EP2411495B1 - Agent de blanchiment à effet ménagé - Google Patents

Agent de blanchiment à effet ménagé Download PDF

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Publication number
EP2411495B1
EP2411495B1 EP10707548.3A EP10707548A EP2411495B1 EP 2411495 B1 EP2411495 B1 EP 2411495B1 EP 10707548 A EP10707548 A EP 10707548A EP 2411495 B1 EP2411495 B1 EP 2411495B1
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EP
European Patent Office
Prior art keywords
acid
bleach
transition metal
metal complex
weight
Prior art date
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EP10707548.3A
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German (de)
English (en)
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EP2411495A1 (fr
Inventor
Anette Nordskog
Dorota SENDOR-MÜLLER
Wolfgang Rybinski Von
Peter Schmiedel
Ursula Huchel
Thomas Weber
Siglinde Erpenbach
Andrea Krlejova
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Publication of EP2411495A1 publication Critical patent/EP2411495A1/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
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/226—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin esterified
    • 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
    • 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
    • D21C9/16—Bleaching ; Apparatus therefor with per compounds
    • D21C9/163—Bleaching ; Apparatus therefor with per compounds with peroxides

Definitions

  • the present invention relates to the use of cellulose acetate for reducing the damage of bleach-enhancing transition metal complexes in treating cellulosic material, particularly in the washing of textiles, a gentle process for treating cellulosic material in the presence of a pers oxygen-containing bleach and a bleach-enhancing transition metal complex, and bleaching agent containing oxygenated oxygen , bleach-enhancing transition metal complex and cellulose acetate.
  • Inorganic peroxygen compounds particularly hydrogen peroxide and solid peroxygen 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 disinfecting 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 ° 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 lowering the damage of the cellulose-containing material, for example a textile, when using bleach-active catalysts in the bleaching treatment of cellulose-containing material, for example in the washing of textiles, without significantly influencing the bleaching performance.
  • the invention relates in a first aspect to a process for the bleaching treatment of cellulosic material, in particular in the production of pulp or paper or in the washing of textiles, in the presence of a peroxygen bleaching agent and a bleach-enhancing transition metal complex, which is characterized in that it in presence of cellulose acetate.
  • cellulose acetate averaged 0.1 to 3.0, in particular 0.5 to 2.6 acetate groups per Anhydroglykosemonomerhim included.
  • cellulose is usually acetylated under acid catalysis. This gives cellulose acetates averaged over 2.9 acetate groups per anhydroglucose monomer unit, commonly referred to as cellulose triacetate. From this can be easily prepared by acidic or alkaline saponification cellulose acetate with a lower content of acetate groups.
  • 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 metal M is manganese.
  • Y is an anion such as chloride, bromide, iodide, nitrate, perchlorate, rhodanide, hexafluorophosphate, sulfate, alkylsulfate, alkylsulfonate or acetate; when the charge z is negative, Y is a cation, such as an alkali ion, ammonium ion or alkaline earth metal ion.
  • 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 (II),
  • R 10 and R 11 independently of one another represent hydrogen, a C 1-18 -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 a C 1-18 alkyl group
  • R 13 , R 14 and R 15 are independently hydrogen, a C 1-4 alkyl or hydroxyalkyl group and X is halogen and
  • A is a charge-balancing anion ligands, which depending on its charge and the type and number of other charges, in particular the charge of the manganese central atom, also missing or may be present several times.
  • Manganese can have the oxidation state II, III, IV or V therein as well as in the complexes according to formula (I). 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 in the range of 20 ° C to 40 ° C.
  • the process according to the invention can be carried out at pH values in the weakly acidic to alkaline range, in particular in the range from pH 5 to pH 12, preferably pH 8 to pH 11.
  • 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 100 ⁇ mol / l, in particular from 0.5 ⁇ mol / l to 25 ⁇ 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 cellulose acetate 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 cellulose acetate 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 cellulose acetate for reducing the damage to cellulose-containing material, for example textiles, by the presence of bleaching-enhancing transition metal complexes in the bleaching treatment of cellulose-containing material, for example in the washing of textiles.
  • the use of the cellulose acetate not only reduces the damage to the cellulosic material, but also improves the bleaching performance of the system of bleaching agent containing peroxygen and bleach-enhancing transition metal complex.
  • Another object of the invention is therefore the use of cellulose acetate to improve the bleaching performance of bleach-enhancing transition metal complex in aqueous solutions containing peroxygen-containing bleach.
  • 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 in situ, and cellulose acetate.
  • 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.
  • 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 are accessible to an oxidative attack.
  • Another application of such means is the removal of local stains on otherwise clean surfaces, so that a more complex washing or cleaning process of the corresponding overall structure, be it now a piece of clothing or a carpet or furniture upholstery, avoid.
  • an agent according to the invention optionally together with an amount of water which is insufficient for complete dissolution of the agent, to the textile surface or its part to be cleaned, optionally mechanical energy, for example by rubbing with a cloth or a sponge. and, after a period of time to be determined by the user, remove the agent and the oxidatively disrupted soiling by washing with water, for example with the aid of a moistened cloth or sponge.
  • 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, 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 cellulose acetate in principle contain all known ingredients customary in such agents.
  • the detergents and cleaners according to the invention may in particular be builders, surface-active Surfactants, enzymes, sequestrants, electrolytes, pH regulators, special effect polymers such as soil release polymers, dye transfer inhibitors, grayness inhibitors, anti-crease agents and shape-retaining agents, and other adjuvants such as optical brighteners, foam regulators, additional peroxygen activators, colorants and Contain 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 partially or preferably entirely replaces the persoxy-containing bleaching agent therein can.
