Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0073—Anticorrosion compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/046—Salts
• • 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
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
  • C11D3/1273—Crystalline layered silicates of type NaMeSixO2x+1YH2O
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2075—Carboxylic acids-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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2075—Carboxylic acids-salts thereof
  • C11D3/2082—Polycarboxylic acids-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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2075—Carboxylic acids-salts thereof
  • C11D3/2086—Hydroxy carboxylic acids-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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/28—Heterocyclic compounds containing nitrogen in the ring
• • 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
  • C11D3/34—Organic compounds containing sulfur
  • C11D3/3418—Toluene -, xylene -, cumene -, benzene - or naphthalene sulfonates or sulfates
• • 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
  • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
  • C11D2111/10—Objects to be cleaned
  • C11D2111/14—Hard surfaces
  • C11D2111/18—Glass; Plastics

Definitions

• the present invention is in the field of automatic dishwashing detergents.
• the present invention relates to machine dishwashing detergents which contain zinc salts and certain silicates.
• the so-called low-alkaline cleaners required for machine dishwashing often contain, as alkali carriers, mixtures of sodium disilicate and soda, builders such as citric acid, for example in conjunction with polycarboxylates, and preferably low-foaming, nonionic surfactants. Bleach, bleach activators, silver and anti-corrosion agents and, to enhance cleaning ability, enzymes can also be present.
• the dishes placed in baskets are cleaned by intensive contact with the aqueous cleaning solution at about 65 ° C and pH values between 9 and 11 and then rinsed clear.
• phosphate-containing automatic dishwashing detergents which contain a powdery to granular additive which, as essential constituents, comprises a crystalline layered silicate of the general formula NaMSi x ⁇ 2 ⁇ +. y H 2 0, in which M represents sodium or hydrogen, x is a number from 1.9 to 22 and y stands for a number from 0 to 33, and have (co) polymeric polycarboxylic acid and, in addition to glass or decor-sparing effects also have excellent cleaning performance.
• the present invention was based on the object of providing a machine dishwashing detergent which, even when used repeatedly, does not corrosively change the surfaces of glassware, in particular does not cause clouding, streaks or scratches but also does not cause the glass surfaces to become iridescent.
• An additive for a machine dishwashing detergent should preferably be provided, which is suitable as a component of machine dishwashing detergents of any supply form, for example as a component of powder, tablet, liquid formulations, cleaning foams or depot products, without restricting the formulation.
• machine dishwashing agents or machine dishwashing aids which, in addition to at least one zinc salt, also contain at least one crystalline layered silicate.
• the present application therefore relates to automatic dishwashing agents or automatic dishwashing auxiliaries containing at least one zinc salt and at least one crystalline layered silicate of the general formula (I)
• A is an alkali metal and / or hydrogen
• B an alkaline earth metal and / or a subgroup element, preferably an element from the group zinc, iron manganese
• C an element of the third main group of the periodic table and / or a subgroup element, preferably iron, and D.
• Element of the fifth main group of the periodic table and / or a subgroup element and also applies that 0 ⁇ a ⁇ 1; 0 ⁇ b ⁇ 0.5; 0 ⁇ c / x ⁇ 0.05; 0 ⁇ d / x ⁇ 0.25; 1.9 ⁇ x ⁇ 22; 0 ⁇ f ⁇ 40.
• the machine dishwashing agent or machine dishwashing aid contains at least one zinc salt and at least one crystalline layered silicate of the general formula (I)
• A is an alkali metal and / or hydrogen
• B is an alkaline earth metal and / or zinc
• C is an element of the third main group of the periodic table
• D is an element of the fifth main group of the periodic table and furthermore applies that 0 - a ⁇ 1; 0- -b ⁇ 0.5; 0 ⁇ c / x ⁇ 0.05; 0 ⁇ d / x ⁇ 0.25; 1,9 ⁇ x ⁇ 22 0 - f ⁇ 40.
• the machine dishwashing agent or machine dishwashing aid has at least one zinc salt and at least one crystalline layered silicate of the general formula (I)
• A is an alkali metal and / or hydrogen
• B is an alkaline earth metal
• C is an element of the third main group of the periodic table
• D is an element of the fifth main group of the periodic table and furthermore applies that 0 - a ⁇ 1; 0 - b - 0.5; 0 ⁇ c / x ⁇ 0.05; 0 ⁇ d / x ⁇ 0.25; 1.9 - x ⁇ 22; 0 ⁇ f ⁇ 40.
• the crystalline layered silicate contains, based on its weight, up to 10 mol%, preferably between 0.01 and 10 mol%, preferably between 0.01 and 8 mol% and in particular between 0.01 and 5 mol% boron.
• the crystalline, layered silicate contains up to 50 mol%, preferably between 0.01 and 50 mol%, preferably between 0.01 and 40 mol% and in particular between 0.01 and 20 Mol% phosphorus.
• the preferred subject matter of the present application are therefore automatic dishwashing agents or automatic dishwashing aids containing at least one zinc salt and at least one crystalline layered silicate of the general formula (Ia)
• M represents sodium or hydrogen
• x is a number from 1.9 to 22, preferably from 1.9 to
• 1:50 preferably from 5: 1 to 1:30 and in particular from 3: 1 to 1:10 are contained in these agents.
• the crystalline layered silicates of the formula (Ia) are sold, for example, by Clariant GmbH (Germany) under the trade name Na-SKS, e.g. Na-SKS-1
• Na-SKS-2 Na 2 Si 14 0 29 xH 2 0, Magadiite
• Na-SKS-3 Na 2 Si 8 0 1 7 xH 2 0
• Na-SKS-4 Na 2 Si 4 0 9 xH 2 0, makatite
• Na-SKS-5 (-Na 2 Si 2 0 5 ), Na-SKS-7 (ß-Na 2 Si 2 0 5 , natrosilite), Na-SKS-9 (NaHSi 2 0 5 ⁇ 2 0), Na-
• preferred automatic dishwashing agents or automatic dishwashing aids have a weight fraction of the crystalline layered silicate of the general formula (I) or of the general formula (Ia) of 0.1 to 20% by weight, preferably of 0.2 to 15 % By weight and in particular from 0.4 to 10% by weight, in each case based on the total weight of these compositions.
• agents according to the invention contain zinc salts, preference being given to using both inorganic and organic salts. The following table shows a non-exhaustive list of some preferred zinc salts:
• non-soluble inorganic zinc salts i.e. salts which have a solubility below 100 mg / L (20 ° C), preferably below 10 mg / L (20 ° C), in particular no solubility (20 ° C) (e.g. zinc oxide )
• the soluble inorganic interest salts that is to say salts which have a solubility in water of above 100 mg / L, preferably above 500 mg / L, particularly preferably above 1 g / L and in particular above 5 g / L , preferred component of agents according to the invention.
• Preferred soluble inorganic salts include zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate.
• machine dishwashing agents or machine dishwashing aids which contain at least one zinc salt selected from the group of inorganic zinc salts, preferably from the group of soluble inorganic zinc salts, in particular from the group of zinc bromide, zinc chloride, zinc iodide, zinc nitrate and zinc sulfate ,
• the spectrum of the zinc salts of organic acids extends from salts which are not soluble in water, i.e. have a solubility below 100 mg / L, preferably below 10 mg / L, in particular no solubility, to salts which solubility in water above 100 mg / L, preferably above 500 mg / L, particularly preferably above 1 g / L and in particular above 5 g / L (all solubilities at 20 ° C water temperature).
• the first group of zinc salts includes, for example, zinc citrate, zinc laurate, zinc oleate, zinc oxalate, zinc tartrate and zinc stearate
• the group of soluble organic zinc salts includes, for example, zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, the zinc gluconate, the zinc valerate and the zinc salt of p-toluenesulfonic acid.
• automatic dishwashing agents or automatic dishwashing aids according to the invention therefore contain at least one zinc salt selected from the group of the organic zinc salts, preferably from the group of the soluble organic zinc salts, particularly preferably from the group of the soluble zinc salts of monomeric or polymeric organic acids, in particular from the group Group zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate, zinc p-toluenesulfonate.
• group of the organic zinc salts preferably from the group of the soluble organic zinc salts, particularly preferably from the group of the soluble zinc salts of monomeric or polymeric organic acids, in particular from the group Group zinc acetate, zinc acetylacetonate, zinc benzoate, zinc formate, zinc lactate, zinc gluconate, zinc ricinoleate, zinc abietate, zinc valerate, zinc p-tol
• preferred agents according to the invention can also include mixtures of organic and inorganic zinc salts, in particular mixtures of soluble organic zinc salts with non-soluble inorganic zinc salts or mixtures of soluble organic zinc salts with soluble inorganic zinc salts or mixtures of non-soluble organic zinc salts with non-soluble inorganic zinc salts or mixtures of non-soluble organic zinc salts with soluble inorganic zinc salts.
• machine dishwashing agents or machine dishwashing aids are preferred in which the weight fraction of the zinc salt, based on the total weight of this agent, is 0.1 to 10% by weight, preferably 0.2 to 7% by weight and in particular 0 Is 4 to 4% by weight, regardless of which zinc salts are used, in particular regardless of whether organic or inorganic zinc salts, soluble or insoluble zinc salts or mixtures thereof are used.
• Machine dishwashing agents or machine dishwashing aids in the context of the present invention can therefore be provided both in solid and in liquid form.
• the agents according to the invention release active substances and / or active substance preparations contained in a time-controlled manner.
• This time-controlled release can take place by different mechanisms or, in other words, by different "switches”.
• these active substances preferably together, but at different times from one or more other active substances and / or active substance preparations, such as builders (builders, cobuilders), surfactants, bleaching agents, bleach activators, enzymes , Dyes, fragrances, anti-corrosion agents or polymers are released.
• the zinc salt and / or the layered silicate can be released into the aqueous liquor both before and after the release of these active substances.
• Liquid funds often dissolve faster than solid funds
• solid agents with a large surface area e.g. powders, granules
• dissolve faster than solid agents with a comparatively small surface area e.g. tablets
• mechanical stability which - depending on time, temperature or other parameters - can be a factor determining disintegration; the temperature, d. H. reaching a certain temperature value in the course of
• Embodiment the pH, d. H. the setting of a certain pH value in the course of a washing,
• the agent according to the invention which contains the zinc salt and the layered silicate, is preferably only contained in one of these agents.
• Liquids, powders, granules, compactates, extrudates, castings, gels, and dispersions are considered to be different confection forms / aggregate states in the present application.
• Such different means can be packaged to form a combination product, for example by means of a common, preferably water-soluble packaging, which has one, two, three, four or more receiving chambers.
• Methods for producing such packaging are known to the person skilled in the art. These processes include, for example, deep-drawing, injection molding or casting processes. In the following, some combinations of differently prepared agents are described using one- and two-chamber packaging:
• Agent according to the invention in a granulate and compact
• Agent according to the invention in a granulate and dimensionally stable gel
• the water-soluble and / or water-dispersible film made of (acetalized) polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin, starch and starch derivative (s), cellulose and cellulose derivative (s), in particular methyl cellulose and / or mixtures of these substances exists, which list is to be regarded as exemplary and not to limit the invention.
• the film (s) comprises / comprise one or more materials from the group consisting of acrylic acid-containing polymers, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters and polyethers and mixtures thereof ,
• Polyvinyl alcohol or poly (vinyl alcohol - co - vinyl acetate) with molecular weights in the range from 10,000 to 200,000 g / mol and acetate contents from 0 to 30 mol%; these can include processing additives such as plasticizers (glycerin, sorbitol, water, PEG etc.), lubricants (stearic acid and other mono-, di- and tricarboxylic acids), so-called “slip agents” (e.g. "Aerosil”), organic and inorganic pigments, salts, blowing agents (citric acid-sodium bicarbonate mixtures); Acrylic acid-containing polymers, such as. B.
• plasticizers glycerin, sorbitol, water, PEG etc.
• lubricants stearic acid and other mono-, di- and tricarboxylic acids
• so-called “slip agents” e.g. "Aerosil”
• copolymers, terpolymers or tetrapolymers which contain at least 20% acrylic acid and have a molecular weight of 5,000 to 500,000 g / mol; as comonomers, particularly preferred are acrylate such as ethyl acrylate, methyl acrylate, hydroxy ethyl acrylate, ethylhexyl acrylate, butyl acrylate, and salts of acrylic acid such as sodium acrylate, methacrylic acid and salts and esters thereof such as methyl methacrylate, ethyl methacrylate, Trimethylammoniummethylmethacrylatchlorid (TMAEMC), methacrylate amidopropyl trimethyl ammonium chloride (MAPTAC ).
• TMAEMC Trimethylammoniummethylmethacrylatchlorid
• MATAC methacrylate amidopropyl trimethyl ammonium chloride
• polyalkylene oxides preferably polyethylene oxides with molecular weights of 600 to 100,000 g / mol and their derivatives modified by graft copolymerization with monomers such as vinyl acetate, acrylic acid and their salts and their esters, methacrylic acid and their salts and their esters, acrylamide, styrene, styrene sulfonate and vinyl pyrrolidone (example: Poly (ethylene glycol - graft - vinyl acetate)
• the polyglycol content should be 5 to 100% by weight, the graft fraction should be 0 to 95% by weight, the latter may consist of one or more monomers Graft fraction of 5 to 70% by weight; the water solubility decreases with the graft fraction;
• Polyvinyl pyrrolidone with a molecular weight of 2,500 to 750,000 g / mol
• Polyacrylamide with a molecular weight of 5,000 to 5,000,000 g / mol
• Polyethyloxazoline and polymethyloxazoline with a molecular weight of 5,000 to 100,000 g / mol
• Polystyrene sulfonates and their copolymers with comonomers such as ethyl (meth) acrylate, methyl (meth) acrylate, hydroxyethyl (meth) acrylate, ethylhexyl (meth) acrylate, butyl (meth) acrylate and the salts of (meth) Acrylic acid such as sodium (meth) acrylate, acrylamide, styrene, vinyl acetate, maleic anhydride, vinyl pyrrolidone; the comonomer content should be 0 to 80 mol% and the molecular weight should be in the range of 5,000 to 500,000 g / mol; Polyurethanes, especially the reaction products of diisocyanates (e.g. TMXDI) with polyalkylene glycols, especially polyethylene glycols with a molecular weight of 200 to 35,000, or with other difunctional alcohols to products with molecular weights of
• Polyesters with molecular weights of 4,000 to 100,000 g / mol based on dicarboxylic acids (e.g. terephthalic acid, isophthalic acid, phthalic acid, sulfoisophthalic acid, oxalic acid, succinic acid, sulfosuccinic acid, glutaric acid, adipic acid, sebacic acid, etc.) and diols (e.g. polyethylene glycols, for example with molecular weights of 200 to 35,000 g / mol); Cellulose ether / ester, e.g. B.
• dicarboxylic acids e.g. terephthalic acid, isophthalic acid, phthalic acid, sulfoisophthalic acid, oxalic acid, succinic acid, sulfosuccinic acid, glutaric acid, adipic acid, sebacic acid, etc.
• diols e.g. polyethylene glyco
• Embodiments of the water-soluble films which are particularly preferred according to the invention also take into account the fact that the active substances and / or active substance preparations contained in the receiving troughs are particularly advantageous, if not mandatory, by virtue of a - preferably controllable - water solubility of the film material at a particular point in time of washing, cleaning or Rinsing process, for example when a certain temperature is reached, or when a certain pH value or a certain ionic strength of the washing liquor is reached, or also due to other controllable events or conditions, can be fed into the aqueous liquor.
• the method is characterized in that the thickness of the water-soluble film is between 1 ⁇ m and 1000 ⁇ m, preferably between 5 ⁇ m and 500 ⁇ m and in particular between 10 ⁇ m and 200 ⁇ m.
• Different film thicknesses with the aim of delayed release of active substances and / or active substance preparations can also advantageously be achieved, for example, by multiple sealing of one or more receiving chambers by means of one or more identical or different water-soluble films.
• the thickness of the water-soluble film in the sense of the present invention then results as the sum of the thicknesses of the water-soluble individual films which are sealed one above the other and lie on top of one another.
