WO1995020034A1 - Adjuvant pour detergents et nettoyants - Google Patents

Adjuvant pour detergents et nettoyants Download PDF

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Publication number
WO1995020034A1
WO1995020034A1 PCT/EP1995/000151 EP9500151W WO9520034A1 WO 1995020034 A1 WO1995020034 A1 WO 1995020034A1 EP 9500151 W EP9500151 W EP 9500151W WO 9520034 A1 WO9520034 A1 WO 9520034A1
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Prior art keywords
weight
acetylated
salts
acid
hydroxybenzoic
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PCT/EP1995/000151
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German (de)
English (en)
Inventor
Christian Nitsch
Maria Liphard
Beatrix Kottwitz
Karlheinz Hill
Harald KÜSTER
Christian Block
Heribert Kaiser
Hans-Christian Raths
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Henkel Kommanditgesellschaft Auf Aktien
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Publication of WO1995020034A1 publication Critical patent/WO1995020034A1/fr

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    • 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
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
    • C07C65/01—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups
    • C07C65/03—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing hydroxy or O-metal groups monocyclic and having all hydroxy or O-metal groups bound to the ring

Definitions

  • the invention relates to detergents or cleaning agents which contain benzoic acid derivatives as builders. These benzoic acid derivatives are polyfunctional and are also distinguished, for example, by their action as bleach activators.
  • EP-A-0 448 298 describes detergents which contain zeolite and 3 to 18% by weight sodium citrate, zeolite and citrate being used in a specific weight ratio. In these agents, polyacrylates can be replaced by citrates without any loss in washing performance.
  • the object of the invention was to find further effective builders for detergents or cleaning agents which, however, not only prevent or reduce the formation of incrustations when used, but which show polyfunctional, or at least bifunctional, effects which are the same for detergents or cleaning agents Are interested.
  • the invention accordingly relates in a first embodiment to the use of benzoic acid derivatives from the group of the hydroxybenzoic acids or the hydroxybenzoic acid salts with at least one hydroxy group and the acetylated hydroxybenzoic acids or the acetylated hydroxybenzoic acid salts with at least one acetate Group as builders in washing or cleaning agents.
  • the number of hydroxyl groups in the hydroxybenzoic acids or the acetate groups in the acetylated hydroxybenzoic acids can in each case be between 1 and 5. 1 to 3 hydroxyl or acetate groups are preferred. In the case of acetylated hydroxybenzoic acids with more than 1 hydroxy group, it is possible for all the hydroxy groups or only part of the hydroxy groups present to be acetylated. It is particularly preferred that the agents contain acetylated hydroxybenzoic acids in which each hydroxyl group has been converted into an acetate group (full acetylation).
  • Monohydroxybenzoic acid or acetylated monohydroxybenzoic acid in particular the benzoic acids substituted in the p-position, and 3,4,5-trihydroxybenzoic acid, which is also called gallic acid, and gallic acid triacetate are particularly advantageous.
  • All of the benzoic acid derivatives mentioned, but in particular the preferred gallic acid can be used in non-acetylated, partially acetylated, fully acetylated form or as a mixture of these acids or their salts.
  • the benzoic acid derivatives used according to the invention can be used alone or in combination with other conventional builders.
  • gallic acid is used as a substitute or partial substitute for the conventional builders such as zeolites, phosphates or crystalline layered silicates.
  • the salts can be used in particular as alkali metal salts, such as sodium and / or potassium salts, as ammonium salts or as organically modified ammonium salts.
  • the magnesium salts may also be of interest because of their solubility behavior.
  • the substances in their acidity insert form When they are used in detergents or cleaning agents, they are converted into the salt form in an alkaline medium anyway, so that neutralization of the acids beforehand is not necessary.
  • the partially or fully acetylated hydroxybenzoic acids can generally be prepared in the manner known in the art by reacting the acids with a corresponding amount of acetic acid or acetic anhydride at room temperature or moderately elevated temperatures. If full acetylation is desired, an excess of acetic anhydride in two to five times the amount, based on the hydroxyl groups to be acetylated, is recommended.
  • An inorganic acid preferably hydrochloric acid or sulfuric acid and in particular concentrated sulfuric acid, is then added as a catalyst under temperature control. After the reaction has taken place, the reaction mixture can be stirred for a further several, for example 2 to 10 hours, at elevated temperatures of preferably 80 to 160 ° C. and in particular 100 to 150 ° C.
  • the anhydride used in excess can then be removed from the reaction mixture without problems using customary methods.
