EP1619237A1 - Aqueous cleaning concentrates for rough preferably profiled tiles and plates - Google Patents
Aqueous cleaning concentrates for rough preferably profiled tiles and plates Download PDFInfo
- Publication number
- EP1619237A1 EP1619237A1 EP05014931A EP05014931A EP1619237A1 EP 1619237 A1 EP1619237 A1 EP 1619237A1 EP 05014931 A EP05014931 A EP 05014931A EP 05014931 A EP05014931 A EP 05014931A EP 1619237 A1 EP1619237 A1 EP 1619237A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- cleaning agent
- aqueous cleaning
- optionally
- agent concentrates
- concentrates according
- 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.)
- Granted
Links
- 238000004140 cleaning Methods 0.000 title claims abstract description 42
- 239000012141 concentrate Substances 0.000 title claims abstract description 21
- -1 sorbitan ester Chemical class 0.000 claims abstract description 30
- 239000012459 cleaning agent Substances 0.000 claims abstract description 27
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- 125000000129 anionic group Chemical group 0.000 claims abstract description 11
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- 239000000654 additive Substances 0.000 claims abstract description 9
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- 239000000203 mixture Substances 0.000 claims description 21
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- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
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- 239000002736 nonionic surfactant Substances 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
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- 239000001257 hydrogen Substances 0.000 claims description 5
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- IPCSVZSSVZVIGE-UHFFFAOYSA-N palmitic acid group Chemical group C(CCCCCCCCCCCCCCC)(=O)O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- RPACBEVZENYWOL-XFULWGLBSA-M sodium;(2r)-2-[6-(4-chlorophenoxy)hexyl]oxirane-2-carboxylate Chemical compound [Na+].C=1C=C(Cl)C=CC=1OCCCCCC[C@]1(C(=O)[O-])CO1 RPACBEVZENYWOL-XFULWGLBSA-M 0.000 description 1
- 239000004071 soot Substances 0.000 description 1
- 229940075582 sorbic acid Drugs 0.000 description 1
- 235000010199 sorbic acid Nutrition 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000003784 tall oil Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- GYBINGQBXROMRS-UHFFFAOYSA-J tetrasodium;2-(1,2-dicarboxylatoethylamino)butanedioate Chemical class [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CC(C([O-])=O)NC(C([O-])=O)CC([O-])=O GYBINGQBXROMRS-UHFFFAOYSA-J 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- UFTFJSFQGQCHQW-UHFFFAOYSA-N triformin Chemical compound O=COCC(OC=O)COC=O UFTFJSFQGQCHQW-UHFFFAOYSA-N 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 235000019871 vegetable fat Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
- PAPBSGBWRJIAAV-UHFFFAOYSA-N ε-Caprolactone Chemical compound O=C1CCCCCO1 PAPBSGBWRJIAAV-UHFFFAOYSA-N 0.000 description 1
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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/88—Ampholytes; Electroneutral compounds
- C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/667—Neutral esters, e.g. sorbitan esters
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
-
- C11D2111/24—
Definitions
- the invention relates to aqueous cleaning agent concentrates for rough, in particular profiled, stoneware tiles and boards based on nonionic, anionic, or amphoteric surfactants which contain sorbitan esters as cleaning intensifiers.
- stoneware stands for hard-fired tiles and slabs, which may be glazed or unglazed with or without a baked ceramic surface finish.
- DIN standard a subdivision is made of water absorption capacity and type of production.
- DIN EN 176 defines stoneware tiles and porcelain stoneware tiles.
- the displacement space (V) according to DIN 51 130 is also specified for profiled slabs and tiles.
- R 10 For areas with increased risk of slipping, areas in which floors and stairs are in contact with friction-reducing and / or sliding media such as water, waste residues, starchy residues, animal and vegetable fats or oils, mineral fats or oils, soaps, pigment soiling, rubber abrasion, silicones the evaluation groups> R 10, in particular R 12 and R 13 are appropriate.
- Tiles and sheets are generally considered to be easy to clean and easy to clean. This applies unconditionally to flat, smooth and hard surfaces of R-Classes 9 to 11. With increasing R-Class, however, the surfaces become increasingly rougher. Problematic are fine-grained substrates of class R 12 and in particular profiled tiles and slabs of classes R 12 to 13 and V 8 to 10, so-called porcelain stoneware tiles / slabs.
- the cleaning effort increases significantly with increasing roughness / unevenness of the substrate, especially if due to porosity additional surface enlargement is given.
- cleaners for manual and machine cleaning are generally complex mixtures of anionic, nonionic and amphoteric / zwitterionic surfactants, which contain customary auxiliaries and additives such as alkalis, complexing agents, solubilizers, sodium hypochlorite and optionally mild abrasives. They are used in concentrations of about 0.5 to 10 wt .-% for use.
- GB-A-2 334 723 describes cleaning compositions for glass, smooth, shiny and shiny surfaces consisting of one or more ethoxylated quaternary ammonium compounds, at least one glycol ether and / or C 1-22 alcohol and at least one anionic surfactant.
- the cleaning agent should not stain or streak after cleaning, have anti-microbial and antistatic properties.
- the special problem of cleaning rough, non-glossy profiled surfaces and the effect of spreading improvement by alkoxylated ammonium compounds is not mentioned here either.
- ethoxylated quats which are no longer acceptable under ecological considerations, show good cleaning-enhancing properties, they no longer meet the requirements for surfactants in detergents. They do not reach the required biodegradation values according to OECD 301 A-F.
- the cationic surfactants used in DE-A-100 38 198 or US Pat. No. 5,929,024 are ethoxylated alkylamidoalkyl-dialkylammonium salts which are known to be problematic and difficult to produce without serious side-effects and to have an increased aquatic toxicity as well Have worse total degradation than the commonly used nonionic or anionic surfactants.
- Ethoxylated quats can be irritating to the skin and some of these compounds may even be toxic to aquatic organisms.
- the material compatibility is not given on different surfaces. Here are mainly metallic surfaces to call on which cationic surfactants, even on stainless steel, lead to corrosion, especially to pitting. Essential for this are the counterions, mostly chloride ions.
- the object of the present invention was therefore to overcome these disadvantages of the known commercially available cleaning agents and to provide improved cleaning agents which ensure reliable cleaning of rough and profiled tiles and panels, so-called porcelain stoneware, at the same or reduced application concentrations.
- Another object of the invention is the use of the aqueous cleaning agent concentrates according to one or more of the claims for cleaning porcelain stoneware tiles.
- aqueous detergent concentrates according to the present invention contain, based on the total mixture, water in the range of about 45 to about 95 parts by weight, preferably about 70 to about 90 parts by weight. In case of application, they can be diluted with additional water to the particular desired or usual or required application concentration of about 0.3 parts by weight to about 10 parts by weight.
- Suitable sorbitan esters are the mono-, di- and. Triesters of sorbitans with fatty acids as well as sorbitan sesquiester or polysorbates. As Sorbitansesquiester called the mixture of mono- u. Diesters of fatty acids with sorbitan. The ethoxylated sorbitan esters are referred to as polysorbates. (J. Am., Oil Chem Soc 66, 1581 (1989) Surfactants Surf., Deterg., 27, 350 (1990).
- Fatty acids which can be used according to the invention are those with R based on saturated or unsaturated monobasic or unsaturated natural or synthetic aliphatic fatty acids having 6 to 22 carbon atoms, preferably 6 to 18, in particular 6 to 10 carbon atoms which may optionally be branched, optionally substituted and or contain heteroatoms.
- Suitable fatty acids are, in particular, fatty acids which have a chain distribution of about 6 to about 18, in particular about 6 to about 10 carbon atoms and are both branched, substituted, preferably -OH-substituted, saturated and also may be unsaturated, such as on known and conventional monobasic fatty acids based on natural vegetable or animal oils having 6 to 22 carbon atoms such as undecanoic, lauric, myristic, palmitic, palmitoleic, isostearic, stearic, oleic, linoleic, petroselic, elaidic, arachidic, behenic , Eurucic acid, gadoleic acid, rapeseed oil fatty acid, soybean oil fatty acid, sunflower oil fatty acid, tall oil fatty acid which can be used alone or mixed in the form of their glycerides, methyl or ethyl esters or as free acids, and the technical mixtures obtained in the pressure cracking.
- fatty acids with a similar chain distribution are suitable.
- Particularly preferred according to the invention are caproic acid, hydroxycaproic acid or caprolactone, sorbic acid, enanthic acid, caprylic acid, 2-ethylhexanoic acid, pelargonic acid, capric acid.
- Suitable alkoxylating agents are ethylene oxide, propylene oxide or butylene oxide, alone or as copolymers with both random and blockwise distribution.
- the degree of alkoxylation is determined by the desired hydrophilicity of the compound. It is on average between 1 to 25, especially 4 to 20.
