WO2010108784A1 - Agent de blanchiment non agressif - Google Patents

Agent de blanchiment non agressif Download PDF

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Publication number
WO2010108784A1
WO2010108784A1 PCT/EP2010/053082 EP2010053082W WO2010108784A1 WO 2010108784 A1 WO2010108784 A1 WO 2010108784A1 EP 2010053082 W EP2010053082 W EP 2010053082W WO 2010108784 A1 WO2010108784 A1 WO 2010108784A1
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WO
WIPO (PCT)
Prior art keywords
acid
bleach
transition metal
metal complex
weight
Prior art date
Application number
PCT/EP2010/053082
Other languages
German (de)
English (en)
Inventor
Anette Nordskog
Siglinde Erpenbach
Dorota SENDOR-MÜLLER
Peter Schmiedel
Wolfgang Rybinski Von
Ursula Huchel
Thomas Weber
Birgit Middelhauve
Original Assignee
Henkel Ag & Co. Kgaa
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Application filed by Henkel Ag & Co. Kgaa filed Critical Henkel Ag & Co. Kgaa
Publication of WO2010108784A1 publication Critical patent/WO2010108784A1/fr

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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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3905—Bleach activators or bleach catalysts
    • C11D3/3932—Inorganic compounds or complexes
    • 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
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
    • D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/1026—Other features in bleaching processes
    • D21C9/1036—Use of compounds accelerating or improving the efficiency of the processes
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/1026—Other features in bleaching processes
    • D21C9/1042—Use of chelating agents
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
    • D21C9/00—After-treatment of cellulose pulp, e.g. of wood pulp, or cotton linters ; Treatment of dilute or dewatered pulp or process improvement taking place after obtaining the raw cellulosic material and not provided for elsewhere
    • D21C9/10—Bleaching ; Apparatus therefor
    • D21C9/1026—Other features in bleaching processes
    • D21C9/1047—Conserving the bleached pulp

Definitions

  • the present invention relates to the use of hydantoins to reduce the damage of bleach-enhancing transition metal complexes in the treatment of cellulosic material, in particular in the washing of textiles, a gentle process for treating cellulosic material in the presence of a peroxygen bleaching agent and a bleach-enhancing transition metal complex and bleach containing peroxygen , bleach-enhancing transition metal complex and hydantoin.
  • Inorganic peroxygen compounds particularly hydrogen peroxide, and solid persompound compounds which dissolve in water to release hydrogen peroxide, such as sodium perborate and sodium carbonate perhydrate, have long been used as oxidizing agents for disinfection and bleaching purposes.
  • the oxidation effect of these substances in dilute solutions depends strongly on the temperature; Thus, for example, with H 2 O 2 or perborate in alkaline bleaching liquors only at temperatures above about 80 0 C, a sufficiently fast bleaching of soiled textiles.
  • the oxidation effect of the inorganic peroxygen compounds can be improved by adding so-called bleach activators, for the numerous proposals, especially from the classes of N- or O-acyl compounds, for example, polyacylated alkylenediamines, especially tetraacetylethylenediamine, acylated glycolurils, in particular tetraacetylglycoluril, N- acylated hydantoins, hydrazides, triazoles, hydrotriazines, urazoles, diketopiperazines, sulfururamides and cyanurates, in addition carboxylic acid anhydrides, in particular phthalic anhydride, carboxylic acid esters, in particular sodium nonanoyloxy-benzenesulfonate, sodium isononanoyloxy-benzenesulfonate and acylated sugar derivatives, such as pentaacetylglucose, have become known in the literature , By adding these substances,
  • the present invention aims at the bleaching treatment of cellulose-containing material, for example when washing cotton-containing textiles, to reduce the damage to the cellulose-containing material, for example a cotton-containing textile, when using bleach-active catalysts, without significantly influencing the bleaching performance.
  • the invention in a first aspect is a process for the bleaching treatment of cellulose-containing material, in particular in the production of pulp or paper or in the washing of cotton-containing textiles, in the presence of a persoxy-containing bleaching agent and a bleach-enhancing transition metal complex, which is characterized in that Presence of hydantoin is performed.
  • a hydantoin is to be understood as meaning a compound of the general formula (I)
  • X and Y independently of one another denote hydrogen or an optionally hydroxyl- and / or carboxy-substituted alkyl chain having 1 to 20 carbon atoms.
  • X and Y are the same.
  • at least one of the substituents X and Y is a group -CH 2 OH.
  • the hydatins can be used anhydrous or in the form of their hydrates. In the case of the presence of carboxy substituents, these are preferably in salt form, in particular as alkali salts such as sodium or Potassium salts, before.