  • hydroxybenzoic acids or the acetylated hydroxybenzoic acids have polyfunctional effects.
  • some of them show effects similar to conventional bleach activators, for example tetraacetylethylene diamine, so that detergents or cleaning agents containing peroxy bleach, which usually have a bleach activator for washing or cleaning at temperatures below 60 ° C., do without conventional bleach activators or at least their content can be reduced.
  • Hydroxybenzoic acids or acetylated hydroxybenzoic acids are therefore particularly suitable for use in detergents or cleaning agents which contain bleaching agents, preferably peroxy bleaching agents.
  • the invention thus relates to a washing or cleaning agent which zeolite and / or crystalline, layered sodium silicates of the formula NaMSi x 02 ⁇ + yH20, 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 are 2, 3 or 4, this agent also comprising benzoic acid derivatives from the group of the hydroxybenzoic acids or the hydroxybenzoic acid salts with at least one hydroxy group and / or the acetylated hydroxybenzoic acids or contains the acetylated hydroxybenzoic acid salts with at least one acetate group.
  • the content of hydroxybenzoic acid or its salts and / or acetylated hydroxybenzoic acids or its salts in the agent according to the invention can vary within a wide range and is, for example, 0.5 to 50% by weight. High amounts above 20% by weight are advantageously contained in agents in which these benzoic acid derivatives serve as partial substitutes for zeolites or crystalline layered silicates.
  • the benzoic acid derivatives used according to the invention are contained in the compositions in combination with the builders zeolite and / or crystalline layered sodium silicates and, if appropriate, additionally small amounts of phosphates, with the proviso that the content of the benzoic acid derivatives up to is a maximum of 20% by weight and in particular in amounts of 1 to 15% by weight.
  • the invention also relates to washing or cleaning agents containing builders, which benzoic acid derivatives from the group of the hydroxybenzoic acids or the hydroxybenzoic acid salts with at least one hydroxyl group and / or the acetylated hydroxybenzoic acids or the acetylated hydroxybenzoic acid salts with contain at least one acetate group in amounts above 5 wt .-%.
  • the use of the preferred benzoic acid derivatives mentioned above is particularly another advantage.
  • Preferred embodiments are agents which have the stated hydroxybenzoic acids and / or the acetylated hydroxybenzoic acids or their salts in amounts of 5.5 to 15% by weight.
  • benzoic acid derivatives mentioned can also be present in these compositions as a substitute or at least as a partial substitute for zeolites, crystalline layered sodium silicates or phosphates. Their content is then preferably more than 20% by weight and can be up to about 50% by weight.
  • this invention also relates to detergents or cleaning agents which contain partially or fully acetylated hydroxybenzoic acids or hydroxybenzoic acid salts with at least one hydroxyl group, but not non-acetylated benzoic acid derivatives. It is particularly preferred that the agents contain the partially or fully acetylated hydroxybenzoic acids or hydroxybenzoic acid salts in amounts of 0.5 to 50% by weight, preferably up to 20% by weight and in particular in amounts of 1 to 15% by weight exhibit.
  • a particularly advantageous embodiment of these agents are machine dishwashing agents which contain gallic acid triacetate.
  • These agents also advantageously contain 20 to 60% by weight, preferably 30 to 50% by weight, phosphates, polycarboxylates, preferably citrate, or mixtures of these in any ratio, optionally additionally up to 15% by weight, preferably up to 8% by weight of polycarboxylic acid, in particular citric acid, optionally up to 12% by weight of polymers, optionally up to 20% by weight, preferably 5 to 12% by weight of carbonates, if appropriate up to 10 % By weight, preferably up to 4% by weight of amorphous silicates, optionally up to 50% by weight, preferably 5 to 45% by weight and in particular above 20% by weight of bicarbonates.
  • agents in particular for detergents and machine dishwashing detergents, it applies that they preferably contain peroxy bleaching agents such as perborate or percarbonate, and in particular in amounts of 5 to 25% by weight.
  • Dishwashing detergents can also have active chlorine compounds as bleaching agents, but peroxy bleaching agents are also preferred in these embodiments.
  • the agents can additionally contain other conventional bleach activators. Particularly in the case of machine dishwashing detergents, however, it is preferred not to use any additional bleach activators. In all other embodiments it is possible, but not absolutely necessary, to use additional bleach activators such as, for example, tetraacetylethylenediamine. In these cases, the content of optionally acetylated hydroxybenzoic acids or their salts is preferably limited to a maximum of 10% by weight and in particular to a maximum of 5% by weight.