- These compounds are prepared by the known processes by chemical condensation processes in the desired molar ratio or by enzyme-catalyzed esterification or transesterification. While it is possible to prepare substantially pure mono- or diesters with the enzyme-catalyzed processes, the chemically catalyzed reaction products are present as technical mixtures which, in addition to the desired mono-, di- or triester, always also contain fractions of the other esters. These technical esters can be purified by the known methods, ie concentrated to the respective mono / di / tri portions, but are also readily usable.
- cleaning formulations consisting of mixtures of one or more surfactants from the group of anionic, nonionic, amphoteric compounds and optionally conventional auxiliaries and additives such as alkalis, complexing agents, solubilizers, chlorine bleach and mild abrasives in amounts of about 0.1 to 5, especially 0 , 5 to 3 parts by weight added.
- the surface-active compounds which can be used according to the invention are the anionic, nonionic, amphoteric / zwitterionic surfactants customary in this field for the preparation of household and industrial cleaners.
- the compounds can be used individually or as mixtures and are, for example, anionic, nonionic and amphoteric surfactants such as alkali metal, ammonium or magnesium alkyl sulfates or alkyl ether sulfates, secondary alkanesulfonates, alkali ⁇ -olefin sulfonates, sulfosuccinates, acyl isethionates, sarcosides, taurides, ether citrates , Carboxylates, ether carboxylates, alkyl amide ether sulfates and amine oxides, alkyl betaines, alkyl amidobetaines, propionates, glycinates, acetates and sulfobetaines and sodium, potassium or triethanolamine soaps.
- anionic, nonionic and amphoteric surfactants such as alkali metal, ammonium or magnesium alkyl sulfates or alkyl ether sul
- secondary alkanesulfonates or alkyl sulfates or linear alkylbenzenesulfonates are used in the detergent formulation according to the invention; C 8-14- alkyl sulfates and C 8 -alkanesulfonates are particularly preferred.
- Preferred nonionic surfactants are the fatty alcohol polyglycol ethers.
- EO ethylene
- PO propylene oxide
- amphoteric surfactants are commonly used in such systems.
- amphoglycinates in particular capryliminodipropionate and caprylamphopropionate, are preferred here, since both surfactants show good cleaning performance and good resistance at high pH values and introduce a low foam load into the system.
- the builder system consists of alkali hydroxide, in which case the potassium hydroxide is preferred and a complexing agent which can be selected from the following group:
- NTA nitrilotriacetic acid and its sodium salts
- EDTA DTPA
- diethylenetriaminepentaacetic acid PDTA
- propylenediaminetetraacetic acid ADA
- alaninediacetic acid Na salt
- MGDA methylglycinediacetic acid
- IDS-Na salt iminodisuccinic acid sodium salts
- octaquest E ethylenediamine-N, N'-disuccinic acid , Trisodium salt, citrates (salts of citric acid), gluconates (salts of gluconic acid), phosphates (diphosphates, metaphosphates and polyphosphates), phosphonates such as ATMP, aminotrimethylenephosphonic acid, EDTMP, ethylenediaminetetra (methylenephosphonic acid), DTPMP, diethylenetriaminepenta (methylenephosphonic acid), HEDP, 1- Hydroxyethane-1,1-
- the cleaners prepared as shown in the table above were used at a 1.2% dilution and the contact angle on Villeroy & Boch tiles of the "ATHOS" brand was determined using the contact angle measuring device "Krüss DSA 10 HS".
- the cleaners according to the invention were heated to 1.2% dilution to 20.0 ° C. and measured in a room conditioned at 20 ° C.
- the contaminated tiles were first coarse with water and then with ethyl acetate p. A. of the evt1. leftover residues of the use dilution cleaned.
- the tiles were stored in a box at 20 ° C in an air-conditioned room to protect them from environmental influences and dust and to ensure the measuring temperature of 20 ° C.
- Test solution E contains only short-chain anionic surfactants, in such surfactant systems, a weakness in the emulsification behavior is known.
- the emulsification behavior of low-emulsifying, short-chain anionic surfactant solutions is greatly optimized by adding the cleaning intensifiers according to the invention.
- the emulsion breaks water now settles in place of the oil. This settling water does not affect the cleaning power or the dirt carrying capacity during cleaning.
- the sorbitan esters show a significant gain in emulsifying power, i. translates for cleaning applications increased dirt carrying capacity.
- the sunflower oil was aged under heat and then with an organic solvent in the Ratio 1: 1 added. This mixture was stirred for 24 hours and then the remaining components of the soiling were added. This soil suspension was then sprayed on pre-cleaned porcelain stoneware tiles and dried defined.
- test products the following dilutions were made with city water (12 ° dH).
- the soiled test surfaces were cleaned after drying with a wiper tester.
- the wiper tester offers the possibility of testing up to four cleaners in parallel on a test surface. Care was taken to ensure that the position of the cleaners to be examined on the surface to be cleaned was randomized.
- the cloths were clamped in the holders and subjected to the dilute cleaning solution.
- the cloths with the products to be examined wiped side by side over the soiled test area.
- Table 1 Average rating (% soil solution) after n wiping strokes of the individual test products Cleaner group PF Number of strokes Cleaner E 01 Cleaner V 03 Cleaner V 02 Cleaner V 01 10 11 10 10 10 20 24 20 21 19 30 36 29 30 28
Abstract
Description
Gegenstand der Erfindung sind wässrige Reinigungsmittelkonzentrate für raue, insbesondere profilierte Steinzeugfliesen und Platten auf Basis von nichtionischen, anionischen, oder amphoteren Tensiden, welche als Reinigungsverstärker Sorbitanester enthalten.The invention relates to aqueous cleaning agent concentrates for rough, in particular profiled, stoneware tiles and boards based on nonionic, anionic, or amphoteric surfactants which contain sorbitan esters as cleaning intensifiers.
Aus optischen und hygienischen Gründen werden sowohl in gewerblich genutzten als auch in öffentlichen Gebäuden und Einkaufszentren die Arbeitsbereiche, Verkehrswege und Treppen zunehmend mit Natur- und Steinzeug-Fliesen und Platten ausgelegt.For visual and hygienic reasons, the work areas, traffic routes and stairs are increasingly being designed with natural and stoneware tiles and slabs in commercial as well as in public buildings and shopping centers.
Zur Vermeidung von Unfällen durch Stolpern und Rutschen müssen diese Fußbodenbeläge gewisse Anforderungen hinsichtlich ihrer Trittsicherheit erfüllen. So müssen sie gemäß den gesetzlichen Vorgaben (Richtlinien der Arbeitsstättenverordnung) eben, rutschhemmend und leicht zu reinigen sein.To avoid accidents caused by tripping and slipping, these floor coverings must meet certain requirements for slip resistance. So they must be in accordance with the legal requirements (guidelines of the workplace regulation) even, slip-resistant and easy to clean.
Der Begriff Steinzeug steht für hart gebrannte Fliesen und Platten, welche mit oder ohne eingebrannter keramischer Oberflächenvergütung glasiert oder unglasiert sein können. Gemäß DIN-Norm erfolgt eine Unterteilung über Wasseraufnahmevermögen und Fertigungsart. Die DIN EN 176 definiert Steinzeugfliesen und Feinsteinzeugfliesen.The term stoneware stands for hard-fired tiles and slabs, which may be glazed or unglazed with or without a baked ceramic surface finish. In accordance with the DIN standard, a subdivision is made of water absorption capacity and type of production. DIN EN 176 defines stoneware tiles and porcelain stoneware tiles.
Für die Rutschsicherheit ist jedoch die Oberflächenrauhigkeit entscheidend. Daher werden in den Merkblättern der Berufsgenossenschaft (ZH 1/571) bzw. der Gemeindeunfallversicherer (GUV 26.17; 26.18) für die diversen Anwendungsbereiche genau bestimmte Rutschhemmklassen (R-Klasse) vorgegeben, wobei höhere R-Werte für eine stärkere Rutschhemmung stehen.For the slip resistance, however, the surface roughness is crucial. Therefore, in the leaflets of the employers' liability insurance association (ZH 1/571) or community accident insurers (GUV 26.17, 26.18) for the various applications specified slip resistance classes (R-class) specified, with higher R values for a stronger slip resistance.
Die Bestimmung erfolgt gemäß DIN 51 130 im Versuch an der schiefen Ebene und wird in Neigungswinkelbereichen angegeben: R 9 = 3° bis 10° Neigungswinkel; R 10 = 10° bis 19° Neigungswinkel; R 11 = 19° bis 27° Neigungswinkel; R 12 = 27° bis 35° Neigungswinkel; R 13 = > 35° Neigungswinkel.The determination is carried out in accordance with DIN 51 130 in the experiment at the inclined plane and is given in tilt angle ranges: R 9 = 3 ° to 10 ° tilt angle; R 10 = 10 ° to 19 ° tilt angle; R 11 = 19 ° to 27 ° tilt angle; R 12 = 27 ° to 35 ° tilt angle; R 13 => 35 ° inclination angle.
