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EP0013450A1 - Wäschereinigungsmittelzusammensetzung, Verfahren zur Herstellung und Verwendung derselben - Google Patents

Wäschereinigungsmittelzusammensetzung, Verfahren zur Herstellung und Verwendung derselben Download PDF

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Publication number
EP0013450A1
EP0013450A1 EP19790200782 EP79200782A EP0013450A1 EP 0013450 A1 EP0013450 A1 EP 0013450A1 EP 19790200782 EP19790200782 EP 19790200782 EP 79200782 A EP79200782 A EP 79200782A EP 0013450 A1 EP0013450 A1 EP 0013450A1
Authority
EP
European Patent Office
Prior art keywords
amine
substrate
carbon atoms
mixture
alkyl
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.)
Granted
Application number
EP19790200782
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English (en)
French (fr)
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EP0013450B1 (de
Inventor
Gianfranco Luigi Spadini
Giuseppe Antonio Fontanari
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.)
Procter and Gamble Ltd
Procter and Gamble Co
Original Assignee
Procter and Gamble Ltd
Procter and Gamble Co
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 Procter and Gamble Ltd, Procter and Gamble Co filed Critical Procter and Gamble Ltd
Publication of EP0013450A1 publication Critical patent/EP0013450A1/de
Application granted granted Critical
Publication of EP0013450B1 publication Critical patent/EP0013450B1/de
Expired 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
    • 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
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/40—Monoamines or polyamines; Salts thereof
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/835—Mixtures of non-ionic with cationic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/86—Mixtures of anionic, cationic, and non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • This invention relates to laundry products adapted to provide grease and oil removal benefits and more especially to laundry products in non-particulate solid form that incorporate amine surfactants.
  • Detergent compositions containing alkyl amine surfactants are known in the art, particularly for the purpose of degreasing metals and other hard surfaces. Examples of such compositions in liquid form are disclosed in BP 1438948, USP 3468804 and South African Application No. 6806992, while exemplary particulate detergent compositions are disclosed in DTAS 1034307. A further application of amines as surfactants is in the dry cleaning of textiles, a typical disclosure being that in DTAS 1057275.
  • Fabric-softening products comprising amines absorbed on non-particulate substrates, designed for addition to drum dryers, have also been suggested in USP 4077891, USP 3895128 and Belgian Patent No. 840402.
  • the present invention seeks to provide a product in solid non-particulate form adapted to provide enhanced grease and oily soil removal from textiles in an aqueous textile cleaning bath.
  • a laundry detergent product adapted to provide grease and oily soil removal from textiles comprising
  • the amount of (c) present in the mixture being from 0.1 to 10 parts by weight per part of the amine moiety of (b) the mixture being water dispersible or water soluble at 30°C, the total amount of (b) and (c) being from 0.1 to 30 parts by weight per part of (a) .
  • the amine is a primary or tertiary amine or amine salt containing not more than 20 atoms in the amine radical and most preferably the amine is a mono C 12-14 alkyl primary or tertiary amine salt. Mixtures of amines or amine salts can be used.
  • the amines suitable for the purposes of the present invention are saturated or unsaturated primary, secondary and tertiary amines or salts thereof, in which the amine portion of the molecule contains not more than 40 carbon atoms and in which at least one and not more than two of the organic groups attached to the nitrogen atom in the amine portion contain an alkyl or alkenyl chain of at least 8 carbon atoms.
  • the organic group or groups containing more than 8 carbon atoms can be saturated or unsaturated aliphatic in nature, as in material derived from naturally occurring oils and fats such as coconut and palm oil, tallowfat and soya bean oil and marine oils. These aliphatic groups can also be derived from synthetic hydrocarbon materials such as Ziegler olefins and OXO alcohols and can be substantially linear or highly branched in nature.
  • the aliphatic groups may form part of an aralkyl group such as an alkyl-benzyl group in which the alkyl portion can have from 8-15 carbon atoms and can be derived from any of the sources given above.
  • the remaining group or groups in amines useful in the present invention are selected from hydrogen, C 1 -C 7 alkyl, C l -C 4 hydroxy alkyl and benzyl moieties.
  • Preferred groups are hydrogen, methyl and hydroxy ethyl, and no more than one benzyl should be attached directly to the nitrogen atom.
  • Synthesis of the amines can be by any of the methods well-known in the art and which form no part of the present invention.
  • the amines may be present as such or in the protonated form as salts.
  • any of the conventional anions can be used, viz. halides (chlorides, bromides and iodides) sulphates, silicates, methosulphates, borates, phosphates and carboxylates.
