EP1708968A1 - Systeme d'adoucissement de l'eau par precipitation, destine a des detergents, des adjuvants de detergents, des agents de blanchiment, des detergents pour lave-vaisselle et detergents pour vaisselle a la main - Google Patents

Systeme d'adoucissement de l'eau par precipitation, destine a des detergents, des adjuvants de detergents, des agents de blanchiment, des detergents pour lave-vaisselle et detergents pour vaisselle a la main

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Publication number
EP1708968A1
EP1708968A1 EP05700759A EP05700759A EP1708968A1 EP 1708968 A1 EP1708968 A1 EP 1708968A1 EP 05700759 A EP05700759 A EP 05700759A EP 05700759 A EP05700759 A EP 05700759A EP 1708968 A1 EP1708968 A1 EP 1708968A1
Authority
EP
European Patent Office
Prior art keywords
acid
alkali
water
dispersant
mixtures
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.)
Withdrawn
Application number
EP05700759A
Other languages
German (de)
English (en)
Inventor
Rudolf Weber
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP1708968A1 publication Critical patent/EP1708968A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/02—Softening water by precipitation of the hardness
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
    • C02F1/683—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water by addition of complex-forming compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/02—Softening water by precipitation of the hardness
    • C02F5/06—Softening water by precipitation of the hardness using calcium compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/12—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen
    • C02F5/125—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing nitrogen combined with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
    • C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
    • C02F5/10—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances
    • C02F5/14—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus
    • C02F5/145—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents using organic substances containing phosphorus combined with inorganic substances
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707—Polyethers, e.g. polyalkyleneoxides
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides
    • 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
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • C11D7/12—Carbonates bicarbonates
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • C11D7/14—Silicates
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/02—Non-contaminated water, e.g. for industrial water supply
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • 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
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/146—Sulfuric acid esters

Definitions

  • This invention relates to a method for softening water by the combined use of dispersant (s), fatty acid (s) and / or their alkali salt (s) and case softener, and a corresponding water softening agent and its use, and detergents and cleaning agents containing such water softening agents include.
  • the new water softening process described below makes it possible to work with formulations containing high levels of soda without the occurrence of annoying calcium carbonate deposits on the laundry and washing machines.
  • the basic idea of the invention is a gradual softening of the water with simultaneous dispersion of the disruptive precipitation products.
  • softener such as soda, sodium bicarbonate, potassium carbonate, potassium bicarbonate or water-soluble silicates used very quickly reacting with the water hardness soap.
  • the soap immediately forms insoluble calcium soap in the first reaction, the slower reacting soda (or sodium bicarbonate etc.) therefore no longer finds calcium in the water and there are no further precipitation reactions.
  • a dispersant in particular the sodium salt of polyaspartic acid.
  • Polyaspartate e.g. disperses the calcium soap very finely and keeps it in suspension, so that opalescent solutions result and the well-known flaky lime soap deposits do not occur.
  • the present invention therefore relates to a process for softening water by combined use of dispersant (s), fatty acid (s) and / or their alkali salt (s) and a precipitant softener, advantageously alkali carbonate and / or alkali bicarbonate and / or water-soluble silicate.
  • the dispersant is selected from polyaspartic acid, the water-soluble polyaspartic acid salts, polyacrylic acid, the water-soluble polyacrylic acid salts, sulfonated or sulfated oils (eg Turkish red oil), block copolymers of the PEP-PEO type (copolymers of polyethylene propylene and polyethylene oxide), sodium dodecyl sulfate, polymeric polycarboxylates, sodium phosphates and mixtures thereof.
  • the polymeric polycarboxylates are preferably homopolymers or copolymers which contain acrylic acid and / or maleic acid units.
  • particularly preferred homopolymers are used, if appropriate in combination with copolymers, polyacrylates being preferred.
  • the polyacrylates are usually used in the form of sodium salts.
  • polyacrylates which preferably have a molecular weight of 3000 to 8000 and particularly preferably 4000 to 5000 g / mol, have proven to be particularly suitable according to the invention.
  • the molar masses given in this document for polymeric polycarboxylates are weight-average molar masses Mw, which were basically determined by means of gel permeation chromatography (GPC), a UV detector being used.
  • the measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight data for which polystyrene sulphide fonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally higher than the molecular weights given in this document.
  • the copolymeric polycarboxylates are, in particular, those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid, which have a molar mass between 20,000 and 70,000 g / mol.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • the polymers can also contain allylsulfonic acids, allyloxybenzenesulfonic acid and methallylsulfonic acid as monomers.