Zusätzlich wird für profilierte Platten und Fliesen auch der Verdrängungsraum (V) entsprechend DIN 51 130 angegeben. Der Verdrängungsraum gibt das Volumen zwischen der oberen Gehebene und der unteren Entwässerungsebene an. Er liegt zwischen V 4 (= 4 cm3/dm2) und V 10 (= 10 cm3/dm2).In addition, the displacement space (V) according to DIN 51 130 is also specified for profiled slabs and tiles. The displacement space indicates the volume between the upper level and the lower level of drainage. It lies between V 4 (= 4 cm 3 / dm 2 ) and V 10 (= 10 cm 3 / dm 2 ).
Für Bereiche mit erhöhtem Ausrutschrisiko, das sind Bereiche in denen Fußböden und Treppenstufen mit reibungsmindernden und/oder gleitfördernden Medien wie Wasser, Abfallresten, stärkehaltigen Rückständen, tierischen und pflanzlichen Fetten oder Ölen, mineralischen Fetten oder Ölen, Seifen, Pigmentschmutz, Gummiabrieb, Siliconen in Kontakt kommen, sind die Bewertungsgruppen > R 10, insbesondere R 12 und R 13 angebracht.For areas with increased risk of slipping, areas in which floors and stairs are in contact with friction-reducing and / or sliding media such as water, waste residues, starchy residues, animal and vegetable fats or oils, mineral fats or oils, soaps, pigment soiling, rubber abrasion, silicones the evaluation groups> R 10, in particular R 12 and R 13 are appropriate.
Fliesen und Platten gelten im Allgemeinen als pflegeleicht und reinigungsfreundlich. Dies gilt uneingeschränkt für ebene, glatte und harte Untergründe der R-Klassen 9 bis 11. Mit steigender R-Klasse werden die Oberflächen jedoch zunehmend rauer. Problematisch gelten feinraue Untergründe der Klasse R 12 und insbesondere profilierte Fliesen und Platten der Klassen R 12 bis 13 und V 8 bis 10, so genannte Feinsteinzeugfliesen/-platten.Tiles and sheets are generally considered to be easy to clean and easy to clean. This applies unconditionally to flat, smooth and hard surfaces of R-Classes 9 to 11. With increasing R-Class, however, the surfaces become increasingly rougher. Problematic are fine-grained substrates of class R 12 and in particular profiled tiles and slabs of classes R 12 to 13 and V 8 to 10, so-called porcelain stoneware tiles / slabs.
Der Reinigungsaufwand vergrößert sich bei zunehmender Rauhigkeit/Unebenheit des Untergrundes erheblich, insbesondere wenn aufgrund von Porösizität zusätzliche Oberflächenvergrößerung gegeben ist.The cleaning effort increases significantly with increasing roughness / unevenness of the substrate, especially if due to porosity additional surface enlargement is given.
Es hat daher in der Vergangenheit nicht an Versuchen gemangelt, neben speziellen mechanisch wirkenden Reinigungsmaschinen auch neue Reinigungsverfahren zu entwickeln und zusätzlich durch universell anwendbare Allzweckreiniger insbesondere genau auf den jeweiligen Bodenbelagstyp und Verschmutzungsart abgestimmte Reinigungsmittel den Reinigungsaufwand zu minimieren und den Reinigungseffekt zu optimieren.Therefore, it has not lacked attempts in the past, in addition to special mechanical cleaning machines as well To develop new cleaning methods and additionally by universally applicable all-purpose cleaner in particular exactly on the particular type of flooring and type of dirt matched cleaning agents to minimize the cleaning effort and to optimize the cleaning effect.
Handelsübliche Reinigungsmittel für die manuelle und maschinelle Reinigung sind in der Regel komplexe Mischungen aus anionischen, nichtionischen und amphoteren/zwitterionischen Tensiden, welche übliche Hilfs- und Zusatzstoffe wie Alkalien, Komplexbildner, Lösungsvermittler, Chlorbleichlaugezusatz und gegebenenfalls milde Scheuermittel enthalten. Sie kommen in Konzentrationen von ca. 0,5 bis 10 Gew.-% zur Anwendung.Commercially available cleaners for manual and machine cleaning are generally complex mixtures of anionic, nonionic and amphoteric / zwitterionic surfactants, which contain customary auxiliaries and additives such as alkalis, complexing agents, solubilizers, sodium hypochlorite and optionally mild abrasives. They are used in concentrations of about 0.5 to 10 wt .-% for use.
In der Praxis hat sich jedoch gezeigt, dass auch bei großer mechanischer Unterstützung durch Einsatz von Mikrofaserpads, Schrubber oder Hochdruckgeräten, Scheuersaug- oder Bürstenwalzen und zusätzlichem intensiven Nachspülgang mit Wasser bei den problematischen Untergründen aus Feinsteinzeug der Schmutz oftmals nicht vollständig im ersten Arbeitsgang entfernt werden konnte. Zusätzliche Reinigungsgänge waren erforderlich.In practice, however, it has been shown that even with great mechanical support by using microfiber pads, scrubbers or high pressure equipment, scrubbing or brush rollers and additional intensive rinsing with water in the problematic porcelain stoneware substrates, the dirt could often not be completely removed in the first operation , Additional cleaning was required.
Abgesehen von dem erheblichen personellen, maschinellen Mehraufwand und zusätzlicher Umweltbelastung durch Reinigungsmittel wird durch die Abrasivwirkung der mechanischen Belastung die Trittsicherung des Bodenbelages schneller gemindert.Apart from the considerable personnel, machine overhead and additional environmental impact of cleaning agents, the slip resistance of the flooring is reduced faster by the abrasive action of mechanical stress.
In der EP-B-0 928 829 werden Reinigungsmittel beschrieben, enthaltend Mischungen aus mindestens 4 Komponenten:
- a) mindestens eine quartäre Ammoniumverbindung mit einem C1-6-Kohlenwasserstoffrest und drei Alkoxygruppen,
- b) mindestens eine wasserlösliche alkalische Substanz aus der Gruppe Alkalihydroxide und Alkanolamine,
- c) mindestens ein Alkylpolyglykosid und
- d) mindestens ein Lösungsvermittler aus der Gruppe wasserlöslicher Alkohole und Glykolether,
die speziell für die Reinigung von harten, insbesondere vertikalen Oberflächen konzipiert wurden und beim Vermischen mit Wasser eine verdickende Lösung mit rheopexenen Eigenschaften liefern sollen. Durch Auswahl der Komponenten a), b), c) und d) und deren Konzentrationen kann die Rheopexie und das Schaumverhalten gesteuert werden. Auf die spezielle Problematik der Reinigung von Feinsteinzeugfliesen und den Effekt der Spreitungsverbesserung durch alkoxylierte Ammoniumverbindungen findet sich kein Hinweis.EP-B-0 928 829 describes cleaning compositions containing mixtures of at least 4 components:
- a) at least one quaternary ammonium compound having a C 1-6 -hydrocarbon radical and three alkoxy groups,
- b) at least one water-soluble alkaline substance from the group of alkali metal hydroxides and alkanolamines,
- c) at least one alkyl polyglycoside and
- d) at least one solubilizer from the group of water-soluble alcohols and glycol ethers,
specially designed for cleaning hard, especially vertical surfaces and when mixed with water to provide a thickening solution with rheophobic properties. By selecting the components a), b), c) and d) and their concentrations, the rheopexy and the foaming behavior can be controlled. There is no indication of the special problem of cleaning porcelain stoneware tiles and the effect of spreading improvement by alkoxylated ammonium compounds.
Die GB-A-2 334 723 beschreibt Reinigungsmittel für Glas, glatte, blanke und glänzende Oberflächen, bestehend aus einer oder mehreren ethoxylierten quartären Ammoniumverbindungen, mindestens einem Glykolether und/oder C1-22-Alkohols und mindestens einem anionischen Tensid. Das Reinigungsmittel soll nach der Reinigung keine Flecken oder Streifen hinterlassen, antimikrobielle und antistatische Eigenschaften aufweisen. Auf die spezielle Problematik der Reinigung von rauhen, nicht glänzenden profilierten Oberflächen und den Effekt der Spreitungsverbesserung durch alkoxylierte Ammoniumverbindungen findet sich auch hier kein Hinweis.GB-A-2 334 723 describes cleaning compositions for glass, smooth, shiny and shiny surfaces consisting of one or more ethoxylated quaternary ammonium compounds, at least one glycol ether and / or C 1-22 alcohol and at least one anionic surfactant. The cleaning agent should not stain or streak after cleaning, have anti-microbial and antistatic properties. The special problem of cleaning rough, non-glossy profiled surfaces and the effect of spreading improvement by alkoxylated ammonium compounds is not mentioned here either.