  • Suitable carboxylates include formates, acetates, propionates and the C 12 -C 18 fatty acid carboxylates derived from naturally occurring triglycerides, especially stearates.
  • the amine salts may be formed prior to the processing of the product or may in certain instances be formed in situ in a manner to be described.
  • Preferred amines are the alkyl primary and tertiary amines in which the alkyl group is derived from middle cut coconut alcohol, hardened tallow or synthetic C 12 -C 13 alcohol produced by olefin build-up.
  • the invention embreres the use of amines containing up to 40 carbon atoms; it has been found that the grease and oily soil efficiency declines as the amine molecular weig increases i.e., a larger amount of amine or amine is required to achieve the same level of performance
  • preferred amines are those containing not more than 20 carbon atoms in the amine radical and only one group contains more than 8 carbon atoms.
  • the amines are primary C 12 - C 14 alkyl amines or tertiary C 12 -C 14 dimethyl amines.
  • the amines are utilised as salts, the most preferred embodiments being those in which the amine salts, particularly the long chain carboxylates, are formed iu situ during the processing of the product.
  • An essential component of the present invention is a co-surfactant which may be nonionic or anionic in character.
  • Suitable nonionic detergent materials for the purposes of the present invention can be broadly defined as compounds produced by the condensation of alkylene oxide groups having a hydrophilic nature with an organic hydrophobic compound having a reactive hydrogen atom.
  • the hydrophobic groups may be aliphatic or alkylaromatic in nature and the size of the polyoxyalkylene group which is condensed with any particular hydrophobic group can be readily adjusted to provide a water soluble compound having the desired balance between hydrophilic and liphophilic characteristics.
  • Suitable nonionic detergents include buthionic detergents
  • nonionic surfactant should have a lower consolute temperature in the range 25-65°C preferably in the range 30-50 C .
  • Preferred nonionic surfactants having this characteristic are the ethoxylated primary or secondary C 9 -C 15 alcohols containing 2-12 ethylene oxide groups per mole of alcohol, more particularly the C12-C15 alcohols containing 6-9 ethylene oxide groups per mole of alcohol.
  • Particularly preferred nonionics are these marketed under the trade names Dobanol 45-7 and Dobanol 45-9 by Shell Oil Company.
  • Synthetic anionic surfactants can also be employed as co-surfactants in the products of the present invention.
  • a highly preferred class of anionic detergents includes water-soluble salts, particularly the alkali metal, ammonium and alkanolammonium salts of organic sulfuric reaction products having in their molecular structure an alkyl or alkaryl group containing from about 8 to about 22, especially from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • alkyl is the alkyl portion of acyl groups.
  • Examples of this group of synthetic detergents which form part of the detergent compositions of the present invention are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C 8 -C 18 ) carbon atoms produced by reducing the glycerides of tallow or coconut oil. and sodium and potassium alkyl benzene sulfonates, in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g. those of the type described in USP 2,220,099 and 2,477,383. Especially valuable are linear straight chain alkyl benzene sulfonates in which the average of the alkyl group is about 11.8 carbon atoms, abbreviated as C 11.8 LAS.
  • a preferred alkyl ether sulfate surfactant component of the present invention is a mixture of alkyl ether sulfates, said mixture having an average (arithmetic mean) carbon chain length within the range of about 12 to 16 carbon atoms, preferably from about 14 to 15 carbon atoms, and an average (arithmetic mean) degree of ethoxylation of from about 1 to 4 moles of ethylene oxide.
  • anionic detergent compounds herein include the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; and sodium or potassium salts of alkyl phenol ethylene oxide ether sulfate containing about'l to about 10 units of ethylene oxide per molecule and wherein the alkyl groups contain about 8 to about 12 carbon atoms.
  • Other useful anionic detergent compounds herein include the water-soluble ⁇ -sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-1-sulfonic acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; alkyl ether sulfates containing from about 10 to 20 carbon atoms in the alkyl group and from about 1 to 30 moles of ethylene oxide; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; water-soluble salts of paraffin sulfonates containing from about 8 to 24, expecially 14 to 18 carbon atoms, and s-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8
  • Anionic surfactant mixtures can also be employed, for example 5:1 to 1:5 mixtures of an alkyl benzene sulfonate having from 9 to 15 carbon atoms in the alkyl radical and mixtures thereof, the cation being an alkali metal preferably sodium; and from about 2% to about 15% by weight of an alkyl ethoxy sulfate having from 10 to 20 carbon atoms in the alkyl radical and from 1 to 30 ethoxy groups and mixtures thereof, having an alkali metal cation, preferably sodium
  • the co-surfactant may comparative nonionic or anionic surfactant or a mixture of the two, the relative proportions in such a mixture not being of importance for the purpose of the present invention.