  • bleach-activating agents in particular conventional bleach activators, that is to say compounds which contain perbenzoic acid which is optionally substituted under perhydrolysis conditions and / or peroxycarboxylic acids having 1 to 10 C atoms, in particular 2 to 4 C, may be present in the compositions according to the invention. Atoms are used. Suitable are customary bleach activators which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • 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
  • peritrile-forming nitriles such as 4-morpholinecarbonitrile or acetonitriles bearing ammonium groups
  • 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 of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups.
  • N-alkyl-amines vicinal diols, fatty acid esters and fatty acid amides, which correspond to said long-chain alcohol derivatives with respect to the alkyl part, and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical.
  • 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 methylglycinediacetic 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 or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content 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 allylsulfonic 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. Crystalline or amorphous alkali metal aluminosilicates, in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are particularly suitable as water-insoluble, water-dispersible inorganic builder materials. used.
  • 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 is usually 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 below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form.
  • 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, the so-called module, 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.
  • 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 from 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.
  • the detergents or cleaners according to the invention are preferably present in the detergents or cleaners according to the invention in amounts of up to 60% by weight, in particular from 5% by weight to 40% by weight, while the disinfectants according to the invention are preferably free from the complexing only of the components of the water hardness Builder substances are and preferably not more than 20% by weight, in particular from 0.1% by weight to 5% by weight, of heavy metal complexing substances, preferably from the group comprising aminopolycarboxylic acids, aminopolyphosphonic acids and hydroxypolyphosphonic acids and their water-soluble salts and mixtures thereof, contain.
  • 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.
  • inventive compositions are 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 wt .-% to 5 wt .-% alkali carbonate, which may be at least partially replaced by alkali metal bicarbonate included. 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 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 dimethylaminomethane diphosphonic acid, 3-aminopropane-1-hydroxy-1,1-diphosphonic acid, 1-amino-1-phenylmethane diphosphonic 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.
  • dimethylaminomethane diphosphonic acid 3-aminopropane-1-hydroxy-1,1-diphosphonic acid
  • 1-amino-1-phenylmethane diphosphonic 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.
  • HEDP 1-hydroxyethane 1,1-diphosphonic acid
  • alkali metal phosphate in particular trisodium polyphosphate, are contained.
  • Alkaliphosphat is the summary term for the alkali metal (especially sodium and potassium) salts of the 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 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and pass on Madrell's salt.
  • NaH 2 PO 4 is acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate (potassium phosphate primary or monobasic potassium, potassium biphosphate, KDP), KH 2 PO 4 , is a white salt of density 2.33 gcm -3 , has a melting point of 253 ° (decomposition to form (KPO 3 ) x , potassium polyphosphate) and is slightly 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 prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator.
  • Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is readily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless Crystals containing as dodecahydrate a density of 1.62 gcm -3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -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.
  • Tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder of density 2.56 gcm -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 gcm -3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals.
  • 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 gcm -3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4.
  • Condensation of the NaH 2 PO 4 or of the KH 2 PO 4 gives rise to relatively high molecular weight sodium and potassium phosphates, in which cyclic representatives, the sodium or potassium metaphosphates and chain types, the sodium or potassium polyphosphates, can be distinguished.
  • 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: (NaPO 3 ) 3 + 2 KOH ⁇ Na 3 K 2 P 3 O 10 + H 2 O
  • component e) in a preferred embodiment of the composition according to the invention 1.5 wt .-% to 5 wt .-% polymeric 2Polycarboxylat, in particular selected from the polymerization or copolymerization of acrylic acid, methacrylic acid and / or maleic acid.
  • polymeric 2Polycarboxylat 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.
  • compositions of the invention system and environmentally acceptable acids, in particular 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.
  • Such pH regulators are preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight, in the compositions according to the invention.
  • 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.
  • HOOC-Ph-COOH may be small Shares, in particular not more than 10 mol% based on the proportion of Ph having the meaning given above, of other acids having at least two carboxyl groups, 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.
  • 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.
  • Particularly preferred among the polymeric diols is polyethylene glycol having an average molecular weight in the range of 1000 to 6000.
  • these polyesters may also be end developmentver consideration, with alkyl groups having 1 to 22 carbon atoms and esters of monocarboxylic acids in question as end groups.
  • 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.
  • the color transfer inhibitors which are suitable for use in laundry detergents according to the invention are 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, -alkylolamides 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.
  • Suitable salts are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which, instead of 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.
  • 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 preferably bound to 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, III, 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 substrates provided with standardized tea soiling were treated for 30 minutes at 30 ° C in the respective solutions.
  • the treated fabric substrate was rinsed under running water and then dried and color measured.
  • the following table shows the brightness value of the cotton measuring pieces.
  • cotton strips of defined width were treated 20 times for 45 minutes each at 60 ° 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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Claims (14)