• a release process can capture the film as a whole or only a part of it, so that parts of the film come loose when a certain parameter combination is set, while other parts do not come off (but only later) or not at all.
• the latter can be achieved through different quality of the material as well as through different amounts of material (thickness) or different geometries of the water-insoluble container.
• the external shape of the water-insoluble container makes it difficult to access water and thus delay the dissolving process.
• the foils of different thicknesses (nevertheless from the same material) and thus to enable them to be removed earlier at the thinner points.
• the films can be produced from materials of different water solubility, for example from polyvinyl alcohols (PVAL) with different residual acetate content.
• the water-soluble and / or water-dispersible film may contain, in addition to the ingredients mentioned, one or more washing and cleaning-active substances or consist of these substances (for example: polyvinyl alcohols as film material and builder).
• these substances for example: polyvinyl alcohols as film material and builder.
• wash-active, cleaning-active or rinse-active substances which are only present in small amounts in the preparations and whose uniform incorporation is therefore not unproblematic, can be incorporated into the film or a part of the film, for example one that is in the stage of Washing, cleaning or rinsing steps in which the active substance is needed can be incorporated, so that when the film is dissolved it is released into the liquor at the right time.
• An example of this may be fragrances which are desired in the last phase of the washing or cleaning or rinsing process, but also optical brighteners, UV protection substances, dyes and other washing-active, cleaning-active or rinsing-active preparations.
• agents according to the invention which is likewise preferred in the context of the present application, is the time-controlled release of one or more of the active substances (s) and / or active substance preparation (s) contained in these agents by incorporating matrix or coating materials of different solubility or melting temperature.
• meltable or softenable substances as matrix or coating material for the active substances or active substance preparations is particularly preferred.
• coating includes, in addition to the coating of one or more sides or surfaces of an object such as, for example, a solid particulate agent, also the complete coating, that is to say the encapsulation of this particulate object.
• the sealing of a receptacle by a fusible substance pouring such a substance onto a particulate or gel-like active substance / active substance preparation is referred to as a coating.
• active substances or “active substance preparations” includes both the zinc salts / layered silicates which are characteristic of the agents according to the invention and also all other optional included Ingredients.
• Preferred meltable substances according to the invention have a melting point above 30 C C. If active substance preparations are to be released at different times, for example during the different rinsing stages of a cleaning process, this can be done, for example, by using one or different fusible matrices or coatings. If two or more different meltable matrices are used, the melting points are preferably adapted to the temperature profile of this cleaning process, the difference between the melting points being sufficient to ensure the separate dissolution of the individual matrices or coatings.
• Such substances are preferred for the different matrices and / or coatings which differ in terms of their melting point by at least 5 ° C., preferably by 10 ° C., particularly preferably by 15 ° C. and in particular by at least 20 ° C., it also being preferred is that the melting point of at least one of the fusible substances which form a matrix or a coating is below 30 ° C, while the melting point of at least one further substance which form a further matrix or coating is above 30 ° C.
• this mass which can be softened under the influence of temperature can be made up by mixing the desired further ingredients with this meltable or softenable substance and heating the mixture to temperatures in the softening range of this substance and is shaped at these temperatures.
• the softenable substances are used as coating agents, such a coating can be carried out, for example, by dipping, spraying or circulating in a drum coater or coating pan. Waxes, paraffins, polyalkylene glycols etc. are particularly preferably used as meltable or softenable substances for the matrices or the coatings.
• meltable or softenable substances do not have a sharply defined melting point, as is usually the case with pure, crystalline substances, but instead have a melting range that may include several degrees Celsius.
• the meltable or softenable substances preferably have a melting range which is between approximately 35 ° C. and approximately 75 ° C. In the present case, this means that the melting range occurs within the specified temperature interval and does not indicate the width of the melting range.
• the width of the melting range is preferably at least 1 ° C., preferably about 2 to about 3 ° C.
• Another preferred possibility for the delayed release of active substances or active substance preparations is the staggered spatial arrangement of these substances in the receiving chamber of a preferably water-soluble packaging or within a casting or pressing body (onion model) with the aim of a staggered release.
• a spatially staggered arrangement is, for example, the layer or phase arrangement of the active substances or active substance preparations, for which layer-by-layer tabletting or layer-by-layer pouring of liquid active substances or active substance mixtures and their subsequent solidification by solidification and / or crystallization are suitable. Since access to the solvent in the case of pressed or cast molded articles can only take place over their surface, this layered arrangement leads to the release of those active substances or active substance mixtures which are on the surface of such a multi-phase mixture. The phases are consequently removed in time, the ingredients of which are released in time.
• a program for the automatic cleaning of crockery generally comprises various cleaning cycles, the type and number of these cleaning cycles being able to be determined by the consumer by means of a program selection. Examples of such cleaning cycles are the pre-rinse cycle, intermediate and main rinse cycles or the rinse cycle. All of these different cleaning cycles require an optimal result of the targeted dosing of appropriate active substances or active substance mixtures.
• Solid forms of supply of the automatic dishwashing agents or automatic dishwashing aids according to the invention are, for example, fine to coarse-grained powders, as are obtained, for example, by spray drying or granulation, compacted mixtures of substances from roller compaction, but also solidified melts or moldings obtained by extrusion or tableting.
• such shaped bodies can have practically all expediently manageable configurations, for example in the form of a table, in the form of bars or bars, a cube, a cuboid and the like Have space element with flat side surfaces and in particular cylindrical configurations with a circular or oval cross section.
• This last embodiment encompasses the form of presentation from the actual tablet to compact cylinder pieces with a ratio of height to diameter above 1.
• Preferred tableted or extruded agents have two or more phases in the context of the present invention, which can be determined, for example, by their composition Share in the total volume of the molded body and / or their visual appearance.
• the phases of such multiphase molded articles can additionally be distinguished by a different dissolution behavior in the aqueous phase.
• Shaped bodies of this type are suitable for the time-controlled release of certain ingredients (controlled release), for example in certain rinse cycles of the automatic washing program.
• one of the phases of the molded body has meltable or softenable substances from the group of waxes, paraffins and / or polyalkylene glycols as the main constituent.
• the molded body or molded body component containing these meltable or softenable substances is at least largely water-insoluble.
• the solubility in water should not exceed about 10 mg / l at a temperature of about 30 ° C. and should preferably be below 5 mg / l.
• the meltable or softenable substances should have the lowest possible solubility in water, even in water at an elevated temperature, in order to largely avoid a temperature-independent release of the active substances.
• the active substance is released in this way when the melting or softening point is reached.
• Another preferred procedure for obtaining a controlled release of ingredients, in particular the combination of zinc salt and layered silicate, from multiphase tablets is to compact the two or more individual phases with different pressures. Since the disintegration and dissolving properties of tablets or tablet phases are known to depend, inter alia, on the compacting pressure exerted on the tablet phase during tableting, tablet phases with different disintegrating and dissolving properties can be produced solely by using different compacting pressures.
• the combination of zinc salt and layered silicate according to the invention are together in the phase which was exposed to the comparatively higher tableting pressure and therefore disintegrates later.
• it is also preferred to assemble zinc salt and layered silicate in different tablet phases the zinc salt in one advantageous embodiment being in the comparatively highly compacted tablet phase, while in another preferred embodiment it is in the comparatively less compacted tablet phase.
• machine dishwashing aids are those which are metered in in addition to a commercially available cleaning agent, for example in the form of a special glass protective agent. Such a dosage can take place both before the start of each washing program and in the form of a depot product which brings about a continuous release of the agent according to the invention.
• Preferred solid agents according to the invention are in the form of a metering unit sufficient for a cleaning cycle.
• Dishwasher (auxiliary) medium tablets are an example of such types of confection.
• the agents according to the invention are in solid particulate form, but not in the form of divided dosage units, the problem of separation of individual components arises for these agents, wherein it is particularly important to avoid separation of the zinc salts and silicates contained in the agents according to the invention.
• Examples of such particulate forms of supply are powders or granules.
• Preferred solid forms of supply of the automatic dishwashing agent according to the invention contain, for example, fine to coarse-grained powders, such as are obtained, for example, by spray drying or granulation.
• powders can be marketed as a commercial product or used as a premix for compacting, for example for tableting, and generally have a particle size in the range from 0.1 to 10 mm.
• it is preferred that these compounds have a particle size comparable to that of the powders.
• a preferred subject of the present application is therefore a machine dishwashing detergent, characterized in that the particle size of the zinc salts and / or crystalline layered silicates made up of one or more active and / or builders is 0.1 and 10 mm, preferably 0.2 and 8 mm and in particular 0.5 and 5 mm, preferred particulate compounds to avoid segregation processes additionally having a density of 0.1 to 2.0 g / cm 3 , preferably 0.2 to 1.6 g / cm 3 and in particular have from 0.4 to 1.2 g / cm 3 .
• Automatic dishwashing agents preferred according to the invention are characterized in particular in that the particles of the zinc salts and / or crystalline layered silicates made up with one or more active and / or framework substances have a weight fraction of the zinc salts or crystalline layered silicates of 0.1 to 80% by weight, particularly preferably from 0.2 to 70% by weight and particularly preferably from 0.5 to 60% by weight, in each case based on the total weight of the particles.
• the aforementioned particulate compounds are preferably obtained by spray drying and / or granulation and / or extrusion and / or roller compaction and / or tableting and / or solidification and / or crystallization, but in particular by spray drying and / or granulation.
• an aqueous slurry (“slurry”) which, in addition to the zinc salts according to the invention, can contain further thermally stable active and / or framework substances which do not volatilize or decompose under the spray drying conditions and these then pumped into the spray tower and sprayed through nozzles located in the top of the tower. Rising hot air dries the slurry and evaporates the adhering water so that the detergent components are obtained as fine powders at the outlet of the tower. These can be further tempered if necessary - Unstable components, such as bleach or fragrances, are added.
• compositions according to the invention can also be packaged using a granulation process, a fluidized bed process being particularly preferred in which fine-grained bulk material is stored on horizontal, perforated floors and may contain further active and / or framework substances in addition to the zinc salts according to the invention.
• gases e.g. hot air
• a state arises that resembles that of a boiling liquid; the layer creates bubbles and the particles of the bulk material are in a constant, swirling up and down movement within the layer and thus remain in a state of suspension.
• the large surface of the fluidized material then enables, for example, the reaction with other substances such as solvents, solutions of active and / or framework substances, liquid active substances or other ingredients which are present as a solid at room temperature by increasing the temperature and / or adding very limited amounts of liquid
• additives soften at least superficially and / or develop an adhesive and adhesive strength under the influence of temperature.
• Typical examples of the abovementioned substances are water and aqueous solutions, it also being possible, for example, to use aqueous solutions of the zinc salts according to the invention, surfactant compounds which are liquid or solid at room temperature, in particular nonionic surfactants, or else polymer compounds of synthetic and / or natural origin, for example (co) polymeric carboxylates ,
• Another preferred procedure for the granulation is the use of mixers / compressors, as they are provided for this purpose in addition to other providers, for example also by the company Lödige, and which are particularly suitable for the production of particles made up according to the invention because they are produced by the user Variation of various process parameters such as the number of revolutions of the mixer, the dwell time of the individual components, the dosing time of individual components during the mixing process, the geometry of the mixing elements used or the energy input offer the possibility of targeted control of the product properties of the granules obtained.
• the grain size and / or density of granules can also be influenced in a targeted manner in this way, and the preparation of zinc salts according to the invention with one or more further active and / or framework substance (s) in the aforementioned mixers / compressors is therefore within the scope of the present invention particularly preferred.
• mixtures of silicates and / or zinc salts with further active and / or framework substances characterized in that the bulk densities of the individual components mixed with one another are not more than 200 g / l, preferably not more than 150 g / l, preferably differ by a maximum of 100 g / l and in particular by a maximum of 50 g / l.
• the framework and / or active substances which can be used in the above-described packaging of preferred automatic dishwashing detergents according to the invention include, in addition to other customary constituents of cleaning agents, for example builders (builders, cobuilders), surfactants, bleaching agents, bleach activators, enzymes, dyes, fragrances, corrosion inhibitors or polymers.
• builders builders, cobuilders
• surfactants for example surfactants, bleaching agents, bleach activators, enzymes, dyes, fragrances, corrosion inhibitors or polymers.
• machine dishwashing agents or machine dishwashing aids are particularly preferred in the context of the present invention in which those are packaged with one or more active and / or builders substances
• Zinc salt compounds, active and / or builder substances from the group of the phosphates, carbonates, hydrogen carbonates, sulfates, silicates, citrates, citric acid, acetates, preferably in amounts of 20 to 99% by weight, particularly preferably 30 to 98% by weight and particularly preferably from 40 to 95% by weight, based in each case on the total weight of the particles.
• Further active and / or builder substances which are particularly preferred for the preparation of the zinc salts in the context of the present invention are the surfactants, preferably the nonionic surfactants, and / or the polymeric carboxylates, in particular the polysulfocarboxylates.
• silicates contained in the automatic dishwashing agents or machine dishwashing aids according to the invention are also preferably present in these agents with other active or framework substances, active or framework substances from the group of organic mono- or polycarboxylic acids, hydroxypolycarboxylic acids and phosphonic acids being used here in particular.
• Another preferred subject of the present application are therefore machine dishwashing detergents or machine dishwashing aids, characterized in that the crystalline layered silicate (s) of the general formula (I) or of the general formula (Ia) have a or several other active and / or framework substances, preferably with one or more further active and / or framework substances from the group of organic mono- or polycarboxylic acids, hydroxypolycarboxylic acids and phosphonic acids, in particulate form, as a compound / available.
• the particulate zinc salts and / or crystalline layered silicates prepared with one or more active and / or framework substances can be provided with a coating (coating) to protect environmental influences and thus to improve their storage stability or to influence the dissolution behavior. Coating materials and methods for coating particulate agents are widely described in the literature and are only to be explained below with respect to particularly preferred embodiments.
• meltable or softenable substances as coating material is particularly preferred.
• coating means, in addition to the coating of one or more sides or surfaces of a particulate agent which is made up according to the invention, also a complete coating, that is to say the encapsulation of this particulate object.
• Meltable substances preferred according to the invention have a melting point above this 30 ° C.
• the compounded zinc salts and / or crystalline layered silicates are to be released at different times, for example during the different rinsing stages of a cleaning process, this can be done, for example, by using different meltable coatings which differ in terms of their melting point, the melting points of these substances preferably being based on the Temperature course of this cleaning process are adjusted and the difference in melting points is sufficient to ensure the separate dissolution of the individual matrices or coatings. If, for example, it is intended to release zinc salts and crystalline layered silicates at different times, then those substances are preferred for the different coatings which have a melting point of at least 5 ° C., preferably 10 ° C., particularly preferably 15 ° C.
• the melting point of at least one of the fusible substances which form a coating is below 30 ° C, while the melting point of at least one further substance which form a further matrix or coating is above 30 ° C lies.
• Such coatings can be applied, for example, by dipping, spraying or circulating in a drum coater or coating pan.
• Waxes, paraffins, polyalkylene glycols, etc. are particularly preferably used as meltable or softenable substances for the coatings.
• meltable or softenable substances do not have a sharply defined melting point, as is usually the case with pure, crystalline substances, but instead have a melting range that may include several degrees Celsius.
• the meltable or softenable substances preferably have a melting range which is between approximately 45 ° C. and approximately 75 ° C. In the present case, this means that the melting range occurs within the specified temperature interval and does not indicate the width of the melting range.
• the width of the melting range is preferably at least 1 ° C., preferably about 2 to about 3 ° C.
• waxes are understood to mean a number of natural or artificially obtained substances which generally melt above 40 ° C. without decomposition and which are relatively low-viscosity and not stringy even a little above the melting point. They have a strongly temperature-dependent consistency and solubility.
• the waxes are divided into three groups according to their origin, natural waxes, chemically modified waxes and synthetic waxes.
