WO1987005344A1 - Procede de lavage et/ou de nettoyage de produits textiles sales - Google Patents

Procede de lavage et/ou de nettoyage de produits textiles sales Download PDF

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Publication number
WO1987005344A1
WO1987005344A1 PCT/EP1987/000096 EP8700096W WO8705344A1 WO 1987005344 A1 WO1987005344 A1 WO 1987005344A1 EP 8700096 W EP8700096 W EP 8700096W WO 8705344 A1 WO8705344 A1 WO 8705344A1
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WO
WIPO (PCT)
Prior art keywords
dirt
pqav
washing
pigment
insoluble
Prior art date
Application number
PCT/EP1987/000096
Other languages
German (de)
English (en)
Inventor
Alfred Meffert
Brigitte Giesen
Andreas Syldatk
Ingo Wegener
Johann Friedrich Fues
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
Priority claimed from DE19863606729 external-priority patent/DE3606729A1/de
Priority claimed from DE19863610386 external-priority patent/DE3610386A1/de
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1987005344A1 publication Critical patent/WO1987005344A1/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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
    • C11D17/046—Insoluble free body dispenser
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C11D3/1286—Stabilised aqueous aluminosilicate suspensions
    • 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
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/128—Aluminium silicates, e.g. zeolites
    • C11D3/1293—Feldspar; Perlite; Pumice or Portland cement
    • 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
    • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
    • 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
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • 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
    • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
    • D06L1/12—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents
    • D06L1/16—Multi-step processes
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/40—Specific cleaning or washing processes
    • C11D2111/46—Specific cleaning or washing processes applying energy, e.g. irradiation