  • Suitable bleach-activating transition metal complex compounds are in particular those of the metals Fe, Mn, Co, V, Ru, Ti, Mo, W, Cu and / or Cr, for example manganese, iron, cobalt, ruthenium or molybdenum-salene complexes, manganese , Iron, cobalt, ruthenium or molybdenum carbonyl complexes, manganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium and copper complexes with nitrogen-containing tripod ligands, cobalt, iron, , Copper and ruthenium ammine complexes, and iron or manganese complexes with polyazacycloalkane ligands such as TACN.
  • the metals Fe, Mn, Co, V, Ru, Ti, Mo, W, Cu and / or Cr for example manganese, iron, cobalt, ruthenium or molybdenum-salene complexes, manganese , Iron, co
  • Preferred bleach-enhancing transition metal complex compounds include metal complexes of the formula (II),
  • M means manganese or iron or mixtures of these metals, which may be in the oxidation state II, III, IV or V, or in mixtures thereof
  • n and m are independently integers having a value of 1 to 4
  • X is a coordinating or bridging Represents species
  • p is an integer from 0 to 12
  • Y is a counterion whose type depends on the charge z of the complex, which may be positive, zero or negative
  • q z / [charge Y]
  • L is a ligand which is a macrocyclic organic molecule of the general formula
  • Preferred metal M is manganese.
  • Y is an anion such as chloride, bromide, iodide, nitrate, perchlorate, rhodanide, hexafluorophosphate, sulfate, alkyl sulfate, alkyl sulfonate or acetate; when the charge z is negative, Y is a cation such as an alkali ion, ammonium ion or alkaline earth metal ion.
  • the preferred ligands L include 1, 4,7-triazacyclononane, 1, 4,7-trimethyl-1, 4,7-triazacyclononane, 1, 5,9-trimethyl-1, 5,9-triazacyclododecane and 1, 2, 4,7-tetramethyl-1, 4,7-triazacyclononane.
  • the bleach-enhancing transition metal complex compound corresponds to the general formula (III)
  • R 10 and R 11 are each independently hydrogen, a C- M s-alkyl group, a group -NR 13 R 14 , a group -N + R 13 R 14 R 15 or a group
  • R 12 is hydrogen, -OH, or Ci_i 8 alkyl group
  • R 13 is 14 and R 15 independently represents halogen, hydrogen, an alkyl or hydroxyalkyl group and CI_ 4 and A is a charge-compensating anion ligand is, which depending on its charge and the nature and number of other charges, in particular the charge of the manganese central atom, also missing or may be present several times.
  • manganese may have the oxidation state II, Ml, IV or V. If desired, though less preferred, other transition metals such as Fe, Co, Ni, V, Ru, Ti, Mo, W, Cu and / or Cr may be present in such complex compounds instead of the Mn central atom.
  • the process according to the invention can be carried out at temperatures in the range from 10 ° C. to 95 ° C.
  • the temperature is preferably in the range from 20 ° C. to 40 ° C.
  • the process according to the invention can be carried out at pH values in the neutral to alkaline range, in particular in the range from pH 7 to pH 12, preferably pH 9 to pH 11.
  • concentrations of 0.0001 g / l to 2 g / l, in particular 0.001 g / l to 1 g / l of hydantoin in the aqueous treatment solution preferably concentrations of 0.0001 g / l to 2 g / l, in particular 0.001 g / l to 1 g / l of hydantoin in the aqueous treatment solution.
  • preferred peroxygen concentrations (calculated as H 2 O 2 ) in the wash liquor are in the range of 0.001 g / l to 10 g / l, in particular 0.1 g / l to 1 g / l.
  • concentration of bleach-enhancing transition metal complex in the wash liquor is preferably in the range from 0.1 ⁇ mol / to 50 ⁇ mol / l, in particular from 0.5 ⁇ mol / l to 10 ⁇ mol / l.
  • the process according to the invention can be realized, for example, by adding peroxygen-containing bleach, bleach-enhancing transition metal complex and the hydantoin separately to a treatment solution for cellulose-containing material, for example a wash solution which may contain a conventional detergent. It is also possible not to use the final bleach-enhancing transition metal complex but separately one or more ligands which can form a bleach-enhancing transition metal complex in situ with a transition metal; The transition metal can then also be metered separately in the form of a salt or non-bleach-enhancing complex, or it is in the process as part of the process water used for this purpose or on the cellulosic material to be treated, in textiles to be cleaned, for example as part of the soiling to be removed in introduced the process. It is possible and preferred, the bleach-enhancing transition metal complex and the hydantoin at the same time, in particular preferably present as a water-containing or present as an aqueous solution premix together.
