or tyrosine, but especi-ally glycine, alanine, valine, leucine and isoleucine.
Glycine or alkali metal or ammonium salts thereof, for ~ - , ~0 94/29420 216 5 2 8 5 CT/EP94/01830 example sodium glycinate, are particularly preferred.
Besides the amino acids, alkali metal, alkaline earth metal or ammonium salts thereof, especially the sodium salts, may also be present in the dishwashing detergents according to the invention.
The amino acids or their salts may be used in powder or granular form, optionally together with such auxili-aries as, for example, sodium citrate.
By varying the ratio of amino acids to their salts, a certain required pH value can be established as easily as with the hydrogen carbonate/carbonate system. How-ever, the amino acid/amino acid salt alkali carrier system is distinctly superior to the hydrogen carbonate/
carbonate carrier system in regard to the inhibition of lime coatings.
Amino acids or amino acid salts are present in the detergents according to the invention in quantities of 0.5 to 60% by weight and preferably in quantities of 10 to 50% by weight. Mixtures of different amino acids or amino acid salts may also be used. Carbonate and/or hydrogen carbonate, more particularly alkali metal carbonates and/or hydrogen carbonates, may optionally be ~ present in quantities of up to-15% by weight, based on the dishwashing detergent as a whole. However, the dishwashing detergents according to the invention are preferably free from carbonates and/or hydrogen carbon-ates. Highly alkaline metasilicates, for example sodium metasilicate, are preferably not used. By contrast, disilicates with a molar sio2 to Na20 ratio of 1.5:1 to 2.5:1 in the form of their alkali metal salts may option-ally be present in quantities of 0.1 to 20% by weight, based on the dishwashing detergent as a whole.
Suitable builder components which perform the actual function of complexing hardness salts in water and keeping lime precipitated dispersed in the wash liquor so - ~ Wo 94/29420 4 2165 285pcT/Ep94/ol83o - as to prevent lime coatings are, for example, organo-phosphonic acids and salts thereof, crystalline layer silicates, zeolites, dibasic and polybasic organic carboxylic acids and salts thereof, oxidized starch and polycarboxylic acids or polycarboxylates and polyamino acids, such as polyaspartic acid for example. The phosphates previously used, for example pentasodium triphosphate, which may also be present in principle, are preferably not used for ecological reasons.
Preferred builder components are dibasic or poly-basic organic carboxylic acids and salts thereof, more particularly citric acid and salts thereof and/or syn-thetic polycarboxylic acids or polycarboxylates, which are present in a total quantity of 1 to 60% by weight and preferably 20 to 50% by weight, based on the dishwashing detergent as a whole.
In the context of the invention, synthetic polycar-boxylic acids and polycarboxylates are understood to be the synthetic polymers or their salts of polymerization products of unsaturated carboxylic acids or salts there-of, including for example polyacrylic acid, polymethacry-lic acid, polymaleic acid or copolymers of acrylic acid ~ with maleic-acid or maleic anhydride.
Suitable polyacrylates are, for example, Alcosperse~
102, 104, 106, 404, 406, all products of Alco; Acrysols~
A Nl, LMW 45 N, LMW 10 N, products of Norsohaas; Dega-pas~, a product of Degussa AG. Suitable copolymers of polyacrylic acid and maleic acid are, for example, Soka-lan~ CP 5, CP 7, products of BASF: Acrysol~ QR 1014, a product of Norsohaas; and Alcosperse~ 175, a product of Alco.
In addition, the dishwashing detergents according to the invention must contain oxygen-containing bleaching agents, more particularly perborates and/or percarbon-ates, in a quantity of 0.5 to 20% by weight and prefer-- ~ WO 94/2942Q 5 ~/ ~
ably in a quantity of 5 to 12% by weight, based on the dishwashing detergent as a whole.
Sodium perborate tetrahydrate (NaBO2 H202 3H20), sodium perborate monohydrate (NaBO2 H202) and peroxycar-bonate (Na2CO3 1.5 H202) are particularly important. Other useful bleaching agents are, for example, peracidic salts of organic acids, such as perbenzoates or salts of diper-dodecanedioic acid. In addition, bleach activators are optionally present. Suitable bleach activators are, in particular, N-acyl and O-acyl compounds, preferably tetraacylated diamines, such as N,N,N',N'-tetraacetyl ethylenediamine (TAED). The detergents according to the invention contain typical bleach activators such as these in a quantity of 0.1 to 10% by weight and preferably in a quantity of 1 to 5% by weight. The detergents accord-ing to the invention may also optionally contain active chlorine donors, for example trichloroisocyanuric acid.
However, they are preferably free from active chlorine donors.