  1. Procédé de blanchiment d'une matière contenant de la cellulose, notamment lors la fabrication de pâte de cellulose ou de papier, ou lors du lavage de textiles, en présence d'un agent de blanchiment peroxygéné et d'un complexe de métal de transition renforçant le blanchiment, caractérisé en ce qu'il est mis en oeuvre en présence d'acétate de cellulose.
  2. Procédé selon la revendication 1, caractérisé en ce qu'il est réalisé à des températures dans la gamme allant de 10°C à 95°C, notamment dans la gamme allant de 20°C à 40°C.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce qu'il est réalisé à des valeurs de pH dans la gamme allant de pH 5 à pH 12, notamment de pH 8 à pH 11.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que l'on utilise des concentrations allant de 0,0001 g/l à 2 g/l, notamment 0,01 g/l à 1 g/l d'acétate de cellulose.
  5. Procédé de lavage de textile selon l'une des revendications 1 à 4, caractérisé en ce que les concentrations en peroxygène (calculé en H2O2) dans la lessive dans la gamme allant de 0,001 g/l à 10 g/l, notamment de 0,1 g/l à 1 g/l.
  6. Procédé de lavage de textile selon l'une des revendications 1 à 5, caractérisé en ce que la concentration en complexe de métal de transition renforçant le blanchiment dans la lessive est dans la gamme allant de 0,1 µmol/l à 100 µmol/l, notamment de 0,5 µmol/l à 25 µmol/l.
  7. Procédé selon l'une des revendications 1 à 6, caractérisé en ce que l'on utilise non pas le complexe de métal de transition final renforçant le blanchiment, mais séparément un ou plusieurs ligands qui peuvent former, dans le processus avec un métal de transition in situ, un complexe de métal de transition renforçant le blanchiment, et l'on ajoute de façon dosée le métal de transition également séparément sous la forme d'un sel ou d'un complexe ne renforçant pas le blanchiment ou on l'introduit dans le processus comme ingrédient de l'eau industrielle utilisée à cette fin ou par le biais de la matière à traiter contenant de la cellulose.
  8. Utilisation de l'acétate de cellulose pour diminuer les dommages causés à une matière contenant de la cellulose par la présence de complexes de métaux de transition renforçant le blanchiment lors du blanchiment d'une matière contenant de la cellulose.
  9. Utilisation de l'acétate de cellulose pour améliorer la capacité de blanchiment d'un complexe de métal de transition renforçant le blanchiment dans des solutions aqueuses contenant des agents de blanchiment peroxygénés.
  10. Détergent protégeant les textiles, ledit détergeant contenant un agent de blanchiment peroxygéné, un complexe de métal de transition renforçant le blanchiment ou un ou plusieurs ligands pouvant former, dans le processus de lavage avec un métal de transition in situ, un complexe de métal de transition renforçant le blanchiment, et de l'acétate de cellulose.
  11. Procédé, utilisation ou agent selon l'une des revendications 1 à 10, caractérisé en ce que l'acétate de cellulose contient en moyenne 0,1 à 3,0, notamment 0,5 à 2,6, groupes acétate par unité de monomère anhydroglucose.
  12. Procédé, utilisation ou agent selon l'une des revendications 1 à 11, caractérisé en ce que le composé complexe de métal de transition renforçant le blanchiment est un complexe métallique de la formule (I),