  • a second object of the invention is the use of hydantoin for reducing the damage to cellulosic material, for example cotton-containing textiles, by the presence of bleach-enhancing transition metal complexes in the bleaching treatment of cellulosic material, for example, in the washing of cotton-containing textiles.
  • an agent which contains peroxygen-containing bleach, bleach-enhancing transition metal complex or a ligand which can in situ form a bleach-enhancing transition metal complex with a transition metal and hydantoin.
  • a textile-sparing detergent is a further object of the invention.
  • Detergents according to the invention which may be present in solid form or as liquids or pastes, can be used as such in mechanical or manual washing processes, but can also be used as detergent additives and / or as laundry or textile pretreatment agents.
  • a detergent additive agents of the invention are used together with a conventional detergent. This is especially useful if the user wants to improve the usual detergent in its bleaching performance.
  • the agents according to the invention are used to improve the removal of encrusted dirt or stains, in particular "problem spots" such as coffee, tea, red wine, grass or fruit juice, which are difficult to remove by washing with conventional textile detergents, but
  • a further field of application of such agents is the removal of local soiling from otherwise clean surfaces, so that a more complex washing or cleaning process of the corresponding overall structure, be it a piece of clothing or a carpet or a piece of furniture upholstery, can be avoided can be in a simple manner an inventive means, optionally together with an amount of water which is insufficient for complete dissolution of the agent, apply to the textile surface or its part to be cleaned, optionally mechanical energy, for example by friction with a cloth or a sponge, and after a period of time to be determined by the user, remove the agent and the oxidatively broken stain by washing with water, for example with the
  • the agents according to the invention preferably comprise from 0.01% by weight to 0.5% by weight, in particular from 0.02% by weight to 0.3% by weight, of bleach-enhancing transition metal complex.
  • the agent according to the invention can also contain only one or more ligands which can form a bleach-enhancing transition metal complex in situ in the washing process with a transition metal.
  • the transition metal can also be present in the detergent in the form of a salt or non-bleach-enhancing complex or is introduced into the washing process as part of the process water used for this purpose or via the textile to be cleaned, for example as part of the soiling to be removed.
  • the detergents and cleaners according to the invention can contain, in addition to the peroxygen-containing bleach, the bleach-enhancing transition metal complex or the ligand which can form the bleach-enhancing transition metal complex in situ, and the hydantoin, in principle, all known ingredients customary in such agents.
  • the detergents and cleaners according to the invention may in particular be builders, surface active surfactants, enzymes, sequestering agents, electrolytes, pH regulators, polymers with special effects, such as soil release polymers, dye transfer inhibitors, grayness inhibitors, crease-reducing active ingredients and shape-retaining active ingredients, and further auxiliaries, such as optical brighteners, foam regulators, additional peroxygen activators, colorants and fragrances.
  • Suitable peroxygen compounds for use in the process according to the invention, in the use according to the invention and in agents according to the invention are in particular organic peracids or persistent salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the washing conditions, including alkali metal perborate , Alkali percarbonate, persilicate and / or persulfate such as caroate include, into consideration.
  • organic peracids or persistent salts of organic acids such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and inorganic salts which release hydrogen peroxide under the washing conditions, including alkali metal perborate , Alkali percarbonate, persilicate and / or persulfate such as caroate include, into consideration.
  • An agent according to the invention preferably contains 15% by weight to 50% by weight, in particular 18% by weight to 35% by weight, of peroxygen-containing bleaching agent, in particular alkali percarbonate.
  • peroxygen-containing bleaching agent in particular alkali percarbonate.
  • hydrogen peroxide can also be produced by an enzymatic system, namely an oxidase in combination with its substrate, which in a preferred embodiment of the invention is a constituent of the agent according to the invention and in which the pers oxygen-containing bleach partially or preferably completely can replace.
  • bleach-activating agents in particular conventional bleach activators, that is to say compounds which are optionally substituted perbenzoic acid under perhydrolysis conditions and / or peroxocarboxylic acids having 1 to 10 carbon atoms, in particular 2 to 4, may be present in the compositions according to the invention C atoms arise, are used.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated phenylsulfonates , in particular nonanoyloxy or isononanoyloxybenzenesulfonate, N-acylated capro- or valerolactams, in particular N-acetylcaprolactam, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran as well as acetylated sorbitol and mannitol, and acylated sugar derivatives.
  • TAED
  • vate in particular pentaacetylglucose (PAG), pentaacetyl fructose, tetraacetylxylose and octaacetyl lactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone.
  • PAG pentaacetylglucose
  • pentaacetyl fructose pentaacetyl fructose
  • tetraacetylxylose tetraacetylxylose
  • octaacetyl lactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone.