Definitions

  • the invention relates to a new method for washing and / or cleaning soiled textile goods by treatment in a detergent-containing washing liquor.
  • the method according to the invention is suitable for the improved removal of pigment and / or grease stains, which can also be present together with so-called problem stains, for the elimination of which washing and / or cleaning aids of a special kind are usually required.
  • the best-known examples of this are the use of bleaching agents for the particularly oxidative bleaching of particularly resistant dye stains and the use of enzymatically active washing aids, in particular the known detergent proteases, for removing, for example, protein-based stains, and the process according to the invention also includes the use of such additional cleaning aids Can make use of.
  • the new method can be carried out in one or more stages, the invention particularly relating to the improved multi-stage treatment of soiled textiles which, in addition to pigment and / or greasy soiling, at least partially also have problem soiling, for example of the type mentioned above.
  • the essence of the teaching according to the invention is to facilitate the washing or cleaning process on the textile by the action of ultrasound on the washing liquor loaded with the dirty textile.
  • the cleaning of hard surfaces in aqueous and / or organic washing baths under the influence of ultrasound has been known for decades and has been implemented on an industrial scale.
  • the application of this measure to the washing or cleaning of textiles has also long been known as a wish.
  • proposals that are useful in practice have not been made known to date.
  • the teaching of the invention relates on the one hand to elements which are to be taken into account in the ultrasonic washing stage.
  • the teaching of the invention relates to the sensible combination of such an ultrasonic wash with known further measures of textile washing or cleaning, in particular for Removal of residual parts from the area of so-called problem soiling.
  • the invention in its most general form relates to a method for washing and / or cleaning contaminated textile goods by treatment in a detergent-containing washing liquor, if desired with the addition of further washing and / or cleaning aids, the new method being characterized thereby that the detachment of pigment and / or grease stains at least partially under the influence of ultrasound! is carried out and a fleet is used which contains in this fleet at least largely insoluble catchers for the absorption of at least part of the detached pigment and / or greasy dirt, these catchers being designed in such a way that they are cleaned manually and / or mechanically - and if desired also from the wash liquor - can be separated.
  • the undissolved catchers used in the surfactant-containing washing liquor in the surfactant-containing washing liquor for the pigment and / or grease dirt detached under the action of ultrasound are designed in such a way that under the washing conditions they substantially transfer back the dirt particles absorbed to the Prevent textile goods to be cleaned. Details of this are explained in detail below.
  • the invention relates in particular to measures which are expedient in the context of a combination treatment in which ultrasound washing is preferably used to detach pigment and / or grease stains, while problem stains which have not been removed or are not adequately eliminated in separate process steps of the washing process.
  • a combination treatment that works with the use of enzymatic and / or bleaching washing or cleaning aids.
  • the bleaching and / or the enzymatic cleaning of the soiled textiles is carried out at least in part following a previous ultrasound treatment to remove at least the substantial proportion of the pigment and / or fat soiling.
  • Such prior ultrasonic washing exposes the areas of problem soiling for the separate and targeted treatment of these contaminants. It is obvious that a particularly effective and simplified removal of residual problem soiling is possible in a corresponding multi-stage process.
  • the process according to the invention provides the use of ultrasound as a washing aid, in particular in a process step which is aimed at removing pigment and / or grease stains, subsequent process steps being provided with or without the use of ultrasound in which the more stubborn residual dirt can be removed.
  • the invention provides as an essential element the use of so-called catchers for the absorption of at least part of the detached pigment and / or grease dirt.
  • these catchers are insoluble in the wash liquor and are present in such a form that they can be separated manually and / or mechanically from the cleaned goods and, if desired, from the wash liquor used.
  • Such insoluble capture substances are in particular the corresponding components, which are described in the earlier applications P 35 45 990.5 (D 7478/7495], P 36 05 716 .9 CD 7538] and in particular in the patent application P 36 06 729. 6 CD 7554] are described.
  • a first class of such capture substances which is particularly important according to the invention, is insoluble and / or polyfunctional quaternary ammonium compounds (CPQAV) present immobilized on correspondingly insoluble solid carriers, which are used in particular in the form of their insoluble or immobilized PQAV / surfactant complexes and in particular in the older applications and here again in particular in application P 36 06 729.6 CD 7554] are described.
  • CPQAV polyfunctional quaternary ammonium compounds
  • P 35 45 990.5 CD 7478/7495 is the use of polyfunctional quaternary ammonium compounds (PQAV) which are insoluble in and / or on the aqueous process, in the form of water-surfactant washing or cleaning solutions, even under the temperature loads of the washing process aqueous solutions corresponding to insoluble solids are not washable, immobilized, as a particle-dirt-collecting cleaning booster in aqueous-surfactant washing or cleaning solutions, which can be manually and / or mechanically separated from the material to be cleaned after washing or cleaning