The foaming behavior of the surfactants suitable for use in the detergents according to the invention is a key factor. In view of the mechanics of dishwashing ma-~ chines, low-foaming compounds are preferred. These are, above all, nonionic surfactants. In principle, however, the dishwashing detergents according to the invention may also contain very small quantities of anionic, cationic or amphoteric surfactants, but are preferably free from such surfactants. The nonionic surfactant content is at most 5% by weight and preferably at most 2% by weight, based on the dishwashing detergent as a whole. Suitable nonionic surfactants are, above all, adducts of 1 to 20 moles of ethylene oxide (EO) and/or 1 to 20 moles of propylene oxide (PO) with 1 mole of an aliphatic compound containing 10 to 20 carbon atoms from the group of alcohols, carboxylic acids, fatty amines, carboxylic acid - - i WO 94/29420 ~165285 PCT/EP94/01830 amides and alkane sulfonamides. Besides water-soluble nonionic surfactants, however, water-insoluble or sub-stantially water-insoluble polyglycol ethers containing 2 to 7 ethylene glycol ether groups in the molecule are also important, preferably being used in combination with water-soluble nonionic surfactants. In addition, alkyl polyglycosides corresponding to the general formula R-O-(G)~, in which R is a primary, linear or branched aliphatic radical containing 8 to 22 and preferably 12 to 18 carbon atoms, G is a glycose unit containing 5 or 6 carbon atoms and the degree of oligomerization x is between 1 and 10, may also be used as nonionic surfac-tants.
To improve the removal of protein- or starch-con-taining food residues, the detergents may advantageouslycontain enzymes, such as proteases, amylases, lipases or cellulases, for example proteases, such as BLAP~ 140, a product of Henkel KGaA, OptimaseX M-440, Optimase~ M-330, Opticlean~ M-375, Opticlean~ M-250, products of Solvay 20 Enzymes: Maxacal~ CX 450.000, Maxapem~, products of Ibis;
Savinase~ 4.0 T, 6.0 T, 8.0 T, products of Novo; Ex-perase~ T, a product of Ibis; amylases, such as TermamylX
~ ~ 60 T, 90 T,-products of Novo; Amylase-LTX, a product of Solvay Enzymes; or MaxamylX P 5000, CXT 5000 or CXT 2900, products of Ibis; lipases, such as Lipolase~ 30 T, a product of Novo; cellulases, such as Celluzym~ 0.7 T, a product of Novo Nordisk. Enzymes may be present in the - detergents according to the invention in a quantity of 0.1 to 5% by weight and preferably in a quantity of 1 to 3% by weight, based on the dishwashing detergent as a whole.
The dishwashing detergents according to the inven-tion are preferably powder-form, granular or tablet-form formulations which may be produced in known manner, for example by mixing, granulation, roll compacting and/or by ~ - ; W0 94/29420 2 I ~ S 2 8 5 PcT/Ep94/0l830 spray drying. Another advantage of the alkali carrier ~ system consisting predominantly of organic raw materials is that it affords advantages in terms of making-up, particularly in the production of granules, tablets or extrudates.
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 1500-105 Pa. Breaking-resistant tablets which still dissolve sufficiently quickly under in-use conditions with flexural strengths of normally above 150 N are nor-mally obtained in this way. A tablet produced in this way preferably has a weight of 15 g to 40 g and, more particularly, 20 g to 30 g for a diameter of 35 mm to 40 mm.
The production of the machine dishwashing detergents in the form of non-dust-emitting, storage-stable free-flowing powders and/or granules with high apparent densi-ties preferably in the range from 750 to 1000 g/l is carried out, for example, by mixing the builder compo-~ nents with at least part of the liquid mixture componentsin a first stage of the process, the apparent density of the premix being increased, and then combining the other constituents of the machine dishwashing detergent with the premix thus obtained, if desired after intermediate drying.
The liquid phase used in the first stage of the process consists in particular of the surfactant com-pounds liquid under normal conditions, i.e. in particular the corresponding nonionic surfactants, and/or other liquid components of the formulation as a whole. These include the fragrances dissolved in the carrier liquids and/or limited quantities of water or aqueous solutions ~ - Wo 94/29420 8 21~5285 PCT/EPg4/01830 of mixture components of the required dishwashing deter-~ gent.
In the first stage of the mixing process, the builder is generally mixed with the liquid components in the form of a mixture with at least one other component of the dishwashing detergent. This may be done, for example, in a preliminary stage in which the builder component is exposed to and thoroughly mixed with the liquid nonionic surfactants and/or the solution of fragrances in the form of a mixture with perborate. The remaining components are then added and the mixture as a whole is compounded and homogenized in the mixer. There is generally no need to use additional quantities of liquid, i.e. additional water. The mixture obtained is a free-flowing, non-dust-emitting powder with the re-quired high apparent densities in the range from about 800 to 900 g/l.