  • peritrile-forming nitriles such as 4-morpholinecarbonitrile or acetonitriles carrying ammonium groups, under perhydrolysis conditions.
  • the agents according to the invention are free from such conventional bleach activators.
  • compositions of the invention may contain one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof come into question.
  • Suitable nonionic surfactants are, in particular, alkyl glycosides and ethoxylation and / or propoxylation products of alkyl glycosides or linear or branched alcohols having in each case 12 to 18 C atoms in the alkyl moiety and 3 to 20, preferably 4 to 10, alkyl ether groups.
  • N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which, with regard to the alkyl moiety, correspond to the long-chain alcohol derivatives mentioned, and of alkylphenols having from 5 to 12 carbon atoms in the alkyl group rest usable.
  • Suitable anionic surfactants are in particular soaps and those which contain sulfate or sulfonate groups with preferably alkali ions as cations.
  • Usable soaps are preferably the alkali salts of the saturated or unsaturated fatty acids having 12 to 18 carbon atoms. Such fatty acids can also be used in incompletely neutralized form.
  • Useful surfactants of the sulfate type include the salts of the sulfuric acid half-esters of fatty alcohols having 12 to 18 carbon atoms and the sulfation products of said nonionic surfactants having a low degree of ethoxylation.
  • Suitable surfactants of the sulfonate type include linear alkylbenzenesulfonates having 9 to 14 carbon atoms in the alkyl moiety, alkane sulfonates having 12 to 18 carbon atoms, and olefin sulfonates having 12 to 18 carbon atoms, which are formed in the reaction of corresponding monoolefins with sulfur trioxide, and alpha-sulfofatty acid esters resulting from the sulfonation of fatty acid methyl or ethyl esters.
  • Such surfactants are present in the detergents or detergents according to the invention in amounts of preferably from 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight.
  • An agent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.
  • the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycine diacetic acid, nitrilotriacetic acid, ethylenediamine-N, N'-disuccinic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), Ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1, 1-di- phosphonic acid, polymeric hydroxy compounds such as dextrin and also polymeric (poly) carboxylic acids, in particular the polycarboxylates obtainable by oxidation of polysaccharides or dextrins, polymeric acrylic acids, methacrylic acids, maleic
  • the molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 5,000 and 200,000, that of the copolymers between 2,000 and 200,000, preferably 50,000 to 120,000, in each case based on the free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 50,000 to 100,000.
  • Suitable, although less preferred, compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight.
  • the first acidic monomer or its salt is derived from a monoethylenically unsaturated C 3 -C 8 -carboxylic acid and preferably from a C 3 -C 4 -monocarboxylic acid, in particular from (meth) acrylic acid.
  • the second acidic monomer or its salt may be a derivative of a C 4 -C 8 -dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an alkylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical ,
  • Such polymers generally have a molecular weight between 1,000 and 200,000.
  • Further preferred copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • organic builder substances may be present in amounts of up to 40% by weight, in particular up to 25% by weight and preferably from 1% by weight to 8% by weight.
  • Suitable water-soluble inorganic builder materials are, in particular, polymeric alkali metal phosphates, which may be in the form of their alkaline neutral or acidic sodium or potassium salts. Examples of these are tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate and the corresponding potassium salts or mixtures of sodium and potassium salts.
  • water-insoluble, water-dispersible inorganic builder materials are in particular crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40 wt .-% and in liquid agents, in particular from 1 wt .-% to 5 wt .-%, used.
  • preferred are the detergent grade crystalline sodium aluminosilicates, especially zeolite A, P and optionally X. Amounts near the above upper limit are preferably used in solid, particulate agents.
  • suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m.
  • Their calcium binding capacity which can be determined according to the specifications of the German patent DE 24 12 837, is generally in the range of 100 to 200 mg CaO per gram.
  • Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates.
  • the alkali metal silicates useful as builders in the compositions according to the invention preferably have a molar ratio of alkali metal oxide to SiO 2 of less than 0.95, in particular of 1: 1, 1 to 1: 12, and may be amorphous or crystalline.
  • Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of 1: 2 to 1: 2.8.
  • the crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na 2 Si x O y are used 2x + 1 H 2 O, in which x, known as the modulus, an integer of 1, 9 to 4 and y is a number from 0 to 20 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates (Na 2 Si 2 O 5 y H 2 O) are preferred.
  • compositions according to the invention can be prepared from amorphous alkali silicates, practically anhydrous crystalline alkali silicates of the abovementioned general formula in which x is a number from 1, 9 to 2.1, can be used in inventive compositions.
  • a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda. Crystalline sodium silicates with a modulus in the range of 1.9 to 3.5 are used in a further preferred embodiment of compositions according to the invention.
