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WO1997046659A1 - Agents de blanchiment aqueux - Google Patents

Agents de blanchiment aqueux Download PDF

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Publication number
WO1997046659A1
WO1997046659A1 PCT/EP1997/002626 EP9702626W WO9746659A1 WO 1997046659 A1 WO1997046659 A1 WO 1997046659A1 EP 9702626 W EP9702626 W EP 9702626W WO 9746659 A1 WO9746659 A1 WO 9746659A1
Authority
WO
WIPO (PCT)
Prior art keywords
carbon atoms
alkyl
contain
composition according
radical
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP1997/002626
Other languages
German (de)
English (en)
Inventor
Mercedes Mendoza
Maite Canellas
Jaume Jose
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from DE19624843A external-priority patent/DE19624843C2/de
Application filed by Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Priority to DE59708205T priority Critical patent/DE59708205D1/de
Priority to EP97924975A priority patent/EP0918841B1/fr
Publication of WO1997046659A1 publication Critical patent/WO1997046659A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395—Bleaching agents
    • C11D3/3956—Liquid compositions

Definitions

  • the invention relates to new aqueous bleaching agents containing alkali hypochlorites and polyacrylic acid compounds and to the use of the polyacrylic acid compounds as stabilizers for the production of aqueous bleaching agents.
  • EP-A 0 274 885 recommends the use of mixtures of linear and branched amine oxides for the production of viscous hypochlorite bleaches.
  • EP-A 0 145 084 Uni-lever
  • mixtures of amine oxides with soaps, sarcosinates, taurides or sugar esters can also be used for this purpose.
  • EP-A 0137551 and EP-A 0447261 (Unilever) 'is the use of amine oxides with soap or sarcosinate and other anionic surfactants such as alkyl sulfates, alkyl ether sulfates, secondary alkane sulfonates or Alkylbenzolsulfo- naten as thickening component known for hypochlorite solutions.
  • EP-A 0 156 438 reports on the use of alkyl aryl sulfonates as thickeners in aqueous bleaches which contain certain stilbene dyes as optical brighteners.
  • ES-A 8801389 (Henkel Iberica) are bleaching agents based on aqueous hypochlorite solutions, which mainly contain alkyl ether sulfates and small amounts of amine oxides as surfactant components.
  • aqueous bleaching compositions containing sodium hypochlorite and anionic surfactants are also known.
  • the hypochlorite concentration of these agents is 0.1 to 8 and preferably 0.5 to 5% by weight of active chlorine.
  • German patent DE-C1 43 33 100 the applicant finally proposed aqueous bleaching and cleaning agents based on hypochlorites, fatty alcohol ether sulfates, amine oxides and amine oxide phosphonic acids.
  • the bleaching agent of the type mentioned places high demands on the consumer: it must be compatible with textiles, i.e. treatment with the aggressive chemical hypochlorite means that the stains must be removed without attacking the tissue. Since skin contact with the bleaching agents is not excluded, the preparations must also be as dermatologically compatible as possible. Another problem is that hypochlorite solutions also attack metals and the dissolved metal traces can be deposited on the textile fibers during washing, which is ultimately reflected in the yellowing of the fabric. Market means are trying to prevent this redeposition by using silicates, but in practice this measure does not always prove to be satisfactory.
  • the complex object of the invention was to provide aqueous bleaching agents which are simultaneously chlorine-stable, gentle on textiles and as kind to the skin as possible, have a sufficiently high viscosity and reliably prevent the deposition of metal traces on the fabric with a high stain removal capacity.
  • the invention relates to aqueous bleaching agents containing - based on the agents -
  • the addition of small amounts of polyacrylic acid compounds to the hypochlorite solutions sig- nalled the deposition of metals on the fabric during washing. significantly reduced and counteracts the yellowing of the fibers.
  • the invention includes the knowledge that the use of mild, chlorine-stable surfactants such as preferably alkyl ether sulfates, amine oxides, alkyl and / or alkenyl oligoglycosides and fatty acid salts leads to a further improvement in cleaning performance and dermatological compatibility.
  • the agents according to the invention have a sufficiently high viscosity so that metering by the consumer is possible without any problems.