The machine dishwashing detergents according to the invention containing amino acids and/or salts thereof as alkali carriers represent products which, apart from their ready biodegradability, are superior to convention-al modern dishwashing detergents, in which the alkali ~ carrier system consists predominantly of carbonate and/or hydrogen carbonate, in regard to the inhibition of lime coatings.
E x a m p 1 e s I. Granular dishwashing detergents with the following composition (detergents A and B according to the inven-tion, comparison detergent C and detergents D, E and F
according to the invention) were produced.
Detergent A contained 31.9% by weight of glycine and 17.2% by weight of sodium glycinate as the alkali carrier system; the pH value of a 1% by weight aqueous solution ~ - , , W0 94/29420 9 ~16S285 PCT/EPg4/01830 was 9.5. Detergent B contained 49.1% by weight of sodium glycinate as the alkali carrier system; the pH value of a 1% by weight aqueous solution was correspondingly higher at 10.9. Comparison detergent C contained 36.1%
by weight of sodium hydrogen carbonate and 13.0% by weight of sodium carbonate as the alkali carrier system;
the pH value of a 1% by weight aqueous solution was 9.5.
Detergents D, E and F according to the invention contained 24.0% by weight of glycine/16.0% by weight of sodium glycinate (D), 25.3% by weight of glycine/10.8% by weight of sodium glycinate (E) and 37.5% by weight of sodium glycinate (F).
Sodium glycinate may be used in powder form or as granules. The granules may be produced, for example, as follows:
Na glycinate and a mixture - prepared in a standard pilot-scale Lodige mixer - of Na glycinate and Na citrate (90:10) was compacted in a roll press (roll temperature 20C, linear pressure 17 kN/cm) to form sheets. The sheets were then ground and a fraction of < 1.6 mm was removed by sieving.
This fraction was then introduced into a Niro ~ Aeromatic fluidized-bed apparatus operated in batches and sprayed for 30 minutes with a paraffin wax (Mp. 42-45C) which was introduced into the fluidized bed through a two-component nozzle. The fluidizing air was kept at 30C. With a ratio of roll compactate to paraffin wax of 9:1, the granules formed were slightly tacky, but remain-ed stable even in formulations containing "stray" water by virtue of the externally applied hydrophobic layer.
. WO 94/29420 10 2165285 PCT/EPg4/0l830 - A B C D E F
% by % by % by % by % by % by weight weight weight weight weight weight Na citrate 30.0 30.0 30.0 45.0 45.0 45.0 Sokalan~ CP5 (acrylate/maleate copolymer of 10 BASF) 10.0 10.0 10.0 - - -Na2C03 - - 13.0 NaHCO3 - - 36.1 Glycine 31.9 - - 24.0 25.3 Sodium gly-15 cinate 17.2 49.1 - 16.0 10.8 37.5 Na perborate monohydrate 5.0 5.0 5.0 Na percarbonate - - - 6.5 12.0 10.0 TAED 2.0 2.0 2.0 5.0 4.0 4.0 20 Amylase 1.5 1.5 1.5 1.0 1.0 1.0 Protease 1.5 1.5 1.5 1.0 1.0 1.0 PlurafacX LF 403 (C12_l8 fatty al-cohol-EO-4PO of 25 BASF) 0.9 0.9 0.9 1.5 0.9 1.5 Bloom inhibition The tendency of detergents A, B and C to form lime coatings was tested in a Miele G 590 dishwashing machine (program: universal, 65C) with dosages of 20 g in 6.2 1 of water (16dH) containing 50 g of added pumpable soils (mixture of ketchup, gravy, mustard, potato starch, egg yolk, milk, margarine) in the presence of 3.0 ml of a commercially available rinse aid over 10 wash cycles.
Bloom formation was evaluated on a scale of o (= very heavy bloom) to 3 (= no bloom). The results of the bloom tests obtained with detergents A and B according to the invention and comparison detergent C are as follows:
. W0 94/29420 11 ~1~5 28~ PCT/EP94/01830 detergent A according to the invention: 1.0 detergent B according to the invention: 1.0 comparison detergent C: 0.2 detergent D according to the invention: 2.2 detergent E according to the invention: 2.6 detergent F according to the invention: 2.6 It can be seen that detergents A, B, D, E and F
according to the invention are distinctly superior to comparison detergent C in regard to bloom inhibition.
a 1~5~5 P~ F ~ ~1 C~ c~ L~
~sa~, LL~ ~ ~
-Dishwashing detergents with a reduced tendency toward~ bloom formation This invention relates to dishwashing detergents for dishwashing machines, more particularly low-alkali dishwashing detergents with an in-use pH value of 9 to 11, which contain amino acids, preferably lower ~-amino acids, as alkali carriers.
Low-alkali machine dishwashing detergents of the latest generation contain alkali carriers, for example soda, hydrogen carbonate or disilicate, in addition to water-soluble builders, oxygen-based bleaching agents, surfactants and enzymes.