  • the agents according to the invention can contain all ingredients normally used in detergents or cleaning agents, for example anionic, nonionic, cationic, phot and / or nonionic surfactants, conventional builders as well as cobuilders, bleaching agents and optionally additional bleach activators, with an alkaline reaction in water Salts, solubility improvers such as conventional hydrotropes or polyalkylene glycols, for example polyethylene glycols, foam inhibitors, optical brighteners, enzymes and enzyme stabilizers, contain small amounts of neutral filler salts and colorants and fragrances.
  • solubility improvers such as conventional hydrotropes or polyalkylene glycols, for example polyethylene glycols, foam inhibitors, optical brighteners, enzymes and enzyme stabilizers, contain small amounts of neutral filler salts and colorants and fragrances.
  • the anionic and nonionic surfactants, including soap, in the compositions are preferably 10 to 40% by weight, advantageously 12 to 35% by weight and in particular 15 to 30% by weight.
  • the content of surfactants in automatic dishwashing detergents is preferably limited to a maximum of 10% by weight.
  • the use of nonionic surfactants is particularly preferred here.
  • surfactants of the sulfonate type are Cg-C ⁇ -alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates of the type obtained, for example, from Ci2-Ci8 monoolefins with a terminal or internal double bond Sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products is considered.
  • alkane sulfonates which are obtained from C 1 -C 18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
  • the sulfonate group is along the entire carbon chain statistically distributed, with the secondary alkanesulfonates predominating.
  • the esters of ⁇ -sulfofatty acids are also suitable.
  • esters of ⁇ -sulfofatty acids which are prepared by ⁇ -sulfonation of the methyl esters of fatty acids of plant and / or animal origin with 8 to 20 C atoms in the fatty acid molecule and subsequent neutralization to form water-soluble mono-salts are suitable.
  • ⁇ -sulfonated esters of hydrogenated coconut, palm, palm kernel or tallow fatty acids with sulfonation products of unsaturated fatty acids, for example oleic acid, in small amounts, preferably in amounts not above about 2 to 3% by weight .-%, may be present.
  • ⁇ -sulfofatty acid alkyl esters are preferred which have an alkyl chain with no more than 4 carbon atoms in the ester group, for example methyl esters, ethyl esters, propyl esters and butyl esters.
  • the methyl esters of ⁇ -sulfofatty acids (MES) are used with particular advantage.
  • ⁇ -sulfofatty acids obtainable by ester cleavage of the ⁇ -sulfofatty acid alkyl esters or their di-salts.
  • the mono-salts of the ⁇ -sulfofatty acid alkyl esters are obtained in their industrial production as an aqueous mixture with limited amounts of di-salts.
  • Mixtures of mono salts and di salts with other surfactants, for example with alkylbenzenesulfonate or alkyl sulfates, are also preferred.
  • sulfonated fatty acid glycerol esters are sulfonated fatty acid glycerol esters.
  • Fatty acid glycerol esters are to be understood as the mono-, di- and triesters and their mixtures as obtained in the production by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol become.
  • Preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids having 6 to 22 carbon atoms, for example capric acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
  • fats and oils that is to say natural mixtures of different fatty acid glycerol esters
  • suitable feedstocks are palm oil, palm kernel oil, palm stearin, olive oil, Turnip oil, coriander oil, sunflower oil, cottonseed oil, peanut oil, linseed oil, lard oil or lard. Because of their high natural content of saturated fatty acids, it has proven to be particularly advantageous to start from coconut oil, palm kernel oil or beef tallow.
  • the sulfonation of the saturated fatty acids with 6 to 22 carbon atoms or the mixtures of fatty acid glycerol esters with iodine numbers less than 5, which contain fatty acids with 6 to 22 carbon atoms, is preferably carried out by reaction with gaseous sulfur trioxide and subsequent neutralization with aqueous bases, such as it is specified in international patent application W0-A-91/09009.
  • the sulfonation products are a complex mixture containing mono-, di- and triglyceride sulfonates with an ⁇ -position and / or internal sulfonic acid grouping.
  • Sulfonated fatty acid salts, glyceride sulfates, glycerol sulfates, glycerol and soaps are formed as by-products. If one starts from the sulfonation of saturated fatty acids or hardened fatty acid glycerine ester, the proportion of the ⁇ -sulfonated fatty acid disalts can be up to about 60% by weight, depending on the procedure.
  • Suitable sulfate-type surfactants are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin.
  • the alk (en) yl sulfates are the sulfuric acid half-esters of the Ci2-Ci8 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C ⁇ o-C2 ⁇ _ 0xoalcohols, and those secondary alcohols of this chain length prefers.
  • alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
  • Ci5-Ci8-alk (en) yl sulfates are particularly preferred for washing technology reasons. It can also be particularly advantageous, and particularly advantageous for machine washing agents, to use Ci6-Ci8-alk (en) yl sulfates in combination with lower melting anionic surfactants and in particular with those anionic surfactants which have a lower Krafft point and with relatively low detergents temperatures of, for example, room temperature to 40 ° C.