  • biodegradable polymers composed of more than two different monomer units, which contain salts of acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives as monomers or salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives as monomeric salts.
  • Further preferred copolymers preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
  • both these copolymers and the polyacrylates are used in the process, the ratio of the polyacrylate to the acrylic acid-maleic acid copolymer advantageously in the range from 2: 1 to 1:20, preferably 1: 1 to 1:15 , lies.
  • the fatty acid is selected from caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, lauroleic acid.
  • the weight ratio of fatty acid and / or its alkali salt to the dispersant is 20: 1 to 1: 3, preferably 10: 1 to 2: 1.
  • the weight ratio of precipitate softener, preferably alkali carbonate, alkali bicarbonate, water-soluble silicates and mixtures thereof, to the dispersant is 20: 1 to 2: 1, preferably 10: 1 to 2: 1.
  • dispersants fatty acids and / or their alkali metal salts and precipitant softener is used in concentrations in the range from 10 to 60% by weight, in particular 16 to 50% by weight, based on the total agent, in particular detergent, then there is one another preferred embodiment of the invention.
  • highly complexing compounds such as, in particular, the Ca complexing agents mentioned above or having a comparable action, are additionally used.
  • the weight ratio of dispersant to the highly complexing compounds is 5: 1 to 1: 5, preferably 1: 1 to 3: 1.
  • the phosphonates are, in particular, hydroxyalkane or aminoalkanephosphonates.
  • hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance.
  • HEDP 1-hydroxyethane-1,1-diphosphonate
  • Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of the neutral sodium salts, e.g. B.
  • the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • Such phosphonates are advantageously contained in the agents in amounts of 0.05 to 2.0% by weight, preferably in amounts of 0.1 to 1% by weight.
  • Suitable complexing agents are, for example, the following complexing agents designated according to INCI in English, which are described in more detail in the International Cosmetic Ingredient Dictionary and Handbook: Aminotrimethylene Phosphonic Acid, Beta-Alanine Diacetic Acid, Calcium Disodium EDTA, Cyclodextrin, Cyclohexanediamine Tetraacetic Acid, Diammonium EDTA, Diethylenetriamine Pentamethylene Phosphonic Acid, Dipotassium EDTA, Disodium Azacycloheptane Diphosphonate, Disodium EDTA, Disodium Pyrophosphate, EDTA, Etidronic Acid, Galactaric Acid, Gluconic Acid, Glucuronic Acid, HEDTA, Hydroxypropyl Cyclodextrin, Methyl Cyclododium Triphosphate, Pentate Pentapotasodium, Pentate Pentasodium Pentate Triphosphate, Pentetic Acid, Phytic Acid, Potassium Citrate, Potassium Gluconate,
  • Tertiary amines in particular tertiary alkanolamines (amino alcohols), can also be used as complexing agents.
  • the alkanolamines have both amino and hydroxyl and / or ether groups as functional groups.
  • Particularly preferred tertiary alkanolamines are triethanolamine and tetra-2-hydroxypropylethylenediamine (N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine).
  • Another object of the invention is a water softener containing dispersant, fatty acid and / or its alkali salt and precipitate softener, which is preferably selected from alkali carbonate and / or alkali bicarbonate and / or water-soluble silicate.
  • the statements made above preferably also apply to the water softener. According to a preferred embodiment, it contains 10 to 70% by weight of precipitation softener, preferably alkali carbonate and / or alkali bicarbonate, 5 to 20% by weight of fatty acid and or its alkali salt, 0-25% by weight, preferably 8 to 20% by weight.
  • % Peroxygen compound 0 to 10% by weight, preferably 2 to 8% by weight of nonionic surfactant, 0 to 15% by weight, preferably 3 to 10% by weight of anionic surfactant and dispersant, preferably in amounts of 4 to 25% by weight .-%, advantageously from 5 to 25% by weight, in a further advantageous manner from 6 to 20% by weight, in a still further advantageous manner from 7 to 16% by weight, in particular from 8 to 12% by weight ,
  • the water softener can be applied to, or integrated into, conventional detergent formulations, for example those based on layered silicate (e.g. SKS-6) or zeolite-based.
  • conventional detergent formulations for example those based on layered silicate (e.g. SKS-6) or zeolite-based.
  • the formulations preferably contain water-soluble builders, which corresponds to a preferred embodiment, in which case it is advantageous if the proportion of water-insoluble builders is below 3% by weight, based on the overall formulation.