  • the total amount of the co-surfactant should be such as to provide from 0.1 to 10 parts by weight of co-surfactant per part of amine, preferably from 1 to 10 parts by weight and most preferably from 1.5 to 5 parts by weight.
  • aminc-co-surfactant mixture should be water soluble or water-dispersible at 30 0 C.
  • the composition embodying the amine-cosurfactant mixtu should also be solid at this temperature. Mixtures of amines and nonionic and/or anionic surfactants do not have a sharply defined melting point and the requirement that the mixture be solid at 30 0 C is also intended to that the mixture should not soften at 30 0 C and below.
  • the third essential component of the present invention is a flexible non-particulate substrate with which the other components are in water-releasable combination.
  • a water-releasable combination is one that is capable of being separated by water through solution, dispersion, leaching, softening or melting.
  • the substrate itself may be water-soluble or water insoluble and in the latter case, it should possess sufficient structural integrity under the conditions of the wash to be recovered from a washing machine at the end of the laundry cycle. Structures that are water-disintegratable i.e., that break down in aqueous media to individual fibres or insoluble particles are not considered satisfactory for the purposes of the present invention.
  • Water soluble materials include certain cellulose ethers, alginates, polyvinyl alcohol and water soluble polyvinyl pyrrolidone polymers, which can be formed into non-woven and woven fibrous structures.
  • Suitable water insoluble materials include, but are not restricted to, natural and synthetic fibres, foams, sponges and films.
  • the substrate may have any one of a number of physical forms such as sheets, blocks, rings, balls, rods or tubes. Such forms should be amenable to unit usage by the consumer, i.e., they should be capable of addition to the washing liquor in measured amounts, such as individual sheets, blocks or balls and unit lengths of rods or tubes. Certain of these substrate types can also be adapted for single or multiple uses and can accept loadings up to 30 times the substrate weight.
  • a highly preferred substrate type is a sheet, the form of which is the most advantageous for releasing material rapidly into a wash liquour, particularly under the limited time conditions prevailing in automatic washing machine cycles.
  • the sheet is water pervious i.e., water can pass from one surface of the sheet to the opposite surface and, for film type substrates, perforation of the sheet is desirable.
  • the most preferred form of the substrate is a sheet of woven or non-woven fabric or a thin sheet of cellular plastic material.
  • Woven fabric sheets can take the form of a plain weave natural or synthetic fibre of low fibre count/unit length, such as is used , for surgical dressings, or of the type known as cheese cloth.
  • Non-woven sheet type substrates limit the amount of material that can be applied to the sheet to a maximum of about ten times the sheet weight.
  • Suitable material which can be used as sheet-type substrates include, among others, sponges, paper and woven and non-woven cloth.
  • a sponge sheet will be in the form of an absorbent foam-like material.
  • absorbent foam-like material is intended to encompass three dimensional absorptive materials such as "gas blown foams", natural sponges and composite fibrous based structures such as are disclosed in US Patent Nos. 3311115 and 3430630 specifically incorporated herein by reference.
  • Synthetic organic polymeric plastics material such as polyether, polyurethane, polyester, polystyrene, polyvinylchloride, nylon, polyethylene and polypropylene are most often employed and a particularly preferred material of this type is a hydrophilic polyurethane foam in which the internal cellular walls of the foam have been broken by reticulation.
  • Foams of this type are described in detail in Dulle US Patent No. 3794029 which is hereby specifically incorporated by reference.
  • a preferred example of this foam type comprises a hyrophilic polyurethane foam of density about 0.038 g/cubic centimetres with a cell count of between 8 and 40 cells per cm. , preferably about 24 to 32 per cm. available from the Scott Paper Company, Eddystone, Pennsylvania, USA, under the Registerd Trade Mark "Hydrofoam”.
  • Paper sheets can also be used in products of the present invention provided that they possess sufficient wet strength to maintain their integrity during use.
  • a paper-based sheet of a type suitable for the purpose of the inventions is disclosed in BP 1370112, the disclosures of which are hereby specifically incorporated by reference.
  • the preferred non-woven cloth substrates usable in the invention herein can generally be defined as adhesively bonded fibrous or filamentous products, having a web or carded fibre structure where the fibre strength is suitable to allow or comprising fibrous mats, in which the fibres or filaments are distributed haphazardly or in array (i.e., an array of fibres in a carded web partial orientation of the fibres is frequently as well as a completely haphazard distributional orientation) or substantially aligned.