  • the compositions therefore contain mixtures of short-chain and long-chain fatty alkyl sulfates, preferably mixtures of C12-C14 fatty alkyl sulfates or Ci2-Ci8 fatty alkyl sulfates with Ci-Cis-fatty alkyl sulfates and in particular Ci2-Ci6-fatty alkyl sulfates with Ci6-C ⁇ s-fatty alkyl sulfates.
  • not only saturated alkyl sulfates but also unsaturated alkenyl sulfates with an alkenyl chain length of preferably C15 to C22 are used.
  • the sulfuric acid monoesters of the straight-chain or branched C7-C2i alcohols ethoxylated with 1 to 6 moles of ethylene oxide such as 2-methyl-branched Cg-Cn alcohols with an average of 3.5 moles of ethylene oxide (EO) or Ci2-Ci8 -Fatty alcohols with 2 to 4 EO are suitable. Because of their high foaming behavior, they are used in detergents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
  • Preferred anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C ⁇ to Ci8 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols which, viewed in isolation, are nonionic surfactants (for a description, see below).
  • sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Preferred granular detergents or cleaning agents contain, as anionic surfactants, alkylbenzene sulfonate and / or alkyl sulfate, preferably fatty alkyl sulfate, and / or sulfated fatty acid glycerol esters. Agents which contain alkyl sulfates and / or alkylbenzenesulfonates as anionic surfactants are particularly preferred.
  • Suitable anionic surfactants are, in particular, soaps, preferably in amounts of 0.2 to 8% by weight and in particular 0.5 to 5% by weight.
  • Saturated fatty acid soaps are suitable, such as the salts of lauric acid, myristic acid, palmitic acid or stearic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or taig fatty acids, derived soap mixtures.
  • those soap mixtures are preferred which are composed of 50 to 100% by weight of saturated Ci2-C24 fatty acid soaps and 0 to 50% by weight of oleic acid soap.
  • the anionic surfactants and soaps can be present in the form of their sodium, potassium or ammonium salts and 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.
  • the granular detergents or cleaning agents also contain nonionic surfactants in addition to the anionic surfactants, preferably in amounts of 1 to 15% by weight and in particular in amounts of 2 to 12% by weight.
  • the nonionic surfactants used are preferably ethoxylated and / or propoxylated alcohols which are derived from primary alcohols with preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (E0) per mole of alcohol in which the alcohol radical is linear or preferably in 2-position can be methyl-branched, or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 E0 per mole of alcohol are particularly preferred.
  • Preferred ethoxylated alcohols include for example Ci2-Ci4 alcohols with 3 EO or 4 EO, Cg-Cn alcohol with 7 EO, Ci3-Ci5 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, Ci2-Ci8 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C12-Ci4 alcohol with 3 EO and Ci2-Ci8 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.
  • alkyl glycosides of the general formula R0 (G) x in which R is a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C., can also be used as further nonionic surfactants -Atoms means and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • nonionic surfactants which are used either as the sole nonionic surfactant or in combination with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated, fatty acid alkyl esters, preferably with 1 to 4 carbon atoms in the Alkyl chain, in particular fatty acid methyl esters, as described, for example, in Japanese patent application JP 58/217598 or which are preferably prepared by the process described in international patent application WO-A-90/13533.
  • 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 non-ionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of them.
  • Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I),
  • R 2 is C0 for an aliphatic acyl radical having 6 to 22 carbon atoms
  • R3 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 is up to 10 hydroxyl groups.
  • the fine crystalline, synthetic and bound water-containing zeolite used is preferably zeolite NaA in detergent quality.
  • zeolite NaX, zeolite P and mixtures of A, X and / or P are also suitable.
  • the zeolite can be used as a spray-dried powder or as an undried stabilized suspension which is still moist from its production.
  • the zeolite may contain minor additions of nonionic surfactants as stabilizers, for example 1 to 3% by weight, based on zeolite, of ethoxylated C 12 -C 8 -fatty alcohols with 2 to 5 ethylene oxide groups, Ci2-Ci4 fatty alcohols with 4 to 5 ethylene oxide groups or ethoxylated isotridecanols.
  • Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22, in particular 20 to 22,% by weight of bound water.
  • Suitable substitutes or partial substitutes for phosphates and zeolites are crystalline, layered sodium silicates of the formula NaMSi x ⁇ 2 ⁇ + ⁇ -yH2 ⁇ , 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.
  • Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
  • Preferred crystalline sheet silicates are those in which M represents sodium and x assumes the values 2 or 3.