• Natural waxes include, for example, vegetable waxes such as candelilla wax, carnauba wax, japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, or montan wax, animal waxes such as beeswax, shellac wax, walnut, lanolin (wool wax), or broom wax, mineral wax or ozokerite (earth wax), or petrochemical waxes such as petrolatum, paraffin waxes or micro waxes.
• vegetable waxes such as candelilla wax, carnauba wax, japan wax, esparto grass wax, cork wax, guaruma wax, rice germ oil wax, sugar cane wax, ouricury wax, or montan wax
• animal waxes such as beeswax, shellac wax, walnut, lanolin (wool wax), or broom wax, mineral wax or ozokerite (earth wax), or
• the chemically modified waxes include hard waxes such as montan ester waxes, Sassol waxes or hydrogenated jojoba waxes.
• Synthetic waxes are generally understood to mean polyalkylene waxes or polyalkylene glycol waxes. Compounds from other classes of material which meet the stated softening point requirements can also be used as meltable or softenable substances for the masses hardening by cooling. As suitable synthetic compounds have, for example, higher esters of phthalic acid, in particular dicyclohexyl, which is commercially available under the name Unimoll 66 ® (Bayer AG), proved. Are also suitable Synthetic waxes of lower carboxylic acids and fatty alcohols, such as dimyristyl tartrate, sold under the name Cosmacol ® ETLP (Condea). Conversely, synthetic or partially synthetic esters from lower alcohols with fatty acids from native sources can also be used.
• Tegin ® 90 (Goldschmidt), a glycerol monostearate palmitate, falls into this class of substances.
• Shellac for example Shellac-KPS-Dreiring-SP (Kalkhoff GmbH), can also be used as meltable or softenable substances.
• Wax alcohols are high molecular weight, water-insoluble Fatty alcohols usually with about 22 to 40 carbon atoms.
• the wax alcohols occur, for example, in the form of wax esters of higher molecular fatty acids (wax acids) as the main component of many natural waxes.
• wax alcohols are lignoceryl alcohol (1-tetracosanol), cetyl alcohol, myristyl alcohol or melissyl alcohol.
• the enclosure of the assembled zinc salts or crystalline layered silicates can optionally also contain wool wax alcohols which are understood to be triterpenoid and steroid alcohols, for example lanolin, which is obtainable for example under the trade name Argowax ® (Pamentier & Co).
• wool wax alcohols which are understood to be triterpenoid and steroid alcohols, for example lanolin, which is obtainable for example under the trade name Argowax ® (Pamentier & Co).
• Fatty acid glycerol esters or fatty acid alkanolamides but optionally also water-insoluble or only slightly water-soluble polyalkylene glycol compounds, can likewise be used at least in part as a constituent of the meltable or softenable substances.
• meltable or softenable substances are those from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG), polyethylene glycols with molecular weights between 1500 and 36,000 being preferred, those with molecular weights from 2000 to 6000 being particularly preferred and those with molecular weights of 3000 to 5000 are particularly preferred.
• PEG polyethylene glycols
• PPG polypropylene glycols
• plastically deformable mass (s) contain / contain at least one substance from the group of polyethylene glycols (PEG) and / or polypropylene glycols (PPG) are preferred.
• coating agents which contain propylene glycols (PPG) and / or polyethylene glycols (PEG) as the only meltable or softenable substances.
• PPG propylene glycols
• PEG polyethylene glycols
• Polypropylene glycols (abbreviation PPG) which can be used according to the invention are polymers of propylene glycol which have the following general formula
• n can take values between 10 and 2000.
• Preferred PPGs have molar masses between 1000 and 10,000, corresponding to values of n between 17 and approximately 170.
• Polyethylene glycols which can preferably be used according to the invention are polymers of ethylene glycol which have the general formula
• n can have values between 20 and approx. 1000.
• the preferred molecular weight ranges mentioned above correspond to preferred ranges of the value n in formula IV from approximately 30 to approximately 820 (exactly: from 34 to 818), particularly preferably from approximately 40 to approximately 150 (precisely: from 45 to 136) and in particular from about 70 to about 120 (exactly: from 68 to 113).
• the coating materials contain paraffin wax.
• Paraffin waxes have the advantage over the other natural waxes mentioned in the context of the present invention that there is no hydrolysis of the waxes in an alkaline detergent environment (as is to be expected, for example, from the wax esters), since paraffin wax contains no hydrolyzable groups.
• Paraffin waxes consist mainly of alkanes and low levels of iso- and cycloalkanes.
• the paraffin to be used according to the invention preferably has essentially no constituents with a melting point of more than 70 ° C., particularly preferably of more than 60 ° C. Portions of high-melting alkanes in the paraffin can leave undesired wax residues on the surfaces to be cleaned or the goods to be cleaned if the melting temperature in the detergent solution drops below this. Such wax residues usually lead to an unsightly appearance on the cleaned surface and should therefore be avoided.
• Preferred fusible or softenable substances contain at least one paraffin wax with a melting range from 50 ° C to 60 ° C
• preferred coating materials are characterized in that they contain a paraffin wax with a melting range from 50 ° C to 55 ° C.
• the paraffin wax content of alkanes, isoalkanes and cycloalkanes which are solid at ambient temperature is as high as possible.
• the more solid wax components present in a wax at room temperature the more useful it is within the scope of the present invention.
• the process end products' ability to withstand impacts or friction on other surfaces increases, which leads to longer-lasting protection.
• High levels of oils or liquid wax components can weaken the coating, opening pores and exposing the active ingredients to the environment.
• meltable or softenable substances can also contain one or more of the above-mentioned waxes or wax-like substances as the main constituent.
• the mixture forming the meltable or softenable substances should be such that the mass and the coating formed from it are at least largely water-insoluble.
• the solubility in water should not exceed about 10 mg / l at a temperature of about 30 ° C. and should preferably be below 5 mg / l.
• meltable or softenable substances should have the lowest possible solubility in water, even in water at an elevated temperature, in order to largely avoid a temperature-independent release of the active substances.
• Preferred coating materials to be processed according to the invention are characterized in that, as meltable or softenable substances, they contain one or more substances with a melting range of 40 ° C to 75 ° C in amounts of 6 to 30% by weight, preferably 7.5 to 25% Wt .-% and in particular from 10 to 20 wt .-%, each based on the weight of the coating material.
• the dissolving behavior of the zinc salt or silicate compounds can also be influenced by the above-mentioned compaction processes.
• the choice of the co-assembled active and / or framework substances is particularly important.
• Compact silicates, in particular disilicates, and / or polycarboxylates and / or mixtures of various polycarboxylates are particularly suitable because of their delayed dissolution / dispersion or due to the gelation of these substances or mixture of substances in aqueous liquor as "depot substances" for the zinc salts or crystalline layered form silicates.
• polymer matrices Another particularly preferred form of manufacturing machine dishwashing detergents or machine dishwashing aids according to the invention is polymer matrices.
• Polymer matrices of this type can be used universally in various program programs, are characterized by a simple and inexpensive production method and can contain varying amounts of active agent.
• preferred subject matter of the present application are machine dishwashing agents or machine dishwashing aids, in which the zinc salt (s) and / or the crystalline (s) layered silicate (s) are present in a polymer matrix.
• the active ingredient-containing polymer matrices can be manufactured cheaply and in a wide variety of shapes.
• the composition according to the invention can even be formulated as packaging for automatic dishwashing detergents or as a basket into which the detergents are introduced. It is also possible to combine the two types of introduction with one another, for example, in that a carrier basket made of water-insoluble, active substance-old polymer matrix contains a polymer body made of water-soluble, active substance-containing polymer matrix. Products of this type can release the active agents to different extents from the various matrices at different times, which leads to an optimal concentration of active substance at any time during the cleaning program.
• both the zinc salt and the silicate are present in a polymer matrix in preferred agents according to the invention, this assembly can take place in preferred embodiments of the present invention both in the same polymer matrix and in different matrices, which means that the zinc salt is present, for example, in polymer A is made up, while the silicate was made up in a polymer B.
• zinc salt and silicate can also be made up using the same polymer, but in separate matrices.
• the agents according to the invention can accordingly be implemented both with water-insoluble and with water-soluble polymers or mixtures thereof.
• Preferred machine dishwashing agents or machine dishwashing aids are characterized in that the polymer matrix comprises one or more water-soluble polymer (s).
• compositions according to the invention can be formulated universally. For example, it is possible to provide pre-soaking agents, pre-rinsing agents, cleaning agents for the main rinse cycle or rinse aid according to the invention.
• compositions according to the invention can also be combination products which combine two or more of the aforementioned agents.
• the formulation of compositions according to the invention as an addition product, which is, for example, suspended in the dishwasher, is also possible without problems.
• the active ingredient-containing polymer matrix can be incorporated into the compositions according to the invention in particulate form, but it can also be a compact shaped body, which is, for example, either a core which fills a depression in a detergent tablet, or a shaped body which, as an addition product, is like a deodorant hanger in the dishwasher is introduced. Baskets that are suitable for holding detergent tablets can also be made from the active ingredient-containing polymer matrix.
• the polymer matrix containing the active ingredient can also be used as packaging for automatic dishwashing detergents. This is particularly the case with completely water-soluble active substance-containing polymer matrices attractive because the consumer does not have to unpack the product, avoids direct contact with the product, which is perceived as undesirable, and also saves other packaging materials.
• Agents according to the invention are particularly preferably characterized in that the polymer matrix a) 5 to 99.5% by weight of one or more polymers, b) at least one zinc salt and at least one crystalline layered silicate of the general formula (Ia)
• M represents sodium or hydrogen
• x is a number from 1.9 to 22, preferably from 1.9 to 4 and y is a number from 0 to 33
• the sum of the parts by weight of the zinc salt (s) (see ) and the crystalline silicate (s) is 0.5 to 95% by weight
• the polymer matrix of the agents preferred according to the invention comprises 5 to 99.5% by weight of one or more polymers.
• polymers based on the IUPAC definition, denotes substances which are made up of a collective of chemically uniformly structured macromolecules which, as a rule, are composed with respect to the degree of polymerization, molar mass and chain length of the term not taking into account the IUPAC definition is a polymer "a substance which is composed of a large number of molecules in which one type or more types of atoms or atom groups (so-called constitutive units, basic building blocks or repeating units) are repeatedly strung together" ,
• the different sized macromolecules of a polymer are made up of so many identical or similar low molecular weight building blocks (monomers) that the physical properties of the substance, especially the viscoelasticity, do not change noticeably with a slight increase or decrease in the number of building blocks.
• the size of the macromolecules means that the end groups have relatively little effect on the properties of the
• the polymers forming the matrix of the compositions according to the invention can be of both natural and synthetic origin.
• Preferred agents according to the invention are characterized in that the polymer matrix is 7.5 to 95% by weight, preferably 10 to 90% by weight, particularly preferably 12.5 to 85% by weight, more preferably 15 to 82.5% by weight and in particular comprises 20 to 80% by weight of one or more polymers, the weight data relating to the active substance-containing polymer matrix.
• the average molar mass of the polymers contained in the preferred agents according to the invention is preferably at least 5000 g / mol, particularly preferably at least 10,000 g / mol and in particular at least 12,000 g / mol.
• the agents preferred according to the invention can contain both water-insoluble and water-soluble polymers and mixtures of these polymers.
• Preferred compositions according to the invention based on water-insoluble polymer matrices are characterized in that the polymer matrix comprises one or more water-insoluble polymers from the group consisting of polyethylene, polypropylene, polytetrafluoroethylene, polystyrene, polyethylene terephthalate, polycarbonate, polyvinyl chloride, the polyurethanes, the polyamides and mixtures thereof.
• water-soluble polymers of natural or synthetic origin can also form the polymer matrix.
• the polymer matrix comprises one or more water-soluble polymers, the water-soluble polymer (s) preferably being selected from:
• Copolymers and their salts xv) Copolymers of xv-i) unsaturated carboxylic acids and their salts xv-ii) cationically derivatized unsaturated carboxylic acids and their salts xvi) acrylamidoalkyltrialkylammonium chloride / acrylic acid copolymers and their alkali and ammonium salts xvii) acrylamidoalkylt alkylammonium chloride / methacrylic their
• Copolymers obtained in groups: xxiii-i) esters of unsaturated alcohols and short-chain saturated carboxylic acids and / or esters of short-chain saturated alcohols and unsaturated carboxylic acids, xxiii-i) unsaturated carboxylic acids, xxiii-iii) esters of long-chain carboxylic acids and unsaturated alcohols and / or esters from the carboxylic acids the group d6ii) with saturated or unsaturated, straight-chain or branched C 8 - ⁇ B alcohol.
• the active substance-containing polymer matrix contains at least one zinc salt and / or at least one crystalline layered silicate of the general formula (I) or the general formula (Ia), which can be released from the matrix.
• Agents preferred according to the invention are characterized in that they contain at least one zinc salt and at least one crystalline layered silicate of the general formula (I) or of the general formula (Ia), the sum of the parts by weight of these constituents preferably being 1 to 90% by weight 1.5 to 80% by weight, particularly preferably 2nd to 70% by weight, more preferably 2.5 to 60% by weight and in particular 3 to 50% by weight, in each case based on the total weight of the polymer matrix containing the active ingredient.
• the automatic dishwashing agents or automatic dishwashing aids according to the invention can contain the active ingredient-containing polymer matrix in different amounts. Depending on whether the active ingredient-containing polymer matrix is contained in the compositions, for example as a finely divided powder or granulate, as part of a shaped body, or whether it encloses the composition as packaging, the proportions of the active ingredient-containing polymer matrix in the overall composition can vary. Compositions according to the invention are preferred here which, based on the total mass of the composition, 1 to 40% by weight, preferably 1.5 to 35% by weight, particularly preferably 2 to 30% by weight and in particular 2.5 to 20% % By weight of the active ingredient-containing polymer matrix.
• Particularly preferred polymer matrices contain at least one zinc salt in amounts such that the composition zinc in oxidized form in parts by weight of from 0.01 to 1% by weight, preferably from 0.02 to 0.5% by weight and in particular from 0.04 up to 0.2 wt .-%, based in each case on the total weight of the polymer matrix.
• compositions according to the invention does not impose any restriction on the forms of supply or the formulations of these compositions.
• pre-rinse or pre-rinse products, rinse aids, machine cleaners or additional products can also be provided as the composition according to the invention.
• a preferred embodiment of the composition according to the invention provides that the polymer matrix is provided as a molded part to be introduced separately into the dishwasher, which releases the agents from the polymer matrix over several rinse cycles. This molded part can either be a dosing basket for other products, such as the cleaner, but it can also embody the additional benefit of protecting the glass as a separate and independent molded part.
• Possible shapes are based, for example, on the known dishwasher dodorants.
• the design of the plastic part in a translucent, opalescent or completely clear form, for example in the form of a stylized diamond, is visually appealing.
• Such product designs make it possible to visualize the gloss resulting from the gentle use of glass in a consumer-friendly manner.
• the active ingredient-containing polymer matrices can easily be reshaped using standard methods.
• the shaping processing is carried out according to the methods customary in the plastics processing industry, with film production and further processing, blow molding and injection molding being preferred in particular. All processes have in common that a plastic granulate is melted with the help of an extruder and fed to shaping tools.
• the plastic granules can already contain the agents for glass corrosion inhibition, but these can also be added during the melting in the extruder, which enables particularly cost-effective production of the active ingredient-containing polymer matrices preferred according to the invention.
• the automatic dishwashing agents or automatic dishwashing aids according to the invention are made up in a manner which enables the active substances contained in these agents to be applied and metered in a targeted manner.
• the form of a pencil is suitable, which, similar to a glue stick, does not change its spatial-geometric shape during storage and transport, but this does, if the shape of the offer is moved over a surface under the action of pressure, in its contact area with the surface due to the shear forces occurring there.
• the agent is smeared as a result of the shear forces acting on the surface and remains there in its new spatial-geometric shape after the action of the shear forces has ended, and is therefore again dimensionally stable.
• agents according to the invention can be applied and metered in a targeted manner.
