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WO1993001270A1 - Produit de lavage liquide - Google Patents

Produit de lavage liquide Download PDF

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Publication number
WO1993001270A1
WO1993001270A1 PCT/EP1992/001508 EP9201508W WO9301270A1 WO 1993001270 A1 WO1993001270 A1 WO 1993001270A1 EP 9201508 W EP9201508 W EP 9201508W WO 9301270 A1 WO9301270 A1 WO 9301270A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
water
hydrogen peroxide
agents
surfactants
Prior art date
Application number
PCT/EP1992/001508
Other languages
German (de)
English (en)
Inventor
Hans-Jürgen Riebe
Walter Parchatka
Reiner Schackmann
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
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
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1993001270A1 publication Critical patent/WO1993001270A1/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
    • C11D3/3947—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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
    • C11D3/3937—Stabilising agents
    • 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

Definitions

  • the present invention is in the field of textile detergents and relates to a liquid textile detergent containing bleach.
  • Solid inorganic peroxo compounds such as sodium perborate
  • bleaching agents are primarily used as bleaching agents (see, for example, DE 37 04 874).
  • a disadvantage of these agents is the need to use disproportionately large amounts of nonionic surfactants or organic solvents which, in addition to high costs, also cause unnecessary pollution of the waste water.
  • liquid detergents are known, for example from patent applications WO 90/15857 and WO 91/902, in which the bleaching agent is suspended in a predominantly aqueous phase.
  • large amounts of auxiliary substances are required in order to achieve sufficient results with regard to stability and washing effectiveness.
  • a third direction of development relates to liquid detergents in a homogeneous, mostly predominantly aqueous phase, in which hydrogen peroxide in the form of a solution is primarily used as the bleaching agent (see for example EP 86511 and US 4430236). Because of the low stability of hydrogen peroxide in the alkaline range, it is necessary to make these detergents largely pH neutral or slightly acidic. However, this results in a loss of washing effectiveness, since the dirt removal is generally quicker and more thorough at alkaline pH values. Work is therefore still ongoing to improve these liquid detergents containing bleach.
  • the present invention offers a solution to these problems in the form of an aqueous liquid detergent with a pH of not more than 8.5, which contains surfactant, hydrogen peroxide and, if appropriate, other active substances which are customary in detergents and which is distinguished in that it additionally contains 1 to Contains 20 percent by weight of water-soluble borate and the molar ratio of hydrogen peroxide to boron is at least 1.5: 1.
  • the new detergent In its undiluted state, the new detergent has a pH value near the neutral point and thus ensures a high stability of the hydrogen peroxide it contains during storage.
  • the pH value rises to alkaline ranges, so that not only good bleaching effects but also excellent washing performance are achieved with the washing liquors.
  • the new detergents are distinguished by the fact that they can be formulated as homogeneous, single-phase systems, so that sedimentation problems during storage are also eliminated.
  • Suitable surfactants for the new detergents are all surfactants from the classes of the nonionic surfactants, the anionic surfactants, the surfactants with betaine structure and the cationic surfactants which are usually used in liquid detergents, provided that they are combined with the other constituents of the detergent, in particular with the hydrogen peroxide are tolerated.
  • Synthetic anionic surfactants, nonionic surfactants and mixtures of these types of surfactants and mixtures of these surfactants with soaps are particularly preferred.
  • Suitable synthetic anionic surfactants are in particular those of the sulfonate and sulfate type.
  • the surfactants of the sulfonate type are alkylbenzenesulfonates with a Cg_i5-alkyl radical, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, such as are obtained, for example, from C12-Ci8 ⁇ monoolefins with terminal or internal double bond by sulfonating with gaseous Sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products are considered.
  • alkanesulfonates which are obtainable from (2- Cjg-alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or neutralization or by bisulfite addition to olefins, as well as the esters of alpha-sulfo fatty acids, e.g. the alpha-sulfonated methyl
  • Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural or synthetic origin, ie from fatty alcohols, such as, for example, coconut fatty alcohols, tallow fatty alcohols, lauryl, myristyl alcohols.
  • EO ethylene oxide
  • Suitable anionic surfactants based on natural raw materials are primarily the wash-active soaps, i.e. H. the salts of the fatty acids with preferably 12 to 18 carbon atoms. Longer-chain soaps can be present as foam inhibitors. All anionic surfactants are preferably used as alkali salts, in particular as sodium salts. Particularly preferred anionic surfactants are the alkylbenzenesulfonates and the soaps.