Their in-use pH value is generally between 10 and 11. Unfortunately, the formulations involved have the disadvantage that lime coatings build up on the articles washed in the machine in the main wash and final rinse cycles at residual water hardness values of 4dH and higher. The partial replacement of carbonate by hydrogen carbonate can reduce the in-use pH value to 9-10 which increases the complexing effect of certain builder ~ components s-o that the tendency-to form lime coatings can be reduced. Where very hard water (above 16dH is used, however, the inhibiting effect on the formation of lime coatings is not entirely satisfactory, even at a reduced in-use pH value.
Accordingly, the problem addressed by the present invention was to provide an alkali carrier system which would not have any of the above-described disadvantages of increased lime coating formation and which would be compatible with the builder components typically used in machine dishwashing detergents. At the same time, the alkali carriers would be readily biodegradable substan-ces. It has now been found that amino acids, more ~ - , WO 94/29420 2 21652~ PCT/EP94/01830 particularly lower ~-amino acids, meet the requirements ~ the new alkali carriers are expected to satisfy to a particular degree.
DE-OS8 19 42 236 and 19 64 792 disclose laundry detergents in which protein-dissolving enzymes are completely or partly replaced by sulfur-free amino acids.
However, there are no references to the fact that amino acids can be used as a replacement for conventional alkali carriers in machine dishwashing detergents.
The use of substituted ~-alanine derivatives as builders in machine dishwashing detergents is claimed in DB-O~ 40 36 695.
The present invention relates to a machine dishwash-ing detergent of which a 1% by weight aqueous solution has a pH value of 8 to 12 and preferably 9 to 11 and which contains water-soluble builder components and oxygen-based bleaching agents, characterized in that it contains one or more amino acids or alkali metal or ammonium salts thereof as alkali carriers in a quantity of 0.5 to 60% by weight and preferably 10 to 50% by weight, based on the detergent as a whole.
Amino acids in the context of the invention are - ~ amino acids of which the amino function is not substitu-ted, i.e. of which the amino functions carry only hydro-gens.
Suitable amino acids are synthetic or naturally occurring amino acids obtainable, for example, by hydro-lysis from vegetable or animal proteins, such as col-lagen, keratin, casein, elastin, soya protein, wheat gluten or almond protein.
Preferred amino acids are ~-amino acids, for example serine, threonine, ornithine, arginine, lysine, aspara-gine, glucamine, phenyl alanine or tyrosine, but especi-ally glycine, alanine, valine, leucine and isoleucine.
Glycine or alkali metal or ammonium salts thereof, for ~ - , ~0 94/29420 216 5 2 8 5 CT/EP94/01830 example sodium glycinate, are particularly preferred.
Besides the amino acids, alkali metal, alkaline earth metal or ammonium salts thereof, especially the sodium salts, may also be present in the dishwashing detergents according to the invention.
The amino acids or their salts may be used in powder or granular form, optionally together with such auxili-aries as, for example, sodium citrate.
By varying the ratio of amino acids to their salts, a certain required pH value can be established as easily as with the hydrogen carbonate/carbonate system. How-ever, the amino acid/amino acid salt alkali carrier system is distinctly superior to the hydrogen carbonate/
carbonate carrier system in regard to the inhibition of lime coatings.
Amino acids or amino acid salts are present in the detergents according to the invention in quantities of 0.5 to 60% by weight and preferably in quantities of 10 to 50% by weight. Mixtures of different amino acids or amino acid salts may also be used. Carbonate and/or hydrogen carbonate, more particularly alkali metal carbonates and/or hydrogen carbonates, may optionally be ~ present in quantities of up to-15% by weight, based on the dishwashing detergent as a whole. However, the dishwashing detergents according to the invention are preferably free from carbonates and/or hydrogen carbon-ates. Highly alkaline metasilicates, for example sodium metasilicate, are preferably not used. By contrast, disilicates with a molar sio2 to Na20 ratio of 1.5:1 to 2.5:1 in the form of their alkali metal salts may option-ally be present in quantities of 0.1 to 20% by weight, based on the dishwashing detergent as a whole.
Suitable builder components which perform the actual function of complexing hardness salts in water and keeping lime precipitated dispersed in the wash liquor so - ~ Wo 94/29420 4 2165 285pcT/Ep94/ol83o - as to prevent lime coatings are, for example, organo-phosphonic acids and salts thereof, crystalline layer silicates, zeolites, dibasic and polybasic organic carboxylic acids and salts thereof, oxidized starch and polycarboxylic acids or polycarboxylates and polyamino acids, such as polyaspartic acid for example. The phosphates previously used, for example pentasodium triphosphate, which may also be present in principle, are preferably not used for ecological reasons.