Gegenstand der DE-A-100 38 198 ist die Verwendung von wässrigen Reinigungsmittelkonzentraten auf Basis von nichtionischen, anionischen, amphoteren Tensiden, gegebenenfalls unter Mitverwendung von üblichen Hilfs- und Zusatzstoffen, welches dadurch gekennzeichnet ist, dass sie alkoxylierte Aminverbindungen der allgemeinen Formel
[R1, R2, R3, R4N] + X-
mit der Bedeutung
- R1
- ein geradkettiger, gegebenenfalls verzweigter, gegebenenfalls Mehrfachbindungen enthaltender Alkylrest mit 8 bis 22 C-Atomen,
- R2
- -(CH2CHR5O)n-R6 mit R5 = H, -CH3, -C2H5; R6 = H, -CH3, -C2H5, -C3H7 oder -C4H9 und n = 1 bis 25,
- R3
- R1 oder R2,
- R4
- -CH3 oder -C2H5 und
- X-
- anionischer Rest, insbesondere Methylsulfat, Ethylsulfat, Phosphat, Chlorid, Bromid, Jodid
als Reinigungsverstärker zur Reinigung von Feinsteinzeugfliesen enthalten.
[R 1 , R 2 , R 3 , R 4 N] + X-
with the meaning
- R 1
- a straight-chain, optionally branched, optionally multiple bond-containing alkyl radical having 8 to 22 C atoms,
- R 2
- - (CH 2 CHR 5 O) n -R 6 where R 5 = H, -CH 3 , -C 2 H 5 ; R 6 = H, -CH 3 , -C 2 H 5 , -C 3 H 7 or -C 4 H 9 and n = 1 to 25,
- R 3
- R 1 or R 2 ,
- R 4
- -CH 3 or -C 2 H 5 and
- X
- anionic radical, in particular methylsulfate, ethylsulfate, phosphate, chloride, bromide, iodide
as a cleaning booster for cleaning porcelain stoneware tiles included.
Die unter ökologischer Betrachtung nicht mehr akzeptablen ethoxylierten Quats zeigen zwar gute reinigungsverstärkende Eigenschaften, jedoch entsprechen sie nicht mehr den Anforderungen für Tenside in Reinigungsmitteln. Sie erreichen nicht die erforderlichen Werte im biologischen Abbau nach OECD 301 A-F. Die in DE-A-100 38 198 oder US-5 929 024 mitverwendeten kationischen Tenside sind ethoxilierte Alkylamidoalkyl-dialkylammoniumsalze, von denen bekannt ist, dass sie einmal problematisch und nicht ohne bedenkliche Nebenprodukte herzustellen sind und dass sie ein erhöhtes aquatoxisches Verhalten und auch einen schlechteren Totalabbau als die üblicherweise verwendeten nichtionischen- bzw. anionischen Tenside aufweisen.Although the ethoxylated quats, which are no longer acceptable under ecological considerations, show good cleaning-enhancing properties, they no longer meet the requirements for surfactants in detergents. They do not reach the required biodegradation values according to OECD 301 A-F. The cationic surfactants used in DE-A-100 38 198 or US Pat. No. 5,929,024 are ethoxylated alkylamidoalkyl-dialkylammonium salts which are known to be problematic and difficult to produce without serious side-effects and to have an increased aquatic toxicity as well Have worse total degradation than the commonly used nonionic or anionic surfactants.
Ethoxylierte Quats können reizend im Hautkontakt und manche dieser Verbindungen können gar giftig für Wasserorganismen sein. Auch die Materialverträglichkeit ist auf verschiedenen Oberflächen nicht gegeben. Hier sind vor allem metallische Oberflächen zu nennen, auf denen kationischen Tenside, selbst auf Edelstahl, zu Korrosionserscheinung, vor allem zu Lochkorrosion führen. Wesentlich hierfür sind die Gegenionen, zumeist Chloridionen.Ethoxylated quats can be irritating to the skin and some of these compounds may even be toxic to aquatic organisms. The material compatibility is not given on different surfaces. Here are mainly metallic surfaces to call on which cationic surfactants, even on stainless steel, lead to corrosion, especially to pitting. Essential for this are the counterions, mostly chloride ions.
In modernen Reinigungsmitteln werden ethoxylierte Quats aufgrund ihres erhöhten Umweltrisikos daher nicht mehr toleriert.In modern detergents, ethoxylated quats are therefore no longer tolerated due to their increased environmental risk.
Aufgabe der vorliegenden Erfindung war es daher, diese Nachteile der bekannten handelsüblichen Reinigungsmittel zu überwinden und verbesserte Reinigungsmittel zur Verfügung zu stellen, welche bei gleichen oder verminderten Anwendungskonzentrationen eine zuverlässige Reinigung von rauen und profilierten Fliesen und Platten, so genanntem Feinsteinzeug, gewährleisten.The object of the present invention was therefore to overcome these disadvantages of the known commercially available cleaning agents and to provide improved cleaning agents which ensure reliable cleaning of rough and profiled tiles and panels, so-called porcelain stoneware, at the same or reduced application concentrations.
Diese Aufgabe wird gelöst durch Reinigungsmittel auf Basis von Tensiden, welche als Reinigungsverstärker Sorbitanester enthalten.This object is achieved by detergents based on surfactants which contain sorbitan esters as cleaning intensifiers.
Ein Gegenstand der vorliegenden Erfindung sind daher wässrige Reinigungsmittelkonzentrate für raue, insbesondere profilierte Fliesen und Platten auf Basis von nichtionischen, anionischen, amphoteren Tensiden, gegebenenfalls unter Mitverwendung von üblichen Hilfs- und Zusatzstoffen, welche dadurch gekennzeichnet sind, dass sie als Reinigungsverstärker mindestens einen Sorbitanester der allgemeinen Formel (I) enthalten
- R
- ein gegebenenfalls verzweigter, gegebenenfalls substituierter und/oder Heteroatome enthaltender gesättigter oder ungesättigter Acylrest mit 6 bis 22 C-Atomen sein kann,
- R1 und R2
- unabhängig voneinander Wasserstoff oder R sein können,
- Alk
- mindestens ein Rest ist aus der Gruppe Ethylen-, i-Propylen-, Butylen-,
- a, b, c,
- unabhängig voneinander Werte zwischen 0 bis 25 sein können, wobei die Summe aus a + b + c = 0 bis 25 beträgt.
- R
- may be an optionally branched, optionally substituted and / or heteroatom-containing saturated or unsaturated acyl radical having 6 to 22 carbon atoms,
- R 1 and R 2
- independently of one another can be hydrogen or R,
- auk
- at least one radical is selected from the group ethylene, i-propylene, butylene,
- a, b, c,
- independently of one another may be values between 0 to 25, the sum of a + b + c = 0 to 25.
Ein weiterer Gegenstand der Erfindung sind wässrige Reinigungsmittelkonzentrate, welche, bezogen auf die Gesamtmischung, außer Wasser im Wesentlichen:
- 0,1 bis 10, insbesondere 1 bis 10 Gew.-Teile mindestens eines anionischen Tensids, gegebenenfalls
- 0,0 bis 20, insbesondere 0,1 bis 5 Gew.-Teile mindestens eines nichtionischen Tensids, gegebenenfalls
- 0,0 bis 10, insbesondere 0,1 bis 8 Gew.-Teile mindestens eines amphoteren/zwitterionischen Tensids und gegebenenfalls
- 0,1 bis 10 Gew.-Teile üblicher Hilfs- und Zusatzstoffe, welche dadurch gekennzeichnet sind, dass die Reinigungsmittelkonzentrate
- 0,1 bis 10, insbesondere 0,5 bis 3 Gew.-Teile mindestens einen Sorbitanester der allgemeinen Formel (I) enthalten.
- 0.1 to 10, especially 1 to 10 parts by weight of at least one anionic surfactant, optionally
- 0.0 to 20, in particular 0.1 to 5 parts by weight of at least one nonionic surfactant, if appropriate
- 0.0 to 10, especially 0.1 to 8 parts by weight of at least one amphoteric / zwitterionic surfactant and optionally
- 0.1 to 10 parts by weight of conventional auxiliaries and additives, which are characterized in that the cleaning agent concentrates
- 0.1 to 10, in particular 0.5 to 3 parts by weight of at least one sorbitan ester of the general formula (I).
Ein weiterer Gegenstand der Erfindung ist die Verwendung der wässrigen Reinigungsmittelkonzentrate gemäß einem oder mehreren der Ansprüche zur Reinigung von Feinsteinzeugfliesen.Another object of the invention is the use of the aqueous cleaning agent concentrates according to one or more of the claims for cleaning porcelain stoneware tiles.
Weitere Gegenstände der Erfindung sind gekennzeichnet durch die Ansprüche.Further objects of the invention are characterized by the claims.
Die wässrigen Reinigungsmittelkonzentrate gemäß der vorliegenden Erfindung enthalten, bezogen auf die Gesamtmischung, Wasser im Bereich von ca. 45 bis ca. 95 Gew.-Teile, vorzugsweise ca. 70 bis ca. 90 Gew.-Teile. Sie können im Anwendungsfall mit zusätzlichem Wasser auf die jeweils gewünschte bzw. übliche oder erforderliche Anwendungskonzentration von ca. 0,3 Gew.-Teile bis ca. 10 Gew.-Teile verdünnt werden.The aqueous detergent concentrates according to the present invention contain, based on the total mixture, water in the range of about 45 to about 95 parts by weight, preferably about 70 to about 90 parts by weight. In case of application, they can be diluted with additional water to the particular desired or usual or required application concentration of about 0.3 parts by weight to about 10 parts by weight.