  • Nonionic surfactants are the addition products of 3 to 20 moles of ethylene oxide (EO) with primary C ⁇ o-C2 ⁇ - A lkohole w ⁇ e f z "B" are on coconut or tallow fatty, oxoalcohols or secondary alcohols with the same Ket ⁇ tenil particularly important.
  • EO ethylene oxide
  • B coconut or tallow fatty, oxoalcohols or secondary alcohols with the same Ket ⁇ tenil particularly important.
  • the water-insoluble or not completely water-soluble compounds low ethoxylated fatty alcohol polyglycol ethers with 3 to 7 ethylene glycol ether residues in the molecule can be of importance if they are used together with water-soluble nonionic or anionic surfactants.
  • the non-ionic surfactants are also the water-soluble addition products containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups of ethylene oxide on polypropylene glycol, alkylene diamine polypropylene glycol and on alkyl polypropylene glycols with 1 to 10 carbon atoms in the Alkyl chain in which the polypropylene glycol chain acts as a hydrophobic residue.
  • Nonionic surfactants of the amine oxide or sulfoxide type can also be used, for example the compound N-cocoalkyl-N, N-dimethylamine oxide.
  • suitable as nonionic surfactants are the addition products of ethylene oxide and long-chain fatty acids and fatty acid amides with 12-18 C atoms, and the water-soluble alkylglucosides, the hydrophobic Cg-C20-alkyl radical of which is linked to a mostly oligomeric, hydrophilic glucoside radical.
  • the preferred nonionic surfactants are the addition products of ethylene oxide and long-chain alkanols, especially fatty alcohols.
  • the surfactants with betaine structure primarily include the quaternary ammonium compounds which, in addition to a longer alkyl chain with about 12 to 18 carbon atoms on nitrogen, carry a substituent with carboxyl or sulfonate groups.
  • these substituents are the carboxymethyl or the omega-sulfopropyl group.
  • Quaternary ammonium compounds which carry a long-chain alkyl group with preferably 12 to 18 carbon atoms in addition to three short-chain alkyl groups which are optionally substituted by hydroxyl groups are particularly important as cationic surfactants.
  • the agents according to the invention preferably contain not only one surfactant, but a mixture of several surfactants. Mixtures of alkylbenzenesulfonates and water-soluble additive products of ethylene oxide with long-chain alcohols and mixtures which contain these two types of surfactant together with soap are particularly preferred.
  • the total amount of surfactants is 1 to 60 percent by weight, preferably 10 to 40 percent by weight, in the agents according to the invention.
  • the agents contain hydrogen peroxide as a further essential component, which is responsible for the bleaching performance of the agents.
  • the amount of hydrogen peroxide in the compositions is preferably 2 to 30 percent by weight and in particular 5 to 10 percent by weight. Preparations with up to 10 percent by weight of H2O2 are generally not considered to be corrosive, so that these preparations are also suitable for manual handling.
  • To produce the agents according to the invention it is of course also possible to start from more highly concentrated hydrogen peroxide or from hydrogen peroxide addition compounds, for example on urea.
  • the third essential component of the new agents are the water-soluble borates.
  • These are alkali salts, preferably sodium salts, of the most diverse boric acids, for example sodium methaborate (NaBÜ2) and borax (Na2B4Ü7.10 H2O).
  • the amount of borates is 1 to 20 percent by weight, preferably 3 to 15 percent by weight of the finished agent, the amount of borate being calculated as if all of the boron were present as sodium metaborate tetrahydrate. This also applies if, due to the pH value, there is actually a mixture of boric acids and borates.
  • the decisive factor for the properties of the new agents is the molar ratio of hydrogen peroxide to boron, which should be at least 1.5: 1, preferably at least 2: 1 and in particular at least 4: 1.
  • the upper limit of this ratio is about 150: 1, preferably not more than 50: 1.
  • Sodium perborate, in particular the readily water-soluble sodium perborate monohydrate, and additional hydrogen peroxide can also be used to produce this ratio. It is noteworthy that when these molar ratios are selected, a fully sufficient pH jump is achieved without the addition of cis-diols which form complexes with boron. The content of fiber which is not actually washing-active can thus be kept low.
  • the new agents can also add other components such as: are known in liquid detergents. When selecting these ingredients, care must also be taken to ensure that there are no incompatibilities with other components, in particular with hydrogen peroxide.
  • optional components are water-miscible organic solvents, hydrotropes, complexing agents for heavy metals and / or for the ions of water hardness, pH regulators, perfume, optical brighteners, dispersants, bleach activators, foam inhibitors, enzymes, and graying inhibitors.