            [LnMmXp]z Yq     (I)

    où M est le manganèse ou le fer, ou des mélanges de ces métaux qui peuvent être présents à l'état d'oxydation II, III, IV ou V, ou des mélanges de ceux-ci, n et m sont indépendamment des nombres entiers ayant une valeur de 1 à 4, X est une espèce de coordination ou de pontage, p est un nombre entier ayant une valeur de 0 à 12, Y est un contre-ion dont le type dépend de la charge z du complexe qui peut être positive, nulle ou négative, q = z/[charge Y], et L est un ligand qui est une molécule organique macrocyclique de la formule générale
    Figure imgb0010
     où chacun des radicaux R1 et R2 peut être zéro, H, un groupe alkyle ou aryle, éventuellement substitué ; t et t' sont indépendamment 2 ou 3 ; D et D' sont indépendamment N, NR, PR, O ou S, où R est H, un groupe alkyle ou aryle, éventuellement substitué, et s est un nombre entier ayant une valeur de 2 à 5, où, si D = N, l'une des liaisons hétérocarbone à celui-ci est insaturée, ce qui entraîne la génération d'un sous-groupe fonctionnel N = CR1-.
  13. Procédé, utilisation ou agent selon la revendication 12, caractérisé en ce que le complexe correspond à la formule (I) où M = manganèse et L = 1,4,7-triazacyclononane, 1,4,7-Triméthyl-1,4,7-triazacyclononane, 1,5,9-Triméthy-1,5,9-triazacyclododécane ou 1,2,4,7-Tétraméthyl-1,4,7-triazacyclononane.
  14. Procédé, utilisation ou agent selon l'une des revendications 1 à 11, caractérisé en ce que le composé complexe de métal de transition renforçant le blanchiment est un complexe de manganèse de la formule (II),
    Figure imgb0011
     dans laquelle R10 et R11 représentent indépendamment l'hydrogène, un groupe alkyle en C1-18, un groupe -NR13R14, un groupe -N+R13R14R15 ou un groupe
    Figure imgb0012
     R12 représente l'hydrogène, -OH, ou un groupe alkyle en C1-18, R13, R14 et R15 représentent indépendamment l'hydrogène, un groupe alkyle en C1-4 ou un groupe hydroxyalkyle et X est un halogène, et A est un anion équilibrant la charge, qui en fonction de sa charge, du type et du nombre d'autres charges, notamment la charge de l'atome central de manganèse, peut également être absent ou présent plusieurs fois.
EP10707548.3A 2009-03-24 2010-03-11 Agent de blanchiment à effet ménagé Not-in-force EP2411495B1 (fr)

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WO1996006155A1 (fr) * 1994-08-24 1996-02-29 The Procter & Gamble Company Compositions de blanchiment comprenant des catalyseurs de blanchiment metalliferes et des sels d'ammonium
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