  • PQAV dirt collectors in particular the strengthening of the washing power of conventional aqueous-alkaline textile detergent solutions by the use of such PQAV dirt collectors, at least a considerable proportion of the dirt, particularly pigmented dirt, solubilized in textile washing, is present in the solid phase en PQAV and thus ultimately transferred from the originally soiled and cleaned textile material to the dirt collector.
  • aqueous alkaline cleaning liquors if desired containing surfactants, in particular washing solutions from textile washing, can be subjected to regeneration in such a way that either during washing and / or afterwards the soiled cleaning liquor with the insoluble or. immobilized PQAV treated and thereby at least partially freed of solubilized dirt, in particular pigment dirt.
  • the washing solution treated in this way can be reused - for example in the context of textile washing.
  • PQAV or PQAV / surfactant complex compounds as from the reaction of PQAV with surfactant components, in particular anionic, amphoteric and / or nonionic surface-active agents, as a dirt-absorbing weight-loss agent for reducing the need for conventional chemicals in washing and / or cleaning agents is the subject of said patent application P 36 06 729.6 CD 7554].
  • surfactant components in particular anionic, amphoteric and / or nonionic surface-active agents
  • CPQAV Polyfunctional quaternary ammonium compounds
  • An important area of application for such compounds is the field of cosmetic preparations, in particular for the treatment or conditioning of hair. It is a known characteristic of PQAV that they are capable of being coated on solid surfaces, and this capability can also be present in the presence of conventional surfactant components. Depending on the constitution, the absorption capacity and the adhesive strength of the PQAV on the solid base are different. The individual constitution of the PQAV plays a decisive role here. Interaction with, in particular, anionic surfactant components can also be of decisive importance for the behavior of PQAV under the action of aqueous surfactant baths.
  • the corresponding anionic surfactant salt In the case of stoichiometric or approximately stoichiometric amounts of the anionic surfactant components, the corresponding anionic surfactant salt generally forms on the quaternary ammonium group.
  • Such PQAV anionic surfactant salts generally show a greatly reduced water solubility.
  • PQAV salts have been proposed as antistatic agents for application to fibers.
  • these previously known PQAV are oligomers and / or polymers which have a plurality or a plurality of quaternary ammonium groups on their oligomeric or polymeric matrix. Adequate water solubility of the PQAV is generally required for use in the field of cosmetics.
  • the use of the PQAV according to the invention requires the insolubility of the PQAV-based auxiliaries used as dirt collectors in the aqueous surfactant washing or cleaning solutions.
  • the insolubility of the PQAV components used as dirt collectors in the sense of the invention is in fact an indispensable prerequisite, in particular for the field of textile washing. If this critical precondition according to the invention is not met, the washing result is reversed. IQsf ⁇ che PQAV fractions sliding into the wash bath are absorbed onto the textile goods to be washed and bind additional amounts of pigment dirt there in an undesirable manner.
  • Suitable originally water-soluble or water-insoluble PQAVs within the meaning of the invention preferably have an average molecular weight of at least about 200, preferably at least about 300 and in particular at least about 1,000.
  • the upper limit of the PQAV is basically insignificant and is, for example, 50 Millions, e.g. B. 10 million . This is understandable from the requirement for the PQAV to be insoluble according to the invention. If this is ensured, there are no upper limits to the molecular weight.
  • polymers which carry quaternary ammonium groups either in the polymer chain or bound to the polymer chain are suitable as PQAV which are initially water-soluble but then immobilized on an insoluble support.
  • Such quaternary ammonium groups can also be derived from cyclically bound nitrogen. Examples of such quaternary ammonium groups are corresponding members of 5- or 6-membered ring systems, eg. B. of morpholine, piperidine, piperazine or indazole rings. Numerous examples of such water solutions Lent PQAV are e.g. B. in U.S. Patent 4,240,450.
  • suitable PQAV are, for example, cellulose ethers, the anhydroglucose units of which bear substituents with quaternary ammonium groups which are bonded via ether oxygen.
  • Such polymers are e.g. B. known from US-PS 3,472,840.
  • One with this structure is e.g. B. the poly
  • cationic polymers are e.g. B. the known from US-PS 3 910 862 and z.
  • Suitable copolymers with a polycationic character are also the polyacrylamide copolymers described in the published European patent application 0 153 146, which in particular contain up to 50 mol% of a quaternized aminoalkyl ester of acrylic acid or methacrylic acid in addition to at least 50 minor acrylamide units. These copolymers are water soluble. There they are applied to cloths based on cellulose fibers and are drawn up there due to their natural tensile strength. Cloths of this type can be washed out and should then be used together with non-surfactant-free surfactant systems for cleaning hard surfaces, especially for glass cleaning. Under these conditions, they are characterized by an increased protection capacity.
  • Preferred PQAV as starting material are those compounds which, in solid form, cause difficulties in dissolving in water.
  • Such cationic polymers are primarily those from, for example. GB-PS 1 136 842 known cationic polygalactomannan derivatives.