Als Sorbitanester geeignet sind die Mono-, Di- u. Triester der Sorbitane mit Fettsäuren sowie Sorbitansesquiester oder die Polysorbate. Als Sorbitansesquiester bezeichnet man die Mischung des Mono- u. Diesters der Fettsäuren mit Sorbitan. Die ethoxylierten Sorbitanester werden als Polysorbate bezeichnet. (J. Am. Oil Chem. Soc. 66, 1581 (1989); Tenside Surf. Deterg. 27, 350 (1990).Suitable sorbitan esters are the mono-, di- and. Triesters of sorbitans with fatty acids as well as sorbitan sesquiester or polysorbates. As Sorbitansesquiester called the mixture of mono- u. Diesters of fatty acids with sorbitan. The ethoxylated sorbitan esters are referred to as polysorbates. (J. Am., Oil Chem Soc 66, 1581 (1989) Surfactants Surf., Deterg., 27, 350 (1990).
Die erfindungsgemäß bevorzugt mitverwendeten Reinigungsverstärker sind Sorbitanester der allgemeinen Formel
worin
- R
- ein gegebenenfalls verzweigter und/oder Heteroatome enthaltender gesättigter oder ungesättigter Acylrest mit 6 bis 18 C-Atomen, insbesondere mit 6 bis 10 C-Atomen sein kann,
- R1 oder R2 =
- R sind und die Summe aus a + b + c < 5, insbesondere 0 ist.
wherein
- R
- an optionally branched and / or heteroatom-containing saturated or unsaturated acyl radical having 6 to 18 C atoms, in particular having 6 to 10 C atoms,
- R 1 or R 2 =
- R are and the sum of a + b + c <5, in particular 0.
Erfindungsgemäß mitverwenbare Fettsäuren sind solche mit R auf Basis von gesättigten oder ungesättigten natürlichen oder synthetischen einbasischen aliphatischen Fettsäuren mit 6 bis 22 Kohlenstoffatomen, vorzugsweise 6 bis 18, insbesondere mit 6 bis 10 C-Atomen welche gegebenenfalls verzweigt, gegebenenfalls substituiert und oder Heteroatome enthalten können.Fatty acids which can be used according to the invention are those with R based on saturated or unsaturated monobasic or unsaturated natural or synthetic aliphatic fatty acids having 6 to 22 carbon atoms, preferably 6 to 18, in particular 6 to 10 carbon atoms which may optionally be branched, optionally substituted and or contain heteroatoms.
Als Fettsäuren kommen hier insbesondere Fettsäuren in Betracht, welche eine Kettenverteilung von ca. 6 bis ca. 18, insbesondere ca. 6 bis ca. 10 C-Atomen aufweisen und sowohl verzweigt, substituiert, vorzugsweise -OH substituiert, gesättigt als auch ungesättigt sein können, wie die auf bekannten und üblichen einbasischen Fettsäuren auf Basis natürlicher pflanzlicher oder tierischer Öle mit 6 bis 22 Kohlenstoffatomen wie Undecansäure, Laurinsäure, Myristinsäure, Palmitinsäure, Palmitoleinsäure, Isostearinsäure, Stearinsäure, Ölsäure, Linolsäure, Petroselinsäure, Elaidinsäure, Arachinsäure, Behensäure, Eurucasäure, Gadoleinsäure, Rapsölfettsäure, Sojaölfettsäure, Sonnenblumenölfettsäure, Tallölfettsäure welche allein oder in Mischung in Form ihrer Glyceride, Methyl- oder Ethylester oder als freie Säuren eingesetzt werden können, sowie die bei der Druckspaltung anfallenden technischen Mischungen. Geeignet sind prinzipiell alle Fettsäuren mit ähnlicher Kettenverteilung. Erfindungsgemäß besonders bevorzugt sind Capronsäure, Hydroxycapronsäure bzw. Caprolacton, Sorbinsäure, Önanthsäure, Caprylsäure, 2-Ethylhexansäure, Pelargonsäure, Caprinsäure.Suitable fatty acids are, in particular, fatty acids which have a chain distribution of about 6 to about 18, in particular about 6 to about 10 carbon atoms and are both branched, substituted, preferably -OH-substituted, saturated and also may be unsaturated, such as on known and conventional monobasic fatty acids based on natural vegetable or animal oils having 6 to 22 carbon atoms such as undecanoic, lauric, myristic, palmitic, palmitoleic, isostearic, stearic, oleic, linoleic, petroselic, elaidic, arachidic, behenic , Eurucic acid, gadoleic acid, rapeseed oil fatty acid, soybean oil fatty acid, sunflower oil fatty acid, tall oil fatty acid which can be used alone or mixed in the form of their glycerides, methyl or ethyl esters or as free acids, and the technical mixtures obtained in the pressure cracking. In principle, all fatty acids with a similar chain distribution are suitable. Particularly preferred according to the invention are caproic acid, hydroxycaproic acid or caprolactone, sorbic acid, enanthic acid, caprylic acid, 2-ethylhexanoic acid, pelargonic acid, capric acid.
Als Alkoxilierungsmittel kommen Ethylenoxid, Propylenoxid oder Butylenoxid allein oder als Copolymere mit sowohl statistischer als auch blockweiser Verteilung in Betracht. Der Alkoxilierungsgrad wird mitbestimmt durch die angestrebte Hydrophilie der Verbindung. Er liegt im Mittel zwischen 1 bis 25, insbesondere 4 bis 20.Suitable alkoxylating agents are ethylene oxide, propylene oxide or butylene oxide, alone or as copolymers with both random and blockwise distribution. The degree of alkoxylation is determined by the desired hydrophilicity of the compound. It is on average between 1 to 25, especially 4 to 20.
Diese Verbindungen werden nach den bekannten Verfahren durch chemische Kondensationsverfahren im gewünschten Molverhältnis oder durch enzymkatalysierte Ver- bzw. Umesterung hergestellt. Während mit den enzymkatalysierten Verfahren weitgehend reine Mono- oder Diester herstellbar sind, liegen die chemisch katalysierten Reaktionsprodukte als technische Gemische vor, die neben dem gewünschten Mono-, Di- oder Triester immer auch Anteile der anderen Ester enthalten. Diese technischen Ester können nach den bekannten Verfahren gereinigt, d.h. auf die jeweiligen Mono/di/tri-Anteile konzentriert werden, sind aber auch ohne weiteres einsetzbar.These compounds are prepared by the known processes by chemical condensation processes in the desired molar ratio or by enzyme-catalyzed esterification or transesterification. While it is possible to prepare substantially pure mono- or diesters with the enzyme-catalyzed processes, the chemically catalyzed reaction products are present as technical mixtures which, in addition to the desired mono-, di- or triester, always also contain fractions of the other esters. These technical esters can be purified by the known methods, ie concentrated to the respective mono / di / tri portions, but are also readily usable.
Sie werden Reinigungsformulierungen bestehend aus Mischungen ein oder mehrerer Tenside aus der Gruppe anionischer, nichtionischer, amphoterer Verbindungen und gegebenenfalls üblicher Hilfs- und Zusatzstoffe wie Alkalien, Komplexbildner, Lösungsvermittler, Chlorbleichlaugezusatz und milden Scheuermitteln in Mengen von ca. 0,1 bis 5, insbesondere 0,5 bis 3 Gew.-Teile zugesetzt.They are cleaning formulations consisting of mixtures of one or more surfactants from the group of anionic, nonionic, amphoteric compounds and optionally conventional auxiliaries and additives such as alkalis, complexing agents, solubilizers, chlorine bleach and mild abrasives in amounts of about 0.1 to 5, especially 0 , 5 to 3 parts by weight added.
Überraschenderweise zeigen diese nichtionischen Reinigungsverstärker nicht die Werte eines einzelnen technischen Effektes zu Lasten der anderen Eigenschaften sondern heben insgesamt das allgemeine Niveau:
- Die erfindungsgemäß mitverwendeten Sorbitanester weisen eine gute Umweltverträglichkeit auf.
- Sie zeigen ein besseres Spreiten auf porösen Oberflächen, z.B. Feinsteinzeugfliesen: (optimiertes Benetzungsverhalten führt gerade auf porösen Oberflächen - hier entspricht die reale Oberfläche einem Vielfachen der eigentlichen Grundfläche - zu einem besseren Ablöseverhalten des Schmutzes. Auch die Schattenbereiche der rutschhemmenden Erhöhungen werden ausreichend benetzt und gereinigt).