  • the fibres of filaments can be natural (e.g. wool, sil, jute, hemp, cotton, linen, sisal, or ramie) or synthetic (e.g. rayon, cellulose, or polyesters).
  • non-woven cloths are not a part of this invention and being well known in the art, are not described in detail herein.
  • such cloths are made by air or water laying processes in which the fibres or filaments are first cut to lengths from long strands, passed into a water or stream, and then deposited onto a screen through which the fibre-laden air or water is passed. The deposited fibres or filaments are then adhesively bonded together, dried, cured and otherwise treated as desired to form the non-woven cloth.
  • Non-woven cloths made of polyesters, polyamides, vinyl resins, and other thermoplastic fibres can be spunbonded, i.e., the fibres are spun out onto a flat-surface and bonded (melted) together by heat or by chemical reactions.
  • the absorbent properties desired herein are particularly easy to obtain with non-woven cloths and are provided merely by building up the thickness of the cloth, i.e., by superimposing a plurality of carded webs or mats to a thickness adequate to obtain the necessary absorbent properties, or by allowing a sufficient thickness of the fibres to deposit on the screen.
  • Any diameter or denier of the fibre can be used, inasmuch as it is the free space between each fibre that makes the thickness of the cloth directly related to the absorbent capacity of the cloth, and which further makes the non-woven cloth especially suitable for impregnation by means of intersectional or capillary action.
  • any thickness necessary to obtain the required absorbent capacity can be used.
  • binder-resins used in the manufacture of non-woven cloths can provide substrates possessing a variety of desirable traits.
  • the absorbent capacity of the cloth can be increased, decreased, or regulated by respectively using a hydrophilic binder-resin, a hydrophobic binder-resin or a mixture thereof in the fibre bonding step.
  • the hydrophobic binder-resin when r:,ed singly or as the predominant compound of a hydrophobic- hydrophilic mixture, provides non-woven cloths which are especially useful as substrates when the surfactant- substrate combinations disclosed herein are used in an automatic washer.
  • the substrate herein is a non-woven cloth made from fibres, deposited haphazardly or in randc array on the screen, the compositions exhibit excellent strength in all directions and are not prone to tear or separate when used in the washer.
  • Apertured non-woven substrates are also useful for the purposes of the present invention.
  • the apertures, which extend between opposite surfaces of the substrate are normally in a pattern and are formed during laydown of the fibres to produce the substrate.
  • Exemplary apertured non-woven substrates are disclosed in US Patent Nos. 3,741,724, 3,930,086 and 3,750,237, the disclosures of which are specifically incorporated herein by reference.
  • the non-woven cloth is water-laid or air-laid and is made from cellulosic fibres, particularly from regenerated cellulose or rayon, which are lubricated with standard textile lubricant.
  • the fibres are from 45 to 50 mm in length and are from 1.5 to 5 denier (Denier internationally recognised unit in yarn measure, corresponding to the weight in grams of a length of yarn).
  • the fibres are a least partially orientated haphazardly, particularly substantially haphazardly, and are adhesively bonder together with hydrophobic or substantially hydrophobic binder-resin, particularly with a nonionic self- crosslinking acrylic polymer or polymers.
  • the cloth comprises about 70% fibre and 30% binder-resin polymer by weight and has a basis weight of from 10 to about 100, preferably 20 to 60 grammes per square yard.
  • a particularly preferred example is an air-laid non-woven cloth comprising 70% regenerated cellulose (American Viscose Corporation) and 30% hydrophobic binder-resins (Rhoplex HA-8 on one side of the cloth, Rhoplex HA-16 on the other; Rohm & Haas, Inc.).
  • the cloth has a thickness of 4 to 5 mils., a basis weight of about 2 8 g. per square metre and an absorbent capacity of 6.
  • the fibres are 1/4 in length, 1.5 denier and are orientated substantially haphazardly.
  • the fibres are lubricated with sodium oleate.
  • a further preferred substrate is a water-laid, non-woven cloth commercially available from C.H. Dexter Co. Inc.
  • the fibres are regenerated cellulose, about 0.95 cm. in length, about 1.5 denier, and are lubricated with a similar standard textile lubricant.
  • the fibres comprise about 70% of the non-woven cloth by weight and are orientated substantially haphazardly; the binder-resin (HA-8) comprise about 30% by weight of the cloth.
  • the substrate is about 4 mils. thick, and it has a basis weight of about 28 g. per square metre and an absorbent capacity of 5.7.
  • the total loading of water releasable components on the substrate should be such as not to exceed 30 times the substrate weight and in the case of sheet-type substrates should be limited to 10 times the substrate weight, preferably from 2-7 times the substrate weight.