  • Galactomannans are polysaccharides that occur in the endosperm cells of many legume seeds, but which are obtained on an industrial scale only from locust bean gum Clocust bean gum], guar gum f guar gum) and tara gum ctara gum]. They are made up of a linear mannan main chain, consisting of beta-f l .4] glycosidically linked mannopyranose units, to which individual galactopyranose residues in alpha-Cl. 6] glycosidic bond are fixed as branches. The individual polygalactoman ⁇ anes differ mainly in the mannose-lactose ratio.
  • the cationic derivatives of the polygalactomannans are produced by reacting hydroxyl groups of the polysaccharide with reactive quaternary ammonium compounds. Suitable reactive quaternary ammonium compounds are, for. B. those of the general formula
  • R 1 2 3 4 in the R, R and R z.
  • B methyl or ethyl groups and R is an epoxyalkyl group of the formula
  • R is an alkylene group with 1-3 C atoms
  • X chlorine or bromine
  • Z is an anion such as.
  • B. is chloride, bromide, iodide or hydrogen sulfate. The degree of substitution should be at least 0.01 and preferably at least 0.05 and is typically between 0.05 and 0.5.
  • a particularly suitable quaternary ammonium derivative of a polygalactomannan is e.g. B. the guar-hydroxypropyl-trimethylammonium chloride, which is bound to the oxygen atoms of the hydroxyl groups of the polysaccharide cationic groups of the formula
  • Such cationic guar derivatives are e.g. B. on the market under the trade name "Cosmedia Guar C 261".
  • the degree of substitution CDS) of Cosmedia Guar C 261 is around 0.07.
  • the PQAV used are insoluble in the wash liquor under the conditions of use, so that the surface of the arbitrarily shaped agent can be loaded with dirt particles and hold it until the process is complete.
  • insoluble PQAV There are several ways to obtain such insoluble PQAV. It is known, for example, to crosslink water-soluble PQAV by reaction with at least bifunctional crosslinking agents in such a way that water-insolubility which is sufficient for the purposes of the invention is achieved.
  • the selection of the appropriate crosslinking agent is determined by the structure of the compounds to be crosslinked, which is present in the individual case, taking into account general chemical specialist knowledge.
  • the surface of insoluble or insolubilized, shaped natural products and / or corresponding synthesis products can be equipped with quaternary ammonium groups by chemical reaction. Process steps are used for this, as are known in principle for the production of water-soluble and / or water-swellable PQAV from the literature cited at the beginning. This is exemplified as follows: a flat building, e.g. B. a random fiber fleece or.
  • the embodiments which have a water-insoluble carrier in flat or granular form and on the surface of which PQAV are applied by means of sufficient fixation, preferably in a thin layer, are immobilized in such a way that they do not slide off into the wash bath during the washing process.
  • the quaternary ammonium group in the PQAV components used according to the invention preferably contains 1 to 3 lower alkyl radicals each having 1 to 6, in particular 1 to 3, carbon atoms.
  • the quaternary ammonium group, which has 1 to 3 alkyl radicals and contains, as counterion, radicals of such acids, as are usually to be expected in the washing process, can be of particular importance. Examples of this counterion are chloride and / or sulfate, which, however, convert to the corresponding anionic salt group in the presence of anionic surfactants, see the references DE-OS 22 42 914 and "SF ⁇ W" 1985, 530.
  • any insoluble materials of an inorganic and / or organic type are suitable as insoluble carrier materials for fixing PQAV and thus for the immobilization of these dirt-collecting active components, provided that they are otherwise inert in the washing solutions.
  • Suitable organic materials can be of vegetable origin.
  • Preferred inorganic carriers are mineral substances of natural and / or synthetic origin, which are in the form of finely divided solids.
  • PQAV-coated carrier substances with a specific surface area of at least about 0.5 m 2 / g are preferably used according to the invention, this specific surface area preferably being at least 1 m 2 / g. Specific surface is understood to be the area that can be covered with PQAV.
  • Certain particularly suitable mineral substances have additional surface areas inside the solid phase - be it due to their pore structure or their ability to swell - which, however, are not or only to a limited extent accessible with PQAV.
  • the flexible outer surface can, however, reach considerable values, which lead to the range of 100 m 2 / g or even up to, for example, 300 m 2 / g.
  • colloidal silicas are examples of such extreme occupancy with Surfaces accessible to PQAV.
  • the maximum particle sizes of the PQAV-loaded fine particles are preferably not above about 100 ⁇ , preferably not above about 40 ⁇ - these numerical values are based on the absolute particle diameter and mean that all or at least the vast majority of the existing fine particles correspond to these general conditions. Particles which have a particle size (volume average) of at most about 10 ⁇ m can be particularly useful for textile washing, the absolute particle size of at least the majority of all solid particles also being below this value.
  • Suitable inorganic carriers are in particular insoluble and oil-like salts, oxides, silicates and the like.
  • aluminosilicates of the type of zeolites or zeolite-like compounds are particularly suitable, in particular the sodium zeolite A which is widely used in detergents today. In its place, zeolite A can also be used in an exchanged form. B. find use as calcium salt.
  • a particularly suitable mineral carrier class are swellable, finely divided substances of the type of clays and / or swellable layered silicates, in particular from the smectite class.
  • Swellable inorganic minerals of this type are distinguished by a particularly large surface in the swollen state. This can be used within the scope of the invention.
  • the known smectite clays montmorillonite, hectorite and / or saponite are particularly suitable here.