  • both .beta.- and ⁇ '-Natriumdi- silicates Na2Si2 ⁇ 5 * yH2 ⁇ preferred, with ß-sodium disilicate, for example, can be obtained by the method described in international patent application WO-A-91/08171.
  • the content of zeolites and / or crystalline layered sodium silicates in any weight ratio of the agents is preferably 20 to 60% by weight and in particular 25 to 50% by weight, if these ingredients are not partially or completely due to the benzoic acid derivatives used according to the invention be replaced.
  • Machine dishwashing detergents preferably do not contain zeolite, but rather phosphates and / or crystalline layered sodium silicates in any weight ratio.
  • Useful organic builder substances are, for example, polymeric polycarboxylates.
  • Suitable polymeric polycarboxylates are, for example, the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, 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 5,000 to 200,000, preferably 10,000 to 120,000 and in particular 50,000 to 100,000.
  • the content of (co) polymeric polycarboxylates in the compositions is preferably 0.5 to 10% by weight and in particular 1 to 5% by weight. Because of the good builder properties of the hydroxybenzoic acids and acetylated hydroxybenzoic acids or their salts used according to the invention, the use of cobuilders such as (co) polymeric polycarboxylates is not absolutely necessary. In a preferred embodiment of the invention, the agents, in particular detergents, are therefore free from (co) polymeric polycarboxylates.
  • biodegradable terpolymers for example those which are salts of acrylic acid and maleic acid as monomers and vinyl alcohol or vinyl alcohol derivatives (P 4300772.4) or which are salts of acrylic acid and 2-alkylallylsulfonic acid as monomers and Sugar derivatives (P 4221 381.9) included, preferred.
  • biodegradable terpolymers for example those which are salts of acrylic acid and maleic acid as monomers and vinyl alcohol or vinyl alcohol derivatives (P 4300772.4) or which are salts of acrylic acid and 2-alkylallylsulfonic acid as monomers and Sugar derivatives (P 4221 381.9) included, preferred.
  • Other suitable builder systems are oxidation products of carboxyl-containing polyglucosans and / or their water-soluble salts, as are described, for example, in international patent application WO-A-93/08251 or their preparation, for example, in international patent application WO-A-93/16110 or older German patent application P 43 30393.0 is described.
  • Suitable organic builders naturally also include polycarboxylic acids or their salts, such as citric acid, adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), provided that 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.
  • polycarboxylates in particular citrate, are contained in preferred detergents due to the good (co) builder effects of the benzoic acid derivatives used according to the invention at most in minor amounts, for example in amounts of up to 5% by weight, such as 2 or 3% by weight.
  • These polycarboxylates can be of great importance in automatic dishwashing detergents, since they can also replace phosphates. Their content in automatic dishwashing detergents can even be 20 to 60% by weight, but also significantly less.
  • Suitable ingredients of the agents are water-soluble inorganic salts such as bicarbonates, carbonates, amorphous silicates or mixtures of these;
  • alkali carbonate and amorphous alkali silicate especially sodium silicate with a molar ratio Na2 ⁇ : Si ⁇ 2 from 1: 1 to 1: 4.5, preferably from 1: 2 to 1: 3.5, are used.
  • the content of sodium carbonate in the middle is preferably up to 20% by weight, advantageously between 5 and 15% by weight.
  • the content of sodium silicate in the compositions is generally up to 10% by weight and preferably between 2 and 8% by weight.
  • bicarbonates, in particular sodium bicarbonate are preferably used in the preferred lower-alkaline dishwashing detergents.
  • alkali metal carbonates can also be replaced by sulfur-free, 2 to 11 carbon atoms and, if appropriate, a further carboxyl and / or amino group having amino acids and / or their salts. In the context of this invention, it is preferred that the alkali metal carbonates be partially or completely replaced by glycine or glycinate.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents that can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H2O2-providing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
  • the bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, with perborate monohydrate being advantageously used.
  • the hydroxybenzoic acids and acetylated hydroxybenzoic acids or their salts used according to the invention also have the effect of a bleach activator, in most cases it is not absolutely necessary to use additional bleach activators. Only in those cases in which the optionally acetylated hydroxybenzoic acids are contained in the agents only in relatively small amounts, for example in amounts of maximallO, preferably at most 5% by weight, can it be advantageous if the agents provide additional bleach activators contain conventional type. Examples of these are N-acyl or O-acyl compounds which form organic peracids with H2O2, preferably N, N'-tetraacylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate.