  • the formulations are predominantly zeolite-containing or layered silicate-containing or mixtures of the same, accelerated softening can be achieved using the softening system described here.
  • the builder base in such a case consists of water-insoluble ion exchangers such as preferably layered silicate (e.g. SKS 6) or zeolite, e.g. of type A, X, Y or P.
  • layered silicate e.g. SKS 6
  • zeolite e.g. of type A, X, Y or P.
  • the amounts of ion exchanger advantageously lie between 8 and 70% by weight, preferably between 25 and 50% by weight.
  • the agent according to the invention further contains foam inhibitors, preferably those based on silicone or paraffin oils.
  • foam inhibitors preferably those based on silicone or paraffin oils.
  • bleaching agents alone and in a mixture, Na percarbonate and / or Na perborate, can advantageously be combined with a bleach activator such as TAED ( ⁇ /, N, / ', ⁇ /' - tetraacetylethylene diamine) or Use sodium p-nonanoyloxybenzenesulfonate.
  • TAED ⁇ /, N, / ', ⁇ /' - tetraacetylethylene diamine
  • PAP bleach phthalimidoperoxohexanoic acid
  • a mixture of PAP with percarbonate and TAD results in a bleaching agent for the application range from 20 to 60 ° C, whereby the PAP also uses its antibacterial properties.
  • a water softener according to the invention contains alkali percarbonate, alkali perborate, alkali peracetic acid (TAED), or phthalimidoperoxohexane acid and / or mixtures thereof as peroxygen compound.
  • Another object of the invention is the use of a water softening agent, as described above, as a detergent, washing aid, bleach, cleaning agent, machine and dishwasher detergent or as a component of such agents.
  • Another object of the invention is a washing and cleaning agent which contains a water softening agent as described above.
  • a detergent and cleaning agent can have all the usual features and ingredients which can be found in the prior art and which characterize a detergent and cleaning agent.
  • anionic surfactants in particular anionic surfactants. These include in particular sulfonates and sulfates.
  • Cationic surfactants can also be contained in the detergent and cleaning agent.
  • cationic surfactant is present in amounts of up to 5% by weight, preferably in amounts of up to 4% by weight, in particular in amounts of 1 to 3% by weight, based on the total washing and Detergent containing detergents and cleaning agents. In addition to the softness aspect, this also improves the graying and secondary washing effect.
  • the cationic surfactant contained in the washing and cleaning agent is a quaternary ammonium compound, preferably an alkylated quaternary ammonium compound.
  • this is a quaternary ammonium compound of the formula (I)
  • R 1 , R 2 and R 3 are independently selected from C ⁇ C 4 alkyl, CC 4 hydroxyalkyl, benzyl and - (C 2 H 4 O) x H, with x equal to 2 to 5, and where R4 is a C 8 - C 22 is alkyl, and where X "is an anion, preferably a halide, methosulfate, methophosphate or phosphate ion and mixtures thereof.
  • R 5 is a C 6 -C 24 alkyl or alkenyl, where each R 6 is independently a - (C n H 2n O) x R 8 group, with n equal to 1 to 4 and with x equal to 1 to 14 , and wherein R 8 is methyl ethyl or preferably a hydrogen, and wherein each R 7 is independently a CC 12 alkyl or alkenyl group, where m is 1 to 3, and where X- is an anion, preferably a halide, Methosulfate, methophosphate or phosphate ion and mixtures of these.
  • R 6 is a —CH 2 CH 2 OH group
  • R 7 is in each case independently of one another a CC alkyl, where m is 1 or 2
  • R 5 is a linear C 6 -C 1 alkyl group.
  • the detergents and cleaning agents according to the invention which contain quaternary ammonium compound according to formula (I) and / or (II), are advantageous because they have the appropriate Application lead to the fact that textiles not only become very soft and supple, have a reduced drying time, are easier to iron and may even have an antistatic finish, but that improvements in incrustation, whiteness, graying or secondary washing effects also occur in some cases. There are advantages to the formation of incrustations on substrate surfaces.
  • the cationic surfactant is a C 8 -C 6 -alkyl-di (hydroxyethyl) methyl ammonium compound, preferably a C 2 -C 1 -alkyl-di (hydroxyethyl) methyl ammonium compound.
  • cationic surfactants can also be used, but advantageously alkylated quaternary ammonium compounds, preferably with two hydrophobic groups, in particular via ester or amido bonds with a quaternized di- or triethanolamine or an analog connection.