  • the size and shape of the substrate is a matter of choice and is determined principally associated with the convenience of its use. type substrate should not be so small as crevices of the machine or the or so large as to be awkward dispense from the container in which it is sold.
  • sheets ranging in plan area from 185 sq. cm. to 1850 sq. cm. are acceptable, the preferred area lying the range of from 740 to 1480 sq. cm for foamed sheets.
  • Such a size has the additional advantage of being too large to be swallowed by e.g., small children, thereby minimising the risk of internal damage from ingestion of the materials absorbed on the substrate.
  • a wide range of optional components can be applied to the substrate, subject only to loading limitations, compatibility with the other components and feasibility of incorporation.
  • organic surfactants other than those identified as essential components can also be applied provided that their presence does not detract from the grease and oily soil removal capability of the combination of the present invention.
  • Other materials such as organic chelating agents, anti-redeposition agents, suds modifying agents, fluorescers, perfumes, pigments and dyes can also be incorporated.
  • the invention is particularly adapted to be used in conjunction with the product disclosed in German Patent Application DTOS, 2744642 published April 13th.1978, the disclosures of which are specifically incorporated herein by reference.
  • DTOS 2744642 teaches the incorporation of an organic peroxy bleach precursor on a flexible non-particulate substrate, for the purpose of providing enhanced removal of oxidisable stains from textiles when added to a laundry wash liquor containing an inorganic persalt.
  • a preferred optional ingredient in the product of the present invention is a processing aid which serves as a plasticiser for the other materials during their application onto or into the substrate and also enhances the tactile aesthetics of the product.
  • Suitable materials for this function include C 12 -C 18 fatty acids and polyethylene glycols of MWt > 4000 more preferably MWt ; 6000.
  • Thickening agents are also useful ingredients in of the present invention and are defined as increase the viscosity or reduce the the mixture such as silica, talc,kaolinite morillonite as well as High MWt organic materials cellulose derivatives, alginates, axyasrylates and starch.
  • the level of incorporation for individual optional ingredients is in the range 0.1-3.0 parts by weight per part of substrate.
  • the product of the present invention can be made in a variety of ways and is not critically dependent on any particular manufacturing route.
  • aqueous or non-aqueous solutions and dispersions and molten mixtures of the components can be formed and applied to the flexible non-particulate substrate.
  • One technique of application is by immersion of the substrate in the component solution or dispersion followed by removal of the excess liquor by squeeze rolls.
  • the mixture of amine, surfactants etc., in liquid form is placed into a pan or trough which can be heated, if necessary, to maintain the contents in liquid form.
  • To the liquid mixture is then added any further additive.
  • a roll of absorbent substrate is then set up on an apparatus so that it can unroll freely. As the substrate unrolls, it travels downwardly and, submersed, passes through the pan or trough containing the liquid mixture at a slow enough speed to allow sufficient impregnation.
  • the treated substrate then travels, at the same speed, upwardly and through a pair of rollerswhich squeeze off excess bath liquid.
  • the impregnated substrate is then cooled to room temperature, after lengths, and subsequently packaged any or used.
  • rollers used resemble squeeze rolls" used by those in the paper and paper-making art; they can be made of hard rubber or steel.
  • the rollers are adjustable, so that the orifice between their respective surfaces can be regulated to control the amount of the liquid on the substrate.
  • the amine and other ingredients in liquid form is sprayed onto an absorbent substrate as it unrolls.
  • the unrolled substrate web is arranged to slide over the spray nozzle which comprises a horizontally disposed tube formed with a slit extending along its top surface.
  • the molten slurry of amine co-surfactant mixture and any additives mixed therewith is forced through the slit into the substrate and the excess liquid is then squeezed off by the use of squeeze rollers.
  • a melt temperature in the range of 40 o -80 o C preferably 45°-75°c is used and the molten material should have a viscosity of less than 5000 centipoises at 50°C, preferably no more than 500 centipoises.
  • This variation additionally involves the use of metal rollers which can be heated to maintain the impregnating mixture as a liquid
  • a further method involves separately treating a desired number of the individual plies of a multi-ply paper and subsequently adhesively joining the plies with a known adhesive-joiner this provides a composition which can be on one of its outer sides, yet contains plies, each of which is treated on both sheet-type substratcs of the any of the above techniques can be the most convenient process has been found employing a molten mixture of the components at a temperature in the range 40-100 o C. For systems of this type that contain suspended solids, some refinements are desirable in order to prevent segregation of the suspended solids and also to prevent build-up of solidified molten material over long periods of operation.