• Such dimensionally stable machine dishwashing agents or machine dishwashing aids which due to their material properties can be spread on a surface under the action of a shear force, but remain in their spatial shape without the action of a shear force, can advantageously be characterized by their penetration numbers.
• the penetration number is the numerical value which results when the hardness of the agents according to the invention is determined by means of a texture analyzer, model TA-XT2-I from Stable Micro Systems. The following test parameters are set to carry out this measurement:
• PPS 200 The penetration number is determined by pressing a specific measuring tool (TA-15 45 ° cone made of stainless steel) into the test material with a defined feed rate (0.5 mm / s) to a defined depth of penetration (5.0 mm) and then with a defined speed (0.2 mm / s) is pulled out of this material.
• the test materials examined had a temperature of 23 ° C, the measurements were carried out at 20 ° C room temperature. Based on the experimental setup described, the measuring device determined a numerical value in the unit gram [gj. In the context of the present application, this numerical value is referred to as the penetration number.
• the preferred dimensionally stable machine dishwashing agents or machine dishwashing aids have penetration numbers from 200 to 1000 g, preferably from 250 to 900 g, particularly preferably from 300 to 800 g and in particular from 350 to 700 g.
• Another preferred object of the present invention are therefore automatic dishwashing agents or automatic dishwashing aids according to the invention which are dimensionally stable and have a penetration number of 200 to 1000 g, preferably 250 to 900 g, particularly preferably 300 to 800 g and in particular 350 to 700 g.
• the term “dimensionally stable” denotes machine dishwashing detergents or machine dishwashing auxiliaries which have an inherent dimensional stability which enables them, under customary conditions of manufacture, storage, transport and handling by the consumer, to be stable against breakage, not to have a disintegrating spatial shape that does not change over a long period of time even under the conditions mentioned, that is to say, under the usual conditions of manufacture, storage, transport and handling by the consumer, in the spatial-geometric shape resulting from the manufacture , that is, for example, does not melt away.
• the penetration number of 200 to 1000 g which is characteristic of preferred agents according to the invention, cannot be achieved in their pure form by active substances such as zinc salts or layered silicates. It is therefore necessary to provide a carrier material or matrix material for these active substances that meets the physical requirements mentioned for an agent according to the invention.
• a carrier material or matrix material for these active substances that meets the physical requirements mentioned for an agent according to the invention.
• Such a matrix should also be compatible with the active agents contained in it, that is to say in particular do not react with them but stabilize them.
• the carrier materials should also not call into question the desired cleaning process, that is to say they should also be compatible with all other substances used during the cleaning and / or care process.
• the matrix material should preferably be water-soluble or water-dispersible in order to prevent residues from occurring to avoid after using the agent according to the invention.
• carrier materials which, in addition to the function as a matrix for the active substance, also have a cleaning or care function. From the large number of possible carrier materials, a number of groups of substances have proven to be particularly advantageous in the context of the present invention. These substances will be discussed in more detail below.
• preferably dimensionally stable machine dishwashing agents or machine dishwashing aids are therefore characterized in that they contain polyvinylpyrrolidone (s) and / or polyvinyl alcohol (s) and / or polyvinyl acetate (s) and / or polyacrylate (s) and / or Polyalkylene glycol (s) and / or fat (s) and / or fatty acid (s) and / or fatty acid esters and / or fatty acid amide (s) and / or fatty alcohols and / or wax (s) and / or paraffin (s) and / or Contain wax alcohols and / or surfactant (s), preferably non-ionic surfactant (s), and / or dextrin (s) and / or starch ether, the weight fraction of this component / these components in the total weight of the dimensionally stable machine dishwashing and / or Dishwashing aid is preferably between 30 and
• Machine dishwashing agents or machine dishwashing aids according to the invention can, in addition to the solid or dimensionally stable forms described, also be made up in the form of liquid or flowable agents.
• the automatic dishwashing agents or automatic dishwashing aids therefore have a viscosity of 500 to 500,000 mPas, preferably 900 to 200,000 mPas and in particular 1300 to 100,000 mPas.
• the viscosity of the agents according to the invention is measured using customary standard methods (for example Brookfield viscometer LVT-II at 20 rpm and 20 ° C., spindle 3).
• the expression "liquid or flowable agents” is used below for agents which have a viscosity of 500 to 500,000 mPas, preferably from 900 to 200,000 mPas and in particular from 1300 to 100,000 mPas.
• such preferred liquid or flowable agents according to the invention contain one or more non-aqueous solvents.
• non-aqueous solvents come, for example, from the groups of the mono-alcohols, diols, triols or polyols, the ethers, esters and / or amides.
• Non-aqueous solvents which are water-soluble are particularly preferred, "water-soluble" solvents for the purposes of the present application being solvents which are completely miscible with water at room temperature, ie without a miscibility gap.
• Suitable non-aqueous solvents preferably come from the group of mono- or polyhydric alcohols, alkanolamines or glycol ethers, provided that they are miscible with water in the concentration range indicated.
• the solvents are preferably selected from ethanol, n- or i-propanol, butanols, glycol, propane or butanediol, glycerol, diglycol, propyl or butyl diglycol, hexylene glycol, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol propyl ether, ethylene glycol mono-n-butyl ether,
• Diethylene glycol methyl ether diethylene glycol ethyl ether, propylene glycol methyl, ethyl or propyl ether, dipropylene glycol methyl or ethyl ether, methoxy, ethoxy or butoxytriglycol, 1-butoxyethoxy-2-propanol, 3-methyl-3-methoxybutanol, propylene glycol t-butyl ether and mixtures of these solvents.
• Nonionic surfactants which are liquid at room temperature are also preferred nonaqueous solvents in the context of the application.
• a particularly preferred liquid or flowable machine dishwashing agent or machine dishwashing aid in the context of the present invention is characterized in that it contains non-aqueous solvent (s), the solvent (s) preferably being selected from the group of polyethylene glycols and polypropylene glycols, glycerol, glycerol carbonate , Triacetin, ethylene glycol, propylene glycol, propylene carbonate, hexylene glycol, ethanol and n-propanol and / or iso-propanol.
• solvent (s) preferably being selected from the group of polyethylene glycols and polypropylene glycols, glycerol, glycerol carbonate , Triacetin, ethylene glycol, propylene glycol, propylene carbonate, hexylene glycol, ethanol and n-propanol and / or iso-propanol.
• PEG Polyethylene glycols
• II Polyethylene glycols
• n can have values between 1 (ethylene glycol, see below) and approx. 16.
• polyethylene glycols that can lead to confusion.
• the specification of the average relative molecular weight following the specification "PEG” is customary in technical terms, so that "PEG 200” characterizes a polyethylene glycol with a relative molecular weight of approximately 190 to approximately 210. According to this nomenclature, the technically customary polyethylene glycols PEG 200, PEG 300, PEG 400 and PEG 600 can be used in the context of the present invention.
• polyethylene glycols are, for example, under the trade name Carbowax ® PEG 200 (Union Carbide), Emkapol ® 200 (ICI Americas), Lipoxol ® 200 MED (Huls America), polyglycol ® E-200 (Dow Chemical), Alkapol ® PEG 300 (Rhone -Poulenc), Lutrol ® E300 (BASF) and the corresponding trade names with higher numbers.
• Polypropylene glycols which can be used according to the invention are polymers of propylene glycol which have the general formula (IM)
• n values can be between 1 (propylene glycol, see below) and approx. 12.
• n values can be between 1 (propylene glycol, see below) and approx. 12.
• Glycerin is a colorless, clear, difficult to move, odorless, sweet-tasting hygroscopic liquid with a density of 1, 261 that solidifies at 18.2 ° C. Glycerin was originally only a by-product of fat saponification, but is now technically synthesized in large quantities. Most technical processes are based on propene, which is processed into glycerol via the intermediate stages allyl chloride, epichlorohydrin. Another technical process is the hydroxylation of allyl alcohol with hydrogen peroxide at the W0 3 contact via the glycide stage.
• Glycerol carbonate can be obtained by transesterification of ethylene carbonate or dimethyl carbonate with glycerin, ethylene glycol or methanol being obtained as by-products. Another synthetic route starts from glycidol (2,3-epoxy-1-propanol), which is reacted under pressure in the presence of catalysts with CO 2 to give glycerol carbonate. Glycerol carbonate is a clear, easily movable liquid with a density of 1, 398 "3 , which boils at 125-130 ° C (0.15 mbar).
• Ethylene glycol (1,2-ethanediol, "glycol") is a colorless, viscous, sweet-tasting, strongly hygroscopic liquid that is miscible with water, alcohols and acetone and has a density of 1.113.
• the solidification point of ethylene glycol is around -11.5 ° C, the liquid boils at 198 ° C.
• ethylene glycol is obtained from ethylene oxide by heating with water under pressure. Promising manufacturing processes can also be based on the acetoxylation of ethylene and subsequent hydrolysis or on synthesis gas reactions.
• 1,3-propanediol trimethylene glycol
• 1,3-propanediol can be prepared from acrolein and water with subsequent catalytic hydrogenation.
• 2-propanediol (propylene glycol), which is an oily, colorless, almost odorless liquid, density 1, 0381, which solidifies at -60 ° C and boils at 188 ° C.
• 2-propanediol is made from propylene oxide by adding water.
• Propylene carbonate is a water-bright, easy-to-move liquid, with a density of 1, 21 like "3 , the melting point is -49 ° C, the boiling point is 242 ° C. Propylene carbonate is also commercially available through the reaction of propylene oxide and C0 2 at 200 ° C and 80 bar accessible.
• the non-aqueous solvent (s) is / are present in amounts of 0.1 to 70% by weight, preferably 0.5 to 60% by weight, particularly preferably of 1 to 50 wt .-%, very particularly preferably from 2 to 40 wt .-% and in particular from 2.5 to 30 wt .-%, each based on the total agent.
• non-aqueous is understood to mean a state in which the free water content in the compositions is clearly below 5% by weight, based on the composition. It is preferred that the amount of free, i.e.. water not present in the form of water of hydration and / or constitutional water is below 10% by weight, preferably below 8% by weight and in particular even below 6% by weight, in each case based on the composition. Accordingly, water can essentially only be introduced into the agent in chemically and / or physically bound form or as a constituent of the raw materials or compounds present as a solid, but not as a liquid, solution or dispersion.
• preferred liquid or flowable machine dishwashing detergents or machine dishwashing aids contain one or more nonionic surfactants, in short nonionic surfactants.
• the amounts in which the nonionic surfactants are used are, according to the invention, preferably between 5 and 30% by weight, with agents according to the invention which are particularly preferred being 1 to 25% by weight, preferably contain 2 to 22.5% by weight, particularly preferably 3 to 20% by weight and in particular 4 to 17.5% by weight of nonionic surfactant (s).
• the agents according to the invention can contain further ingredients, with the use of which, for example, the settling behavior or the pourability or flowability can be specifically controlled.
• the settling behavior or the pourability or flowability can be specifically controlled.
• combinations of structuring agents and thickeners have proven particularly useful.
• Machine dishwashing detergents preferred in the context of the present invention further comprise a) 0.1 to 1.0% by weight of one or more structurants from the group of the bentonites and / or at least partially etherified sorbitols, and b) 5.0 to 30% by weight % of one or more thickeners from the group of carbonates, sulfates and amorphous or crystalline disilicates.
• the structuring agent a) comes from the group of bentonites and / or at least partially etherified sorbitols. These substances are used to ensure the physical stability of the agents and to adjust the viscosity. Although conventional thickeners such as polyacrylates or polyurethanes fail in non-aqueous media, the viscosity can be controlled with the substances mentioned in the non-aqueous system.
• Bentonites are contaminated clays that are formed by weathering volcanic tuffs. Due to their high montmorillonite content, bentonites have valuable properties such as swellability, ion exchange capacity and thixotropy. It is possible to modify the properties of the bentonites according to the intended use. Bentonites are common as a clay component in tropical soils and are used as sodium bentonite e.g. mined in Wyoming / USA. Sodium bentonite has the most favorable application properties (swellability), so that its use is preferred in the context of the present invention. Naturally occurring calcium bentonites originate, for example, from Mississippi / USA or Texas / USA or from Landshut / D. The naturally obtained Ca bentonites are artificially converted into the more swellable Na bentonites by exchanging Ca for Na.
• montmorillonites The main constituents of bentonites are so-called montmorillonites, which can also be used in pure form in the context of the present invention.
• Montmorillonite are too phyllosilicates and clay minerals belonging to the dioctahedral smectites, which crystallize monoclinic-pseudohexagonal. Montmorillonites predominantly form white, gray-white to yellowish, completely amorphous appearing, easily friable, swelling in the water, but not becoming plastic, by the general formulas
• AI 2 [(OH) 2 / Si 4 O 10 ] nH 2 O or AI 2 0 3 -4Si0 2 ⁇ 2 O nH 2 0 or AI 2 [(OH) 2 / Si 4 O 10 ] (at 150 ° dried)
• Preferred machine dishwashing detergents or machine dishwashing aids are characterized in that montmorillonites are used as structure donors.
• Montmorillonites have a three-layer structure that consists of two tetrahedral layers that are electrostatically cross-linked via the cations of an intermediate octahedral layer. The layers are not rigidly connected, but can swell by reversible incorporation of water (in 2-7 times the amount) and other substances such as alcohols, glycols, pyridine, D-picoline, ammonium compounds, hydroxy-aluminosilicate ions, etc.
• the above. Formulas are only approximate formulas since montmorillonites have a large ion exchange capacity.
• AI can be exchanged for Mg, Fe 2+ , Fe 3+ , Zn, Cr, Cu and other ions.
• the layers are negatively charged, which is balanced by other cations, especially Na + and Ca 2+ .
• At least partially etherified sorbitols can be used as structure donors.
• Sorbitol is a hexavalent alcohol (sugar alcohol) that is relatively easy to split off one or two moles of water intramolecularly and forms cyclic ethers (for example sorbitan and sorbide). Splitting off of water is also possible intermolecularly, noncyclic ethers being formed from sorbitol and the alcohols concerned. The formation of monoethers and bisethers is also possible here, although higher degrees of etherification such as 3 and 4 can also occur. At least partially etherified sorbitols to be preferably used in the context of the present invention are double etherified sorbitols, of which dibenzylidene sorbitol is particularly preferred.
• Machine dishwashing detergents are preferred here which contain double etherified sorbitols, in particular dibenzylidene sorbitol, as structuring agents.
• the preferred liquid or flowable agents according to the invention can contain the structuring agents in amounts of 0.1 to 1.0% by weight, based on the total agent and on the active substance of the structuring agents.
• Preferred agents contain the structuring agent in amounts of 0.2 to 0.9% by weight, preferably in amounts of 0.25 to 0.75% by weight and in particular in amounts of 0.3 to 0.5% by weight. %, each based on the total mean.
• the preferred liquid or flowable agents according to the invention can contain inorganic salts from the group of carbonates, sulfates and amorphous or crystalline disilicates as thickeners.
• the salts of all metals mentioned can be used, the alkali metal salts being preferred.
• Alkali carbonate (s), alkali sulfate (s) and / or amorphous (s) and / or crystalline (s) alkali disilicate (s), preferably sodium carbonate, sodium sulfate and / or amorphous or crystalline sodium disilicate, are particularly preferably used as thickeners in the context of the present invention ,
• the preferred liquid or flowable agents according to the invention contain the thickeners in amounts of 5 to 30% by weight, based on the total agent.
• Particularly preferred agents contain the thickener (s) in amounts of 7.5 to 28% by weight, preferably in amounts of 10 to 26% by weight and in particular in amounts of 12.5 to 25% by weight, in each case based on the entire mean.
• the solids contained in the agents according to the invention are used as finely as possible. This is particularly advantageous for inorganic thickeners and bleaches.
• Machine dishwashing detergents according to the invention are preferred here, in which the average particle size of the bleaching agents and thickeners and of the optional builders is less than 75 ⁇ m, preferably less than 50 ⁇ m and in particular less than 25 ⁇ m.
• liquid machine dishwashing detergents according to the invention can also contain other viscosity regulators or thickening agents in order to set a possibly higher viscosity. All known thickeners can be used here, that is to say those based on natural or synthetic polymers.