  • R9 represents an aliphatic alkyl radical having 12 to 22 carbon atoms with 0, 1, 2 or 3 double bonds
  • R 10 stands for H, OH or in particular O (CO) R 12
  • R 11 stands independently of R 10 for H, OH or O (CO) R 13
  • R 12 and R 13 each independently represent an aliphatic alkyl radical having 12 is up to 22 carbon atoms with 0, 1, 2 or 3 double bonds
  • a, b and c can each independently have the value 1, 2 or 3
  • X " is a suitable anion, preferably a halide, methosulfate, methophosphate or Phosphate ion and mixtures of these, and / or the formula (IV):
  • R 14 , R 15 and R 16 independently of one another represent a C 1 _ 4 alkyl, alkenyl or hydroxyalkyl group
  • R 17 and R 18 are each independently selected a C 8 _ 28 alkyl group with 0, 1, 2 or 3 represents double bonds and u is a number between 0 and 5
  • X ⁇ is a suitable anion, preferably a halide, methosulfate, methophosphate or phosphate ion and mixtures thereof.
  • Preferred representatives of this genus are N-methyl-N (2-hydroxyethyl) -N, N- (ditalgacyloxyethyl) ammonium methosulfate or N-methyl-N (2-hydroxyethyl) -N, N- (dipalmitoylethyl) ammonium methosulfate.
  • Preferred surfactants of the sulfonate type are C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates, that is to say mixtures of alkene and hydroxyalkanesulfonates and disulfonates of the kind obtained, for example, from C 12 -C 18 monoolefins having a terminal or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
  • alkanesulfonates which are obtained from C 12 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • esters of alpha sulfo fatty acids e.g. B. the alpha-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, which are produced by alpha-sulfonation of the methyl esters of fatty acids of vegetable and / or animal origin with 8 to 20 carbon atoms in the fatty acid molecule and subsequent neutralization to form water-soluble mono-salts be considered.
  • alpha -sulfofatty acid alkyl esters are preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl ester, ethyl ester, propyl ester and butyl ester.
  • the methyl esters of alpha-sulfofatty acids (MES), but also their saponified disalts, are used with particular advantage.
  • Suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters as well as their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol be preserved.
  • the alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 0 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. From the washing are C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 - C 15 alkyl sulfates are particularly preferred.
  • the sulfuric acid monoesters of the straight-chain or branched C 7 -C 21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12 -C 18 fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and especially ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures thereof.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is the same possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alkyl (en) yl chain or salts thereof.
  • Fatty acid derivatives of amino acids for example of N-methyl taurine (taurides) and / or of N-methyl glycine (sarcosides) are suitable as further anionic surfactants.
  • the anionic surfactants can be in the form of their sodium, potassium or ammonium salts and also as soluble salts of organic bases, such as mono-, di- or thanolamine.
  • the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • nonionic surfactants are particularly preferred.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol residue can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • EO ethylene oxide
  • alcohol ethoxylates with linear residues from alcohols of native origin with 12 to 18 carbon atoms for. B. from coconut, palm, tall fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, Cg-C ⁇ alcohols with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 -C 4 alcohol with 3 EO and C 2 -C 18 alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used, as described above. Examples of these are (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • the nonionic surfactants also include alkyl glycosides of the general formula RO (G) x, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G for one Glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G for one Glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as an analytically determinable variable, can also take fractional values - between 1 and 10; x is preferably 1.2 to 1.4.
  • polyhydroxy fatty acid amides of the formula (V) in which R 19 is CO for an aliphatic acyl radical with 6 to 22 carbon atoms, R 20 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and Z for a linear or branched polyhydroxyalkyl radical with 3 up to 10 carbon atoms and 3 to 10 hydroxyl groups:
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars with 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula (VI)
  • R 21 for a linear or branched alkyl or alkenyl radical with 7 to 12 carbon atoms
  • R 22 for a linear, branched or cyclic alkylene radical or an arylene radical with 2 to 8 carbon atoms
  • R 23 for a linear, branched or cyclic alkyl radical or an aryl radical or an oxy-alkyl radical with 1 to 8 carbon atoms, CC 4 -alkyl or phenyl radicals being preferred
  • Z for a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this residue.
  • Z is also preferably obtained here by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then, for example, by reaction with fatty Acid methyl esters are converted into the desired polyhydroxy fatty acid amides in the presence of an alkoxide as a catalyst.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598.
  • nonionic surfactants are C 2 -C 18 fatty acid methyl esters with an average of 3 to 15 EO, in particular with an average of 5 to 12 EO, while as a binder - as described above - above all higher ethoxylated fatty acid methyl esters are advantageous.