  • the suspension in the form of a uniform dispersion is fed into a v-shaped trough formed by the generally upright portion of the face of a heated, rotating horizontal roll and a plate inclined thereto so as to leave a small clearance between the bottom of the plate and the roll face.
  • a thin coating of suspension is carried downwards through the clearance and is transferred to a second horizontal roll in contact with the first but rotating in the opposite direction.
  • This second roll is in contact with a continuously advancing web of substrate material and its direction of rotation is such as to make its direction of movement opposite to that of the substrate at the point of contact. Under these conditions the coating on the roll transfers to the substrate and impregnates it without any build-up of the suspended solids occurring on the roll.
  • the impregnated substrate is preferably passed over one or more further counter rotating rolls that serve to spread the suspension evenly over the substrate before it is cooled in an air stream to solidify the impregnating material
  • ccrtain of the amine-co-surfactant mixtures suitable for the purposes of the invention need to be blended with a plasticising or thickening agent.
  • a processing aid is not essential in the preferred method of manufacture of products in accordance with the invention.
  • Such mixtures inherently possess the correct viscosity characteristics for satisfactory application to the substrate and indeed may themselves be used as carriers for other, optional, ingredients, such as chelating agents, high melting point bleach precursors and soil suspending agents.
  • additives of a waxy character may still be employed in order to provided robustness to the process, for example, by reducing dust or by modifying the range of temperatures over which the application process can be carried out.
  • the additives may also servea funtional purpose in the productby enhancing the rate of release and dissolution of the amine-co-surfactant mixture in aqueous media and by modifying the tactile impression created by the product.
  • the amine can be incorporated as such or in the form of an amine salt.
  • the latter form is preferred and a highly preferred salt is a long chain ratty acid salt of the amine.
  • This salt can be formed prior to the mixture of the components and their application to the substrate but more preferably the salt is formed in situ in the molten mixture by reaction of the free the chosen fatty acid. A slight excess acid is added relative to that required for reaction with the amine and this acts in the manner described above. made in accordance with the present adapted to provide grease and oily soil benefits when used as the sole source of detergent for a standard 3.5 k g load of soiled fabrics in a conventional washing machine holding 20 litres of water.
  • n-dodecylamine hydrochloride 1 50 g. of powdered n-dodecylamine hydrochloride are added to 500 g. of C 14 -C 15 primary alcohol (a substantially linear alcohol with ⁇ 25% 2-methyl branching) condensed with an average of seven moles of ethylene oxide per mole of alcohol and the mixture heated to 70°C with agitation to give a homogeneous dispersion.
  • the dispersion is transferred to a hold tank before being pumped to the applicator which comprises a head formed with a rectangular slot orifice having a length of 25 cms.
  • the applicator head extends laterally of, and is in contact with the surface of, a continuous web of 0.5 cm thick Hydrofoam 2 polyurethane foam substrate which is drawn from a reel past the orifice by a system of rolls. After impregnation by the mixture, the treated substrate is cooled and rewound on to a product reel before being cut into pieces approximately 25 cms square.
  • Each sheet contains 5.0 g. of alcohol ethoxylate and 1.5 g. of amine hydrochloride and provides grease and oily-soil removal when added to a 3.5 kg load of soiled fabrics in 20 litres of water at 30°C.
  • a similar benefit is also seen when the sheet is added together with 3.5 kg of soiled fabrics to 20 litres of a wash liquor containing any one of the following detergent compositions at 0.625% product concentration.
  • the amine can be replaced by any one of dodecyl dimethyl amine, lauryl dihydroxycthy lamine, myristyl amine, decyl diethylamine, dioctyl amine and tallow dimethyl amine.
  • the nonionic co- surfactant can be replaced by: Tallow alcohol condensed with respectively 11 and 25 moles of ethylene oxide per mole of alcohol, Dobanol 45-9, a C 14 -C 15 primary alcohol condensed with an average of nine moles of ethylene oxide per mole of alcohol, Dobanol 45-11, a C 14 -C 15 primary alcohol condensed with an average of eleven moles of ethylene oxide per mole of alcohol, Neodol 23-6 a C 12 -C 13 primary alcohol condensed with an average of six moles of ethylene oxide per mole of alcohol, marketed by the Shell Oil Co., Synperonic (RTM) A7, A9, All, A14 and A20, a range of primary C 13 -C 15 alcohols with about 50% 2-methyl branching condensed with an average of respectively 7, 9, 11, 14 and 20 moles of ethylene oxide per mole of alcohol supplied by Imperial Chemical Industries Ltd., Lial 125E4,a highly branched C 12 -C 15 primary alcohol con
  • 150 g. of powdered n-dodecylaminc hydrochloride are added to 500 g. of Dobanoj 45-7 nonionic surfactant and 450 g. of technical grade stearic acid and the mixture is heated with agitation to 7 0 0 C to provide a uniform dispersion. This is then pumped to an applicator assembly comprising two heated horizontally disposed,steel-faced rolls.