  • comparable synthetic materials with only limited swellability are also suitable, as are described, for example, in the earlier application P 35 26 405.5 CD 7031).
  • insoluble and / or PQAVs immobilized on insoluble carriers are used as dirt-absorbing emollients, the counteranions of which - originally present from the quaternization reaction - are at least partially replaced by surface-active agents even before use in the washing or cleaning liquor . It may be preferred to use corresponding reaction products between the original PQAV and the surface-active agents, in which at least 50 equivalent percent and in particular at least about 80 equivalent percent of the quaternary ammonium groups are activated with regard to their counteranions by exchange with the surface-active agents.
  • the activation of the quaternary ammonium groupings is carried out by using at least equivalent amounts of PQAV on the one hand and surface-active agent on the other hand in the preparation stage of the dirt-absorbing leaner.
  • Excesses of the surfactants do no harm and can even be preferred.
  • Surfactant components which are capable of such an exchange of the counteranion originally present are used in particular as surface-active agents.
  • the counter anion can be replaced by known anionic surfactants with a surfactant character.
  • Suitable agents for pretreating the PQAV are, however, amphoteric surfactants, for example of the amphoteric - surface-active agent type of the aminocarboxylic acid type.
  • amphoteric surfactants for example of the amphoteric - surface-active agent type of the aminocarboxylic acid type.
  • Non-ionic surfactants are particularly suitable here as activation components. Details on this known class of substance can be found in the already cited literature section "Ullmann" a. O. Within this group, in addition to those common in today's laundry detergents Nonionics - especially from the class of condensation products of longer-chain alcohols, e.g. B.
  • Fatty alcohols with x moles of ethylene oxide (preferably equal to or greater than 3, for example 3 to 10) - also detergent-active alkyl glycosides are of particular importance. Even if the mechanism for such an activation has not yet been clarified, it is true that a noticeable increase in effectiveness can be achieved by pretreating the PQAV scavenger with Nonionics.
  • the insoluble catchers based on PQAV can - as described in detail in the earlier applications - in sheet or. Foil form or also in the form of a wipe used.
  • these essential auxiliaries in the form of finely divided solids, which enable their disperse fine distribution in the washing or cleaning liquors, and thus ensure that, with the most homogeneous possible distribution of the dirt-absorbing PQAV, each contaminated area of the to be cleaned is washed around by the adsorption-ready PQAV.
  • the transport route of a detached dirt particle from its original place to the desired landfill site on the catcher surface is kept as short as possible in this way.
  • the PQAV-based scavengers present as heterogeneous solid phase according to the invention absorb from the dirt-laden one Fleet in particular negatively charged parts, for example corresponding particle dirt.
  • the PQAV solid material can have a cleaning or cleaning-enhancing effect due to other surface forces. In the important further embodiments described below, it is consciously assumed that not only negatively charged dirt particles can be removed from soiled washing liquors.
  • auxiliary is also used in the heterogeneous solid phase, which excels due to its high absorption capacity for oleophilic soiling.
  • selected plastics for example polyethylene or polypropylene or.
  • Polyurethane or superficially highly insoluble solids of any origin which have the ability to pull the oleophilic dirt particles hydrophilized under the action of surfactants from a wash liquor and to hold onto their surface. This working principle is used in this embodiment for the effective cleaning of soiled washing liquors.
  • the collectors for such oleophilic dirt can be used, for example, in the form of flakes, fibers or fibrous structures such as cloths, nonwoven fiber fabrics, poromer skins and the like. What is essential for this component is only the condition previously specified for the PQAV cleaner that a manual and / or mechanical separation between the liquid phase and the dirt collector present in the solid phase is ensured. A particularly important embodiment will be discussed below.
  • the auxiliary substances which collect oleophilic dirt can be used simultaneously with the treatment of the wash liquor by PQAV and / or separately therefrom. The individual working conditions are determined by the nature of the pollution in the wash liquor and the expected pollution of the dirt-collecting auxiliary substances in the solid phase.
  • polyanionic cleaning agents present in a separate solid phase are also used.
  • Polyanionic components in dissolved and / or undissolved form play a considerable role in today's washing and cleaning agents. They are used, for example, as builders or cobuilders for the surfactants. They have a wide range of tasks, the binding of calcium and / or magnesium ions from the present water hardness being mentioned as an example.
  • the teaching according to the invention covers the joint use of the PQAV auxiliaries and the polyanionic insoluble auxiliaries in the presence or in the absence of the previously discussed third collector components, which is particularly suitable for the absorption of the oleophilic dirt from the washing solution.
  • Natural and / or synthetic solids with a plurality of anionic acid residues are particularly suitable as the insoluble polyanionic solid phase.
  • examples include insoluble components containing carboxyl groups, sulfonic acid residues, phosphonic acid groups and the like.
  • catchers which contain the insoluble active component - for example the PQAV / surfactant complex and / or the strongly oleophobic coating - as a surface finish on inherently insoluble solids
  • these active surface finishings in provide the thinnest possible layer on the insoluble solid supports. This ensures optimal use of the dirt-collecting active materials.