- Sie zeigen ein besseres Kalkseifendispergiervermögen (optimiertes Dispergiervermögen: für anorganische nichtlösliche Verschmutzungen verhindert das Absetzen solcher Verschmutzungen. Dies ist besonders wichtig auf porösen Oberflächen, da diese Rückstände sonst nicht entfernt werden können).
- Sie zeigen ein besseres Emulgiervermögen für einfache kostengünstige Tensidsysteme: (optimierte Emulgierfähigkeit, da das gesamte Öl kontinuierlich in der Emulsion vorliegt. Bei dem Absetzen von Wasser kommt es nicht zu einer Wiederanschmutzung durch eine brechende Emulsion). Um die rutschhemmenden Eigenschaften nicht zu reduzieren, ist es hier besonders wichtig alle Rückstände vollständig zu entfernen, damit sich die benötigten Poren nicht zusetzen.
- The inventively used sorbitan esters have good environmental compatibility.
- They show a better spreading on porous surfaces, eg porcelain stoneware tiles: (optimized wetting behavior leads on porous surfaces - here the real surface corresponds to a multiple of the actual surface area - to a better detachment behavior of the dirt.) Also the shadow areas of the slip-resistant elevations are sufficiently moistened and cleaned ).
- They show better lime soap dispersancy (optimized dispersibility: for inorganic non-soluble soils, preventing settling of such soils is particularly important on porous surfaces as these residues can not otherwise be removed).
- They show a better emulsifying power for simple low-cost surfactant systems: (optimized emulsifying ability, since all the oil is continuously present in the emulsion.) Water settling does not lead to re-soiling through a refractive emulsion). In order not to reduce the anti-slip properties, it is here especially important to remove all residues completely, so that the required pores do not clog.
Die erfindungsgemäß mitverwendbaren oberflächenaktiven Verbindungen sind die auf diesem Gebiet üblichen anionischen, nichtionischen, amphoteren/zwitterionischen Tenside zur Herstellung von Reinigungsmitteln für Haushalt und Industrie.The surface-active compounds which can be used according to the invention are the anionic, nonionic, amphoteric / zwitterionic surfactants customary in this field for the preparation of household and industrial cleaners.
Die Verbindungen können einzeln oder als Mischungen verwendet werden und sind beispielsweise anionische, nichtionische und amphotere Tenside wie Alkali-, Ammonium- oder Magnesium-Alkylsulfate bzw. Alkylethersulfate, sekundäre Alkansulfonate, Alkali-α-Olefinsulfonate, Sulfosuccinate, Acylisethionate, Sarkoside, Tauride, Ethercitrate, Carboxylate, Ethercarboxylate, Alkylamidethersulfate sowie Aminoxide, Alkylbetaine, Alkylamidobetaine, Propionate, Glycinate, Acetate und Sulfobetaine und Natrium-, Kalium- oder Triethanolaminseifen.The compounds can be used individually or as mixtures and are, for example, anionic, nonionic and amphoteric surfactants such as alkali metal, ammonium or magnesium alkyl sulfates or alkyl ether sulfates, secondary alkanesulfonates, alkali α-olefin sulfonates, sulfosuccinates, acyl isethionates, sarcosides, taurides, ether citrates , Carboxylates, ether carboxylates, alkyl amide ether sulfates and amine oxides, alkyl betaines, alkyl amidobetaines, propionates, glycinates, acetates and sulfobetaines and sodium, potassium or triethanolamine soaps.
Insbesondere werden in der erfindungsgemäßen Reinigerformulierung sekundäre Alkansulfonate bzw. Alkylsulfate oder lineare Alkylbenzolsulfonate verwendet, besonders bevorzugt sind C8-14-Alkylsulfate und C8-Alkansulfonate.In particular, secondary alkanesulfonates or alkyl sulfates or linear alkylbenzenesulfonates are used in the detergent formulation according to the invention; C 8-14- alkyl sulfates and C 8 -alkanesulfonates are particularly preferred.
Bevorzugt als nichtionische Tenside sind die Fettalkoholpolyglykolether. Unter Fettalkoholpolyglykolethern sind erfindungsgemäß mit Ethylen- (EO) und/oder Propylenoxid (PO) alkoxylierte, unverzweigte oder verzweigte, gesättigte oder ungesättigte C6-22-Alkohole mit einem Alkoxylierungsgrad bis zu 30 zu verstehen, vorzugsweise ethoxylierte C8-14-Fettalkohole mit einem Ethoxylierungsgrad von weniger als 30, bevorzugt mit einem Ethoxylierungsgrad von 1 bis 20, insbesondere von 1 bis 12, besonders bevorzugt von 1 bis 8, äußerst bevorzugt von 2 bis 5, beispielsweise C9-13-Fettalkoholethoxylate mit 2, 3 oder 4 EO oder eine Mischung von der C8-12-Fettalkoholethoxylate mit 3 und 4 EO im Gewichtsverhältnis von 1 zu 1.Preferred nonionic surfactants are the fatty alcohol polyglycol ethers. Under Fettalkoholpolyglykolethern according to the invention with ethylene (EO) and / or propylene oxide (PO) alkoxylated, unbranched or branched, saturated or unsaturated C 6-22 alcohols having a degree of alkoxylation up to 30 to understand, preferably ethoxylated C 8-14 fatty alcohols a degree of ethoxylation of less than 30, preferably with a degree of ethoxylation of 1 to 20, in particular from 1 to 12, particularly preferably from 1 to 8, most preferably from 2 to 5, for example C 9-13 fatty alcohol ethoxylates with 2, 3 or 4 EO or a mixture of the C 8-12 fatty alcohol ethoxylates with 3 and 4 EO in the weight ratio of 1 to 1.
Ebenfalls finden üblicherweise amphotere Tenside in solchen Systemen Verwendung. Erfindungsgemäß werden hier Amphoglycinate, insbesondere das Capryliminodipropionat und das Caprylamphopropionat bevorzugt, da beide Tenside bei hohen ph-Werten gute Reinigungsleistung und eine gute Beständigkeit zeigen und eine geringe Schaumlast in das System eintragen.Also, amphoteric surfactants are commonly used in such systems. According to the invention, amphoglycinates, in particular capryliminodipropionate and caprylamphopropionate, are preferred here, since both surfactants show good cleaning performance and good resistance at high pH values and introduce a low foam load into the system.
Das Buildersystem besteht aus Alkalihydroxid, wobei in diesem Fall das Kaliumhydroxyd bevorzugt wird und einem Komblexbildner der aus der folgenden Gruppe ausgewählt werden kann:The builder system consists of alkali hydroxide, in which case the potassium hydroxide is preferred and a complexing agent which can be selected from the following group:
NTA, Nitrilotriessigsäure und ihre Natriumsalze, EDTA, DTPA, Diethylentriaminpentaessigsäure, PDTA, Propylendiamintetraessigsäure, ADA, Alanindiessigsäure, Na-Salz, MGDA, Methylglycindiessigsäure, IDS-Na-Salz, Iminodibernsteinsäure-Natriumsalze, Octaquest E, Ethylendiamin-N,N'-dibernsteinsäure, Trinatriumsalz, Citrate (Salze der Citronensäure), Gluconate (Salze der Gluconsäure), Phosphate (Diphospghate, Metaphosphate und Polyphosphate), Phosphonate wie ATMP, Aminotrimethylenphosphonsäure, EDTMP, Ethylendiamintetra(methylenphosphonsäure), DTPMP, Diethylentriaminpenta(methylenphosphonsäure), HEDP, 1-Hydroxyethan-1,1-diphosphonsäure, PBTC, 2-Phosphonobutan-1,2,4-tricarbonsäure, HDTMP, Hexamethylendiamintetra-(methylenphosphonsäure).NTA, nitrilotriacetic acid and its sodium salts, EDTA, DTPA, diethylenetriaminepentaacetic acid, PDTA, propylenediaminetetraacetic acid, ADA, alaninediacetic acid, Na salt, MGDA, methylglycinediacetic acid, IDS-Na salt, iminodisuccinic acid sodium salts, octaquest E, ethylenediamine-N, N'-disuccinic acid , Trisodium salt, citrates (salts of citric acid), gluconates (salts of gluconic acid), phosphates (diphosphates, metaphosphates and polyphosphates), phosphonates such as ATMP, aminotrimethylenephosphonic acid, EDTMP, ethylenediaminetetra (methylenephosphonic acid), DTPMP, diethylenetriaminepenta (methylenephosphonic acid), HEDP, 1- Hydroxyethane-1,1-diphosphonic acid, PBTC, 2-phosphonobutane-1,2,4-tricarboxylic acid, HDTMP, hexamethylenediaminetetra (methylenephosphonic acid).
Die auf diesem Gebiet einsetzbaren und üblichen bzw. möglichen Verbindungen der einzelnen Gruppen gehören zum Allgemeinwissen des Fachmanns und können außerdem bei Bedarf in der einschlägigen Fachliteratur sowie in den Rezepturempfehlungen der Hersteller der jeweiligen Tensidklassen nachgelesen werden.The compounds of the individual groups that can be used and are customary or possible in this field are part of the general knowledge of a person skilled in the art and, if necessary, can also be found in the relevant specialist literature and in the recipe recommendations of the manufacturers of the respective classes of surfactants.