  • the first roll is provided with an inwardly inclined plate extending the length of the roll so as to form a v-shaped trough therebetween, the bottom of the trough being constituted by the nip between the roll and the bottom edge of the plate, the direction of rotation of the roll being downward at the nip so as to provide a bead of material on the roll surface.
  • the other roll has a faster speed of rotation in the same direction as the first so that a thin coating of the dispersion is transferred from one roll to the other,at the nip between the rolls, and is carried around the second roll.
  • the second roll is in contact with a continuous web of substrate material and at the point of contact the direction of movement of the roll surface is opposed to the direction of movement of the web so that the dispersion is wiped off the roll on to the substrate.
  • the substrate is a 25 cm wide web of apertured non-woven fibre formed of regenerated cellulose fibres bonded with an ethyl acrylate binder (70% fibre 30% binder solids) having a basis weight of 40 g. per sq. metre and 17 apertures/ sq. cm., available from Chicopee Manufacturing Co., Milltown, New Jersey U.S.A. under the Code No. AK 30ML1379.
  • the substrate web passes over two further counter rotating heated rolls that provide before being in a cooled a stream and wound onto a product reel.
  • the roll of impregnated substrate is subsequently cu. and folded to give sheets of size approximately 25cm x 25cm (weight 25 gr.) each bearinga total weight of
  • the sheets have a smooth slightly sandy feel.
  • Example II is repeated with the addition to the molten dispersion of 150g of Tallow alcohol and 120g of Polyethylene glycol 6000.
  • the sheets so formed have a waxy feel and each contains
  • the Dobanol 45-7 can be replaced by sodium C 12 alkyl benzene sulphonate or by sodium C 12 alkyl sulphate.
  • the n-dodecyl amine hydrochloride can be replaced by coco dimethyl amine hydrochloride or by primary tallow amine hydrochlcride to give a similar product.
  • Example III is repeated except that 300 g of stearate are added to the molten place of the dodecylamine hydrochloride.
  • mxiture is a homogeneous melt, as the melts at approximately 50°C and is the remaining ingredients
  • the sheet produced has a smooth non- gritty
  • Example III is repeated replacing the n-dodecyl amine hydrochloride in the dispersion by 75 g of ditallow methyl amine hydrochloride to give a sheet product comprising
  • the sheet so formed has a waxy, slightly sandy feel and provides similar grease and oil-removal benefits to those provided by the products of Examples I-IV.
  • a sheet used with a heavy duty laundry detergent product at a concentration of 125 grs. product in 20 litres of water also gave some fabric softening benefits.
  • the tallow alcohol, polyethylene glycol, Dobanol 45-7 and stearic acid are mixed and heated with agitation to a temperature of 70°C.
  • the coco dimethylamine is then added and the mixture held for 15 minutes to ensure complete conversion of the amine to the salt.
  • the remaining ingredients are then added as finely powdered solids and mixed well to form a homogeneous dispersion which is then applied to a cellulosic substrate following the procedure in Example II to give a smooth sheet product that contains (per sheet)

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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)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
EP19790200782 1978-12-28 1979-12-19 Wäschereinigungsmittelzusammensetzung, Verfahren zur Herstellung und Verwendung derselben Expired EP0013450B1 (de)

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Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0062372A1 (de) * 1981-04-02 1982-10-13 THE PROCTER & GAMBLE COMPANY Textilweichmacher-Zusammensetzungen
EP0118191A1 (de) * 1983-02-03 1984-09-12 The Procter & Gamble Company Wäschezusatzzusammensetzungen
EP0133804A2 (de) * 1983-08-11 1985-03-06 The Procter & Gamble Company Reinigungsmittel mit Wäscheweichmacher
EP0203626A2 (de) * 1985-03-28 1986-12-03 Procter & Gamble European Technical Center Wäscheweichmacher enthaltendes Reinigungsmittel