  • a granular compound of alkali silicate and alkali carbonate is used, as is commercially available, for example, under the name Nabion® 15.
  • the weight ratio of aluminosilicate to silicate is preferably 1:10 to 10: 1.
  • the weight ratio of amorphous alkali metal silicate to crystalline alkali metal silicate is preferably 1: 2 to 2: 1 and especially 1: 1 to 2: 1.
  • an agent according to the invention has a water-soluble builder block.
  • builder block is intended to express that the agents do not contain any further builder substances than those which are water-soluble, ie all builder substances contained in the agent are combined in the "block” characterized in this way, at most the amounts of Substances are excluded, which may be present as impurities or stabilizing additives in small amounts in the other ingredients of the products commercially.
  • water-soluble is to be understood as meaning that the builder block dissolves without leaving a residue at the concentration which results from the use of the agent containing it under the usual conditions, preferably at least 15% by weight and up to 55% by weight in the agents according to the invention, which preferably consists of the components a) 5% by weight to 35% by weight of citric acid, alkali citrate and, in particular, 25% by weight to 50% by weight of water-soluble builder block b) up to 10% by weight of alkali metal silicate with a modulus in the range from 1.8 to 2.5, c) up to 2% by weight of phosphonic acid and / or alkali metal carbonate, which may also be replaced at least proportionally by alkali metal bicarbonate or Alkaliphosphonat, d) up to 50 wt .-% alkali phosphate, and e) up to 10 wt .-% of polymeric polycarboxylate, wherein the amounts are based on the total detergent or cleaning agent .
  • the water-soluble builder block contains at least 2 of components b), c), d) and e) in amounts greater than 0% by weight.
  • component a in a preferred embodiment of the composition according to the invention, 15% by weight to 25% by weight of alkali carbonate, which may at least partly be replaced by alkali metal hydrogencarbonate, and up to 5% by weight, in particular 0.5% by weight. % to 2.5% by weight of citric acid and / or alkali citrate.
  • compositions according to the invention as component a) 5 wt .-% to 25 wt .-%, in particular 5 wt .-% to 15 wt .-% citric acid and / or alkali citrate and up to 5 wt .-%, in particular 1% by weight to 5% by weight of alkali metal carbonate, which may at least partly be replaced by alkali metal bicarbonate. If both alkali metal carbonate and alkali metal bicarbonate are present, the component comprises a) alkali carbonate and alkali metal bicarbonate, preferably in a weight ratio of 10: 1 to 1: 1.
  • component b) are in a preferred embodiment according to the invention Agent 1 wt .-% to 5 wt .-% alkali metal silicate with a modulus in the range of 1, 8 to 2.5 included.
  • agents according to the invention contain from 0.05% by weight to 1% by weight of phosphonic acids and / or alkali metal phosphonate.
  • Phosphonic acids are also understood as meaning optionally substituted alkyl and aryl phosphonic acids, for example phenylphosphonic acid, which may also have a plurality of phosphonic acid groups (so-called polyphosphonic acids).
  • They are preferably selected from the hydroxy and / or aminoalkylphosphonic acids and / or their alkali salts, for example dimethylaminomethanediphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethanediphosphonic acid, 1 -Hydroxyethane-1, 1-diphosphonic acid (HEDP), amino-tris (methylenephosphonic acid), and acylated derivatives of phosphorous acid, which can also be used in any mixtures.
  • dimethylaminomethanediphosphonic acid 3-aminopropane-1-hydroxy-1,1-diphosphonic acid
  • 1-amino-1-phenylmethanediphosphonic acid 1 -Hydroxyethane-1
  • 1-diphosphonic acid HEDP
  • amino-tris methylenephosphonic acid
  • acylated derivatives of phosphorous acid which can also be used in any mixtures.
  • alkali metal phosphate in particular trisodium polyphosphate, are contained.
  • Alkali phosphate is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to high molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
  • Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1, 91 like “3 , melting point 60 °) and as a monohydrate (density 2.04 like 3. ) Both salts are white powders that are very slightly soluble in water when heated lose the water of crystallization and at 200 0 C in the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7), at a higher temperature into sodium trimetaphosphate pass and Maddrell's salt (9 Na 3 P 3 O).
  • NaH 2 PO 4 reacts acid it is formed when phosphoric acid is adjusted to pH 4.5 and the mash is sprayed with caustic soda
  • Potassium dihydrogen phosphate potassium phosphate or potassium phosphate monobasic, KDP
  • KH 2 PO 4 is a white salt with a density of 2.33 3 , has a melting point of 253 ° (decomposes to form (KPO 3 ) X , potassium polyphosphate) and is readily soluble in water.
  • Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 is a colorless, very slightly water-soluble crystalline salt.
  • Disodium hydrogen phosphate is by neutralization of phosphoric acid with sodium carbonate solution under Use of phenolphthalein as an indicator
  • Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4
  • K 2 HPO 4 is an amorphous, white salt that is readily soluble in water
  • Trisodium phosphate, sodium tertiary phosphate, Na 3 PO 4 are colorless Crystals containing as dodecahydrate a density of 1, 62 like 3 and a melting point of 73-76 0 C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) has a melting point of 100 0 C and in anhydrous form ( corresponding to 39-40% P 2 O 5 ) has a density of 2.536 "3.
  • Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH Potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder of density 2.56 "3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 '3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1, 815-1, 836 like ' 3 , melting point 94 ° with loss of water).
  • decahydrate Density 1, 815-1, 836 like ' 3 , melting point 94 ° with loss of water.
  • Na 4 P 2 O 7 is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying.
  • the decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water.
  • Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33% "3 , which is soluble in water, the pH being 1% Solution at 25 ° C.
  • Pentakaliumtriphosphat, K 5 P 3 O 10 (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P 2 O 5 , 25% K 2 O) in the trade.
  • the potassium polyphosphates are widely used in the washing and cleaning industry.
  • Sodium potassium tripolyphosphates which are also usable in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH:
  • component e) in a preferred embodiment of the composition according to the invention 1.5 to 5 wt .-% polymeric polycarboxylate, in particular selected from the polymerization or copolymerization of acrylic acid, methacrylic acid and / or maleic acid.
  • polymeric polycarboxylate in particular selected from the polymerization or copolymerization of acrylic acid, methacrylic acid and / or maleic acid.
  • homopolymers of acrylic acid and, among these, those having an average molecular weight in the range from 5,000 D to 15,000 D (PA standard).
  • enzymes which can be used in the compositions apart from the abovementioned oxidase, those from the class of the proteases, lipases, cutinases, amylases, pullulanases, mannanases, cellulases, hemicellulases, xylanases and peroxidases and mixtures thereof are suitable, for example proteases such as BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Alcalase®, Esperase®, Savinase®, Durazym® and / or Purafect® OxP, amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and / or Purafect® OxAm, lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®, cellulases such as Celluzyme® and / or Carezyme®.
  • proteases such
  • fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia derived enzymatic agents.
  • the optionally used enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They are preferably present in the detergents, cleaners and disinfectants according to the invention in amounts of up to 10% by weight, in particular from 0.2% by weight to 2% by weight, particular preference being given to stabilizing enzymes which are stabilized against oxidative degradation become.
  • the agent contains 5% by weight to 50% by weight, in particular 8-30% by weight, of anionic and / or nonionic surfactant, up to 60% by weight, in particular 5-40% by weight of builder substance and 0.2% by weight to 2% by weight of enzyme selected from the proteases, lipases, cutinases, amylases, pullulanases, mannanases, cellulases, oxidases and peroxidases and mixtures thereof.
  • enzyme selected from the proteases, lipases, cutinases, amylases, pullulanases, mannanases, cellulases, oxidases and peroxidases and mixtures thereof.
  • the compositions of the invention system and environmentally friendly acids especially citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid, but also mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides.
  • pH regulators are preferably not more than 20 wt .-%, in particular from 1, 2 wt .-% to 17 wt .-%, contained in the inventive compositions.
  • Soil release polymers are, for example, nonionic or cationic cellulose derivatives.
  • the particularly polyester-active soil release polymers include copolyesters of dicarboxylic acids, for example adipic acid, phthalic acid or terephthalic acid, diols, for example ethylene glycol or propylene glycol, and polydiols, for example polyethylene glycol or polypropylene glycol.
  • Preferred soil release polyesters include those compounds which are formally accessible by esterification of two monomeric moieties, the first monomer being a dicarboxylic acid HOOC-Ph-COOH and the second monomer being a diol HO- (CHR 21 -) a OH, also known as polymeric Diol H- (O- (CHR 21 -) a ) b OH may be present.
  • Ph is an o-, m- or p-phenylene radical which can carry 1 to 4 substituents selected from alkyl radicals having 1 to 22 carbon atoms, sulfonic acid groups, carboxyl groups and mixtures thereof
  • R 21 is hydrogen, an alkyl radical having 1 to 22 C atoms and mixtures thereof
  • a is a number from 2 to 6
  • b is a number from 1 to 300.
  • the molar ratio of monomer diol units to polymer diol units is preferably 100: 1 to 1: 100, in particular 10: 1 to 1:10.
  • the degree of polymerization b is preferably in the range of 4 to 200, especially 12 to 140.