• Polymers derived from nature that are used as thickeners are, for example, agar agar, carrageenan, tragacanth, acacia, alginates, pectins, polyoses, guar flour, carob bean flour, starch, dextrins, gelatin and casein.
• Modified natural products come primarily from the group of modified starches and celluloses, examples include carboxymethyl cellulose and other cellulose ethers, hydroxyethyl and propyl cellulose and core meal ether.
• preferred liquid or flowable automatic dishwashing detergents or automatic dishwashing aids contain, as thickeners, hydroxyethyl cellulose and / or hydroxypropyl cellulose, preferably in amounts of 0.01 to 4.0% by weight, particularly preferably in amounts of 0.01 to 3, 0 wt .-% and in particular in amounts of 0.01 to 2.0 wt .-%, each based on the total agent.
• thickeners that are widely used in a wide variety of applications are the fully synthetic polymers such as polyacrylic and polymethacrylic compounds, vinyl polymers, polycarboxylic acids, polyethers, polyimines, polyamides and polyurethanes.
• Thickeners from said substance classes are widely commercially available and are, for example, under the trade names Acusol ® -820
• a preferred polymeric thickener is xanthan, a microbial anionic heteropolysaccharide produced by Xanthomonas campestris and some other species under aerobic conditions and having a molecular weight of 2 to 15 million daltons.
• Xanthan is formed from a chain with ß-1, 4-bound glucose (cellulose) with side chains.
• the structure of the subgroups consists of glucose, mannose, glucuronic acid, acetate and pyruvate, the number of pyruvate units determining the viscosity of the xanthan.
• thickeners which are likewise preferably to be used are polyurethanes or modified polyacrylates which, based on the total agent, can be used, for example, in amounts of 0.1 to 5% by weight.
• Polyurethanes are produced by polyaddition from dihydric and higher alcohols and isocyanates and can be described by the general formula IV
• R 1 is a low molecular weight or polymeric diol radical
• R 2 is an aliphatic or aromatic group
• n is a natural number.
• R 1 is preferably a linear or branched C 2 . 12 -alk (en) yl group, but can also be a radical of a higher alcohol, whereby cross-linked polyurethanes are formed which differ from formula VIII given above in that the radical R 1 contains further -O-CO-NH groups are bound.
• TDI 2,4- or 2,6-toluenediisocyanate
• MDI C 6 H 4 -CH 2 -C 6 H 4
• HMDI, R 2 (CH 2 ) 6 ].
• polyurethane-based thickeners are, for example, Acrysol ® PM 12 V (mixture of 3-5% modified starch and 14-16% PUR resin in water, Rohm & Haas), Borchigel ® L75-N (non-ionic PU dispersion, 50% in water, Borchers), Coatex ® BR-100-P (PUR dispersion, 50% in water / butylglycol, Dimed), Nopco ® DSX-1514 (PUR dispersion, 40% in water / butyltrigylcol.
• Acrysol ® PM 12 V mixture of 3-5% modified starch and 14-16% PUR resin in water, Rohm & Haas
• Borchigel ® L75-N non-ionic PU dispersion, 50% in water, Borchers
• Coatex ® BR-100-P PUR dispersion, 50% in water / butylglycol, Dimed
• Nopco ® DSX-1514 PUR dispersion
• aqueous dispersions For the purposes of the present invention, care must be taken when using aqueous dispersions that the water content of the agents according to the invention remains within the abovementioned limits. If the use of aqueous dispersions is not possible for these reasons, dispersions in other solvents or the solids can be used.
• Modified polyacrylates which can be used in the context of the present invention are derived, for example, from acrylic acid or methacrylic acid and can be described by the general formula V.
• R is H or a branched or unbranched C 1-4 alk (en) yl radical
• X is NR 5 or O
• R 4 is an optionally alkoxylated branched or unbranched, possibly substituted C. 8 22 -alk (en) yl radical
• R 5 is H or R 4 and n is a natural number.
• modified polyacrylates are generally esters or amides of acrylic acid or an ⁇ -substituted acrylic acid. Preferred among these polymers are those in which R 3 represents H or a methyl group.
• the designation of the radicals bound to X represents a statistical mean, which can vary in individual cases with regard to chain length or degree of alkoxylation.
• Formula V only gives formulas for idealized homopolymers.
• copolymers in which the proportion of monomer units which satisfy the formula V is at least 30% by weight can also be used in the context of the present invention.
• copolymers of modified polyacrylates and acrylic acid or their salts can also be used, which still have acidic H atoms or basic -COO ' groups.
• Modified polyacrylates to be used preferably in the context of the present invention are polyacrylate-polymethacrylate copolymers which satisfy the formula Va R 7
• R 6 and R 7 are independently H or CH 3
• the degree of polymerization n is a natural number
• the degree of alkoxylation a is a natural number - in which R 4 is a preferably unbranched, saturated or unsaturated C 8 _ 22 is between 2 and 30, preferably between 10 and 20.
• Products of formula Va are commercially strength, for example, under the name Acusol ® 820 (Rohm & Haas) in the form of 30 wt .-% dispersions in water available.
• R 4 stands for a stearyl radical
• R 6 is a hydrogen atom
• R 7 is H or CH 3
• the degree of ethoxylation a is 20. The same applies to this dispersion for the water content of the agents.
• Liquid or flowable automatic dishwashing agents or automatic dishwashing aids preferred in the context of the present invention are characterized in that they additionally contain 0.01 to 5% by weight, preferably 0.02 to 4% by weight, particularly preferably 0.05 to 3% by weight .-% and in particular 0.1 to 1.5% by weight of a polymeric thickener, preferably from the group of polyurethanes or modified polyacrylates, with particular preference for thickeners of the formula VI
• R 3 is H or a branched or unbranched C ⁇ -Al ⁇ en.ylrest
• X for NR 5 or O
• R 4 for an optionally alkoxylated branched or unbranched, possibly substituted C 8 . 22 alk (en) yl radical
• R 5 is H or R 4 and n is a natural number.
• the solid or dimensionally stable and liquid or flowable machine dishwashing detergents or dishwashing aids according to the invention can be offered to the consumer in conventional containers, for example bottles, screw-top jars, canisters, balloons, beakers or spraying vessels, from which he doses them for use. Highly viscous products can also be offered in tubes or dispensers as they are known from toothpaste or sealants.
• containers are usually made from water-insoluble polymers and can consist, for example, of all the usual water-insoluble packaging materials that are well known to those skilled in the art. In particular, hydrocarbon-based plastics are to be mentioned as preferred polymers.
• the particularly preferred polymers include polyethylene, polypropylene (more preferably oriented polypropylene) and polymer mixtures such as, for example, mixtures of the polymers mentioned with polyethylene terephthalate. Also suitable are one or more polymers from the group consisting of polyvinyl chloride, polysulfones, polyacetals, water-insoluble cellulose derivatives, cellulose acetate, cellulose propionate, cellulose acetobutyrate and mixtures of the polymers mentioned or copolymers comprising the polymers mentioned.
• a particularly preferred embodiment of the present invention aims to provide the consumer with pre-portioned agents according to the invention, so that they can use the dosage advantages known to them from the "tablet” form and combine them with the rapid dissolution and release rate and the performance advantages of the agents according to the invention
• Such pre-portioned compositions according to the invention can also be present in water-insoluble packaging, so that the consumer must open them in a suitable manner before use, but it is also possible and preferred to package portioned compositions according to the invention in such a way that the consumer can use them directly without further handling steps , ie together with the packaging, can be put in the dishwasher.
• Such packaging comprises water-soluble or decomposable packaging such as pouches made of water-soluble film (so-called pouches), pouches or other packaging made of water-resistant Soluble or decomposable nonwovens or also flexible or rigid bodies made of water-soluble polymers, preferably in the form of filled hollow bodies, which can be produced, for example, by deep drawing, injection molding, blow molding, calendering, etc.
• a preferred subject of the present invention are therefore automatic dishwashing agents or automatic dishwashing aids according to the invention which are packaged in portions in a water-soluble envelope.
• Automatic dishwashing agents or dishwashing aids according to the invention preferably comprise a completely or partially water-soluble coating.
• the shape of the wrapper is not limited to certain shapes. Basically, all Archimedean and Platonic bodies, i.e. three-dimensional shaped bodies, can be used as forms of wrapping. Examples of the shape of the covering are capsules, cubes, spheres, egg-shaped moldings, cuboids, cones, rods or bags. Hollow bodies with one or more compartments are also suitable as a covering for the dishwashing detergents.
• the envelopes are in the form of capsules, such as are also used, for example, in pharmacy for the administration of medicaments, spheres or sachets. The latter are preferably welded or glued on at least one side, an adhesive which is water-soluble being used as the adhesive in particularly preferred embodiments of the invention.
• the water-soluble polymer material partially or completely surrounding the automatic dishwashing agent or dishwashing aid is a water-soluble packaging.
• This is understood to mean a flat part which partially or completely surrounds the dishwashing detergent.
• the exact form of such packaging is not critical and can be largely adapted to the conditions of use.
• films which, for example, can be glued and / or sealed to packaging such as hoses, pillows or the like after they have been filled with partial portions of the cleaning agents according to the invention or with the cleaning agents themselves.
• Plastic film packaging made of water-soluble polymer materials is further preferred according to the invention on account of the properties which can be adapted excellently to the desired physical conditions.
• Such films are basically known from the prior art.
• both hollow bodies of any shape which can be produced by injection molding, bottle blowing, deep-drawing, etc., as well as hollow bodies made of foils, in particular bags (so-called pouches), as packaging for portioned portions according to the invention Means preferred.
• Preferred automatic dishwashing agents or automatic dishwashing aids according to the invention are thus characterized in that the water-soluble covering comprises a bag made of water-soluble film and / or an injection molded part and / or a blow molded part and / or a deep-drawn part.
• the one or more enclosures are completed. This has the advantage that the dishwashing detergents are optimally protected against environmental influences, in particular against moisture.
• the invention can be further developed such that the cleaning agents contain at least one gas to protect the contents of the enclosure (s) from moisture, see below.
• the polymer materials can particularly preferably be the groups (optionally partially acetalized) of polyvinyl alcohol, polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose and their derivatives, starch and their derivatives, in particular modified starches, and mixtures (polymer blends, composites, coextrudates etc.) of the belong to the materials mentioned.
• Gelatin and polyvinyl alcohols and the two materials mentioned are particularly preferred in each case in combination with starch or modified starch.
• Inorganic salts and mixtures thereof can also be used as materials for the at least partially water-soluble coating.
• Preferred automatic dishwashing agents or automatic dishwashing aids according to the invention are characterized in that the covering comprises one or more materials from the group consisting of polymers containing acrylic acid, polyacrylamides, oxazoline polymers, polystyrene sulfonates, polyurethanes, polyesters and polyethers and mixtures thereof.
• the coating comprises one or more water-soluble polymer (s), preferably a material from the group (optionally acetalized) polyvinyl alcohol (PVAL), polyvinylpyrrolidone, polyethylene oxide, gelatin, cellulose, and their derivatives and their mixtures, more preferably (optionally acetalized) polyvinyl alcohol (PVAL).
• PVAL polyvinyl alcohol
• PVAL polyvinylpyrrolidone
• Polyvinyl alcohols (abbreviation PVAL, occasionally also PVOH) is the name for polymers of the general structure
• polyvinyl alcohols which are offered as white-yellowish powders or granules with degrees of polymerization in the range from approx. 100 to 2500 (molar masses from approx. 4000 to 100,000 g / mol), have degrees of hydrolysis of 98-99 or 87-89 mol%. , therefore still contain a residual content of acetyl groups.
• the manufacturers characterize the polyvinyl alcohols by stating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification number and the solution viscosity.
• polyvinyl alcohols are soluble in water and a few strongly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); They are not attacked by (chlorinated) hydrocarbons, esters, fats and oils.
• Polyvinyl alcohols are classified as toxicologically safe and are at least partially biodegradable.
• the water solubility can be reduced by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, boric acid or borax.
• the polyvinyl alcohol coatings are largely impervious to gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
• the covering comprises a polyvinyl alcohol, the degree of hydrolysis of which is 70 to 100 mol%, preferably 80 to 90 mol%, particularly preferably 81 to 89 mol% and in particular 82 to 88 mol% ,
• the enclosure comprises a polyvinyl alcohol whose molecular weight ranging from 10,000 to 100,000 gmol " 1 , preferably from 11,000 to 90,000 gmol "1 , particularly preferably from 12,000 to 80,000 gmol " 1 and in particular from 13,000 to 70,000 gmol "1 .
• the degree of polymerization of such preferred polyvinyl alcohols is between approximately 200 to approximately 2100, preferably between approximately 220 to approximately 1890, particularly preferably between approximately 240 to approximately 1680 and in particular between approximately 260 to approximately 1500.
• polyvinyl alcohols described above are widely available commercially, for example under the trade name Mowiol ® (Clariant).
• Mowiol ® Commercially, for example under the trade name Mowiol ® (Clariant).
• particularly suitable polyvinyl alcohols are, for example, Mowiol ® 3-83, Mowiol ® 4-88, Mowiol ® 5-88 and Mowiol ® 8-88.
• ELVANOL 51-05, 52-22, 50-42, 85-82, 75-15, T-25, T-66, 90-50 (trademark of Du Pont)
• ALCOTEX ® 72.5, 78, B72, F80 / 40, F88 / 4, F88 / 26, F88 / 40, F88 / 47 (trademark of Harlow Chemical Co.)
• Gohsenol ® NK- 05, A-300, AH-22, C- 500, GH-20, GL-03, GM-14L, KA-20, KA-500, KH-20, KP-06, N-300, NH-26, NM11Q, KZ-06 (trademark of Nippon Gohsei KK) ,
• the water solubility of PVAL can be changed by post-treatment with aldehydes (acetalization) or ketones (ketalization).
• Polyvinyl alcohols which have been acetalized or ketalized with the aldehyde or keto groups of saccharides or polysaccharides or mixtures thereof have proven to be particularly preferred and particularly advantageous because of their extremely good solubility in cold water.
• the reaction products made of PVAL and starch are extremely advantageous to use.
• the solubility in water can be changed by complexing with Ni or Cu salts or by treatment with dichromates, boric acid, borax and thus specifically adjusted to the desired values.
• PVAL films are largely impenetrable for gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
• PVAL films examples include the PVAL films available from Syntana bottlesgesellschaft E. Harke GmbH & Co. under the name “SOLUBLON ® ". Their solubility in water can be adjusted to the exact degree, and films of this product range are available which are soluble in the aqueous phase in all temperature ranges relevant to the application.
• PVP Polyvinylpyrrolidones
• PVP are produced by radical polymerization of 1-vinyl pyrrolidone.
• Commercial PVPs have molar masses in the range from approx. 2,500 to 750,000 g / mol and are offered as white, hygroscopic powders or as aqueous solutions.
• Polyethylene oxides, PEOX for short, are polyalkylene glycols of the general formula
• Gelatin is a polypeptide (molecular weight: approx. 15,000 to> 250,000 g / mol), which is primarily obtained by hydrolysis of the collagen contained in the skin and bones of animals under acidic or alkaline conditions.
• the amino acid composition of the gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on its provenance.
• the use of gelatin as a water-soluble shell material is extremely widespread, especially in the pharmaceutical industry in the form of hard or soft gelatin capsules. In the form of films, gelatin is used only to a minor extent because of its high price in comparison to the abovementioned polymers.
• Dishwashing detergents whose packaging consists of at least partially water-soluble film made from at least one polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose and mixtures thereof, are also preferred in the context of the present invention.
• Starch is a homoglycan, with the glucose units linked ⁇ -glycosidically. Starch is made up of two components of different molecular weights: approx. 20 to 30% straight-chain amylose (MW. Approx. 50,000 to 150,000) and 70 to 80% branched-chain amylopectin (MW. Approx. 300,000 to 2,000,000). It also contains small amounts of lipids, phosphoric acid and cations. While the amylose forms long, helical, intertwined chains with about 300 to 1,200 glucose molecules due to the binding in the 1,4 position, the chain in the amylopectin branches after an average of 25 glucose units through 1,6 binding to form a knot-like structure with about 1,500 to 12,000 molecules of glucose.