US4648510A (en) * 1985-01-14 1987-03-10 Henkel Kommanditgesellschaft Auf Aktien Easily dispensable detergency booster cloths and dispenser therefor
GB2187750A (en) * 1986-03-11 1987-09-16 Navalon International Limited Non-woven detergent article
EP0252551B1 (de) * 1986-07-05 1990-05-30 The Procter & Gamble Company Weichmacher
EP0474117A1 (de) * 1990-09-04 1992-03-11 IBC Manufacturing Company Zubereitungen
US5312558A (en) * 1991-04-04 1994-05-17 Ibc Manufacturing Company Pesticide composition
US5612372A (en) * 1990-09-04 1997-03-18 Ibc Manufacturing Company Liquid dispersants for pesticides
WO1997035948A2 (de) * 1996-03-26 1997-10-02 Basf Aktiengesellschaft Waschkraftverstärker für waschmittel

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102020216453A1 (de) 2020-12-22 2022-06-23 Henkel Ag & Co. Kgaa Verfahren zur Herstellung eines Reinigungsutensils mit Tensidmischung

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2512616A1 (de) * 1974-03-21 1975-09-25 Procter & Gamble Fluessiges wasch- und reinigungsmittel
DE2539270A1 (de) * 1975-09-04 1977-03-24 Hoechst Ag Textil-weichmacher enthaltende waschmittel
DE2708516A1 (de) * 1976-03-10 1977-09-15 Henkel & Cie Gmbh Fuer die kaltwaesche geeignetes waschmittel
US4080162A (en) * 1972-09-11 1978-03-21 Colgate-Palmolive Company Technical N-alkyl-1,3-propylene diamine and formulations containing same
US4129515A (en) * 1976-09-13 1978-12-12 The Procter & Gamble Company Heavy-duty liquid detergent and process

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4080162A (en) * 1972-09-11 1978-03-21 Colgate-Palmolive Company Technical N-alkyl-1,3-propylene diamine and formulations containing same
DE2512616A1 (de) * 1974-03-21 1975-09-25 Procter & Gamble Fluessiges wasch- und reinigungsmittel
DE2539270A1 (de) * 1975-09-04 1977-03-24 Hoechst Ag Textil-weichmacher enthaltende waschmittel
DE2708516A1 (de) * 1976-03-10 1977-09-15 Henkel & Cie Gmbh Fuer die kaltwaesche geeignetes waschmittel
US4129515A (en) * 1976-09-13 1978-12-12 The Procter & Gamble Company Heavy-duty liquid detergent and process

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0062372A1 (de) * 1981-04-02 1982-10-13 THE PROCTER & GAMBLE COMPANY Textilweichmacher-Zusammensetzungen
EP0118191A1 (de) * 1983-02-03 1984-09-12 The Procter & Gamble Company Wäschezusatzzusammensetzungen
EP0133804A2 (de) * 1983-08-11 1985-03-06 The Procter & Gamble Company Reinigungsmittel mit Wäscheweichmacher
EP0133804A3 (en) * 1983-08-11 1987-05-20 The Procter & Gamble Company Detergent with fabric softener
US4648510A (en) * 1985-01-14 1987-03-10 Henkel Kommanditgesellschaft Auf Aktien Easily dispensable detergency booster cloths and dispenser therefor
EP0203626A2 (de) * 1985-03-28 1986-12-03 Procter & Gamble European Technical Center Wäscheweichmacher enthaltendes Reinigungsmittel
EP0203626A3 (en) * 1985-03-28 1988-08-31 Procter & Gamble European Technical Center Detergent containing a fabric conditioner detergent containing a fabric conditioner
GB2187750A (en) * 1986-03-11 1987-09-16 Navalon International Limited Non-woven detergent article
EP0252551B1 (de) * 1986-07-05 1990-05-30 The Procter & Gamble Company Weichmacher
EP0474117A1 (de) * 1990-09-04 1992-03-11 IBC Manufacturing Company Zubereitungen
AU648579B2 (en) * 1990-09-04 1994-04-28 Ibc Manufacturing Company Pesticide compositions containing a salt or partial salt of an alkyl or dialkylamine and a phosphonic or orthophosphoric acid
US5612372A (en) * 1990-09-04 1997-03-18 Ibc Manufacturing Company Liquid dispersants for pesticides
US5312558A (en) * 1991-04-04 1994-05-17 Ibc Manufacturing Company Pesticide composition
WO1997035948A2 (de) * 1996-03-26 1997-10-02 Basf Aktiengesellschaft Waschkraftverstärker für waschmittel
WO1997035948A3 (de) * 1996-03-26 1997-11-20 Basf Ag Waschkraftverstärker für waschmittel
US6180590B1 (en) 1996-03-26 2001-01-30 Basf Aktiengesellschaft Washing power enhancer for detergents

Also Published As

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DE2965164D1 (en) 1983-05-11
EP0013450B1 (de) 1983-04-06

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