  • the thickness of the coating containing PQAV can reach into the range of monomolecular layers. Accordingly, layer thicknesses of the active substance on the carrier materials in the range up to about 1 ⁇ and below can preferably be used.
  • PQAV or PQAV / surfactant complex to be used in the detergent is matched to the pollution load to be expected. If the intention is to use these dirt absorbers only once, even the smallest amounts of these absorbers are sufficient to bind the pigment dirt usually obtained, for example, in textile washing.
  • PQAV components of the type concerned here are able to bind the same to pigment dirt up to a multiple of their weight - in particular due to the spreading of the PQAV-based catchers on the carrier substrate in the thinnest layer.
  • dirt-absorbing catchers are used which are impregnated with PQAV or PQAV on an organic and / or inorganic insoluble carrier.
  • PQAV / surfactant complex then it may be preferred to use the amount of this impregnation, based on the total weight of the impregnated solid, in the range from about 0.01 to 20% by weight and in particular in the range from about 0.1 to 10 % By weight.
  • the stage of textile cleaning using ultrasound, in particular for removing pigment and / or grease stains, provided in the method according to the invention is such that the material to be cleaned is at least partially - preferably completely - immersed in the sonicated liquor , It may be important to take measures to ensure that the immersed material is largely free of adherent, gaseous fractions - in particular of air inclusions.
  • the temperature of the wash liquor in the ultrasound treatment can be up to about 95 ° C, but is preferably considerably lower and usually does not exceed temperatures of about 80 ° C. Effective cleaning is possible at room temperature lent. Lowering the process temperature toward room temperature is even preferred from the standpoint of promoting desired cavitation formation. On the other hand, it must be taken into account that in the method according to the invention there is a certain interplay of conventional effects of textile cleaning by means of surfactants and the known effect of ultrasonic cleaning. It has often proven to be expedient to carry out the washing step of the ultrasound treatment in the temperature range from about 30 to about 70 ° C. and here in particular in the temperature range from about 35 to about 50 ° C.
  • the frequency range for carrying out the method according to the invention in the stage of ultrasound treatment concerned here is the entire range known today and also partially used in cleaning methods.
  • Particularly preferred frequencies of the sonication are in the range up to about 100 kHz, the lower limit for the ultrasound usually being specified at about 16 kHz. Accordingly, a range of about 20 to 60 kHz for the sound frequency used can be particularly suitable.
  • the devices suitable for carrying out this method stage are generally influenced by a number of parameters. Cited as an example: Setting and selection of the detergent system, size and degree of loading of the cleaning bath, operating conditions of the cleaning bath, accessibility, durability and energy consumption of the sound reinforcement elements as well as expected degree of loading of the device in use, for example in the sense of a practically continuous use in the field of commercial cleaning or only periodically Use in the field of personal household laundry.
  • the invention provides a multi-stage cleaning process which, in addition to the ultrasound treatment with removal of pigment and / or grease stains, also provides for the treatment of the textile goods to be cleaned in order to remove problem soils which are still remaining. It is preferred to carry out these additional work stages at least in part following the ultrasound treatment.
  • the advantage of this use is obvious: the problem soils are now by • pigment and fatty dirt freed before and thus the immediate and targeted attack ge of the cleaning aid used in each case are accessible.
  • the two most important additional cleaning aids are dye-destroying, in particular bleaching additives and enzymatically active washing aids, in particular detergent proteases.
  • the enzymatic and / or bleaching work stages following a first ultrasound treatment can likewise be carried out using ultrasound, but they are preferably carried out at least in part over time without the use of ultrasound. This applies in particular to a subsequent work step with enzymatic action.
  • ferments can be sensitive to the effects of ultrasound and even ineffective.
  • the bleaching and / or enzymatic treatment can be carried out in the original liquor which contains the loaded strainer.
  • the liquor for carrying out these process stages is at least partially freed from the dirt-laden catcher. This can be done in detail as described in the older applications mentioned.
  • the liquor can therefore be pumped over, for example, via separation stages in which the sludge-laden undissolved catcher is retained.
  • the bleaching and / or enzymatically acting detergents can be added to the liquor right from the start and / or separately after the end of the ultrasound treatment stage.
  • Particularly ultrasonic sensitive detergents are preferably added to the cleaning bath after the first sonication stage has been completed.
  • washing tests were carried out with different tissue samples, which were provided with standard soiling. The tests were carried out in a stainless steel tub, which was equipped with ultrasonic vibrating elements on the bottom.
  • washing tub capacity 4 I; Ultrasound frequency transmitted to the washing liquor: 35 kHz.
  • Wash liquor temperature 41 ° C .; Duration of the sonication: 5 minutes; continuous sonication during the first washing stage;
  • the table below summarizes the examined standard test fabrics, the associated reflectance values of the soiled material used and the reflectance values of the cleaned material after the old-sound treatment.