- Hersteller:Manufacturer:
- Villeroy & Boch AGVilleroy & Boch AG
- Bezeichnung der Fliese:Name of the tile:
- ATHOSATHOS
- Material:Material:
- Unglazed vitreousUnglazed vitreous
- Farbe:Colour:
- Natur HellNature bright
- Abmessungen:Dimensions:
- 30,0 x 30,0 cm30.0 x 30.0 cm
- Artikelnummer:Item number:
- 20382038
- Farbcode:Color code:
- VA5MVA5M
- Rutsch-Festigkeit:Slip resistance:
- R 9R 9
Die wie in obiger Tabelle hergestellten Reiniger wurden in einer 1,2 %-Verdünnung eingesetzt und mit dem Kontaktwinkelmessgerät "Krüss DSA 10 HS" der Kontaktwinkel auf Fliesen von Villeroy & Boch der Marke "ATHOS" bestimmt. Dazu wurden die erfindungsgemäßen Reiniger in 1,2 %-Verdünnung auf 20,0 °C temperiert und in einem auf 20 °C klimatisierten Raum gemessen.The cleaners prepared as shown in the table above were used at a 1.2% dilution and the contact angle on Villeroy & Boch tiles of the "ATHOS" brand was determined using the contact angle measuring device "Krüss DSA 10 HS". For this purpose, the cleaners according to the invention were heated to 1.2% dilution to 20.0 ° C. and measured in a room conditioned at 20 ° C.
Die verunreinigten Fliesen wurden erst mit Wasser grob und anschließend mit Essigsäureethylester p. A. von den evt1. übrig gebliebenen Resten der Gebrauchsverdünnung gereinigt.The contaminated tiles were first coarse with water and then with ethyl acetate p. A. of the evt1. leftover residues of the use dilution cleaned.
Die Fliesen wurden bei 20 °C in einem klimatisierten Raum in einer Box aufbewahrt, um diese vor Umwelteinflüssen und Staub zu schützen und um die Messtemperatur von 20 °C zu gewährleisten.The tiles were stored in a box at 20 ° C in an air-conditioned room to protect them from environmental influences and dust and to ensure the measuring temperature of 20 ° C.
Mit dem Messgerät wurden auf der Fliese 4,0 µl der Verdünnung aufgetropft und der Kontaktwinkel, der auf der Fliese spreitenden Lösung, für 6 Sekunden mit 120 Bildern aufgezeichnet. Um einen möglichst genauen Mittelwert des gewünschten Kontaktwinkels zu erhalten, wurden jeweils ca. zwölf Messungen auf drei verschiedenen Fliesen der gleichen Sorte durchgeführt und anschließend die so erfassten Messwerte in das Tabellenkalkulationsprogramm übertragen und der Kontaktwinkel grafisch in Abhängigkeit von der Zeit dargestellt.With the meter, 4.0 μl of the dilution was dropped on the tile and the contact angle of the solution spreading on the tile was recorded for 6 seconds with 120 images. In order to obtain an average value of the desired contact angle that is as accurate as possible, in each case about twelve measurements were carried out on three different tiles of the same grade and then the measured values thus acquired were transferred to the spreadsheet program and the contact angle was graphically displayed as a function of time.
Wie oben beschrieben wurden jeweils drei Messungen der 0,6 % Gerbrauchsverdünnungen der Mikroemulsionen auf drei verschiedenen Fliesen durchgeführt, in einem Diagramm übertragen und daraus ein Mittelwert gebildet. Der exakte Kontaktwinkel bei 5 Sekunden wurde durch Interpolation der Messwerte erhalten, da bei 120 Bildern in 6 Sekunden nicht immer genau bei 5 Sekunden eine Aufnahme vom Messgerät durchgeführt wurde.As described above, in each case three measurements of the 0.6% digestion dilutions of the microemulsions were carried out on three different tiles, transferred in a diagram and an average value formed therefrom. The exact contact angle at 5 seconds was obtained by interpolation of the measurements, as 120 frames in 6 seconds did not always take exactly 5 seconds to record from the meter.
Die aus der Auftragung und Auswertung erhaltenen Kontaktwinkel sind im Folgenden als Ergebnisse zu finden.The contact angles obtained from the application and evaluation can be found below as results.
Hier zeigt sich, dass vor allem die Sorbitanester die aus Fettsäuren < C10 hergestellt wurden eine besondere Leistungsfähigkeit im Hinblick auf ein gutes dynamisches Spreitungsvermögen zeigen. Der Unterschied der Herstellungsmethode, chemisch bzw. enzymatisch, spielt hier eine untergeordnete Rolle, wobei die Monoester jedoch zu bevorzugen sind.Here it can be seen that above all the sorbitan esters, which were produced from fatty acids <C 10 , show a special performance with regard to a good dynamic spreading capacity. The difference of the production method, chemical and enzymatic, plays a minor role here, but the monoesters are to be preferred.
Untersucht wurde hier nur das Verhalten der Testlösung E, da man bei den anderen Reinigern durch den hohen Anteil nichtionischer Tenside keine deutliche Steigerung des Emulgierverhaltens erwarten konnte. Testlösung E enthält nur kurzkettige anionische Tenside, bei solchen Tensidsystemen ist eine Schwäche im Emulgierverhalten bekannt.Only the behavior of the test solution E was investigated, since the other cleaners could not expect a significant increase in the emulsifying behavior due to the high proportion of nonionic surfactants. Test solution E contains only short-chain anionic surfactants, in such surfactant systems, a weakness in the emulsification behavior is known.
100 g Anwendungslösung eines Reinigers wurden mit 90 g (= 100 ml) Ölivenöl gemischt. Dann 30 sek. mit 8.000 U/min im "Ultra-Turrax T25" emulgiert. Diese Emulsion wird in einen 250 ml Standzylinder gegeben. Nach 15, 30, 60, 120, 180 Minuten bzw. nach 24 Stunden wird das Mengenverhältnis der einzelnen Phasen abgelesen.
Wie ersichtlich, wird durch Zusatz der erfindungsgemäßen Reinigungsverstärker das Emulgierverhalten von schwachemulgierenden, kurzkettigen Aniontensidlösungen stark optimiert. Wenn die Emulsion bricht, setzt sich nun Wasser anstelle des Öls ab. Dieses sich absetzende Wasser beeinträchtigt nicht die Reinigungskraft bzw. das Schmutztragevermögen während einer Reinigung. In vergleichbaren Lösungen zeigen hier vor allem die Sorbitanester einen deutlichen Zugewinn an Emulgierleistung, d.h. übersetzt für Reinigungsanwendungen ein erhöhtes Schmutztragevermögen.As can be seen, the emulsification behavior of low-emulsifying, short-chain anionic surfactant solutions is greatly optimized by adding the cleaning intensifiers according to the invention. When the emulsion breaks, water now settles in place of the oil. This settling water does not affect the cleaning power or the dirt carrying capacity during cleaning. In comparable solutions, especially the sorbitan esters show a significant gain in emulsifying power, i. translates for cleaning applications increased dirt carrying capacity.
Neben der dynamischen Spreitungsmessung wurde eine Auswahl der hier genannten Formulierungen von einem unabhängigen Institut, Institut Fresenius, einem standartisierten Reinigungstest unterzogen. Geprüft wurden Fliesenreiniger E 01, Fliesenreiniger V 03 (nach DE-A-100 38 198), Fliesenreiniger V 01, Fliesenreiniger V 02.In addition to the dynamic spreading measurement, a selection of the formulations mentioned here was subjected to a standardized cleaning test by an independent institute, Institut Fresenius. Tile cleaner E 01, tile cleaner V 03 (according to DE-A-100 38 198), tile cleaner V 01, tile cleaner V 02 were tested.
Für die Prüfungen wurde eine Mischung der folgenden Haushaltsfußbodenanschmutzung verwendet:
- gealtertes Sonnenblumenöl
- Humus
- Ruß
- Eisenoxid
- Zement
- Siliciumdioxid
- Lehm
- aged sunflower oil
- humus
- soot
- iron oxide
- cement
- silica
- Clay
Zunächst wurde das Sonnenblumenöl unter Wärmeeinwirkung gealtert und anschließend mit einem organischen Lösemittel im Verhältnis 1 : 1 aufgenommen. Diese Mischung wurde 24 Stunden gerührt und danach die restlichen Komponenten der Anschmutzung zugegeben. Diese Schmutzsuspension wurde dann auf vorgereinigte Feinsteinzeugfliesen aufgesprüht und definiert getrocknet.First, the sunflower oil was aged under heat and then with an organic solvent in the Ratio 1: 1 added. This mixture was stirred for 24 hours and then the remaining components of the soiling were added. This soil suspension was then sprayed on pre-cleaned porcelain stoneware tiles and dried defined.