• starch derivatives which can be obtained by polymer-analogous reactions from starch are also suitable for producing water-soluble coatings for the detergent, dishwashing detergent and cleaning agent portions.
• Such chemically modified starches include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. Starches in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as starch derivatives.
• the group of starch derivatives includes, for example, alkali starches, carboxymethyl starch (CMS), starch esters and starches and amino starches.
• Pure cellulose has the formal gross composition (C 6 H 10 ⁇ 5 ) n and, viewed formally, is a ß-1, 4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5,000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
• Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
• celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
• the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
• Preferred casings made of at least partially water-soluble film contain at least one polymer with a molecular weight between 5,000 and 500,000 g / mol, preferably between 7,500 and 250,000 g / mol and in particular between 10,000 and 100,000 g / mol.
• the covering has different material thicknesses, whereby automatic dishwashing agents or automatic dishwashing aids according to the invention are preferred, in which the wall thickness of the covering is 10 to 5000 ⁇ m, preferably 20 to 3000 ⁇ m, particularly preferably 25 to 2000 ⁇ m and in particular 100 to 1500 ⁇ m ,
• the water-soluble film which forms the wrapper preferably has a thickness of 1 to 300 ⁇ m, preferably 2 to 200 ⁇ m, particularly preferably 5 to 150 ⁇ m and in particular 10 to 100 ⁇ m.
• these water-soluble films can be produced by various manufacturing processes.
• blowing, calendering and casting processes should be mentioned here.
• the films are blown from a melt with air through a blow mandrel to form a tube.
• the raw materials plasticized by suitable additives are atomized to form the films.
• an aqueous polymer preparation is placed on a heatable drying roller; after the water has evaporated, cooling is optional and the film is removed as a film. If necessary, this film is additionally powdered before or during the removal.
• an embodiment is preferred in accordance with which the casing as a whole is water-soluble, that is to say it dissolves completely when used as intended in machine cleaning when the conditions provided for the dissolution have been reached.
• Particularly preferred as completely water-soluble coatings are, for. B. capsules made of gelatin, advantageously made of soft gelatin, or bags made of (optionally partially acetalized) PVAL or balls of gelatin or (optionally partially acetalized) PVAL or of one or more organic and / or inorganic salts, preferably balls made of soft gelatin.
• an important advantage of this embodiment is that the covering at least partially dissolves in a practically relevant short time - as a non-limiting example, a few seconds to 5 minutes - and thus in the cleaning liquor under precisely defined conditions introduces the encapsulated content, ie the cleaning-active material or several materials, into the fleet in accordance with the requirements.
• the water-soluble covering comprises areas which are less or not water-soluble or only water-soluble at a higher temperature and areas which are water-soluble or water-soluble at a low temperature.
• the covering does not consist of a uniform material which has the same water solubility in all areas, but of materials of different water solubility. Areas of good water solubility are to be distinguished on the one hand from areas with less good water solubility, with poor or no water solubility or from areas in which water solubility is only at a higher temperature or at a different pH value or only when the electrolyte concentration has changed achieved, on the other hand.
• the invention is not subject to any restrictions for the formation of such systems. Enclosures can be provided in which a uniform polymer material comprises small areas of incorporated compounds (for example salts) which are more water-soluble than the polymer material. On the other hand, several polymer materials with different water solubility can also be mixed (polymer blend), so that the more rapidly soluble polymer material is disintegrated faster under defined conditions by water or the liquor than the more slowly soluble one.
• water-soluble areas or non-water-soluble areas or only at higher temperatures water-soluble areas of the casing are areas made of a material which chemically essentially corresponds to that of the readily water-soluble areas or at lower temperatures water-soluble areas corresponds, but has a higher layer thickness and / or a changed degree of polymerization of the same polymer and / or a higher degree of crosslinking of the same polymer structure and / or a higher degree of acetalization (in the case of PVAL, for example with saccharides, polysaccharides, such as starch) and / or has a content of water-insoluble salt components and / or has a content of a water-insoluble polymer.
• cleaning agent portions according to the invention can be provided which have advantageous properties when releasing the dishwashing agents into the respective liquor.
• the water-soluble covering material is preferably transparent.
• transparency is understood to mean that the transmittance within the visible spectrum of light (410 to 800 nm) is greater than 20%, preferably greater than 30%, most preferably greater than 40% and in particular greater than 50%. As soon as a wavelength of the visible spectrum of the light has a transmittance greater than 20%, it is to be regarded as transparent in the sense of the invention.
• Dishwashing detergents according to the invention which are packaged in transparent wrappings or containers, can contain a stabilizing agent as an essential component.
• Stabilizing agents in the sense of the invention are materials which protect the detergent components in their water-soluble, transparent coatings from decomposition or deactivation by exposure to light. Antioxidants, UV absorbers and fluorescent dyes have proven to be particularly suitable here.
• Particularly suitable stabilizers in the sense of the invention are the antioxidants.
• the formulations can contain antioxidants.
• Phenols, bisphenols and thiobisphenols substituted by sterically hindered groups can be used as antioxidants.
• Further examples are propyl gallate, butylated hydroxytoluene (BHT), butylated hydroxyanisole (BHA), t-butylhydroquinone (TBHQ), tocopherol and the long-chain (C8-C22) esters of gallic acid, such as dodecyl gallate.
• aromatic amines preferably secondary aromatic amines and substituted p-phenylenediamines
• phosphorus compounds with trivalent phosphorus such as phosphines, phosphites and phosphonites
• citric acids and citric acid derivatives such as isopropyl citrate
• compounds containing endiol groups so-called reductones, such as ascorbic acid and its derivatives, such as ascorbic acid palmitate
• organosulfur compounds such as the esters of 3,3 'thiodipropionic acid with especially C 10 .
• UV absorbers can improve the light resistance of the recipe components. These include organic substances (light protection filters) that are able to absorb ultraviolet rays and release the absorbed energy in the form of longer-wave radiation, eg heat.
• Compounds which have these desired properties are, for example, the compounds and derivatives of benzophenone which are active by radiationless deactivation and have substituents in the 2- and / or 4-position.
• substituted benzotriazoles such as the water-soluble benzenesulfonic acid-3- (2H-benzotriazol-2-yl) - 4-hydroxy-5- (methylpropyl) monosodium salt (Ciba Fast ® H), 3-phenyl-substituted acrylates (cinnamic acid derivatives) , optionally with cyano groups in the 2-position, salicylates, organic Ni complexes and natural substances such as umbelliferone and the body's own urocanoic acid.
• UV-B absorbers are 3-benzylidene camphor and 3-benzylidene norcampher and their derivatives, for example 3- (4-methylbenzylidene) camphor; 4-aminobenzoic acid derivatives, preferably 4-
• esters of salicylic acid preferably salicylic acid 2-ethylhexyl ester, salicylic acid 4-isopropylbenzyl ester, salicylic acid homomethyl ester;
• benzophenone preferably 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2,2'-
• Dihydroxy-4-methoxybenzophenone Esters of benzalmalonic acid, preferably di-2-ethylhexyl 4-methoxybenzmalonate; Triazine derivatives, e.g. 2,4,6-trianilino- (p-carbo-2'-ethyl-1'-hexyloxy) -1, 3,5-triazine and octyl triazone or dioctyl butamido triazone (Uvasorb® HEB); Propane-1,3-dione, e.g.
• Ketotricyclo (5.2.1.0) decane derivatives are also suitable.
• Sulfonic acid derivatives of benzophenones preferably 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid and its salts;
• Sulfonic acid derivatives of 3-benzylidene camphor e.g. 4- (2-oxo-3-bornylidene methyl) benzenesulfonic acid and 2-methyl-5- (2-oxo-3-bornylidene) sulfonic acid and their salts.
• UV-A filters -4'-meth-oxydibenzoylmethane (Parsol 1789), 1-phenyl-3- (4'-isopropylphenyl) propane-1, 3-dione and enamine compounds.
• the UV-A and UV-B filters can of course also be used in mixtures be used.
• insoluble light-protection pigments namely finely dispersed, preferably nanoized metal oxides or salts, are also suitable for this purpose.
• suitable metal oxides are, in particular, zinc oxide and titanium dioxide and, in addition, oxides of iron, zirconium, silicon, manganese, aluminum and cerium and mixtures thereof.
• Silicates (talc), barium sulfate or zinc stearate can be used as salts.
• the oxides and salts are already used in the form of the pigments for skin-care and skin-protecting emulsions and decorative cosmetics.
• the particles should have an average diameter of less than 100 nm, preferably between 5 and 50 nm and in particular between 15 and 30 nm. They can have a spherical shape, but it is also possible to use particles which have an ellipsoidal shape or shape which differs from the spherical shape in some other way.
• the pigments can also be surface-treated, ie hydrophilized or hydrophobicized.
• Typical examples are coated titanium dioxides such as titanium dioxide T 805 (Degussa) or Eusolex® T2000 (Merck). Silicones, and in particular trialkoxyoctylsilanes or simethicones, are particularly suitable as hydrophobic coating agents. Micronized zinc oxide is preferably used.
• UV absorbers can be contained in the dishwashing detergents in amounts of up to 5% by weight, preferably up to 3% by weight, particularly preferably from 0.01 to 2.0 and in particular from 0.03 to 1% by weight.
• Another preferred class of stabilizers is the fluorescent dyes. These include the 4,4'-diamino-2,2 ' -stilbene disulfonic acids (flavonic acids), 4,4'-distyrylbiphenyls, methyl umbelliferones, coumarins, dihydroquinolinones, 1,3-diarylpyrazolines, naphthalic imides, benzoxazole and benzisoxazole and Benzimidazole systems and the pyrene derivatives substituted by heterocycles. Of particular importance are the sulfonic acid salts of the diaminostilbene derivatives and polymeric fluorescent substances, as are disclosed in US Pat. No. 5,082,578.
• Fluorescent substances can be present in the formulations in amounts of up to 5% by weight, preferably up to 1% by weight, particularly preferably from 0.01 to 0.5 and in particular from 0.03 to 0.1% by weight.
• the aforementioned stabilizing agents are used in any mixtures.
• the stabilizing agents are used in amounts of up to 40% by weight, preferably up to 30% by weight, particularly preferably from 0.01 to 20% by weight, in particular from 0.02 to 5% by weight.
• Preferred machine dishwashing detergents or machine dishwashing aids contain, regardless of the way in which they are packaged, at least one washing- or cleaning-active substance from the group of bleaching agents, bleaching activators, polymers, builders, surfactants, enzymes, electrolytes, pH regulators, fragrances, perfume carriers, dyes, hydrotropes, Foam inhibitors, antimicrobial agents, germicides, fungicides, corrosion inhibitors, non-aqueous solvents. These substances will be described in more detail below.
• all builders commonly used in washing and cleaning agents in particular silicates, carbonates, organic cobuilders and also the phosphates, can be incorporated into the machine dishwashing agents or machine dishwashing aids.
• Suitable crystalline, layered sodium silicates have the general formula NaMSi x 0 2x + 1 H 2 0, where M is sodium or hydrogen, x is a number from 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x 2 , 3 or 4 are.
• Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
• both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 0 5 ' yH 2 0 are preferred.
• the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
• the term “amorphous” is also understood to mean “X-ray amorphous”.
• silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
• it can very well lead to particularly good builder properties if the silicate particles deliver washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
• Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
• Both monoalkali metal salts and dialkali metal salts of carbonic acid as well as sesquicarbonates can be included in the compositions as carbonates.
• Preferred alkali metal ions are sodium and / or potassium ions.
• Compounds made of, for example, carbonate, silicate and optionally other auxiliaries such as anionic surfactants or other, in particular organic builder substances, can also be present as separate components in the finished compositions.
• the alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate), are of the greatest importance in the detergent and cleaning agent industry.
• Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HP0 3 ) and orthophosphoric acid H 3 P0 4 in addition to higher molecular weight representatives.
• the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and limescale deposits on the wash ware and also contribute to cleaning performance.
• Suitable phosphates are sodium dihydrogen phosphate, NaH 2 P0 4 , disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HP0 4 , trisodium phosphate, tertiary sodium phosphate, Na 3 P0 4 , tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 0 7 the NaH 2 P0 4 and the KH 2 P0 4 result in higher molecular weight sodium and potassium phosphates, in which one can distinguish cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates, and the pentasodium triphosphate, Na 5 P 3 O ⁇ 0 (sodium tripolyphosphate).
• the corresponding potassium salts or mixtures of these two can also be used; Mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can also be used according to the invention.
• Machine dishwashing detergents or machine dishwashing aids preferred in the context of the present invention contain no sodium and / or potassium hydroxide.
• Other preferred water-soluble builders are, for example, tripotassium citrate and the potassium water glasses.
• Preferred machine dishwashing agents or machine dishwashing aids contain 20 to 60% by weight of one or more water-soluble builders, preferably citrates and / or phosphates, preferably alkali metal phosphates, with particular preference for pentasodium or. Pentapotassium triphosphate (sodium or potassium tripolyphosphate).
• the content of water-soluble builders in the compositions is within narrow limits.
• Machine dishwashing agents or machine dishwashing aids are preferred here, which contain the water-soluble builder (s) in amounts of 22.5 to 55% by weight, preferably 25 to 50% by weight and in particular 27.5 to 45% by weight. -%, each based on the total mean included.
• the agents according to the invention can particularly preferably contain condensed phosphates as water-softening substances. These substances form a group of phosphates - also called melt or glow phosphates due to their production - which can be derived from acidic salts of orthophosphoric acid (phosphoric acids) by condensation.
• the condensed phosphates can be divided into the metaphosphates [Mln (P0 3 ) n ] and polyphosphates (M ' n + 2 P n 0 3n + 1 or M' n H 2 P n 0 3n + ⁇ ).
• Metaphoaphate is obtained as a by-product of Graham's salt, which is incorrectly referred to as sodium hexametaphosphate, by melting NaH 2 P0 4 at temperatures above 620 ° C, with what is known as Maddrell's salt being formed as an intermediate.
• This and Kurrol's salt are linear polyphosphates, which today are usually not counted among the metaphosphates, but which can also be used with preference as water-softening substances in the context of the present invention.
• the quenched, glassy melt is the water-soluble Graham's salt, (NaP0 3 ) 40 . 5 o, or a glass-like condensed phosphate of the composition (NaPO 3) 15-20, which is known as Calgon.
• the misleading name hexametaphosphate is still used for both products.
• Kurrol's salt (NaP0 3 ) n with n »5000, also arises from the melt of the Maddrell salt, which is hot at 600 ° C, if it is left at 500 ° C for a short time. It forms highly polymeric water-soluble fibers.
• machine dishwashing agents or machine dishwashing aids are particularly preferred which additionally contain one or more substances from the group of the acidifying agents, chelate complexing agents or the deposit-inhibiting polymers.
• Both inorganic acids and organic acids are suitable as acidifiers, provided they are compatible with the other ingredients.
• the solid mono-, oligo- and polycarboxylic acids in particular can be used. From this group, preference is again given to citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and polyacrylic acid.
• the anhydrides of these acids can also be used as acidifying agents, maleic anhydride and succinic anhydride in particular being commercially available.
• Organic sulfonic acids such as amidosulfonic acid can also be used. Sokalan ® DCS (trademark of BASF), a mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (commercially available and also preferably used as an acidifying agent in the context of the present invention) max. 33% by weight).
• Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination point on a central atom, ie being at least “bidentate”. In this case, stretching is normally carried out Compounds formed into rings by complex formation via an ion The number of ligands bound depends on the coordination number of the central ion.
• Common chelate complexing agents preferred within the scope of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA).
• Complex-forming polymers that is to say polymers which carry functional groups either in the main chain itself or laterally to it, which can act as ligands and which generally react with suitable metal atoms to form chelate complexes, can be used according to the invention.
• the polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or can belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.