  • the agents can be improved in individual directions of action without impairing the basic properties of the agents. Substances which can be mixed with the other constituents of the compositions to form single-phase systems are preferably used, but it is also possible to incorporate insoluble components if the measures are taken to ensure adequate stability of the dispersion.
  • the amounts of the optional components mainly depend on the purpose that is to be achieved with them.
  • Water-miscible organic solvents preferably lower alcohols with 2 to 3 carbon atoms or ether alcohols with up to 6 carbon atoms, are generally incorporated in amounts not exceeding 40 percent by weight, preferably in amounts between 5 and 20 percent by weight.
  • the organic solvents serve primarily to combine the various constituents of the compositions into a homogeneous solution.
  • hydrotropes examples include the non-surface-active sulfonic acids, carboxylic acids and sulfocarboxylic acids containing 2 to 9 carbon atoms, in particular sodium cumene sulfonate and sodium xylene sulfonate, but also sodium acetate and urea.
  • the amount of hydrotropes is usually not more than 10 percent by weight, preferably between 1 and 8 percent by weight.
  • the main task of complexing agents for heavy metals is to ensure the stability of the hydrogen peroxide in the liquid agents and to prevent fiber damage due to traces of heavy metals when the agents are used.
  • aminopolycarboxylic acids and polyphosphonic acids and their alkali metal salts for example ethylenediamine tetraacetate and hydroxyethane diphosphonic acid, which generally do not exceed 2% by weight, preferably between 0.01 and 1% by weight, are highly suitable for the new agents. Percent can be used.
  • Low-molecular or high-molecular polycarboxylic acids for example citric acid, carboxymethyloxysuccinic acid and homo- or copolymers of acrylic acid, methacrylic acid and maleic acid as such or in the form of their water-soluble salts are usually used for sequestering the water hardness.
  • the amount of sequestering agent is usually not more than 10 percent by weight, preferably between 0.5 and 3 percent by weight, based on the total agent.
  • the amount of the other optional components is generally not more than 10 percent by weight, preferably between 0.1 and 10 percent by weight, based on the total agent.
  • the agents should not have a pH in the undiluted state above 8.5 and preferably between 6 and 8. If this pH value does not automatically result from the choice of suitable starting materials, suitable pH regulators are added. As a rule, these are strong acids or bases, for example sulfuric acid, alkylbenzenesulfonic acid and sodium hydroxide solution. Salts with an acidic or alkaline reaction can also be suitable. Larger proportions of components which have a buffer range in the range between the pH value of the undiluted agent and a pH value of about 10 generally have an unfavorable effect, since this can impair the pH jump inherent in the agents when diluted.
  • suitable pH regulators are added. As a rule, these are strong acids or bases, for example sulfuric acid, alkylbenzenesulfonic acid and sodium hydroxide solution. Salts with an acidic or alkaline reaction can also be suitable. Larger proportions of components which have a buffer range in the range between the pH value of the undiluted agent and a pH value of about 10 generally have an unf
  • liquid detergents according to the invention (a - f) and, for comparison, some corresponding detergents without borate content (g - 1) were produced.
  • the composition of the compositions is given in Table 1, the percentages by weight in each case referring to pure components, while hydrogen peroxide, for example, was used as a 35% strength aqueous solution and alkylbenzenesulfonate as a 55% strength suspension.
  • water was initially introduced, then sodium hydroxide solution and organic solvents were added, and the remaining components were then stirred in in the order given. If necessary, the sodium salts formed from acids. If cloudiness occurred in between, this was dissolved again at the latest when the hydrogen peroxide was added, so that all agents were finally available as water-clear liquids which were viscous at room temperature.
  • Dequest ( R ) 2066 pentasodium salt of ethylenediaminetetramethylenephosphonic acid turpinal ( R ) SL: hydroxyethane diphosphonic acid dehydol ( R ) LT 7: Ci2 / i8 coconut alcohol + 7 ethylene oxide (EO) dehydol ( R ) LST: mixture of Ci2 / i8 coconut alcohol + 5 EO and
  • the detergents listed in Table 1 did not separate out any precipitate or showed phase separation even after prolonged storage.
  • the active oxygen content also proved to be stable.
  • the increase in alkalinity caused by the borate content when diluting the compositions to the use concentration can be seen from the pH values listed in Table 1.
  • the evaluation was carried out by measuring the light remission at 465 nm on the dried lobules with the aid of a Zeiss RFC 24 measuring device.
  • the results on various wash- and bleach-sensitive soiling are given in Table 2 as a percent light remission by way of example for some of the agents. They clearly demonstrate the excellent effectiveness of the agents according to the invention.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Detergent Compositions (AREA)