Preferred builder components are dibasic or poly-basic organic carboxylic acids and salts thereof, more particularly citric acid and salts thereof and/or syn-thetic polycarboxylic acids or polycarboxylates, which are present in a total quantity of 1 to 60% by weight and preferably 20 to 50% by weight, based on the dishwashing detergent as a whole.
In the context of the invention, synthetic polycar-boxylic acids and polycarboxylates are understood to be the synthetic polymers or their salts of polymerization products of unsaturated carboxylic acids or salts there-of, including for example polyacrylic acid, polymethacry-lic acid, polymaleic acid or copolymers of acrylic acid ~ with maleic-acid or maleic anhydride.
Suitable polyacrylates are, for example, Alcosperse~
102, 104, 106, 404, 406, all products of Alco; Acrysols~
A Nl, LMW 45 N, LMW 10 N, products of Norsohaas; Dega-pas~, a product of Degussa AG. Suitable copolymers of polyacrylic acid and maleic acid are, for example, Soka-lan~ CP 5, CP 7, products of BASF: Acrysol~ QR 1014, a product of Norsohaas; and Alcosperse~ 175, a product of Alco.
In addition, the dishwashing detergents according to the invention must contain oxygen-containing bleaching agents, more particularly perborates and/or percarbon-ates, in a quantity of 0.5 to 20% by weight and prefer-- ~ WO 94/2942Q 5 ~/ ~
ably in a quantity of 5 to 12% by weight, based on the dishwashing detergent as a whole.
Sodium perborate tetrahydrate (NaBO2 H202 3H20), sodium perborate monohydrate (NaBO2 H202) and peroxycar-bonate (Na2CO3 1.5 H202) are particularly important. Other useful bleaching agents are, for example, peracidic salts of organic acids, such as perbenzoates or salts of diper-dodecanedioic acid. In addition, bleach activators are optionally present. Suitable bleach activators are, in particular, N-acyl and O-acyl compounds, preferably tetraacylated diamines, such as N,N,N',N'-tetraacetyl ethylenediamine (TAED). The detergents according to the invention contain typical bleach activators such as these in a quantity of 0.1 to 10% by weight and preferably in a quantity of 1 to 5% by weight. The detergents accord-ing to the invention may also optionally contain active chlorine donors, for example trichloroisocyanuric acid.
However, they are preferably free from active chlorine donors.
The foaming behavior of the surfactants suitable for use in the detergents according to the invention is a key factor. In view of the mechanics of dishwashing ma-~ chines, low-foaming compounds are preferred. These are, above all, nonionic surfactants. In principle, however, the dishwashing detergents according to the invention may also contain very small quantities of anionic, cationic or amphoteric surfactants, but are preferably free from such surfactants. The nonionic surfactant content is at most 5% by weight and preferably at most 2% by weight, based on the dishwashing detergent as a whole. Suitable nonionic surfactants are, above all, adducts of 1 to 20 moles of ethylene oxide (EO) and/or 1 to 20 moles of propylene oxide (PO) with 1 mole of an aliphatic compound containing 10 to 20 carbon atoms from the group of alcohols, carboxylic acids, fatty amines, carboxylic acid - - i WO 94/29420 ~165285 PCT/EP94/01830 amides and alkane sulfonamides. Besides water-soluble nonionic surfactants, however, water-insoluble or sub-stantially water-insoluble polyglycol ethers containing 2 to 7 ethylene glycol ether groups in the molecule are also important, preferably being used in combination with water-soluble nonionic surfactants. In addition, alkyl polyglycosides corresponding to the general formula R-O-(G)~, in which R is a primary, linear or branched aliphatic radical containing 8 to 22 and preferably 12 to 18 carbon atoms, G is a glycose unit containing 5 or 6 carbon atoms and the degree of oligomerization x is between 1 and 10, may also be used as nonionic surfac-tants.
To improve the removal of protein- or starch-con-taining food residues, the detergents may advantageouslycontain enzymes, such as proteases, amylases, lipases or cellulases, for example proteases, such as BLAP~ 140, a product of Henkel KGaA, OptimaseX M-440, Optimase~ M-330, Opticlean~ M-375, Opticlean~ M-250, products of Solvay 20 Enzymes: Maxacal~ CX 450.000, Maxapem~, products of Ibis;
Savinase~ 4.0 T, 6.0 T, 8.0 T, products of Novo; Ex-perase~ T, a product of Ibis; amylases, such as TermamylX
~ ~ 60 T, 90 T,-products of Novo; Amylase-LTX, a product of Solvay Enzymes; or MaxamylX P 5000, CXT 5000 or CXT 2900, products of Ibis; lipases, such as Lipolase~ 30 T, a product of Novo; cellulases, such as Celluzym~ 0.7 T, a product of Novo Nordisk. Enzymes may be present in the - detergents according to the invention in a quantity of 0.1 to 5% by weight and preferably in a quantity of 1 to 3% by weight, based on the dishwashing detergent as a whole.