• Complexing groups (ligands) of customary complex-forming polymers are iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, amidoxime, aminophosphoric acid, (cyclic) polyamino, mercapto, 1,3-dicarbonyl - And crown ether residues with z. T. very specific Activities against ions of different metals.
• the base polymers of many commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinyl pyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided with further ligand functionalities by polymer-analogous conversions.
• machine dishwashing agents or machine dishwashing aids which comprise one or more chelate complexing agents from the groups of
• Hydroxyl groups is at least 5,
• Dishwashing detergent included.
• All complexing agents of the prior art can be used in the context of the present invention. These can belong to different chemical groups. The following are preferably used individually or in a mixture:
• polycarboxylic acids a) are understood to mean carboxylic acids, including monocarboxylic acids, in which the sum of carboxyl groups and the hydroxyl groups contained in the molecule is at least 5.
• Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA, are preferred. At the alkaline pH values of the treatment solutions required according to the invention, these complexing agents are at least partially present as anions. It is immaterial whether they are introduced in the form of acids or in the form of salts. In the case of use as salts, alkali metal, ammonium or alkylammonium salts, in particular sodium salts, are preferred.
• Deposit-inhibiting polymers can also be contained in the agents according to the invention. These substances, which can have different chemical structures, originate, for example, from the groups of low molecular weight polyacrylates with molecular weights between 1000 and 20,000 daltons, polymers with molecular weights below 15,000 daltons being preferred.
• Deposit-inhibiting polymers can also have cobuilder properties.
• Organic cobuilders which can be used in the dishwasher detergents according to the invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, Dextrins, other organic cobuilders (see below) and phosphonates can be used. These classes of substances are described below.
• Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
• these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these.
• Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
• the acids themselves can also be used.
• the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents.
• Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
• Polymeric polycarboxylates are also suitable as builders or scale inhibitors, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
• the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was made 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 information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
• Organic cobuilders which can be used in the cleaning agents in the context of the present invention are, in particular, polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates. These classes of substances are described below.
• Usable organic builders are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids being understood to mean those carboxylic acids which carry more than one acid function.
• these are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), as long as such use is not objectionable for ecological reasons, and mixtures of these.
• Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, methylglycinediacetic acid, sugar acids and mixtures of these.
• the acids themselves can also be used.
• the acids typically also have the property of an acidifying component and thus also serve to set a lower and milder pH value of detergents or cleaning agents.
• Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any mixtures thereof can be mentioned in particular.
• Polymeric polycarboxylates are also suitable as builders, for example the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 500 to 70,000 g / mol.
• the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was made 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 information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
• Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of 1000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates with molecular weights from 1000 to 10000 g / mol, and particularly preferably from 1200 to 4000 g / mol, can in turn be preferred from this group.
• Both polyacrylates and copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and optionally other ionic or nonionic monomers are particularly preferably used in the agents according to the invention.
• the copolymers containing sulfonic acid groups are described in detail below.
• products according to the invention which, as so-called “3-in-1” products, combine the conventional cleaners, rinse aids and a salt replacement function.
• automatic dishwashing detergents according to the invention which additionally contain 0.1 to 70% by weight of copolymers are preferred from i) unsaturated carboxylic acids ii) sulfonic acid group-containing monomers iii) optionally further ionic or nonionic monomers
• copolymers have the effect that the items of crockery treated with such agents become significantly cleaner in subsequent cleaning operations than items of crockery that have been washed with conventional agents.
• unsaturated carboxylic acids of the formula VII are preferred as the monomer
• R 1 to R 3 independently of one another are -H -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH 2 , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or - COOR 4 , where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms.
• Preferred among these monomers are those of the formulas Villa, Vlllb and / or Vlllc,
• ionic or nonionic monomers that can be used are, in particular, ethylenically unsaturated compounds.
• the content of monomers of group iii) in the polymers used according to the invention is preferably less than 20% by weight, based on the polymer.
• Polymers to be used with particular preference consist only of monomers of groups i) and ii).
• copolymers are made of
• R 1 to R 3 independently of one another are -H -CH 3 , a straight-chain or branched saturated alkyl radical having 2 to 12 carbon atoms, a straight-chain or branched, mono- or polyunsaturated alkenyl radical having 2 to 12 carbon atoms, with -NH 2 , -OH or - COOH substituted alkyl or alkenyl radicals as defined above or represents -COOH or - COOR 4 , where R 4 is a saturated or unsaturated, straight-chain or branched hydrocarbon radical having 1 to 12 carbon atoms,
• Particularly preferred copolymers consist of
• H 2 C C (CH 3 ) -X-S0 3 H (VIIIb),
• the copolymers contained in the compositions can contain the monomers from groups i) and ii) and optionally iii) in varying amounts, all representatives from group i) with all representatives from group ii) and all representatives from group iii) can be combined.
• Particularly preferred polymers have certain structural units, which are described below.
• agents according to the invention are preferred which are characterized in that they contain one or more copolymers which have structural units of the formula IX - [CH 2 -CHCOOH] m - [CH 2 -CHC (0) -Y-S0 3 H] p - (IX),
• These polymers are produced by copolymerization of acrylic acid with an acrylic acid derivative containing sulfonic acid groups. If the acrylic acid derivative containing sulfonic acid groups is copolymerized with methacrylic acid, another polymer is obtained, the use of which in the agents according to the invention is also preferred and is characterized in that the agents contain one or more copolymers which have structural units of the formula X.
• acrylic acid and / or methacrylic acid can also be copolymerized with methacrylic acid derivatives containing sulfonic acid groups, as a result of which the structural units in the molecule are changed.
• Agents according to the invention which contain one or more copolymers are structural units of the formula XI
• maleic acid can also be used as a particularly preferred monomer from group i).
• preferred agents according to the invention are obtained which are characterized in that they contain one or more copolymers, the structural units of the formula XIII
• machine dishwashing agents or machine dishwashing aids which contain, as ingredient b), one or more copolymers which have structural units of the formulas IX and / or X and / or XI and / or XII and / or XIII and / or XIV
• All or part of the sulfonic acid groups in the polymers can be in neutralized form, i.e. that the acidic hydrogen atom of the sulfonic acid group in some or all sulfonic acid groups can be replaced by metal ions, preferably alkali metal ions and in particular by sodium ions.
• Corresponding agents which are characterized in that the sulfonic acid groups in the copolymer are partially or fully neutralized are preferred according to the invention.
• the monomer distribution of the copolymers used in the agents according to the invention is preferably 5 to 95% by weight i) or ii), particularly preferably 50 to 90% by weight, in the case of copolymers which contain only monomers from groups i) and ii). % Of monomer from group i) and from 10 to 50% by weight of monomer from group ii), in each case based on the polymer.
• terpolymers those which contain 20 to 85% by weight of monomer from group i), 10 to 60% by weight of monomer from group ii) and 5 to 30% by weight of monomer from group iii) are particularly preferred .
• the molar mass of the polymers used in the agents according to the invention can be varied in order to adapt the properties of the polymers to the desired intended use.
• Preferred automatic dishwashing detergents are characterized in that the copolymers have molar masses from 2000 to 200,000 gmol "1 , preferably from 4000 to 25,000 gmol " 1 and in particular from 5000 to 15,000 gmol "1 .
• the content of one or more copolymers in the agents according to the invention can vary depending on the intended use and the desired product performance, preferred dishwasher detergents according to the invention being characterized in that they contain the copolymer (s) in amounts of 0.25 to 50% by weight. %, preferably from 0.5 to 35% by weight, particularly preferably from 0.75 to 20% by weight and in particular from 1 to 15% by weight.
• polyacrylates As already mentioned further above, it is particularly preferred to use both polyacrylates and the above-described copolymers of unsaturated carboxylic acids, monomers containing sulfonic acid groups and, if appropriate, further ionic or nonionic monomers in the agents according to the invention.
• the polyacrylates were described in detail above. Combinations of the above-described copolymers containing sulfonic acid groups with low molecular weight polyacrylates, for example in the range between 1000 and 4000 daltons, are particularly preferred.
• Such polyacrylates are commercially available under the trade names Sokalan ® PA15 or Sokalan ® PA25 (BASF).
• copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
• 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.
• Their relative molecular weight, based on free acids, is generally 2,000 to 100,000 g / mol, preferably 20,000 to 90,000 g / mol and in particular 30,000 to 80,000 g / mol.
• the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
• the content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
• the polymers can also contain allylsulfonic acids, such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
• allylsulfonic acids such as, for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as monomers.
• Biodegradable polymers of more than two different monomer units are also particularly preferred, for example those which, as monomers, are salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or the salts of acrylic acid and 2-alkylallylsulfonic acid as monomers and sugar derivatives.
• copolymers preferably have acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
• builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances.
• Polyaspartic acids or their salts and derivatives are particularly preferred.
• polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 carbon atoms and at least 3 hydroxyl groups.
• Preferred polyacetals are obtained from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
• Suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
• the hydrolysis can be carried out by customary processes, for example acid-catalyzed or enzyme-catalyzed. They are preferably hydrolysis products with average molar masses in the range from 400 to 500,000 g / mol.
• DE dextrose equivalent
• the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
• a product oxidized on C e of the saccharide ring can be particularly advantageous.
• Ethylenediamine-N, N '- disuccinate (EDDS) is preferably in the form of its sodium or magnesium salts.
• Glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts for use in formulations containing zeolite and / or silicate are 3 to 15% by weight.
• organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
• phosphonates are, in particular, hydroxyalkane or aminoalkane phosphonates.
• hydroxyalkane phosphonates 1-hydroxyethane-1,1-diphosphonate (HEDP) is of particular importance as a cobuilder.
• 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.
• HEDP is preferably used as the builder from the class of the phosphonates.
• the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, it may be preferred, particularly if the agents also contain bleach, to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
• Agents according to the invention are characterized in the context of the present application in that they contain builders, preferably from the group of silicates, carbonates, organic cobuilders and / or phosphates in amounts of 0.1 to 99.5% by weight, preferably of 1 to 95 % By weight, particularly preferably from 5 to 90% by weight and in particular from 10 to 80% by weight, in each case based on the composition.
• preferred cleaning agents contain one or more surfactant (s) from the groups of anionic, nonionic, cationic and / or amphoteric surfactants.
• Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
• the surfactants of the sulfonate type are preferably C 9 . 13 -Alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 12 .
• alkanesulfonates which consist of C ⁇ 2 . 18 -alkanes can be obtained, for example, by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
• the esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
• Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
• Fatty acid glycerol esters are to be understood as meaning the mono-, di- and triesters and their mixtures, as obtained in the production by esterification of a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol.
• Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
• alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12 -C 8 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior similar to that of the adequate compounds based on oleochemical raw materials.
• C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates as well as C 14 -C 15 alkyl sulfates are preferred from the point of view of washing technology.
• 2,3-alkyl sulfates which can be obtained as commercial products from Shell Oil Company under the name DAN ®, are suitable anionic surfactants.
• 21 -alcohols such as 2-methyl-branched C 9 .n-Alko.10le with an average of 3.5 moles of ethylene oxide (EO) or C ⁇ 2 - ⁇ 8 fatty alcohols with 1 to 4 EO, are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
• Suitable 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 in particular ethoxylated fatty alcohols.
• alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
• Preferred sulfosuccinates contain C 8 . 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).
• alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alkyl (en) yl chain or salts thereof.
• Soaps are particularly suitable as further anionic surfactants.
• Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
• 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 triethanolamine.
• the anionic surfactants are preferably in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
• non-ionic surfactants 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 radical 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 of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
• the preferred ethoxylated alcohols include, for example, C 12 . 1 - alcohols with 3 EO or 4 EO, Cg-n alcohol with 7 EO, C 13 . 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C ⁇ 2 - ⁇ 8 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 . 14 alcohol with 3 EO and C 12 . 18 alcohol with 5 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. Examples of this are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
• Another class of preferably used nonionic surfactants, which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, 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 ester.
• alkyl polyglycosides Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG).
• Alkypolyglycosides which can be used satisfy the general formula RO (G) z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is Is symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
• the degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
• Linear alkyl polyglucosides, ie alkyl polyglycosides, which consist of a glucose residue and an n-alkyl chain, are preferably used.
• nonionic surfactants which are used either as the sole nonionic surfactant or in combination with other nonionic surfactants, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the alkyl chain.
• 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 alkanolamides 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.
• Suitable surfactants are polyhydroxy fatty acid amides of the formula (XV),
• RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms
• R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms
• [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
• the polyhydroxy fatty acid amides are known substances which are customary can be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
• the group of polyhydroxy fatty acid amides also includes compounds of the formula (XVI)
• R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
• R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
• R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms
• C 1-4 -alkyl or phenyl radicals being preferred
• [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated Derivatives of this rest.
• [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
• surfactants are generally suitable as surfactants.
• the nonionic surfactants described above, and above all the low-foaming nonionic surfactants are preferred for this purpose.
• the alkoxylated alcohols are particularly preferred, especially the ethoxylated and / or propoxylated alcohols.
• alkoxylated alcohols the reaction products of alkylene oxide, preferably ethylene oxide, with alcohols, preferably in the sense of the present invention the longer-chain alcohols (C 10 to C 18 , preferably between C 12 and C 16 , such as Cn- , C 12 -, C 13 -, C 14 -, C 15 -, C 16 -, C 17 - and C 18 - alcohols).
• C 10 to C 18 preferably between C 12 and C 16 , such as Cn- , C 12 -, C 13 -, C 14 -, C 15 -, C 16 -, C 17 - and C 18 - alcohols.
• a complex mixture of addition products of different degrees of ethoxylation is formed from n moles of ethylene oxide and one mole of alcohol, depending on the reaction conditions.
• a further embodiment consists in using mixtures of the alkylene oxides, preferably the mixture of ethylene oxide and propylene oxide.
• final etherification with short-chain alkyl groups such as preferably the butyl group, can also be used to obtain the "closed" alcohol ethoxylates arrive, which can also be used in the sense of the invention.
• short-chain alkyl groups such as preferably the butyl group
• very particularly preferred are highly ethoxylated fatty alcohols or their mixtures with end-capped fatty alcohol ethoxylates.
• Nonionic surfactants which have alternating ethylene oxide and alkylene oxide units have proven to be particularly preferred nonionic surfactants within the scope of the present invention.
• surfactants with EO-AO-EO-AO blocks are preferred, one to ten EO or AO groups being bonded to one another before a block follows from the other groups.
• automatic dishwashing agents according to the invention are preferred which contain surfactants of the general formula XVII as nonionic surfactant (s)
• 24 is alkyl or alkenyl; each group R 2 or R 3 is independently selected from -CH 3 ; -CH 2 CH 3 , -CH 2 CH 2 -CH 3 , -CH (CH 3 ) 2 and the indices w, x, y, z independently represent integers from 1 to 6.
• the preferred nonionic surfactants of the formula XVII can be prepared by known methods from the corresponding alcohols R 1 -OH and ethylene or alkylene oxide.
• the radical R 1 in formula XVII above can vary depending on the origin of the alcohol. If native sources are used, the radical R has an even number of carbon atoms and is generally not shown, the linear radicals being of alcohols of native origin with 12 to 18 carbon atoms, for example coconut, palm, tallow or oleyl alcohol , are preferred.
• Alcohols accessible from synthetic sources are, for example, the Guerbet alcohols or, in the mixture, methyl-branched or linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
• preferred dishwasher detergents according to the invention are those in which R 1 in formula XVII for an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 is up to 11 carbon atoms.
• R 1 in formula XVII for an alkyl radical having 6 to 24, preferably 8 to 20, particularly preferably 9 to 15 and in particular 9 is up to 11 carbon atoms.
• butylene oxide is particularly suitable as the alkylene oxide unit which is present in the preferred nonionic surfactants in alternation with the ethylene oxide unit.
• R 2 or R 3 are selected independently of one another from - CH 2 CH 2 -CH 3 or -CH (CH 3 ) 2 are also suitable.
• Preferred automatic dishwashing agents are characterized in that R 2 and R 3 for a radical -CH 3 , w and x independently of one another stand for values of 3 or 4 and y and z independently of one another for values of 1 or 2.