Von den Testprodukten wurden die folgenden Verdünnungen mit Stadtwasser (12° dH) angesetzt.Of the test products, the following dilutions were made with city water (12 ° dH).
Die angeschmutzten Testoberflächen wurden nach dem Trocknen mit einem Wischprüfgerät gereinigt. Hierbei bietet das Wischprüfgerät die Möglichkeit, bis zu vier Reiniger parallel auf einer Testoberfläche zu prüfen. Hierbei wurde weiterhin darauf geachtet, dass die Position der zu untersuchenden Reiniger auf der zu reinigenden Oberfläche randomisiert erfolgte.The soiled test surfaces were cleaned after drying with a wiper tester. The wiper tester offers the possibility of testing up to four cleaners in parallel on a test surface. Care was taken to ensure that the position of the cleaners to be examined on the surface to be cleaned was randomized.
Die eigentliche Reinigung erfolgte mit gewaschenen und nach Gewicht geclusterten Tüchern, die in die Tuchhalterungen des Wischprüfgerätes eingespannt wurden.The actual cleaning was carried out with washed and weighted by hand towels, which were clamped in the cloth holders of Wischprüfgerätes.
Unmittelbar vor dem Reinigungsvorgang wurden die Tücher in die Halterungen eingespannt und mit der verdünnten Reinigerlösung beaufschlagt. Im Verlauf des Reinigungsvorgangs wischten die Tücher mit den zu untersuchenden Produkten nebeneinander über die angeschmutzte Testfläche.Immediately before the cleaning process, the cloths were clamped in the holders and subjected to the dilute cleaning solution. In the course of the cleaning process, the cloths with the products to be examined wiped side by side over the soiled test area.
Mit diesen Ergebnissen kann gezeigt werden, dass die erfindungsgemäßen Formulierungen auch in der Praxis zu besseren Ergebnissen führt als das System mit ethoxyliertem Quat (V 03) und dies bei wesentlich günstigerem Umweltverhalten.With these results it can be shown that the formulations according to the invention also give better results in practice than the system with ethoxylated quat (V 03) and this with substantially more favorable environmental behavior.
Claims (10)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102004036067A DE102004036067A1 (en) | 2004-07-24 | 2004-07-24 | Aqueous cleaning agent concentrates for rough, in particular profiled tiles |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1619237A1 true EP1619237A1 (en) | 2006-01-25 |
| EP1619237B1 EP1619237B1 (en) | 2007-09-19 |
Family
ID=34937817
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP05014931A Active EP1619237B1 (en) | 2004-07-24 | 2005-07-09 | Aqueous cleaning concentrates for rough preferably profiled tiles and plates |
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| Country | Link |
|---|---|
| US (1) | US7588647B2 (en) |
| EP (1) | EP1619237B1 (en) |
| JP (1) | JP4889255B2 (en) |
| DE (2) | DE102004036067A1 (en) |
| ES (1) | ES2292016T3 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012148530A1 (en) * | 2011-04-26 | 2012-11-01 | Dow Global Technologies Llc | Renewable surfactants derived from sugar alcohols |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102009001748A1 (en) | 2009-03-23 | 2010-09-30 | Evonik Goldschmidt Gmbh | Formulations containing sorbitan carboxylic acid ester |
| US8889900B2 (en) | 2010-12-29 | 2014-11-18 | Ecolab Usa Inc. | Sugar ester peracid on site generator and formulator |
| DE102013204605A1 (en) | 2013-03-15 | 2014-09-18 | Evonik Industries Ag | Phosphoric acid esters, their preparation and use |
| DE102017223123A1 (en) * | 2017-12-18 | 2019-06-19 | Henkel Ag & Co. Kgaa | Machine dishwashing detergent with improved rinsing and cleaning performance, method using this agent and use of the agent |
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|---|---|---|---|---|
| US3962418A (en) * | 1972-12-11 | 1976-06-08 | The Procter & Gamble Company | Mild thickened shampoo compositions with conditioning properties |
| US5866527A (en) * | 1997-08-01 | 1999-02-02 | Colgate Palmolive Company | All purpose liquid cleaning compositions comprising anionic EO nonionic and EO-BO nonionic surfactants |
| US5929024A (en) | 1997-11-20 | 1999-07-27 | Colgate Palmolive Company | Cleaning compositions |
| GB2334723A (en) | 1998-02-26 | 1999-09-01 | Reckitt & Colmann Prod Ltd | Hard surface cleaner |
| US20010009909A1 (en) * | 2000-01-21 | 2001-07-26 | Mireille Maubru | Composition for washing keratin materials, based on weakly ethoxylated sorbitan ester |
| DE10038198A1 (en) | 2000-08-04 | 2002-02-21 | Goldschmidt Ag Th | Aqueous cleaning agent concentrates for rough, especially profiled tiles |
| WO2002045530A2 (en) * | 2000-12-06 | 2002-06-13 | Johnsondiversey, Inc. | Composition for cleaning fruits, vegetables and food contact surfaces |
| US20030153478A1 (en) * | 2002-02-11 | 2003-08-14 | Sutton David C. | Surface maintenance composition |
| EP0928829B1 (en) | 1998-01-08 | 2003-09-03 | Ecolab Inc. | Cleaning of hard surfaces using rheopexic aqueous cleaning agents |
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| US4128484A (en) * | 1975-07-14 | 1978-12-05 | The Procter & Gamble Company | Fabric softening compositions |
| JPH0753989A (en) * | 1993-06-11 | 1995-02-28 | New Japan Chem Co Ltd | Halogene-free detergent composition |
| FR2736936B1 (en) * | 1995-07-19 | 1997-08-14 | Air Liquide | DEGREASING PROCESS BASED ON HYDROGEN PEROXIDE AND APPLICATIONS TO METAL ARTICLES |
| ATE271595T1 (en) * | 1997-02-27 | 2004-08-15 | Procter & Gamble | SOAKING COMPOSITIONS |
| JP5008805B2 (en) * | 2001-08-03 | 2012-08-22 | 株式会社Ａｄｅｋａ | Deodorant composition for CIP cleaning |
| JP2003277788A (en) * | 2002-03-26 | 2003-10-02 | Sekisui Chem Co Ltd | Detergent composition |
| JP2004176022A (en) * | 2002-11-29 | 2004-06-24 | Taiho Ind Co Ltd | Scaly adhered material-removing agent and method for removing the same |
| US20050107275A1 (en) * | 2003-11-14 | 2005-05-19 | Hecht Stacie E. | Liquid detergent composition comprising a solubilizing nonionic surfactant |
-
2004
- 2004-07-24 DE DE102004036067A patent/DE102004036067A1/en not_active Withdrawn
-
2005
- 2005-06-27 US US11/167,691 patent/US7588647B2/en active Active
- 2005-07-09 DE DE502005001519T patent/DE502005001519D1/en active Active
- 2005-07-09 ES ES05014931T patent/ES2292016T3/en active Active
- 2005-07-09 EP EP05014931A patent/EP1619237B1/en active Active
- 2005-07-21 JP JP2005211323A patent/JP4889255B2/en active Active
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| US3962418A (en) * | 1972-12-11 | 1976-06-08 | The Procter & Gamble Company | Mild thickened shampoo compositions with conditioning properties |
| US5866527A (en) * | 1997-08-01 | 1999-02-02 | Colgate Palmolive Company | All purpose liquid cleaning compositions comprising anionic EO nonionic and EO-BO nonionic surfactants |
| US5929024A (en) | 1997-11-20 | 1999-07-27 | Colgate Palmolive Company | Cleaning compositions |
| EP0928829B1 (en) | 1998-01-08 | 2003-09-03 | Ecolab Inc. | Cleaning of hard surfaces using rheopexic aqueous cleaning agents |
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| DE10038198A1 (en) | 2000-08-04 | 2002-02-21 | Goldschmidt Ag Th | Aqueous cleaning agent concentrates for rough, especially profiled tiles |
| WO2002045530A2 (en) * | 2000-12-06 | 2002-06-13 | Johnsondiversey, Inc. | Composition for cleaning fruits, vegetables and food contact surfaces |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012148530A1 (en) * | 2011-04-26 | 2012-11-01 | Dow Global Technologies Llc | Renewable surfactants derived from sugar alcohols |
| US9650321B2 (en) | 2011-04-26 | 2017-05-16 | Dow Global Technologies Llc | Renewable surfactants derived from sugar alcohols |
Also Published As
| Publication number | Publication date |
|---|---|
| ES2292016T3 (en) | 2008-03-01 |
| US7588647B2 (en) | 2009-09-15 |
| DE102004036067A1 (en) | 2006-02-16 |
| JP4889255B2 (en) | 2012-03-07 |
| DE502005001519D1 (en) | 2007-10-31 |
| EP1619237B1 (en) | 2007-09-19 |
| JP2006037102A (en) | 2006-02-09 |
| US20060019864A1 (en) | 2006-01-26 |
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