  • C 12 -C 8 - fatty acid methyl esters with 10 to 12 EO can be used both as surfactants and as binders.
  • Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanol amides can also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • gemini surfactants can be considered as further surfactants. These are generally understood to mean those compounds which have two hydrophilic groups and two hydrophobic groups per molecule. These groups are usually separated from one another by a so-called "spacer". This spacer is usually a carbon chain, which should be long enough that the hydrophilic groups have a sufficient distance so that they can act independently of one another.
  • Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water.
  • gemini surfactants means not only dimeric but also trimeric surfactants. Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers or dimer alcohol bis and trimer alcohol trisulfates and ether sulfates. End group-blocked dimeric and trimeric mixed ethers are particularly characterized by their bi- and multifunctionality. So the called endgroup-sealed surfactants good wetting properties and are low-foaming, so that they are particularly suitable for use in machine washing or cleaning processes. Gemini polyhydroxy fatty acid amides or poly polyhydroxy fatty acid amides can also be used.
  • Bleaching agents have already been mentioned above.
  • sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate are of particular importance.
  • Other useful bleaching agents are, for example, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • sodium percarbonate is used as bleaching agent in a preferred embodiment.
  • the other detergent ingredients include graying inhibitors (dirt carriers), foam inhibitors, bleach activators, optical brighteners, enzymes, fabric softening substances, colorants and fragrances as well as neutral salts such as sulfates and chlorides in the form of their sodium or potassium salts.
  • Bleach activators have already been mentioned above.
  • Bleach activators which can be used are compounds which, under perhydrolysis conditions, give aliphatic peroxocarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable are substances which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
  • Hydrophilically substituted acylacetals and acyllactams are also preferably used.
  • Bleach activators of this type are advantageously present in the customary quantitative range, preferably in amounts of 1% by weight to 10% by weight, in particular 2% by weight to 8% by weight, based on the total detergent and / or cleaning agent.
  • Suitable foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, possibly signed silica, and paraffins, waxes, microcrystalline waxes and their mixtures with signed silica or bistearylethylenediamide. Mixtures of different foam inhibitors are also used with advantages, e.g. B. from silicone, paraffins or waxes.
  • the foam inhibitors, in particular silicone and / or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance.
  • Particularly suitable enzymes are those from the class of hydrolases, such as proteases, lipases or lipolytically active enzymes, amylases, cellulases or mixtures thereof. Oxireductases are also suitable.
  • Enzymes obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus and Humicola insolens, are particularly suitable.
  • Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example, from protease and amylase or protease and lipase or lipolytically active enzymes or protease and cellulase or from cellulase and lipase or lipolytically active enzymes or from protease, amylase and lipase or lipolytically active enzymes or protease, lipase or lipolytic enzymes and cellulase, but especially protease- and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • Known cutinases are examples of such lipolytically active enzymes.
  • Peroxidases or oxidases have also proven to be suitable in some cases.
  • Suitable amylases include in particular alpha - amylases, isoamylases, pullulanases and pectinases.
  • As cellulases are preferably se cellobiohydrolases, endoglucanases and beta-glucosidases, which are also called cellobiases, or mixtures of these are used. Since the various cellulose types differ in their CMCase and avicelase activities, the desired activities can be set by targeted mixtures of the cellulases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • the washing and / or cleaning agents can also contain further enzyme stabilizers.
  • enzyme stabilizers For example, 0.5 to 1% by weight sodium formate can be used. It is also possible to use proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • calcium salts magnesium salts also serve as stabilizers.
  • boron compounds for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H 3 BO 3 ), metaboric acid (HBO2) and pyrobic acid (tetraboric acid H 2 B 4 O 7 ), is particularly advantageous.
  • Graying inhibitors which can preferably be cellulose ethers, such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and also polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the detergents and / or cleaning agents are used.
  • cellulose ethers such as carboxymethyl cellulose (sodium salt)
  • methyl cellulose hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof
  • polyvinylpyrrolidone for example in amounts of 0.1 to 5% by weight, based on the detergents and / or cleaning agents are used.
  • the detergents and / or cleaning agents can contain, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or its alkali metal salts.
  • optical brighteners derivatives of diaminostilbenedisulfonic acid or its alkali metal salts.
  • B Salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similar compounds, instead of the morpholino group carry a diethanol amino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyryl type may be present, e.g. B.
  • the range of possible bulk weights ranges from low bulk weights below 600 g / l, for example 300 g / l, to the range of medium bulk weights from 600 to 750 g / l to the range of high bulk weights of at least 750 g / l.