The dishwashing detergents according to the inven-tion are preferably powder-form, granular or tablet-form formulations which may be produced in known manner, for example by mixing, granulation, roll compacting and/or by ~ - ; W0 94/29420 2 I ~ S 2 8 5 PcT/Ep94/0l830 spray drying. Another advantage of the alkali carrier ~ system consisting predominantly of organic raw materials is that it affords advantages in terms of making-up, particularly in the production of granules, tablets or extrudates.
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 1500-105 Pa. Breaking-resistant tablets which still dissolve sufficiently quickly under in-use conditions with flexural strengths of normally above 150 N are nor-mally obtained in this way. A tablet produced in this way preferably has a weight of 15 g to 40 g and, more particularly, 20 g to 30 g for a diameter of 35 mm to 40 mm.
The production of the machine dishwashing detergents in the form of non-dust-emitting, storage-stable free-flowing powders and/or granules with high apparent densi-ties preferably in the range from 750 to 1000 g/l is carried out, for example, by mixing the builder compo-~ nents with at least part of the liquid mixture componentsin a first stage of the process, the apparent density of the premix being increased, and then combining the other constituents of the machine dishwashing detergent with the premix thus obtained, if desired after intermediate drying.
The liquid phase used in the first stage of the process consists in particular of the surfactant com-pounds liquid under normal conditions, i.e. in particular the corresponding nonionic surfactants, and/or other liquid components of the formulation as a whole. These include the fragrances dissolved in the carrier liquids and/or limited quantities of water or aqueous solutions ~ - Wo 94/29420 8 21~5285 PCT/EPg4/01830 of mixture components of the required dishwashing deter-~ gent.
In the first stage of the mixing process, the builder is generally mixed with the liquid components in the form of a mixture with at least one other component of the dishwashing detergent. This may be done, for example, in a preliminary stage in which the builder component is exposed to and thoroughly mixed with the liquid nonionic surfactants and/or the solution of fragrances in the form of a mixture with perborate. The remaining components are then added and the mixture as a whole is compounded and homogenized in the mixer. There is generally no need to use additional quantities of liquid, i.e. additional water. The mixture obtained is a free-flowing, non-dust-emitting powder with the re-quired high apparent densities in the range from about 800 to 900 g/l.
The machine dishwashing detergents according to the invention containing amino acids and/or salts thereof as alkali carriers represent products which, apart from their ready biodegradability, are superior to convention-al modern dishwashing detergents, in which the alkali ~ carrier system consists predominantly of carbonate and/or hydrogen carbonate, in regard to the inhibition of lime coatings.
E x a m p 1 e s I. Granular dishwashing detergents with the following composition (detergents A and B according to the inven-tion, comparison detergent C and detergents D, E and F
according to the invention) were produced.
Detergent A contained 31.9% by weight of glycine and 17.2% by weight of sodium glycinate as the alkali carrier system; the pH value of a 1% by weight aqueous solution ~ - , , W0 94/29420 9 ~16S285 PCT/EPg4/01830 was 9.5. Detergent B contained 49.1% by weight of sodium glycinate as the alkali carrier system; the pH value of a 1% by weight aqueous solution was correspondingly higher at 10.9. Comparison detergent C contained 36.1%
by weight of sodium hydrogen carbonate and 13.0% by weight of sodium carbonate as the alkali carrier system;
the pH value of a 1% by weight aqueous solution was 9.5.
Detergents D, E and F according to the invention contained 24.0% by weight of glycine/16.0% by weight of sodium glycinate (D), 25.3% by weight of glycine/10.8% by weight of sodium glycinate (E) and 37.5% by weight of sodium glycinate (F).
Sodium glycinate may be used in powder form or as granules. The granules may be produced, for example, as follows:
Na glycinate and a mixture - prepared in a standard pilot-scale Lodige mixer - of Na glycinate and Na citrate (90:10) was compacted in a roll press (roll temperature 20C, linear pressure 17 kN/cm) to form sheets. The sheets were then ground and a fraction of < 1.6 mm was removed by sieving.
This fraction was then introduced into a Niro ~ Aeromatic fluidized-bed apparatus operated in batches and sprayed for 30 minutes with a paraffin wax (Mp. 42-45C) which was introduced into the fluidized bed through a two-component nozzle. The fluidizing air was kept at 30C. With a ratio of roll compactate to paraffin wax of 9:1, the granules formed were slightly tacky, but remain-ed stable even in formulations containing "stray" water by virtue of the externally applied hydrophobic layer.