  • the molecular weight or the average molecular weight or the maximum molecular weight distribution of preferred soil release polyester is in the range of 250 to 100,000, especially 500 to 50,000
  • the acid underlying the remainder Ph is preferably selected from terephthalic acid, isophthalic acid, phthalic acid, trimellitic acid, mellitic acid, the isomers of sulfophthalic acid, sulfoisophthalic acid and sulfoterephthalic acid and mixtures thereof.
  • acids having at least two carboxyl groups may be included in the soil release-capable polyester.
  • alkylene and alkenylene dicarboxylic acids such as malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
  • the preferred diols HO- (CHR 21 -) a OH include those in which R 21 is hydrogen and a is a number from 2 to 6, and those in which a is 2 and R 11 is hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 C-atoms is selected.
  • R 21 is hydrogen and a is a number from 2 to 6
  • R 11 is hydrogen and the alkyl radicals 1 to 10, in particular 1 to 3 C-atoms is selected.
  • those of the formula HO-CH 2 -CHR 11 -OH in which R 11 has the abovementioned meaning are particularly preferred.
  • diol components are ethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 8-octanediol, 1, 2-decanediol, 1, 2-dodecanediol and neopentyl glycol.
  • Polyethylene glycol having an average molecular weight in the range from 1000 to 6000 is particularly preferred among the polymeric diols.
  • these polyesters may also be end-capped, alkyl groups having 1 to 22 carbon atoms and esters of monocarboxylic acids being suitable as end groups.
  • the ester groups bonded via end groups can be based on alkyl, alkenyl and aryl monocarboxylic acids having 5 to 32 carbon atoms, in particular 5 to 18 carbon atoms. These include valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, undecanoic acid, undecenoic acid, lauric acid, lauroleinic acid, tridecanoic acid, myristic acid, myristoleic acid, pentadecanoic acid, palmitic acid, stearic acid, petroselinic acid, petroselaidic acid, oleic acid, linoleic acid, linoleic acid, linolenic acid , Elaeostearic acid, arachidic acid, gadoleic acid, arachidonic acid, behenic acid, erucic acid, brassidic acid, clupanodonic acid, lignoceric acid, cerotic acid,
  • the end groups may also be based on hydroxymonocarboxylic acids having 5 to 22 carbon atoms, which include, for example, hydroxyvaleric acid, hydroxycaproic acid, ricinoleic acid, their hydrogenation product hydroxystearic acid, and o-, m- and p-hydroxybenzoic acid.
  • the hydroxymonocarboxylic acids may in turn be linked to one another via their hydroxyl group and their carboxyl group and thus be present several times in an end group.
  • the number of hydroxymonocarboxylic acid units per end group is in the range from 1 to 50, in particular from 1 to 10.
  • Color transfer inhibiting agents include, in particular, polyvinylpyrrolidones, polyvinylimidazoles, polymeric N-oxides such as poly (vinylpyridine-N-oxide) and copolymers of vinylpyrrolidone with vinylimidazole and optionally other monomers.
  • the inventive compositions for use in the textile laundry may contain anti-crease agents, since textile fabrics, in particular of rayon, wool, cotton and their mixtures, may tend to wrinkle, because the individual fibers are sensitive to bending, buckling, pressing and squeezing transverse to the fiber direction.
  • anti-crease agents since textile fabrics, in particular of rayon, wool, cotton and their mixtures, may tend to wrinkle, because the individual fibers are sensitive to bending, buckling, pressing and squeezing transverse to the fiber direction.
  • These include, for example, synthetic products based on fatty acids, fatty acid esters, fatty acid amides, -alkylol esters, -alkenylolamides or fatty alcohols, which are usually reacted with ethylene oxide, or products based on lecithin or modified phosphoric acid ester.
  • Graying inhibitors have the task of keeping suspended from the hard surface and in particular from the textile fiber suspended dirt in the fleet.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • starch derivatives can be used, for example aldehyde starches.
  • cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the compositions ,
  • the agents may contain optical brighteners, among these in particular derivatives of diaminostilbenedisulfonic acid or their alkali metal salts.
  • optical brighteners among these in particular derivatives of diaminostilbenedisulfonic acid or their alkali metal salts.
  • salts of 4,4'-bis (2-anilino-4-morpholino-1, 3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or similarly constructed compounds which are substituted for the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyrene type may be present, for example, the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl).
  • Mixtures of the aforementioned optical brightener can be used.
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant foam inhibitors are, for example Organopolysiloxanes and mixtures thereof with microfine, optionally silanated silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silica or bis-fatty acid alkylenediamides. It is also advantageous to use mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes.