• nonionic surfactants which have a C 9 . 15 alkyl group having 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units, followed by 1 to 4 ethylene oxide units, followed by 1 to 4 propylene oxide units.
• the automatic dishwashing agents according to the invention particularly preferably contain a nonionic surfactant which has a melting point above room temperature. Accordingly, preferred agents are characterized in that they contain nonionic surfactant (s) with a melting point above 20 ° C., preferably above 25 ° C., particularly preferably between 25 and 60 ° C. and in particular between 26.6 and 43, 3 ° C.
• Suitable, in addition to the nonionic surfactants contained in the compositions according to the invention, which have melting or softening points in the temperature range mentioned, are, for example, low-foaming nonionic surfactants which can be solid or highly viscous at room temperature. If highly viscous nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants that have a waxy consistency at room temperature are also preferred.
• Preferred nonionic surfactants to be used at room temperature originate from the groups of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols, and mixtures of these surfactants with structurally more complex surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
• Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
• the nonionic surfactant with a melting point above room temperature is an ethoxylated nonionic surfactant which results from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms preferably at least 12 moles, particularly preferably at least 15 moles, in particular at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol.
• a particularly preferred solid at room temperature, non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 alcohol and at least 12 mole, preferably at least 15 mol and recovered in particular at least 20 moles of ethylene oxide , Among these, the so-called “narrow ranks ethoxylates" (see above) are particularly preferred.
• particularly preferred agents according to the invention contain ethoxylated nonionic surfactant (s) which consist of C 6 . 2 o-monohydroxyalkanols or C 6 . 20 alkylphenols or C 16 . 20 fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol has been obtained.
• ethoxylated nonionic surfactant consist of C 6 . 2 o-monohydroxyalkanols or C 6 . 20 alkylphenols or C 16 . 20 fatty alcohols and more than 12 moles, preferably more than 15 moles and in particular more than 20 moles of ethylene oxide per mole of alcohol has been obtained.
• the nonionic surfactant preferably additionally has propylene oxide units in the molecule.
• Such PO units preferably make up up to 25% by weight, particularly preferably up to 20% by weight and in particular up to 15% by weight of the total molar mass of the nonionic surfactant.
• Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols, which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
• the alcohol or alkylphenol portion of such nonionic surfactant molecules preferably makes up more than 30% by weight, particularly preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.
• Preferred automatic dishwashing detergents are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule contain up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight of the total molecular weight of the make up nonionic surfactant.
• nonionic surfactants with melting points above room temperature contain 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend which contains 75% by weight of an inverted block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol of propylene oxide and 25% by weight.
• Nonionic surfactants that may be used with particular preference are available, for example under the name Poly Tergent ® SLF-18 from Olin Chemicals.
• a further preferred automatic dishwashing agent according to the invention contains nonionic surfactants of the formula
• R 1 represents a linear or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms or mixtures thereof
• R 2 denotes a linear or branched hydrocarbon radical with 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1, 5 and y stands for a value of at least 15.
• nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula
• R 1 and R 2 represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
• R 3 represents H or a methyl, ethyl, n-propyl, isopropyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical
• x stands for values between 1 and 30, k and j stand for values between 1 and 12, preferably between 1 and 5. If the value x ⁇ 2, each R 3 in the above formula can be different.
• R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, radicals having 8 to 18 carbon atoms being particularly preferred.
• H, -CH 3 or - CH 2 CH 3 are particularly preferred for the radical R 3 .
• Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
• each R 3 in the above formula can be different if x ⁇ 2.
• the value 3 for x has been chosen here by way of example and may well be larger, the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
• R 1 , R 2 and R 3 are as defined above and x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred are surfactants in which the radicals R 1 and R 2 have 9 to 14 carbon atoms, R 3 represents H and x assumes values from 6 to 15.
• dishwashing detergents according to the invention are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula
• R 1 and R 2 represent linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms
• R 3 represents H or a methyl, ethyl, n-propyl, isopropyl, n-butyl, 2-butyl or 2-methyl-2-butyl radical
• x stands for values between 1 and 30
• k and j stand for values between 1 and 12, preferably between 1 and 5, with surfactants of the type
• x stands for numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18, are particularly preferred.
• anionic, cationic and / or amphoteric surfactants can also be used, these being of only minor importance because of their foaming behavior in automatic dishwashing detergents and mostly only in amounts below 10% by weight, mostly even below 5% by weight .-%, for example from 0.01 to 2.5 wt .-%, each based on the agent.
• the agents according to the invention can thus also contain anionic, cationic and / or amphoteric surfactants as the surfactant component.
• surfactant preferably nonionic surfactant (s)
• Amounts of 0.5 to 10 wt .-%, preferably from 0.75 to 7.5 wt .-% and in particular from 1, 0 to 5 wt .-%, each based on the total agent.
• Bleaching agents and bleach activators are important constituents of detergents and cleaning agents and a preferred automatic dishwashing agent or automatic dishwashing auxiliary can contain one or more substances from the groups mentioned within the scope of the present invention.
• Sodium percarbonate is of particular importance among the compounds which serve as bleaching agents and supply H 2 0 2 in water.
• Other usable bleaching agents are, for example, sodium perborate tetrahydrate and the sodium perborate monohydrate.
• Sodium percarbonate is a non-specific term for sodium carbonate peroxohydrates, which strictly speaking are not “percarbonates” (ie salts of percarbonic acid) but hydrogen peroxide adducts with sodium carbonate.
• the merchandise has the average composition 2 Na 2 C0 3 -3 H 2 0 2 and is therefore not peroxycarbonate.
• Sodium percarbonate often forms a white, water-soluble powder with a density of 2.14 "3 , which easily breaks down into sodium carbonate and bleaching or oxidizing oxygen.
• Detergents for automatic dishwashing can also contain bleaches from the group of organic bleaches.
• Typical organic bleaching agents that can be used as ingredients in the context of the present invention are the diacyl peroxides, e.g. Dibenzoyl.
• Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
• Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoxyacidoxy (PAP), )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1, 12-diperoxycarboxylic acid, 1, 9-diperoxyazelaic acid, diperocysebacic acid,
• Diperoxybrassylic acid the diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-diacid, N, N-terephthaloyl-di (6-aminopercaproic acid) can be used.
• chlorine or bromine-releasing substances can also be used as bleaching agents for machine dishwashing.
• Suitable materials that release chlorine or bromine include, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium.
• Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
• Advantageous agents in the context of the present invention contain one or more bleaching agents, preferably from the group of oxygen or halogen bleaching agents, in particular chlorine bleaching agents, with particular preference for sodium percarbonate and / or sodium perborate monohydrate, in amounts of 0.5 to 40% by weight .-%, preferably from 1 to 30 wt .-%, particularly preferably from 2.5 to 25 wt .-% and in particular from 5 to 20 wt .-%, each based on the total agent.
• one or more bleaching agents preferably from the group of oxygen or halogen bleaching agents, in particular chlorine bleaching agents, with particular preference for sodium percarbonate and / or sodium perborate monohydrate, in amounts of 0.5 to 40% by weight .-%, preferably from 1 to 30 wt .-%, particularly preferably from 2.5 to 25 wt .-% and in particular from 5 to 20 wt .-%, each based on the total agent.
• 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 substances are those which carry O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted benzoyl groups.
• TAED tetraacetylethylenediamine
• bleach catalysts can also be incorporated into the cleaning agents according to the present invention.
• These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
• Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes can also be used as bleaching catalysts.
• agents are preferred, one or more substances from the group of bleach activators, in particular from the groups of polyacylated alkylenediamines, in particular tetraacetylethylene diamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), the acylated phenolsulfonates, in particular n- Nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS) and n-methyl-morpholinium-acetonitrile-methyl sulfate (MMA), in amounts of 0.1 to 20% by weight, preferably 0.5 to 15% by weight. % and in particular from 1 to 10 wt .-%, each based on the total agent.
• TAED tetraacetylethylene diamine
• N-acylimides in particular N-nonanoylsuccinimide (NOSI)
• NOSI N-nonanoylsucc
• the bleach activators preferred in the context of the present invention also include the “nitrile quats”, cationic nitriles of the formula (XVIII),
• R 2 and R 3 are independently selected from -CH 2 -CN, - CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 - CH 3 , -CH (CH 3 ) -CH 3 , -CH 2 -OH, -CH 2 -CH 2 -OH, -CH (OH) -CH 3 , -CH 2 - CH 2 -CH 2 -OH, -CH
• the general formula (XVIII) includes a large number of cationic nitriles which can be used in the context of the present invention.
• the laundry detergent tablets according to the invention particularly advantageously contain cationic nitriles in which R 1 is methyl, ethyl, propyl, isopropyl or an n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n- Tetradecyl, n-hexadecyl or n-octadecyl radical.
• R 2 and R 3 are preferably selected from methyl, ethyl, propyl, isopropyl and hydroxyethyl, where one or both radicals can advantageously also be a cyanomethylene radical.
• radicals R 1 to R 3 are identical, for example (CH 3 ) 3 N (+) CH 2 -CN X “ , (CH 3 CH 2 ) 3 N (+) CH 2 -CN X “ , (CH 3 CH 2 CH 2 ) 3 N (+) CH 2 -CN X “ , (CH 3 CH (CH 3 )) 3 N (+) CH 2 -CN X “ , or (HO-CH 2 -CH 2 ) 3 N (+) CH 2 -CN X " , where X " is preferably an anion selected from the group consisting of chloride, bromide, iodide, hydrogen sulfate, methosulfate, p-toluenesulfonate (tosylate) or xylene sulfonate.
• Automatic dishwashing agents or dishwashing aids preferred in the context of the present invention are characterized in that they contain the cationic nitrile of the formula (XVIII) in amounts of 0.1 to 20% by weight, preferably 0.25 to 15% by weight and in particular from 0.5 to 10% by weight, based in each case on the total weight of the composition.
• Particularly suitable enzymes are those from the classes of hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase the softness of the textile by removing pilling and microfibrils. Oxidoreductases can also be used for bleaching or for inhibiting color transfer.
• hydrolases such as proteases, esterases, lipases or lipolytically active enzymes, amylases, cellulases or other glycosyl hydrolases and mixtures of the enzymes mentioned. All these hydrolases help to remove stains such as protein, fat or starchy stains and graying in the laundry. Cellulases and other glycosyl hydrolases can also help to retain color and increase
• Bacillus subtilis Bacillus licheniformis
• Streptomyceus griseus Streptomyceus griseus
• Coprinus Cinereus and Humicola insolens as well as enzymatic active ingredients obtained from their genetically modified variants.
• 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 lipolytically active enzymes and cellulase, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytically active 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, iso-amylases, pullulanases and pectinases.
• Cellobiohydrolases, endoglucanases and glucosidases, which are also called cellobiases, or mixtures thereof, are preferably used as cellulases. Because different cellulase types distinguish themselves through their CMCase and Avicelase activities differentiate, the desired activities can be set by targeted mixtures of the cellulases.
• the enzymes can be adsorbed on carriers or embedded in coating substances to protect them against premature decomposition.
• Preferred agents according to the invention contain enzymes, preferably in the form of liquid and / or solid enzyme preparations, in amounts from 0.1 to 10% by weight, preferably from 0.5 to 8% by weight and in particular from 1 to 5% by weight. , each based on the total mean.
• dyes within the scope of the present invention, the selection of which does not pose any difficulty for the person skilled in the art, have a high storage stability and insensitivity to the other ingredients of the agents and to light, and no pronounced substantivity towards the items to be washed, in order not to stain them.
• Preferred for use in the automatic dishwashing agents or automatic dishwashing aids according to the invention are all colorants which can be oxidatively destroyed in the cleaning process, and also mixtures thereof with suitable blue dyes, so-called blue toners. It has proven to be advantageous to use colorants which are soluble in water or at room temperature in liquid organic substances.
• anionic colorants for example anionic nitroso dyes, are suitable.
• One possible dye is, for example, naphthol green (Color Index (CI) Part 1: Acid Green 1; Part 2: 10020)., That is as a commercial product, for example as Basacid ® Green 970 from BASF, Ludwigshafen available, as well as mixtures thereof with suitable blue dyes.
• Pigmosol ® Blue 6900 (Cl 74160), Pigmosol ® Green 8730 (Cl 74260), Basonyl ® Red 545 FL (Cl 45170), Sandolan ® Rhodamine EB400 (Cl 45100), Basacid ® Yellow 094 (Cl 47005), Sicovit ® Patentblau 85 E 131 (Cl 42051), Acid Blue 183 (CAS 12217-22-0, Cl Acidblue 183), Pigment Blue 15 (Cl 74160), Supranol ® Blau GLW (CAS 12219-32-8, Cl Acidblue 221 )), Nylosan ® Yellow N-7GL SGR (CAS 61814-57-1, Cl Acidyellow 218) and / or Sandolan ® Blue (Cl Acid Blue 182, CAS 12219-26-0). fragrances
• Fragrances are added to the compositions in the context of the present invention in order to improve the aesthetic impression of the products and, in addition to the performance of the product, to provide the consumer with a visually and sensorially “typical and distinctive” product.
• fragrance compounds e.g. the synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type are used.
• Fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalylbenzoate, benzyl formate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallyl propalate and benzylate propionate.
• the ethers include, for example, benzyl ethyl ether, the aldehydes e.g. the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones e.g.
• perfume oils can also contain natural fragrance mixtures as are available from plant sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well as orange blossom oil, neroliol, orange peel oil and sandalwood oil.
• Detergents for machine dishwashing can contain corrosion inhibitors to protect the wash ware or the machine, silver protection agents in particular being particularly important in the area of machine dishwashing.
• the known substances of the prior art can be used.
• silver protection agents selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles and the transition metal salts or complexes can be used in particular.
• benzotriazole and / or alkylaminotriazole are preferred.
• active chlorine-containing agents are often found in cleaner formulations, which can significantly reduce the corroding of the silver surface.
• oxygen- and nitrogen-containing organic redox-active compounds such as di- and trihydric phenols, e.g. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucin, pyrogallol or derivatives of these classes of compounds.
• Salt-like and complex-like inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce, are also frequently used.
• transition metal salts which are selected from the group of the manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate, as well as the manganese complexes
• Me-MeTACN Mn IM (m-0) (m-0Ac) 2 Mn MI (Me-MeTACN)] 2+ (PF 6 _ ) 2 , where Me-TACN for 1, 4,7-trimethyl-1, 4,7-triazacyclononane and Me-MeTACN stands for 1, 2,4,7-tetramethyl-1, 4,7-triazacyclononane.
• Zinc compounds can also be used to prevent corrosion on the wash ware.
• machine dishwashing agents or machine dishwashing aids which additionally have at least one silver protective agent selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles, preferably benzotriazole and / or alkylaminotriazole, in amounts of 0.001 to 1 % By weight, preferably from 0.01 to 0.5% by weight and in particular from 0.05 to 0.25% by weight, in each case based on the total composition.
• at least one silver protective agent selected from the group of the triazoles, the benzotriazoles, the bisbenzotriazoles, the aminotriazoles, the alkylaminotriazoles, preferably benzotriazole and / or alkylaminotriazole, in amounts of 0.001 to 1 % By weight, preferably from 0.01 to 0.5% by weight and in particular from 0.05 to 0.25% by weight, in each case based on the total composition.
• Another object of the present application is the use of an automatic dishwashing agent according to the invention or an automatic dishwashing aid to reduce glass corrosion in automatic dishwashing.
• the table shows that the machine dishwashing detergent according to the invention, which contains the combination of a zinc salt and a crystalline layered silicate, has significantly better gas corrosion properties under the conditions mentioned than dishwashing detergents which contain only zinc salt or only silicate.
• the corrosion-inhibiting effect of the active ingredient combination of zinc salt and silicate is well above the sum of the effects observed for the individual substances.

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• 2002
  • 2002-06-06 DE DE10225116A patent/DE10225116A1/de not_active Ceased
• 2003
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