  • Alkali hypochlorites are to be understood as lithium, potassium and in particular sodium hypochlorite.
  • the hypochlorites can preferably be used in amounts of 1.5 to 8 and in particular 4 to 6% by weight, based on the composition.
  • Polyacrylic acid compounds are preferably to be understood as homopolymers of acrylic acid and methacrylic acid or their esters.
  • esters of the acids can also be polymerized with alcohols having 1 to 4 carbon atoms.
  • Polyacrylic acid compounds with a particularly advantageous stabilizing action are present as alkali salts and have an average molecular weight in the range from 1,000 to 10,000 and in particular 4,000 to 6,000 daltons. The preferred range of use is 0.02 to 0.05% by weight.
  • Alkytether sulfates are known anionic surfactants which are obtained by sulfation of nonionic surfactants of the AI ky f polyglycolethers type and subsequent neutralization.
  • the alkyl ether sulfates which are suitable for the purposes of the agents according to the invention follow the formula (I)
  • R 1 is an alkyl radical having 12 to 18, in particular 12 to 14, carbon atoms
  • n is numbers 2 to 5, in particular 2 to 3
  • X is sodium or potassium.
  • Typical examples are the sodium salts of sulfates of the Ci2 / i4-coconut alcohol-2, -2,3- and -3-EO adduct.
  • the alkyl ether sulfates can have a conventional or narrow homolog distribution.
  • the alkyl ether sulfates are preferably used in amounts of 1 to 8, preferably 1.5 to 6 and in particular 2 to 4% by weight, based on the composition.
  • Amine oxides are also known substances, which are occasionally attributed to the cationic, but usually the nonionic surfactants.
  • the nonionic surfactants For their preparation, one starts from tertiary fatty amines, which usually have either one long and two short or two long and one short alkyl radical, and is oxidized in the presence of hydrogen peroxide.
  • the amine oxides which are suitable for the purposes of the invention follow the formula (II)
  • R 2 represents a linear or branched alkyl radical having 12 to 18 carbon atoms and R 3 and R 4 independently of one another R 2 or an optionally hydroxyl-substituted alkyl radical having 1 to 4 carbon atoms.
  • Amine oxides of the formula (II) are preferably used in which R 2 and R 3 are C12 / 14 or C12 / ⁇ -cocoalkyl radicals and R 4 is a methyl or a hydroxyethyl radical.
  • amine oxides of the formula (II) in which R 2 is a C12 / 14 or C12 / 18 cocoalkyl radical and R 3 and R 4 have the meaning of a methyl or hydroxyethyl radical.
  • the amine oxides are preferably used in amounts of 1.5 to 6, preferably 2 to 4,% by weight, based on the composition.
  • Alkyl and alkenyl oligoglycosides are known nonionic surfactants which follow the formula (III)
  • the alkyl and / or alkenyl oligoglycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose.
  • the preferred alkyl and / or alkenyl oligoglycosides are thus alkyl and / or alkenyl oligoglucosides.
  • Alkyl and / or alkenyl oligoglycosides with an average degree of oligomerization p of 1.1 to 3.0 are preferably used. From an application point of view, preference is given to those alkyl and / or alkenyl oligoglycosides whose degree of oligomerization is less than 1.7 and in particular between 1.2 and 1.4.
  • the alkyl or alkenyl radical R 5 can be derived from primary alcohols having 4 to 11, preferably 8 to 10, carbon atoms.
  • Typical examples are butanol, capro alcohol, caprylic alcohol, capric alcohol and undecyl alcohol and their technical mixtures, such as those obtained in the hydrogenation of technical fatty acid methyl esters or in the course of the hydrogenation of aldehydes from Roelen's oxosynthesis.
  • the alkyl or alkenyl radical R 5 can also be derived from primary alcohols having 12 to 22, preferably 12 to 14, carbon atoms. Typical examples are lauryl alcohol, myristyl alcohol, cetyl alcohol, palmoleyl alcohol, stearyl alcohol, isostearyl alcohol, oleyl alcohol, elaidyl alcohol, petroseyl alcohol, arachyl alcohol, gadoleyl alcohol, behenyl alcohol, erucyl alcohol, brassidyl alcohol and their technical mixtures, which can be obtained as described above.
  • Alkyl oligoglucosides based on hydrogenated Ci2 / 14 coconut alcohol with a DP of 1 to 3 are preferred. The glycosides are preferably used in amounts of 1.5 to 6, preferably 2 to 4% by weight, based on the composition .
  • Fatty acid salts are preferably used in amounts of 1.5 to 6, preferably 2 to 4% by weight, based on the composition .
  • the agents according to the invention can contain fatty acid salts of the formula (IV) as further surfactants,