. WO 94/29420 10 2165285 PCT/EPg4/0l830 - A B C D E F
% by % by % by % by % by % by weight weight weight weight weight weight Na citrate 30.0 30.0 30.0 45.0 45.0 45.0 Sokalan~ CP5 (acrylate/maleate copolymer of 10 BASF) 10.0 10.0 10.0 - - -Na2C03 - - 13.0 NaHCO3 - - 36.1 Glycine 31.9 - - 24.0 25.3 Sodium gly-15 cinate 17.2 49.1 - 16.0 10.8 37.5 Na perborate monohydrate 5.0 5.0 5.0 Na percarbonate - - - 6.5 12.0 10.0 TAED 2.0 2.0 2.0 5.0 4.0 4.0 20 Amylase 1.5 1.5 1.5 1.0 1.0 1.0 Protease 1.5 1.5 1.5 1.0 1.0 1.0 PlurafacX LF 403 (C12_l8 fatty al-cohol-EO-4PO of 25 BASF) 0.9 0.9 0.9 1.5 0.9 1.5 Bloom inhibition The tendency of detergents A, B and C to form lime coatings was tested in a Miele G 590 dishwashing machine (program: universal, 65C) with dosages of 20 g in 6.2 1 of water (16dH) containing 50 g of added pumpable soils (mixture of ketchup, gravy, mustard, potato starch, egg yolk, milk, margarine) in the presence of 3.0 ml of a commercially available rinse aid over 10 wash cycles.
Bloom formation was evaluated on a scale of o (= very heavy bloom) to 3 (= no bloom). The results of the bloom tests obtained with detergents A and B according to the invention and comparison detergent C are as follows:
. W0 94/29420 11 ~1~5 28~ PCT/EP94/01830 detergent A according to the invention: 1.0 detergent B according to the invention: 1.0 comparison detergent C: 0.2 detergent D according to the invention: 2.2 detergent E according to the invention: 2.6 detergent F according to the invention: 2.6 It can be seen that detergents A, B, D, E and F
according to the invention are distinctly superior to comparison detergent C in regard to bloom inhibition.
a 1~5~5 P~ F ~ ~1 C~ c~ L~
~sa~, LL~ ~ ~
Claims (9)
1. A machine dishwashing detergent containing 1 to 60%
by weight and preferably 20 to 50% by weight of water-soluble builder components, 0.5 to 20% by weight and preferably 5 to 12% by weight of oxygen-based bleaching agents and 0.1 to 5% by weight and preferably 1 to 3% by weight of enzymes, characterized in that it contains glycine or alkali metal or ammonium salts thereof in such a quantity that a 1% by weight aqueous solution of the detergent has a pH value of 8 to 12 and preferably 9 to 11, but at least in a quantity of 0.5% by weight, prefer-ably 10% by weight and at most in a quantity of 60% by weight and preferably 50% by weight, based on the deter-gent as a whole.
by weight and preferably 20 to 50% by weight of water-soluble builder components, 0.5 to 20% by weight and preferably 5 to 12% by weight of oxygen-based bleaching agents and 0.1 to 5% by weight and preferably 1 to 3% by weight of enzymes, characterized in that it contains glycine or alkali metal or ammonium salts thereof in such a quantity that a 1% by weight aqueous solution of the detergent has a pH value of 8 to 12 and preferably 9 to 11, but at least in a quantity of 0.5% by weight, prefer-ably 10% by weight and at most in a quantity of 60% by weight and preferably 50% by weight, based on the deter-gent as a whole.
2. A detergent as claimed in claim 1, characterized in that it contains no more than 15% by weight, based on the detergent as a whole, of carbonates and/or hydrogen carbonates.
3. A detergent as claimed in claim 1, characterized in that it is free from carbonates and/or hydrogen car-bonates.
4. A detergent as claimed in claims 1 to 3, charac-terized in that it is free from metasilicates.
5. A detergent as claimed in claims 1 to 4, charac-terized in that it contains dibasic or polybasic organic carboxylic acids or salts thereof, more particularly citric acid or salts thereof and/or synthetic polycar-boxylic acids or polycarboxylates, as the water-soluble builder component.
6. A detergent as claimed in claims 1 to 5, charac-terized in that it contains perborates and/or percar-bonates as the oxygen-based bleaching agent.
7. A detergent as claimed in claims 1 to 6, charac-terized in that it is free from anionic, cationic or amphoteric surfactants and contains no more than 5% by weight and preferably no more than 2% by weight, based on the detergent as a whole, of nonionic surfactants.
8. A tablet-form detergent as claimed in claims 1 to 7, characterized in that it is obtainable by mixing all its constituents in a mixer and tabletting the resulting mixture in a tablet press under pressures of 2107 Pa to 1.5108 Pa.