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

Abstract

On traite sous l'influence d'ultra-sons les produits textiles sales dans un bain détergent contenant des agents tensio-actifs et si voulu d'autres composants usuels de bains détergents. Le bain détergent contient en outre des capteurs insolubles de taches de pigments et/ou de graisse qui peuvent être manuellement ou mécaniquement séparés des textiles nettoyés. Ces capteurs sont des liaisons polyquaternaires d'ammonium, de préférence immobilisées à la surface de supports insolubles. Dans un procédé à plusieurs étapes, après l'élimination des taches de pigments et de graisse, des taches blanchissables et/ou affectées par des enzymes sont éliminées à l'aide d'adjuvants blanchissants et/ou à action enzymatique.
PCT/EP1987/000096 1986-03-01 1987-02-19 Procede de lavage et/ou de nettoyage de produits textiles sales WO1987005344A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
DEP3606729.6 1986-03-01
DE19863606729 DE3606729A1 (de) 1986-03-01 1986-03-01 Wasch- und reinigungsmittel mit verringertem chemikalienbedarf
DE19863610386 DE3610386A1 (de) 1986-03-27 1986-03-27 Verfahren zum waschen und/oder reinigen von verschmutztem textilgut
DEP3610386.1 1986-03-27

Publications (1)

Publication Number Publication Date
WO1987005344A1 true WO1987005344A1 (fr) 1987-09-11

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EP (2) EP0258351A1 (fr)
WO (1) WO1987005344A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6376444B1 (en) * 1998-02-20 2002-04-23 Procter & Gamble Company Garment stain removal product which uses sonic or ultrasonic waves

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3702866C1 (de) * 1987-01-31 1988-07-14 Rheinmetall Gmbh Drallstabilisiertes Geschoss
DE4101981A1 (de) * 1991-01-24 1992-07-30 Licentia Gmbh Verfahren zum waschen von waesche
DE19607120A1 (de) * 1996-02-26 1997-08-28 Deinlein Kalb Hans Verfahren und Einrichtung zur Verbesserung der Reinigungsqualität bei Textilwaschmaschinen
AU1152601A (en) * 1999-10-22 2001-05-08 Reckitt Benckiser France Compositions and their use
CA2464313A1 (fr) * 2001-11-20 2003-05-30 Unilever Plc Procede permettant de nettoyer un substrat
WO2005026307A1 (fr) * 2003-09-12 2005-03-24 Reckitt Benckiser (Uk) Limited Procede de nettoyage et composition de nettoyage
US9890350B2 (en) 2015-10-28 2018-02-13 Ecolab Usa Inc. Methods of using a soil release polymer in a neutral or low alkaline prewash

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2525443A1 (de) * 1975-06-07 1976-12-16 Boco Waeschedienst Ernst Rethw Verfahren zum entfernen von verunreinigungen aus textilgut

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2525443A1 (de) * 1975-06-07 1976-12-16 Boco Waeschedienst Ernst Rethw Verfahren zum entfernen von verunreinigungen aus textilgut

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6376444B1 (en) * 1998-02-20 2002-04-23 Procter & Gamble Company Garment stain removal product which uses sonic or ultrasonic waves
US6689730B2 (en) * 1998-02-20 2004-02-10 The Procter & Gamble Company Garment stain removal product which uses sonic or ultrasonic waves

Also Published As

Publication number Publication date
EP0258351A1 (fr) 1988-03-09
EP0235686A1 (fr) 1987-09-09

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