  • R 6 CO is an acyl radical having 12 to 22 carbon atoms and X is an alkali metal.
  • Typical examples are the sodium and / or potassium salts of lauric acid, myristic acid, palmitic acid, palmoleic acid, stearic acid, isostearic acid, oleic acid, elaidic acid, petroselinic acid, linoleic acid, linolenic acid, elaeostearic acid, arachidic acid, gadoic acid, behenic acid and mixtures thereof and erucas as they occur in the pressure splitting of technical fats and oils. Salts of technical coconut or tallow fatty acids are preferably used.
  • the fatty acids which are neutralized in situ when they are introduced into the mixture can also be used instead of the salts.
  • Those agents according to the invention preferably contain as an optional component fatty acid salts in which a particular low foam level is desired.
  • the soaps are preferably used in amounts of 1.5 to 6, preferably 2 to 4% by weight, based on the composition.
  • the agents according to the invention generally have a non-aqueous content of 5 to 35 and preferably 8 to 15% by weight and are suitable for the treatment of textile fabrics, such as, for example, yarns, fabric webs and in particular textiles. They are usually used at low temperatures, i.e. in the cold wash area (approx. 15 to 25 ° C).
  • the agents are not only distinguished by excellent stain removal, but also reliably prevent metal traces from being deposited on the fibers and thus also prevent yellowing.
  • the actual use of the agents is aimed at removing stains during washing, they are in principle also suitable for other purposes in which hypochlorite solutions are used, for example for cleaning and disinfecting hard surfaces.
  • auxiliaries and additives which may be used include, for example, other chlorine-stable surfactants or hydro tropes, such as, for example, alkyl sulfates, alkyl sulfonates, alkylbenzenesulfonates, xylene sulfonates, sarcosinates, taurides, isethionates, sulfosuccinates, betaines, sugar esters, fatty alcohol polyglycol ethers and fatty alcohols acid N-alkyl glucamides.
  • the sum of all surfactants preferably makes up at most 10 to 15% by weight of the total amount of ingredients in the formulation.
  • the agents according to the invention can contain alkali metal compounds, preferably sodium hydroxide or potassium hydroxide, with the aid of which the pH of the recipes can be adjusted to an optimal value of 12.5 to 14.
  • the agents contain, as further stabilizers, amine oxide phosphonic acids and / or alkali metal or alkaline earth metal silicates, preferably sodium and / or potassium silicates with a modulus in the range from 1.0 to 3.0 and preferably 1, 5 to 2.0, the amount of stabilizers used being 0.1 to 1 and in particular 0.2 to 0.5% by weight, based on the composition. This embodiment is particularly advantageous in terms of additional protection against corrosion if the exposure time of the agents is very long.
  • the agents can contain active chlorine-stable fragrances, optical brighteners, dyes and pigments in a total amount of 0.01 to 0.5% by weight, based on the agents.
  • the fragrances known to be active chlorine-resistant include, for example, monocyclic and bicyclic monoterpene alcohols and their esters with acetic or propionic acid (for example isoborneal, dihydroterpene oil, isobomylacetate, dihydroterpenylacetate).
  • the optical brighteners can be, for example, the potassium salt of 4,4'-bis (1, 2 l 3-triazolyl) - (2 -) - stilbin-2,2-sulfonic acid, which is sold under the Phorwite® BHC brand 766 is distributed.
  • Possible color pigments include green chlorophthalocyanines (Pigmosol® Green, Hostaphine® Green) or yellow Solar Yellow BG 300 (Sandoz).
  • the agents according to the invention are produced by stirring. If necessary, the product obtained can be decanted or filtered to remove foreign bodies and / or agglomerates. The agents also have a viscosity above 100 mPas - measured at 20 ° C in a Brookfield viscometer.
  • soiled fabric was treated with three bleach solutions according to the invention and two comparative formulations.
  • the yellowing of the fabric was determined photometrically, the initial value of the soiled fabric serving as the standard (100%).
  • the measurements were carried out in a liquor with a metal ion content of 300 ppb Fe and 100 ppb Mn; the water hardness was 1000 ppm CaCb, the hydrogen carbonate content was 0.013% by weight.
  • the liquor ratio (tissue: water) was 1:50, the exposure time was 30 minutes at a temperature of 40 ° C.
  • Table 1 The results are summarized in Table 1; the quantities are understood as% by weight:

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne des agents de blanchiment aqueux contenant 1 à 10 % en poids d'hypochlorites alcalins et 0,01 à 1 % en poids de composés d'acide polyacrylique. Les agents selon l'invention réduisent le dépôt de métaux sur le tissu et le jaunissement de celui-ci.
PCT/EP1997/002626 1996-05-31 1997-05-22 Agents de blanchiment aqueux Ceased WO1997046659A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DE59708205T DE59708205D1 (de) 1996-05-31 1997-05-22 Wässrige bleichmittel
EP97924975A EP0918841B1 (fr) 1996-05-31 1997-05-22 Agents de blanchiment aqueux

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DE19621820 1996-05-31
DE19621820.9 1996-05-31
DE19624843A DE19624843C2 (de) 1996-05-31 1996-06-21 Verwendung wäßriger Bleichzusammensetzungen
DE19624843.4 1996-06-21

Publications (1)

Publication Number Publication Date
WO1997046659A1 true WO1997046659A1 (fr) 1997-12-11

Family

ID=26026190

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1997/002626 Ceased WO1997046659A1 (fr) 1996-05-31 1997-05-22 Agents de blanchiment aqueux

Country Status (3)

Country Link
EP (1) EP0918841B1 (fr)
ES (1) ES2182085T3 (fr)
WO (1) WO1997046659A1 (fr)

Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3606989A (en) * 1967-10-19 1971-09-21 Purex Corp Ltd Fabric-treating composition and method
US3663442A (en) * 1970-02-09 1972-05-16 Purex Corp Ltd Household bleach having stable opacifier
US3689421A (en) * 1971-04-09 1972-09-05 Purex Corp Ltd Household hypochlorite bleach with stable latex opacifier
FR2355909A1 (fr) * 1975-05-19 1978-01-20 Jeyes Group Ltd Compositions de blanchiment, renfermant un produit tensio-actif du saccharose et un ou plusieurs autres produits tensio-actifs solubles dans les hypochlorites de metaux alcalins
EP0329419A2 (fr) * 1988-02-17 1989-08-23 Unilever Plc Compositions détergentes contenant des épaississeurs polymériques réticulés et un agent de blanchiment à base d'hypochlorite
EP0373864A2 (fr) * 1988-12-15 1990-06-20 The Procter & Gamble Company Compositions de blanchiment aqueuses, épaissies et stables
EP0491553A2 (fr) * 1990-12-18 1992-06-24 Cussons (International) Limited Composition détergente
DE4333100C1 (de) * 1993-09-29 1994-10-06 Henkel Kgaa Bleich- und Desinfektionsmittel
EP0668345A1 (fr) * 1994-02-22 1995-08-23 The Procter & Gamble Company Compositions de blanchiment d'hypochlorite

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2107938C (fr) * 1993-01-11 2005-01-11 Clement K. Choy Solutions d'hypochlorite epaisses degageant une odeur reduite d'agent de blanchiment, et methode de production
US6297209B1 (en) * 1996-05-10 2001-10-02 The Clorox Company Sequesterants as hypochlorite bleach enhancers

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3606989A (en) * 1967-10-19 1971-09-21 Purex Corp Ltd Fabric-treating composition and method
US3663442A (en) * 1970-02-09 1972-05-16 Purex Corp Ltd Household bleach having stable opacifier
US3689421A (en) * 1971-04-09 1972-09-05 Purex Corp Ltd Household hypochlorite bleach with stable latex opacifier
FR2355909A1 (fr) * 1975-05-19 1978-01-20 Jeyes Group Ltd Compositions de blanchiment, renfermant un produit tensio-actif du saccharose et un ou plusieurs autres produits tensio-actifs solubles dans les hypochlorites de metaux alcalins
EP0329419A2 (fr) * 1988-02-17 1989-08-23 Unilever Plc Compositions détergentes contenant des épaississeurs polymériques réticulés et un agent de blanchiment à base d'hypochlorite
EP0373864A2 (fr) * 1988-12-15 1990-06-20 The Procter & Gamble Company Compositions de blanchiment aqueuses, épaissies et stables
EP0491553A2 (fr) * 1990-12-18 1992-06-24 Cussons (International) Limited Composition détergente
DE4333100C1 (de) * 1993-09-29 1994-10-06 Henkel Kgaa Bleich- und Desinfektionsmittel
EP0668345A1 (fr) * 1994-02-22 1995-08-23 The Procter & Gamble Company Compositions de blanchiment d'hypochlorite

Also Published As

Publication number Publication date
EP0918841B1 (fr) 2002-09-11
ES2182085T3 (es) 2003-03-01
EP0918841A1 (fr) 1999-06-02

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