  • the bulk density is even above 800 g / l, with bulk weights above 850 g / l being particularly advantageous.
  • washing and / or cleaning agents with high bulk density are to be obtained
  • the washing and / or cleaning agent mixtures are finally subjected to a compacting step, e.g. further ingredients are also only added to the washing and / or cleaning agents after the compacting step.
  • the ingredients are compacted in a press agglomeration process.
  • the press agglomeration process to which the solid premix (dried basic detergent) is subjected can be carried out in various apparatuses. Different press agglomeration processes are distinguished depending on the type of agglomerator used.
  • the four most common press agglomeration processes preferred in the context of the present invention are extrusion, roller pressing or compacting, hole pressing (pelletizing) and tableting, so that preferred press agglomeration processes in the context of the present invention are extrusion, roll compacting, pelletizing - or tableting processes.
  • Sokalan CP 5 maleic acid-acrylic acid copolymer Na salt (30:70)
  • FAS fatty alcohol sulfate
  • Lutensol C12-14 fatty alcohols ethoxylated (8 EO)
  • ABS alkylbenzenesulfonate
  • formulations A1 to E1 and G1 which contained soda / soap mixtures and Sokalan CP 5 as a dispersant, gave almost no ash deposits in the form of calcium carbonate.
  • formula F1 which contained no dispersant, showed clear ash deposits.
  • This recipe with polyaspartate as a dispersant also showed an excellent ash value.

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  • Chemical & Material Sciences (AREA)
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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Water Supply & Treatment (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Abstract

L'invention concerne un système pour adoucir l'eau, constitué d'au moins un agent dispersant, d'au moins un acide gras et/ou d'au moins un sel alcalin de ce(s) dernier(s) et d'un adoucissant agissant par précipitation. L'invention concerne également un procédé pour adoucir l'eau, des adoucissants d'eau, l'utilisation de ces derniers, ainsi que des détergents et nettoyants contenant ces adoucissants.
EP05700759A 2004-01-22 2005-01-08 Systeme d'adoucissement de l'eau par precipitation, destine a des detergents, des adjuvants de detergents, des agents de blanchiment, des detergents pour lave-vaisselle et detergents pour vaisselle a la main Withdrawn EP1708968A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004003286A DE102004003286A1 (de) 2004-01-22 2004-01-22 System zur Wasserenthärtung durch Fällenthärtung
PCT/EP2005/000109 WO2005070839A1 (fr) 2004-01-22 2005-01-08 Systeme d'adoucissement de l'eau par precipitation, destine a des detergents, des adjuvants de detergents, des agents de blanchiment, des detergents pour lave-vaisselle et detergents pour vaisselle a la main

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US (1) US20070021315A1 (fr)
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WO (1) WO2005070839A1 (fr)

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KR101520121B1 (ko) * 2007-07-03 2015-05-18 바스프 에스이 알파-알라닌-ｎ,ｎ-디아세트산 및/또는 알파-알라닌-ｎ,ｎ-디아세트산의 1 이상의 유도체를 실질적으로 포함하는 자유유동성의 저장안정성 고체의 제조 방법
EP2421800B1 (fr) * 2009-04-21 2019-08-28 Ecolab USA Inc. Procédés et appareil de réglage de la dureté de l'eau
CN101817599B (zh) * 2010-01-25 2013-02-13 夏光甫 汽车水箱除垢清洗液及其制备方法
CN102452725B (zh) * 2010-10-20 2015-01-14 中国石油化工股份有限公司 一种复合阻垢缓蚀剂及其应用
CN102452722B (zh) * 2010-10-20 2014-04-16 中国石油化工股份有限公司 一种无磷复合阻垢缓蚀剂及其在水处理中的应用
JP5788671B2 (ja) * 2010-12-17 2015-10-07 花王株式会社 自動洗浄機用粉末洗浄剤組成物
US9193610B2 (en) 2011-08-10 2015-11-24 Ecolab USA, Inc. Synergistic interaction of weak cation exchange resin and magnesium oxide
WO2013032479A1 (fr) 2011-09-01 2013-03-07 Colgate-Palmolive Company Procédé pour réaliser un séchage rapide d'un tissu
US9758927B2 (en) 2011-09-01 2017-09-12 Colgate-Palmolive Company Method for ease of ironing
WO2013032480A1 (fr) 2011-09-01 2013-03-07 Colgate-Palmolive Company Procédé permettant de faciliter le repassage
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