  • the bleach activator content of the bleach-containing agents is in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
  • the content of additional bleach activators can advantageously be limited to a maximum of 5% by weight.
  • Particularly preferred bleach activators are N, N, N ', N'-tetraacetylethylenediamine and 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine.
  • Suitable as foam inhibitors Soaps of natural or synthetic origin, for example, which have a high proportion of Ci8 ⁇ C24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of different foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
  • the foam inhibitors, in particular silicone or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediaids are particularly preferred.
  • Suitable enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof. Enzymatic active ingredients obtained from bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus are particularly suitable. Proteases of the subtilisin type and in particular proteases which are obtained from Bacillus lentus are preferably used.
  • Enzyme mixtures for example of protease and amylase or protease and lipase or protease and cellulase or of cellulase and lipase or of protease, amylase and lipase or protease, lipase and cellulase, but in particular mixtures containing cellulase, are of particular interest.
  • Peroxides or oxidases have also proven to be suitable in some cases.
  • the enzymes can be adsorbed on carriers and / or embedded in coating substances in order to protect them against premature decomposition.
  • the proportion of the enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5% by weight, preferably 0.1 to about 2% by weight.
  • the salts of polyphosphonic acids are suitable as stabilizers, in particular for per-compounds and enzymes.
  • proteases which are stabilized with soluble calcium salts and a calcium content of preferably about 1.2% by weight, based on the enzyme.
  • the use is particularly advantageous boron compounds, for example boric acid, boron oxide, borax and other alkali metal borates such as the salts of orthoboric acid (H3BO3), metaboric acid (HBO2) and pyroboric acid (tetraboric acid H2B4O7).
  • Graying inhibitors have the task of keeping the dirt detached from the fiber suspended in the liquor and thus preventing graying.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, e.g. degraded starch, aldehyde starches, etc.
  • Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose, methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and also polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the composition , used.
  • the agents can contain, as optical brighteners, derivatives of diaostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-l, 3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similar compounds, instead of morpholino -Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, e.g.
  • the bulk density of the preferred granular agents is generally 300 to 1200 g / 1, in particular 500 to 1100 g / 1. They can be produced by any of the known processes such as mixing, spray drying, granulating and extruding. Processes in which several partial components, for example spray-dried components and granulated and / or extruded components, are mixed with one another are particularly suitable.
  • spray-dried or granulated components can be subsequently treated, for example with nonionic surfactants, in particular ethoxylated fatty alcohols, by the customary processes.
  • nonionic surfactants in particular ethoxylated fatty alcohols
  • Suitable surface modifiers are known from the prior art.
  • suitable, finely divided zeolites, silicas, amorphous silicates, fatty acids or fatty acid salts for example calcium stearate, but especially mixtures of zeolite and silicas or zeolite and calcium stearate are particularly preferred.
  • the calcium complexing ability was determined potentiometrically using a calcium-sensitive electrode from Orion.
  • 1 liter of water at 30 ° d (corresponding to 30 mg Ca0 / 1) was initially placed in a glass vessel thermostated to 30 ° C., this solution with sodium hydroxide solution to pH 10 and with potassium chloride to simulate an electrolyte content that is usual for a detergent adjusted to a 0.08 molar potassium chloride solution.
  • 1 g each of the substances to be examined were dissolved in 5 ml of ethanol and added to the potassium chloride solution with stirring.
  • the decrease in calcium hardness was determined by means of a computer as a function of time, and the value of the residual hardness was evaluated 10 minutes after the addition of the substance to the solution presented.
  • the bound hardness per g of substance resulted from the difference between the initial hardness and the residual hardness.
  • Gluconic acid 25 mg CaO / g active substance
  • Example 3 Effect as a bleach activator
  • a machine dishwashing detergent consisting of 5% by weight sodium carbonate, 30% by weight sodium bicarbonate, 45% by weight trisodium citrate, 12% by weight percarbonate and 2% by weight gallic acid triacetate and 2% by weight each % Cj2-Ci8 fatty alcohol with 5 E0, foam inhibitor based on paraffin and protease, and the removal of tea soiling on porcelain was assessed.
  • the tea soiling was prepared in such a way that 16 l of cold water (16 ° d) were heated to boiling in a water treatment boiler.