  • the foam inhibitors in particular silicone and / or paraffin-containing foam inhibitors, are bound to a granular, water-soluble or dispersible carrier substance.
  • a granular, water-soluble or dispersible carrier substance In particular, mixtures of paraffins and bistearylethylenediamide are preferred.
  • silver corrosion inhibitors are organic disulfides, dihydric phenols, trihydric phenols, optionally alkyl- or aminoalkyl-substituted triazoles such as benzotriazole and cobalt, manganese, titanium, zirconium, hafnium, vanadium or cerium salts and / or complexes in which the Metals in one of the oxidation states II, IM, IV, V or VI are present.
  • An agent according to the invention may comprise customary antimicrobial agents in addition to the ingredients mentioned above in order to enhance the disinfecting action against specific germs.
  • antimicrobial additives are preferably present in compositions according to the invention in amounts of not more than 10% by weight, in particular from 0.1% by weight to 5% by weight.
  • a hard surface cleaning agent according to the invention may contain abrasive constituents, in particular from the group comprising quartz flours, wood flours, plastic flours, chalks and glass microspheres and mixtures thereof.
  • Abrasive substances are preferably not more than 20% by weight, in particular from 5% by weight to 15% by weight, in the cleaning agents according to the invention.
  • cotton strips of defined width were treated 20 times for 45 minutes each at 6O 0 C in the respective solutions.
  • the strips were dried and dipped in a wetting solution before being torn using a constant rate tensile testing machine.
  • the tensile strength of the treated cotton was compared with the tensile strength of the untreated cotton and the wet tensile strength loss in% was calculated.

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Abstract

La présente invention a pour objet de diminuer l'altération d'une matière cellulosique lorsqu'elle subit un traitement de blanchiment par utilisation de catalyseurs à action blanchissante, sans qu'il y ait d'effet sensible sur l'efficacité du blanchiment. A cet effet, l'invention a trait essentiellement à un procédé de traitement de blanchiment de matière cellulosique en la présence d'un agent de blanchiment contenant des composés peroxygénés et d'un complexe de métal de transition renforçant le blanchiment, ledit procédé étant mis en oeuvre en la présence d'hydantoïne.
PCT/EP2010/053082 2009-03-24 2010-03-11 Agent de blanchiment non agressif WO2010108784A1 (fr)

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DE102009001787.9 2009-03-24
DE102009001787A DE102009001787A1 (de) 2009-03-24 2009-03-24 Schonendes Bleichmittel

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012101149A1 (fr) 2011-01-26 2012-08-02 Novozymes A/S Granules d'enzyme stables au stockage

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2412837A1 (de) 1973-04-13 1974-10-31 Henkel & Cie Gmbh Verfahren zum waschen und reinigen der oberflaechen von festen werkstoffen, insbesondere von textilien, sowie mittel zur durchfuehrung des verfahrens
WO1998051772A1 (fr) * 1997-05-12 1998-11-19 Call, Krimhild Systeme de blanchiment aux enzymes a nouveaux composes renforçant l'action enzymatique
WO2001094692A2 (fr) * 2000-06-08 2001-12-13 Lonza Inc. Donneurs d'aldehyde permettant de stabiliser les peroxydes dans des applications de fabrication du papier
US20020010120A1 (en) * 2000-02-29 2002-01-24 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Composition and method for bleaching a substrate
WO2005116179A1 (fr) * 2004-05-17 2005-12-08 Henkel Kommanditgesellschaft Auf Aktien Agent de lavage comprenant un complexe de metal de transition qui renforce le blanchiment et est produit eventuellement in situ

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2412837A1 (de) 1973-04-13 1974-10-31 Henkel & Cie Gmbh Verfahren zum waschen und reinigen der oberflaechen von festen werkstoffen, insbesondere von textilien, sowie mittel zur durchfuehrung des verfahrens
WO1998051772A1 (fr) * 1997-05-12 1998-11-19 Call, Krimhild Systeme de blanchiment aux enzymes a nouveaux composes renforçant l'action enzymatique
US20020010120A1 (en) * 2000-02-29 2002-01-24 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Composition and method for bleaching a substrate
WO2001094692A2 (fr) * 2000-06-08 2001-12-13 Lonza Inc. Donneurs d'aldehyde permettant de stabiliser les peroxydes dans des applications de fabrication du papier
WO2005116179A1 (fr) * 2004-05-17 2005-12-08 Henkel Kommanditgesellschaft Auf Aktien Agent de lavage comprenant un complexe de metal de transition qui renforce le blanchiment et est produit eventuellement in situ

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012101149A1 (fr) 2011-01-26 2012-08-02 Novozymes A/S Granules d'enzyme stables au stockage

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