Abstract

Il s'agit d'un produit de lavage liquide aqueux comportant un tensio-actif, du peroxyde d'hydrogène et un borate soluble dans l'eau dans une quantité telle que le rapport molaire du H2O2 au bore soit d'au moins 1,5 : 1. Le produit de lavage présente sous sa forme concentrée un pH n'excédant pas 8,5; après d'une dilution jusqu'à la concentration d'utilisation, le pH augmente jusqu'à des valeurs nettement supérieures, de sorte que le bain de lavage permet d'obtenir un bon pouvoir blanchissant et nettoyant.
PCT/EP1992/001508 1991-07-12 1992-07-03 Produit de lavage liquide WO1993001270A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4123142A DE4123142A1 (de) 1991-07-12 1991-07-12 Fluessigwaschmittel
DEP4123142.2 1991-07-12

Publications (1)

Publication Number Publication Date
WO1993001270A1 true WO1993001270A1 (fr) 1993-01-21

Family

ID=6436020

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1992/001508 WO1993001270A1 (fr) 1991-07-12 1992-07-03 Produit de lavage liquide

Country Status (2)

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DE (1) DE4123142A1 (fr)
WO (1) WO1993001270A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997045519A3 (fr) * 1996-05-28 1998-02-19 Warwick Int Group Composition de detergent liquide, alcalin et contenant du peroxyde
US5736497A (en) * 1995-05-05 1998-04-07 Degussa Corporation Phosphorus free stabilized alkaline peroxygen solutions
WO2017004529A1 (fr) * 2015-07-02 2017-01-05 Georgia-Pacific Consumer Products Lp Composition de nettoyage, revêtements préparés à partir de celle-ci et procédé de nettoyage

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2140822A5 (en) * 1971-06-09 1973-01-19 Air Liquide Bleaching liquids - contg hydrogen peroxide or persalts in alkaline medium with stabilisers
EP0376706A1 (fr) * 1988-12-28 1990-07-04 Unilever Plc Composition de blanchiment
WO1991000902A1 (fr) * 1989-07-13 1991-01-24 Unilever N.V. Composition de blanchiment liquide
EP0431747A2 (fr) * 1989-11-30 1991-06-12 The Clorox Company Détergent oxydant aqueux stable

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2140822A5 (en) * 1971-06-09 1973-01-19 Air Liquide Bleaching liquids - contg hydrogen peroxide or persalts in alkaline medium with stabilisers
EP0376706A1 (fr) * 1988-12-28 1990-07-04 Unilever Plc Composition de blanchiment
WO1991000902A1 (fr) * 1989-07-13 1991-01-24 Unilever N.V. Composition de blanchiment liquide
EP0431747A2 (fr) * 1989-11-30 1991-06-12 The Clorox Company Détergent oxydant aqueux stable

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5736497A (en) * 1995-05-05 1998-04-07 Degussa Corporation Phosphorus free stabilized alkaline peroxygen solutions
WO1997045519A3 (fr) * 1996-05-28 1998-02-19 Warwick Int Group Composition de detergent liquide, alcalin et contenant du peroxyde
WO2017004529A1 (fr) * 2015-07-02 2017-01-05 Georgia-Pacific Consumer Products Lp Composition de nettoyage, revêtements préparés à partir de celle-ci et procédé de nettoyage
US20170002299A1 (en) * 2015-07-02 2017-01-05 Georgia-Pacific Consumer Products Lp Cleaning composition, coatings prepared therefrom and method of cleaning

Also Published As

Publication number Publication date
DE4123142A1 (de) 1993-01-14

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