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Abstract

L'invention vise à trouver des adjuvants pour détergents et nettoyants, présentant non seulement la propriété d'éviter ou de réduire la formation d'incrustations, mais également celle de comporter des effets polyfonctionnels ou du moins bifonctionnels, importants pour les détergents ou les nettoyants. Les adjuvants de ce type sont des dérivés d'acide benzoïque issus du groupe des acides hydroxybenzoïques ou des sels d'acide hydroxybenzoïque comportant au moins un groupe hydroxy et/ou des acides hydroxybenzoïques acétylés ou des sels d'acide hydroxybenzoïque acétylés comportant au moins un groupe acétate. Dans les détergents qui contiennent ce type d'adjuvants, la teneur en activateurs de blanchiment classiques peut également être réduite ou les activateurs de blanchiment classiques peuvent être remplacés par ces substances. Dans les agents de rinçage pour vaisselle, ces adjuvants s'avèrent efficaces pour éliminer les traces de thé.
PCT/EP1995/000151 1994-01-25 1995-01-16 Adjuvant pour detergents et nettoyants WO1995020034A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19944402053 DE4402053A1 (de) 1994-01-25 1994-01-25 Gerüststoff für Wasch- oder Reinigungsmittel
DEP4402053.8 1994-01-25

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WO1995020034A1 true WO1995020034A1 (fr) 1995-07-27

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PCT/EP1995/000151 WO1995020034A1 (fr) 1994-01-25 1995-01-16 Adjuvant pour detergents et nettoyants

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0337274A2 (fr) * 1988-04-14 1989-10-18 Unilever N.V. Compositions détergentes pour tissus
EP0592906A1 (fr) * 1992-10-10 1994-04-20 Caramba Chemie GmbH Agent de nettoyage pour jantes

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0337274A2 (fr) * 1988-04-14 1989-10-18 Unilever N.V. Compositions détergentes pour tissus
EP0592906A1 (fr) * 1992-10-10 1994-04-20 Caramba Chemie GmbH Agent de nettoyage pour jantes

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DE4402053A1 (de) 1995-07-27

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