9. A powder-form or granular detergent as claimed in claims 1 to 7, characterized in that it has an apparent density of 750 g/l to 1000 g/l.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4319798.1 | 1993-06-15 | ||
| DE4319798A DE4319798A1 (en) | 1993-06-15 | 1993-06-15 | Dishwashing detergent with reduced tendency to scale up |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2165285A1 true CA2165285A1 (en) | 1994-12-22 |
Family
ID=6490376
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002165285A Abandoned CA2165285A1 (en) | 1993-06-15 | 1994-06-06 | Dishwashing detergents with a reduced tendency towards bloom formation |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0703969B1 (en) |
| JP (1) | JPH10508042A (en) |
| AT (1) | ATE160817T1 (en) |
| CA (1) | CA2165285A1 (en) |
| CZ (1) | CZ286098B6 (en) |
| DE (2) | DE4319798A1 (en) |
| DK (1) | DK0703969T3 (en) |
| ES (1) | ES2109704T3 (en) |
| GR (1) | GR3025871T3 (en) |
| HU (1) | HU216096B (en) |
| PL (1) | PL178743B1 (en) |
| WO (1) | WO1994029420A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4324396A1 (en) * | 1993-07-21 | 1995-01-26 | Henkel Kgaa | Detergents with high wettability |
| US5531934A (en) * | 1994-09-12 | 1996-07-02 | Rohm & Haas Company | Method of inhibiting corrosion in aqueous systems using poly(amino acids) |
| EP0906407B1 (en) * | 1996-06-21 | 2001-09-05 | Reckitt Benckiser N.V. | Low-alkaline mgda-containing dishwasher rinsing agent |
| EP2305785A1 (en) | 2009-10-02 | 2011-04-06 | Unilever N.V. | Use of a carboxylic or amino compound as cleaning aid for hard surfaces and method of cleaning such hard surfaces |
| JP5801941B1 (en) * | 2014-11-21 | 2015-10-28 | 株式会社ニイタカ | Cleaning composition, dishwashing method, liquid cleaning composition kit and cartridge cleaning |
| DE102015007403A1 (en) * | 2015-06-08 | 2016-12-08 | Sodasan Wasch- und Reinigungsmittel GmbH | Phosphate and phosphonate-free machine dishwashing detergent |
| ES2933550T3 (en) * | 2019-11-15 | 2023-02-10 | Basf Se | Cleaning compositions and their use |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD218117A1 (en) * | 1983-08-24 | 1985-01-30 | Bitterfeld Chemie | DETERGENT FOR TEXTILES |
| DE3829847A1 (en) * | 1988-09-02 | 1990-03-15 | Basf Ag | WASHING AND CLEANING AGENT |
-
1993
- 1993-06-15 DE DE4319798A patent/DE4319798A1/en not_active Withdrawn
-
1994
- 1994-06-06 PL PL94312248A patent/PL178743B1/en unknown
- 1994-06-06 EP EP94918388A patent/EP0703969B1/en not_active Expired - Lifetime
- 1994-06-06 CA CA002165285A patent/CA2165285A1/en not_active Abandoned
- 1994-06-06 DE DE59404733T patent/DE59404733D1/en not_active Expired - Fee Related
- 1994-06-06 JP JP7501300A patent/JPH10508042A/en not_active Ceased
- 1994-06-06 AT AT94918388T patent/ATE160817T1/en not_active IP Right Cessation
- 1994-06-06 CZ CZ19953303A patent/CZ286098B6/en not_active IP Right Cessation
- 1994-06-06 ES ES94918388T patent/ES2109704T3/en not_active Expired - Lifetime
- 1994-06-06 DK DK94918388T patent/DK0703969T3/en active
- 1994-06-06 WO PCT/EP1994/001830 patent/WO1994029420A1/en active IP Right Grant
- 1994-06-06 HU HUP9503574A patent/HU216096B/en not_active IP Right Cessation
-
1998
- 1998-01-12 GR GR980400044T patent/GR3025871T3/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| EP0703969B1 (en) | 1997-12-03 |
| JPH10508042A (en) | 1998-08-04 |
| EP0703969A4 (en) | 1995-08-28 |
| CZ286098B6 (en) | 2000-01-12 |
| ES2109704T3 (en) | 1998-01-16 |
| DK0703969T3 (en) | 1998-08-10 |
| HUT75585A (en) | 1997-05-28 |
| EP0703969A1 (en) | 1996-04-03 |
| HU9503574D0 (en) | 1996-02-28 |
| GR3025871T3 (en) | 1998-04-30 |
| PL312248A1 (en) | 1996-04-01 |
| CZ330395A3 (en) | 1996-05-15 |
| ATE160817T1 (en) | 1997-12-15 |
| DE4319798A1 (en) | 1994-12-22 |
| WO1994029420A1 (en) | 1994-12-22 |
| HU216096B (en) | 1999-04-28 |
| DE59404733D1 (en) | 1998-01-15 |
| PL178743B1 (en) | 2000-06-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |