GB1578951A - Fabric treating articles and process - Google Patents
Fabric treating articles and process Download PDFInfo
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- GB1578951A GB1578951A GB29004/77A GB2900477A GB1578951A GB 1578951 A GB1578951 A GB 1578951A GB 29004/77 A GB29004/77 A GB 29004/77A GB 2900477 A GB2900477 A GB 2900477A GB 1578951 A GB1578951 A GB 1578951A
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- fabric
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- fabrics
- air permeability
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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
- C11D17/04—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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/001—Softening compositions
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
- D06F39/00—Details of washing machines not specific to a single type of machines covered by groups D06F9/00 - D06F27/00
- D06F39/02—Devices for adding soap or other washing agents
- D06F39/024—Devices for adding soap or other washing agents mounted on the agitator or the rotating drum; Free body dispensers
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
- D06F58/00—Domestic laundry dryers
- D06F58/20—General details of domestic laundry dryers
- D06F58/203—Laundry conditioning arrangements
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Life Sciences & Earth Sciences (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)
- Chemical Or Physical Treatment Of Fibers (AREA)
- Detergent Compositions (AREA)
Description
(54) FABRIC TREATING ARTICLES AND
PROCESS
(71) We, THE PROCTER ' & GAMBLE COMPANY, a company organised under the laws of the State of
Ohio, United States of America, of 301 East
Sixth Street, Cincinnati, Ohio 45202,
United States of America, do hereby declare the invention, for which we pray that a patent may be granted to us, and the method by which it is to be performed, to be particularly described in and by the following statement:
The present invention relates to articles and methods for supplying conditioning, including softening and antistatic, benefits to fabrics in an automatic clothes washer and/or dryer. The articles comprise a double layered porous receptacle releasably containing a fabric conditioner composition.
Treating fabrics in an automatic clothes dryer has recently been shown to be an effective means for conditioning and imparting desirable tactile properties thereto. In particular, it is becoming common to soften fabrics in an automatic clothes dryer rather than during the rinse cycle of a laundering operation. Treating fabrics in the dryer, rather than in the wash, has enabled the formulator of fabric conditioners to develop and use materials which may not be compatible with detergents when added as a powder to the wash. Moreover, the user of dryer-added conditioners is not compelled to make the special effort required with many rinseadded products.
Although dryer-added conditioners have solved some of the problems inherent in wash or rinse-added conditioners, there still remains the need to improve performance and increase convenience. The ability to add an improved conditioning article at the start of the wash cycle would supply such benefits.
The use of fabric conditioning materials in detergent compositions or other compositions intended for use at the start of the wash cycle has long been attempted.
However, as indicated above, these attempts have met with only modest success due to incompatibility of the actives with the detergent materials or inefficient attachment of the actives to the treated fabrics. The softening and antistatic performance of such prior art compositions falls short of the performance obtained from rinse cycle added or dryer cycle added compositions.
The present invention is based on the discovery that fabrics can receive softening and antistatic benefits from a porous article containing a conditioner composition while being treated in an automatic clothes washer and/or dryer. Superior conditioning benefits are achieved while offering significant additional convenience.
It is an object of the present invention, therefore, to provide articles which can be added to a clothes washer and/or dryer to condition fabrics in a superior manner concurrently with a washer and/or dryer operation.
It is a further object herein to provide methods for conditioning fabrics.
These and other objects will become obvious from the following disclosure.
U.S. Patent Specification No. 3,822,145,
Liebowitz et al., Fabric Softening, issued
July 2, 1974, relates to the use of spherical materials as fabric softening agents. U.S.
Patent Specifications Nos. 3,743,534,
Zamora et al., Process for Softening
Fabrics in a Dryer, issued July 3, 1973; 3,698,095, Grand et al., Fiber Conditioning
Article, issued October 17, 1972; 3,686,025,
Morton, Textile Softening Agents
Impregnated into Absorbent Materials, issued August 22, 1972; 3,676,199, Hewitt et al., Fabric Conditioning Article and use
Thereof, issued July 11, 1972; 3,633,538,
Hoeflin, Spherical Device for Conditioning
Fabrics in Dryer, issued January 11, 1972,; 3,624,947, Furgal, Coating Apparatus, issued January 18, 1972; 3,632,396, Zamora,
Dryer-Added Fabric-Softening
Compositions, issued January 4, 1972; 3,442,692, Gaiser, Method of Conditioning
Fabrics, issued May 6, 1969; and 3,947,971,
Bauer, Fabric Softener and Dispenser, issued April 6, 1976, each relate to articles and methods for conditioning fabrics in automatic dryers. U.S. Patent Specification
No. 3,594,212, Ditsch, Treatment of
Fibrous Materials with Montmorillonite
Clays and Polyamines and Polyquaternary
Ammonium Compounds relates to the treatment of fibrous materials with clays and amine or ammonium compounds.
Granular detergent compositions containing fabric conditioning materials are disclosed in U.S. Patent Specification No.
3,862,058, Nirschl et al., Detergent
Compositions Containing a Smectite-type
Clay and Softening Agent, issued January 21, 1975, and U.S. Patent Specification No.
3,861,870, Edwards et al., Fabric Softening
Compositions Containing Water Insoluble
Particulate, issued January 21, 1975.
According to the present invention, there is provided a fabric conditioning article especially designed for conditioning fabrics in an automatic washer and comprising; (A) a closed, flexible receptacle, at least one wall of said receptacle comprising two superposed layers having a combined air permeability of from 200 to 390 cubic feet per minute per square foot of surface; and (B) an effective amount of fabric conditioner composition, said composition being releasably enclosed within the receptacle.
The invention also provides a process for conditioning fabrics comprising the following steps; (A) combining a fabric conditioning article with fabrics, in a clothes washer, said fabric conditioning article comprising: (1) a closed, flexible receptacle, at least one wall of said receptacle comprising two superposed layers having a combined air permeability of from 200 to 390 cubic feet per minute per square foot of surface; and (2) an effective amount of fabric conditioner composition said composition being releasably enclosed within the receptacle and (B) operating said washer at normal operating conditions through the rinse cycle.
Alternatively, the article may be used only in an automatic clothes dryer and operating the dryer, with tumbling, in standard fashion. Also, alternatively, the article may remain with the fabrics through all the cycles of an automatic washer and be discarded at the end of that time if an automatic dryer is not used. Also, alternatively, the fabric conditioning article may be transferred, with the washed clothes, to a clothes dryer and remain with the clothes during the drying operation.
The articles described herein comprise multiple components each of which is described, in turn, below.
Receptacle
The receptacle which releasably holds the fabric conditioner composition in the present invention is a closed, flexible article having at least one porous wall comprising two superposed layers having a combined air permeability of from 200 to 390 cubic feet per minute square foot of surface. The air permeability is measured according to
ASTM Method D737-69 "Standard
Method of Test for Air Permeability of
Textile Fabrics". Inasmuch as the receptacle is to be used in an automatic clothes washer and an automatic clothes dryer, it should be comprised of a heat resistant and water insoluble material.
Therefore, the receptacle herein can be made of any materials meeting these requirements. The porous wall can be made, for example, of open weave cotton, polyester, and the like, cloth or foams.
In a preferred receptacle herein, one layer associated with the porous wall or walls is an elastic, open cell foam or elastic nonwoven material. The open cell foams are distinguished from closed cell foams in that the closed cell structure substantially
isolates the individual cells while the open cell structure does not.
Open cell foams can be made from polystyrene, polyurethane, polyethylene, poly-(vinyl chloride) cellulose acetate, phenol-formaldehyde and other materials such as cellular rubber. Many of these materials and their method of manufacture are disclosed in standard references such as
Encyclopedia of Polymer Science and
Technology, Interscience Publishers, John
Wiley & Sons, Inc. (1965), incorporated herein by reference.
The preferred nonwoven cloth materials used in the first described layer herein can generally be defined as adhesively bonded fibrous or filamentous products having a web or carded fiber structure (where the fiber strength is suitable to allow carding), or comprising fibrous mats in which the fibers or filaments are distributed haphazardly or in random array (i.e., an array of fibers in a carded web wherein partial orientation of the fibers is frequently present, as well as a completely haphazard distributional orientation), or substantially aligned. The fibers or filaments can be natural (e.g., wool silk, jute, hemp, cotton, linen, sisal, or ramie) or synthetic (e.g., rayon cellulose ester, polyvinyl derivatives, poly-olefins, polyamides, or polyesters).
Preferred materials include polyesters, poly-amides, poly-olefins and polyvinyl derivatives and mixtures of these with rayon or cotton to achieve the desired elasticity.
Methods of making nonwoven cloths are not a part of this invention and, being well known in the art, are not described in detail herein. Generally, however, such cloths are made by air- or water-laying processes in which the fibers or filaments are first cut to desired lengths from long strands, passed into a water or air stream, and then deposited onto a screen through which the fiber-laden air or water is passed. The deposited fibers or filaments are then adhesively bonded together, dried, cured, and otherwise treated as desired to form the nonwoven cloth. Nonwoven cloths made of polysters, poly-amides, vinyl resins, and other thermoplastic fibers can be spanbonded, i.e., the fibers are spun out onto a flat surface and bonded (melted) together by heat or by chemical reactions.
This first described layer serves to preserve the shape of the receptacles herein. Additonally, the layer serves to moderate the release of the conditioner composition. It should not be more controlling in this respect, however, than the second layer.
Especially preferred materials for preparing the above-described layer of the article herein are open pore polyurethane foams and span-bonded nonwoven cloths, especially those made from polyesters. The polyurethane foams preferably have a density of from 0.02 g/cm3 to 0.04 g/cm3 while the polyester preferably has a density of 0.005 g/cm3 to 0.02 g/cm3. The thickness of this layer can vary depending on the release characteristics desired by the manufacturer, but will preferably be from about 0.2 cm to about 2.0 cm for polyurethane and from 0.2 cm to 2.0 cm for polyester.
The other layer of the preferred articles herein is a moderately porous nonwoven fabric. The nonwoven fabric can be any of the above-described nonwovens which meets these requirements but will generally be polyester, polypropylene or mixtures of polyester with rayon or cotton. This other layer has a lower porosity than the firstdescribed layer and will generally be in the range of 200 to 390 cubic feet per minute per square foot of fabric. Since the first described layer should not be more controlling than this second described layer in terms of conditioner release, its air permeability should be greater than 390 cubic feet per minute per square foot of surface.
The receptacles herein provide controlled release of the softening antistat compound during the wash and rinse cycles of an automatic washing machine and, if used, in the drying cycle of an automatic clothes dryer. The double layer feature of the receptacle provides a more efficient release than a single layer receptacle while also providing a more aesthetically pleasing article throughout the entire usage cycles.
Additionally, the double layered feature helps to insure that fabric staining is minimized by preventing a large amount of the conditioner composition to be released at one time.
The ideal fabric conditioner composition release pattern is one where the release is minimized during the wash cycle and the majority of the composition is released in the rinse cycle and dryer cycle. The articles herein provide such a release pattern.
In a preferred article herein the inner layer of the receptacle is the first layer described above and is constructed of spanbonded polyester or polyurethane foam having an air permeability in excess of 390 cubic feet per minute per square foot of surface. The outer layer in the preferred article is a nonwoven polyester having an air permeability of from 200 to 390 cubic feet per minute per square foot of surface.
The article in this preferred embodiment takes the form of a pouch.
Fabric Conditioner Composition
The fabric conditioner composition employed herein can contain any of the wide variety of nonionic and cationic materials known to supply these benefits.
These materials are substantive, and generally have a melting point within the range of from 20"C to 1150C, preferably within the range of from 30"C to 600C. By "substantially water insoluble" herein is meant a water insolubility of 1% by weight, or less, at 300 C. These materials are generally nonionic or cationic and are described in more detail hereinbelow.
The most common type of cationic conditioner materials are the cationic nitrogen-containing compounds such as quaternary ammonium compounds and amines having one or two straight-chain organic groups of at least eight carbon atoms. Preferably, they have one or two such groups of from 12 to 22 carbon atoms.
Preferred cation-active conditioner compounds include the quaternary ammonium conditioner compounds corresponding to the formula
wherein Rl is hydrogen or an aliphatic group of from 1 to 22 carbon atoms; R2 is an aliphatic group having from 12 to 22 carbon atoms; R3 and R4 are each alkyl groups of from 1 to 3 carbon atoms; and X is an anion selected from halogen, acetate, phosphate, nitrate and methyl sulfate radicals.
Because of their excellent softening efficacy and ready availability, preferred cationic conditioner compounds of the invention are the dialkyl dimethyl ammonium chlorides, wherein the alkyl groups have from 12 to 22 carbon atoms and are derived from long-chain fatty acids, such as hydrogenated tallow. As employed herein, alkyl is intended as including unsaturated compounds such as are present in alkyl groups derived from naturally occurring fatty oils. The term "tallow" refers to fatty alkyl groups derived from tallow fatty acids. Such fatty acids give rise to quaternary softener compounds wherein
R, and R2 have predominantly from 16 to 18 carbon atoms. The term "coconut" refers to fatty acid groups from coconut oil fatty acids. The coconut-alkyl R, and R2 groups have from about 8 to about 18 carbon atoms and predominate in C12 to
C,4 alkyl groups. Representative examples of quaternary softeners of the invention include tallow trimethyl ammonium chloride; ditallow dimethyl ammonium chloride; ditallow dimethyl ammonium methyl sulfate; dihexadecyl dimethyl ammonium chloride; di(hydrogenated tallow) dimethyl ammonium chloride; dioctadecyl dimethyl ammonium chloride; dieicosyl dimethyl ammonium chloride; didocosyl dimethyl ammonium chloride; di(hydrogenated tallow) dimethyl ammonium methyl sulfate; dihexadecyl diethyl ammonium chloride; dihexadecyl dimethyl ammonium acetate; ditallow dipropyl ammonium phosphate; ditallow dimethyl ammonium nitrate; di(coconutalkyl) di methyl ammonium chloride.
An especially preferred class of quaternary ammonium conditioners of the invention correspond to the formula
wherein R, and R2 are each straight chain aliphatic groups of from 12 to 22 carbon atoms and X is halogen, e.g., chloride or methyl sulfate. Especially preferred are ditallow dimethyl ammonium methyl sulfate (or chloride) and di(hydrogenated tallow-alkyl) dimethyl ammonium methyl sulfate (or chloride) and di(coconut-alkyl) dimethyl ammonium methyl sulfate (or chloride), these compounds being preferred from the standpoint of excellent softening properties and ready availability.
Suitable cation-active amine conditioner compounds are the primary, secondary and tertiary amine compounds having at least one straight-chain organic group of from 12 to 22 carbon atoms and 1,3-propylene diamine compounds having a straightchain organic group of from 12 to 22 carbon atoms. Examples of such softener actives include primary tallow amine; primary hydrogenated-tallow amine; tallow 1,3propylene diamine; oleyl 1,3-propylene diamine, coconut 1,3-propylene diamine; soya 1,3-propylene diamine and the like.
Other suitable cation-active conditioner compounds herein are the quaternary imidazolinium salts. Preferred salts are those conforming to the formula
wherein R6 in an alkyl containing from 1 to 4, preferably from 1 to 2 carbon atoms, R5 is an alkyl containing from 1 to 4 carbon atoms or a hydrogen radical, Rs is an alkyl containing from 1 to 22, preferably at least 15 carbon atoms or a hydrogen radical, R, is an alkyl containing from 8 to 22, preferably at least 15 carbon atoms, and X is an anion, preferably methylsulfate or chloride ions. Other suitable anions include those disclosed with reference to the cationic quaternary ammonium fabric conditioners described hereinbefore.
Particularly preferred are those imidazolinium compounds in which both R, and R8 are alkyls of from 12 to 22 carbon atoms, e.g., 1 - methyl - 1 - [(stearoyl- amide)ethyl] - 2 - heptadecyl - 4,5 dihydroimidazolinium methyl sulfate; 1 - methyl - 1 - [(palmitoylamide)ethyl] - 2 octadecyl - 4,5 - dihydroimidazolinium chloride and 1 - methyl - I [(tallowamide)ethyll - 2 - tallow imidazolinium methyl sulfate.
Other cationic quaternary ammonium fabric conditioners which are useful herein include, for example, alkyl (C,2 to C22)pryidinium chlorides, alkyl (C,2 to C22)-alkyl (Cl to C3)-morpholinium chlorides and quaternary derivatives of amino acids and amino esters.
Non ironic fabric conditioner materials include a wide variety of materials including sorbitan esters, fatty alcohols and their derivatives, diamine compounds and the like. One preferred type of nonionic fabric conditioner material comprises the esterified cyclic dehydration products of sorbitol, i.e., sorbitan ester. Sorbitol, itself prepared by catalytic hydrogenation of glucose, can be dehydrated in well-known fashion to form mixtures of cyclic 1,4- and 1,5-sorbitol anhydrides and small amounts of isosorbides. (See Brown; U.S. Patent
Specification No. 2,322,821; issued June 29, 1943). The resulting complex mixtures of cyclic anhydrides of sorbitol are collectively referred to herein as "sorbitan". It will be recognized that this "sorbitan" mixture will also contain some free uncyclized sorbitol.
Sorbitan ester fabric conditioner materials useful herein are prepared by esterifying the "sorbitan" mixture with a fatty acyl group in standard fashion, e.g., by reaction with a fatty (C10-C24) acid or fatty acid halide. The esterification reaction can occur at any of the available hydroxyl groups, and various mono-, di-, etc., esters can be prepared. In fact, complex mixtures of mon-, di-, tri-, and tetra-esters almost always result from such reactions, and the stoichiometric ratios of the reactants can simply be adjusted to favour the desired reaction product.
The foregoing complex mixtures of esterified cyclic dehydration products of sorbitol (and small amounts of esterified sorbitol) are collectively referred to herein as "sorbitan esters". Sorbitan mono- and di-esters of lauric, myristic, palmitic, stearic and behenic acids are particularly useful herein for conditioning the fabrics being treated. Mixed sorbitan esters, e.g., mixtures of the foregoing esters, and mixtures prepared by esterifying sorbitan with fatty acid mixtures such as the mixed tallow and hydrogenated palm oil fatty acids, are useful herein and are economically attractive. Unsaturated C10-C18 sorbitan esters, e.g., sorbitan monooleate, usually are present in such mixtures. It is to be recognized that all sorbitan esters, and mixtures thereof, which are essentially water-insoluble and which have fatty hydrocarbyl "tails", are useful fabric conditioner materials in the context of the present invention.
The preferred alkyl sorbitan ester fabric conditioner materials herein comprise sorb it an mon ol aurat e, sorb itan monomyristate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monobehenate, sorbitan dilaurate, sorbitan dimyristate, sorbitan dipalmitate, sorbitan distearate, sorbitan dibehenate, and mixtures thereof, the mixed coconutalkyl sorbitan mono- and di-esters and the mixed tallowalkyl sorbitan mono- and di-esters.
The tri and tetra-esters of sorbitan with lauric, myristic, palmitic, stearic and behenic acids, and mixtures thereof, are also useful herein.
Another useful type of nonionic fabric conditioner material encompasses the substantially water-insoluble compounds chemically classified as fatty alcohols.
Mono-ols, di-ols, and poly-ols having the requisite melting points and waterinsolubility properites set forth above are useful herein. Such alcohol-type fabric conditioning materials also include the mono- and di-fatty glycerides which contain at least one "free" OH group.
All manner of water-insoluble, high melting alcohols (including mono- and diglycerides), are useful herein, inasmuch as all such materials are fabric substantive. Of course, it is desirable to use those materials which are colorless, so as not to alter the color of the fabrics being treated.
Toxicologically acceptable materials which are safe for use in contact with skin should be chosen.
A preferred type of unesterified alcohol useful herein includes the higher melting members of the so-called fatty alcohol class. Although once limited to alcohols obtained from natural fats and oils, the term "fatty alcohols" has come to mean those alcohols which correspond to the alcohols obtainable from fats and oils, and all such alcohols can be made by synthetic processes. Fatty alcohols prepared by the mild oxidation of petroleum products are useful herein.
Another type of material which can be classified as an alcohol and which can be employed as the fabric conditioner material in the instant invention encompasses various esters of polyhydric alcohols. Such "esteralcohol" materials which have a melting point within the range recited herein and which are substantially waterinsoluble can be employed herein when they contain at least one free hydroxyl group, i.e., when they can be classified chemically as alcohols.
The alcoholic di-esters of glycerol useful herein include both the 1,3 - di - glycerides and the 1,2 - di - glycerides. In particular, di-glycerides containing two Cs-C20, preferably C10-C15, alkyl groups in the molecule are useful fabric conditioning agents.
Nonlimiting examples of esteralcohols useful herein include: glycerol - 1,2 dilaurate; glycerol - 1,3 - dilaurate; glycerol - 1,2 - dimyristate; glycerol 1,3 - dimyristate; glycerol - 1,2 dipalmitate; glycerol - 1,3 - dipalmitate; glycerol - 1,2 - distearate and glycerol 1,3 - distearate. Mixed glycerides available from mixed tallowalkyl fatty acids, i.e., 1,2 - ditallowalkyl glycerol and 1,3 ditallow - alkyl glycerol, are economically attractive for use herein. The foregoing ester-alcohols are preferred for use herein due to their ready availability from natural fats and oils.
Mono- and di-ether alcohols, especially the C10-C1a di-ether alcohols having at least one free -OH group, also fall within the definition of alcohols useful as fabric conditioner materials herein. The etheralcohols can be prepared by the classic
Williamson ether synthesis. As with the ester-alcohols, the reaction conditions are chosen such that at least one free, unetherified -OH group remains in the molecule.
Ether-alcohols useful herein include glycerol - 1,2 - dilauryl ether; glycerol 1,3 - distearyl ether; and butane tetra - ol 1,2,3 - trioctanyl ether.
Yet another type of nonionic fabric conditioning agent useful herein encompasses the substantially waterinsoluble (or dispersible) diamine compounds and diamine derivatives. The diamine fabric conditioning agents are selected from the group consisting of particular alkylated or acylated diamine compounds.
Useful diamine compounds have the general formula
wherein R, is an alkyl or acyl group containing from about 12 to 20 carbon atoms; R2 and R3 are hydrogen or alkyl of from about 1 to 20 carbon atoms and R4 is hydrogen, C1-20 alkyl or C12-20 acyl. At least two of R2, R3 and R4 are hydrogen or alkyl containing 1 to 3 carbon atoms, and n is from 2 to 6.
Non-limiting examples of such alkylated diamine compounds include: Cl5H33N(CH3) (CH2)3N(CH3)2 C18H37-N(CH3)(CH2)2-N(C2H5)2
C2H25-N(CH3)-(CH2)3-HN-C12H25
C12H25-N(C2H5HCH2)3-N(C3H7)2
RTallow-NH-(CH2)3-N(C2H5)2 C20H41-N(CH3HCH2)rnN(CH3)2
C15H21-N(C2H5)CH2)3-NH2
C10H37-Nll(CH2)rnHN-CH3
C16H33-NlICH2)rnHN-C16H33
R,a11owN(CH2)(CH2)3N(C2H0)2
C16H33N(CH3)-(CH2),-N(C2H,)2 C12H25N(C2H5)(CH2)2-N(C3H7)2 and C14H29N(CH2)-(CH2)2-(CH,W CH17 wherein the above formulas Tallow is the alkyl group derived from tallow fatty acid.
Other examples of suitable alkylated diamine compounds include N-tetradecyl,
N' - propyl - 1,3 - propane - diamine, N eicosyl,N,N',N' - triethyl - 1,2 - ethane diamine and N - octa - decyl,N,N',N' tripropyl - 1,3 - propane - diamine.
Examples of suitable acylated diamine fabric conditioner materials include C13-20 amido amine derivatives.
The fabric conditioners mentioned above can be used singly or in combination in the practice of the present invention.
Preferred mixtures useful herein are mixtures of dialkyl dimethyl ammonium salts with imidazolinium salts and mixtures of these two materials with sorbitan esters.
An especially preferred mixture includes ditallow dimethyl ammonium methyl sulfate, 1 - methyl - 1 [(tallowamide)ethyl] - 2 - tallow imidazolinium methyl sulfate and sorbitan tristearate in a ratio of from about 65/35/0 to 10/55/35. Tallow alcohol or hydrogenated castor oil may be used to replace sorbitan tristearate in the above mixture with similar results being obtained.
Another especially preferred mixture includes the above mixture wherein the sorbitan tristearate is absent and the other two components are present in a ratio of from about 65:35 to 35:65.
Optional Components
In a preferred article herein the conditioner composition is in the form of a free flowing powder. To facilitate forming such a powder any of a wide variety of filler materials may be used in the present composition. Such fillers include inorganics such as sodium sulfate, calcium carbonate, aluminum oxide and smectite clays and organics such as high molecular weight polyethylene glycols. Smectite clays and aluminum oxide are preferred fillers herein.
A description of smectite clays may be found in U.S. Patent Specification No.
3,862,058, January 21, 1975, to Nirschl et al., incorporated herein by reference. The filler material may be present at a level ranging from about 5% to 35% by weight of the conditioner composition.
The fabric conditioner compositions herein can also optionally contain minor proportions e.g., 0.10/, to 15 /n by weight of various other ingredients which provide additional fabric conditioning benefits.
Such optional ingredients include perfumes, bleaches, fumigants, bactericides, fungicides, optical brighteners and the like. Specific examples of typical solid, water-soluble additives useful herein can be found in any current Year Book of the American Association of Textile
Chemists and Colorists. Such additional components can be selected from those compounds which are known to be compatible with the conditioner agents employed herein, or can be coated with water-soluble coatings such as solid soaps, and the like, and thereby rendered compatible.
A preferred optional ingredient is a fabric substantive perfume having a melting point greater than 100 F. Included among such perfume materials are musk ambrette, musk ketone, musk xylol, ethyl vanillin, musk tibetine, coumarin, aurantiol and mixtures thereof. These perfumes can either be added alone to the conditioner or be encapsulated with a polyvinyl acetate/sodium alignate mixture. The above perfumes are preferably used in an amount of from about 0.1% to about 5% by weight of the fabric conditioner composition.
Other useful optional ingredients berlin include the common inorganic peroxy compounds such as alkali metal and ammonium perborates, percarbonates, monopersulfates and monoperphosphates.
Solid, water-soluble organic peroxy acids, or the water-soluble, e.g., alkali metal, salts thereof of the general formula
wherein R is a substituted or unsubstituted alkylene or arylene group and Y is
or any comprise an inner layer of a polyurethane foam having a density of from 0.02 g/cm3 to 0.04 g/cm3 or a span-bonded polyester nonwoven fabric having a density of from about 0.005 to 0.02 g/cm2, the air permeability of said layer being in excess of 390 cubic feet per minute per square foot of surface. The outer layer in the preferred receptacles herein comprises a nonwoven polyester cloth preferably having an air permeability of from 200 to 390 cubic feet per minute per square foot. The pouch is formed by sealing three edges of the two layers, as by heat sealing, leaving an opening along one edge. The fabric conditioner composition is added to the pouch opening which is then sealed.
The articles of the present invention can be utilized in a variety of ways depending on the desires of the user. In a preferred process, an article prepared as described herein is placed in with a load of fabrics at the start of the wash cycle in a standard clothes washer and left with the fabrics through the entire wash, rinse and spin drying cycles. The temperature of the wash and rinse waters can be any temperatures desired by the user, but generally are in the range of from 4"C to 60"C. The article then remains with the damp fabrics when they are placed in the drum of an automatic clothes dryer, if a dryer is used. The dryer is operated in standard fashion to dry the fabrics, usually at a temperature from 50"C to 800C for a period of from 10 to 60 minutes, depending on the fabric load and type. Alternatively, the articles herein can be combined with the fabrics at either the start of the rinse cycle or at the start of the automatic dryer cycle. The use of the article at the start of the wash cycle is preferred since the article during such usage is able to impart to the fabrics both excellent softness and reduction in static.
The detergent composition which can be used to wash the fabrics during the abovedescribed wash cycle can be any conventional detergent composition. Such a composition generally contains from 1% to 50% of a detersive surfactant. The detergents may be liquid or solid and contain other components such as a detergency builder, bleaches, enzymes, among other detergency adjuvants. The surfactants which may be used include any of the common anionic, nonionic, ampholytic and zwitterionic detersive agents well known in the detergency arts.
Mixtures of surfactants may also be used.
Examples of surfactants are given in U.S.
Patent Specifications Nos. 3,717,630, Booth,
February 20, 1973 and 4,443,880, Kessler et al., July 25, 1967, each incorporated herein by reference.
The detergency builder salts which are oftentimes utilized in detergent compositions include both inorganic, as well as organic, water-soluble builder salts and the various water-insoluble and so-called "seeded" builders. Typical laundry detergent compositions are generally designed to provide a concentration of builder salt of from 50 ppm to 1000 ppm and a concentration of detersive surfactant in the range of 50 ppm to about 1000 ppm.
These concentrations are generally met in the average aqueous solutions used to wash fabrics (5-25 gallons). The amount of detergent composition utilized per wash load is familar to users of laundry products and ranges from about 1/4 cup to 1-1/4 cup.
The performance delivered by the receptacles herein when used as described above is equivalent to a rinse added liquid softener in terms of softness and a dryer added sheet in terms of static control.
The invention will be further illustrated by the following examples:
EXAMPLE I
A fabric conditioning article of the present invention is made in the following manner:
A. Four layers measuring approximately 7-1/2 cm by 9 cm are placed one atop the other in the following order:
1. A layer of nonwoven polyester
approximately 0.33 mm thick and
having an air permeability of
approximately 350 cubic feet per
minute per square foot of surface.
Sontara 8000, E. I. duPont Co.
("Sontara" being a Registered Trade
Mark).
2. A layer of nonwoven polyester
approximately 5 mm thick and having
an air permeability of greater than 500
cubic feet per minute per square foot
of surface ("Bond Air" (Registered
Trade Mark), J. P. Stevens Co.)
3. Same as 2 above.
4. Same as 1 above.
B. The four layer stack from A is heat sealed on three sides forming a rectangular pouch with one open end.
C. Twelve grams of the following fabric conditioner composition is filled into the pouch between layers 2 and 3:
Ditallow dimethyl ammonium
methyl sulfate (90 /gn Active) 34.2 - - Methyl - 1 - [(tallowamide)ethyl] - 2
tallow imidazolinium methyl
sulfate (70% Active) 22.8
Sorbitan tristearate 25.0
Smectite clay (Gelwhite GP,
Georgia Kaolin Co.) 15.0
Perfume 3.0 100.0% The above cdmposition is made as shown in Exarriple II.
EXAMPLE II
The granular conditioner composition used in Example I is made in the following manner:
A. The ditallow dimethyl ammonium methyl sulfate, the imidazolinium salt and the sor-bitan tristearate are comelted together at 190do.
B. The clay and perfume are premixed.
C. Themixture of A is sprayed through a fine nozzle and solidifies into a powder containing' particles ranging in size from about 5 to 150:microns. During the spraying the mixture of B is evenly admixed into the sprayed composition.
EXAMPLE III
The fabric conditioning article of
Example I is added along with a 5.5 Ib.
bundle of soiled fabrics and 69 grams of an anionic detergent to an automatic washer.
The washer is operated for a period of 15 minutes using 100"F temperature water.
After the completion of the wash cycle, the rinse and spin dry cycles are completed.
Finally, the fabrics and the pouch are transferred to an automatic clothes dryer which is operated for a period of 50 minutes at a normal temperature setting. The dried fabrics demonstrate excellent softness and static control.
WHAT WE CLAIM IS;
1. A fabric conditioning article especially designed for conditioning fabrics in an automatic washer and comprising:
(A) a closed, flexible receptacle, at least one wall of said receptacle comprising two superposed layers having a combined air permeability of from 200 to 390 cubic feet per minute per square foot of surface; and
(B) an effective amount of a fabric conditioner composition, said composition being releasably enclosed within the receptacle.
2. An article according to claim 1 wherein one of the two layers is selected from the group consisting of elastic, open cell foams and elastic nonwoven materials and the other layer is a nonwoven material.
3. An article according to either one of claims 1 and 2 wherein the fabric conditioner composition contains a mixture of cationic and nonionic conditioner materials.
4. An article according to any one of claims 1 to 3 wherein the receptacle is in the form of a pouch.
5. An article according to any one of claims 1 to 4 wherein both walls of the pouch are constructed of the two layers having a combined air permeability of from 200 to 390 cubic feet per square foot of surface.
6. An article according to any one of claims 1 to 5 wherein one layer of the pouch walls is selected from the group consisting of polyurethane foams and polyester materials, said layer having an air permeability in excess of 390 cubic feet per minute per square foot of surface and the other layer is a polyester material having an air permeability of from 200 to 390 cubic feet per minute per square foot of surface.
7. An article according to claim 6 wherein the layer having the higher air permeability is the inside layer- and the layer having the lower air permeability is the outside layer.
8. An article according toy any one of claims 1 to 7 wherein the fabric conditioner composition contains a mixture of ditallow dimethyl ammonium methyl sulfate and 1 methyl - 1 - [(tallowamide)ethyll - 2tallow imidazolinium methyl sulfate in a ratio of from 60:40 to 40:60.
9. An article according to any one of claims 1 to 7 wherein the fabric conditioner composition contains a mixture of ditallow dimethyl ammonium methyl sulfate, 1 - methyl - I - [(tallowamide)ethyl] - 2 - tallow imidazolinium methyl sulfate and sorbitan tristearate in a ratio of from 65:35:0 to 10:55:35.
10 An article according to any one of claims 1 to 9 wherein the fabric conditioner composition is in the form of a free flowing powder and additionally contains from 5% to 35% by weight of the conditioner composition of a filler material.
11. An article according to claim 10 wherein the filler material is selected from the group consisting of smectite clay and aluminum oxide.
12. An article according to any one of claims 1 to 11 wherein the fabric conditioner composition contains from about 0.1% to 5% by weight of said composition of a fabric substantive perfume having a melting point greater than 100"F.
13. A process for conditioning fabrics comprising the following steps:
**WARNING** end of DESC field may overlap start of CLMS **.
Claims (24)
1. A fabric conditioning article especially designed for conditioning fabrics in an automatic washer and comprising:
(A) a closed, flexible receptacle, at least one wall of said receptacle comprising two superposed layers having a combined air permeability of from 200 to 390 cubic feet per minute per square foot of surface; and
(B) an effective amount of a fabric conditioner composition, said composition being releasably enclosed within the receptacle.
2. An article according to claim 1 wherein one of the two layers is selected from the group consisting of elastic, open cell foams and elastic nonwoven materials and the other layer is a nonwoven material.
3. An article according to either one of claims 1 and 2 wherein the fabric conditioner composition contains a mixture of cationic and nonionic conditioner materials.
4. An article according to any one of claims 1 to 3 wherein the receptacle is in the form of a pouch.
5. An article according to any one of claims 1 to 4 wherein both walls of the pouch are constructed of the two layers having a combined air permeability of from 200 to 390 cubic feet per square foot of surface.
6. An article according to any one of claims 1 to 5 wherein one layer of the pouch walls is selected from the group consisting of polyurethane foams and polyester materials, said layer having an air permeability in excess of 390 cubic feet per minute per square foot of surface and the other layer is a polyester material having an air permeability of from 200 to 390 cubic feet per minute per square foot of surface.
7. An article according to claim 6 wherein the layer having the higher air permeability is the inside layer- and the layer having the lower air permeability is the outside layer.
8. An article according toy any one of claims 1 to 7 wherein the fabric conditioner composition contains a mixture of ditallow dimethyl ammonium methyl sulfate and 1 methyl - 1 - [(tallowamide)ethyll - 2tallow imidazolinium methyl sulfate in a ratio of from 60:40 to 40:60.
9. An article according to any one of claims 1 to 7 wherein the fabric conditioner composition contains a mixture of ditallow dimethyl ammonium methyl sulfate, 1 - methyl - I - [(tallowamide)ethyl] - 2 - tallow imidazolinium methyl sulfate and sorbitan tristearate in a ratio of from 65:35:0 to 10:55:35.
10 An article according to any one of claims 1 to 9 wherein the fabric conditioner composition is in the form of a free flowing powder and additionally contains from 5% to 35% by weight of the conditioner composition of a filler material.
11. An article according to claim 10 wherein the filler material is selected from the group consisting of smectite clay and aluminum oxide.
12. An article according to any one of claims 1 to 11 wherein the fabric conditioner composition contains from about 0.1% to 5% by weight of said composition of a fabric substantive perfume having a melting point greater than 100"F.
13. A process for conditioning fabrics comprising the following steps:
(A) combining a fabric conditioning article with fabrics in a clothes washer, said fabric conditioning article comprising:
(1) a closed, flexible receptacle, at least
one wall of said receptacle comprising
two superposed layers having a
combined air permeability of from 200
to 390 cubic feet per minute per square
foot of surface ; and
(2) an effective amount of a fabric
conditioner composition said
composition being releasably enclosed
within the receptacle; and
(B) operating said washer at normal operating conditions through the rinse cycle.
14. A process according to claim 13, wherein said fabric conditioning article is combined with fabrics and detergent in a clothes washer, and step (B) further comprises operating said washer at normal operating conditions through the wash, rinse and spin dry cycles.
15. A process according to either one of claims 13 or 14, wherein the following steps are added:
(C) The washed fabrics and fabric conditioning article from step B are transferred to a clothes dryer; and
(D) said dryer is operated for an effective period of time at dryer operating conditions.
16. A process for conditioning fabrics, comprising the following steps:
(A) combining a fabric conditioner article with washed fabrics in a clothes dryer, said fabric conditioning article comprising:
(1) a closed, flexible receptacle, at least
one wall of said receptacle comprising
two superposed layers having a
combined air permeability of from 200
to 390 cubic feet per minute per square
foot of surface; and
(2) an effective amount of a fabric
conditioner composition said
composition being releasably enclosed
within the receptacle; and
(B) operating said dryer at normal operating conditions through the drying cycle.
17. A process according to any one of claims 13 to 16 wherein one of the two layers is selected from the group consisting of open cell foams and elastic nonwoven materials and the other layer is a nonwoven material.
18. A process according to any one of claims 13 to 17 wherein the fabric conditioner composition contains a mixture of cationic and nonionic conditioner materials.
19. A process according to any one of claim 13 to 18 wherein the receptacle is in the form of a pouch.
20. A process according to any one of claims 13 to 19 wherein both walls of the pouch are constructed of the two layers having a combined air permeability of from 200 to 390 cubic feet per minute per square foot of surface.
21. A process according to any one of claims 13 to 20 wherein one layer of the pouch walls is selected from the group consisting of polyurethane foams and polyester materials, said layer having an air permeability in excess of 390 cubic feet per minute per square foot of surface and the other layer is a polyester material having an air permeability of from 200 to 390 cubic feet per minute per square foot of surface.
22. A process according to claim 21 wherein the layer having the higher permeability is the inside layer and the layer having the lower air permeability is the outside layer.
23. A fabric conditioning article substantially as hereinbefore described with reference to Examples I and II.
24. A process for conditioning fabrics substantially as hereinbefore described with reference to Example III.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US70472276A | 1976-07-12 | 1976-07-12 |
Publications (1)
Publication Number | Publication Date |
---|---|
GB1578951A true GB1578951A (en) | 1980-11-12 |
Family
ID=24830627
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB29004/77A Expired GB1578951A (en) | 1976-07-12 | 1977-07-11 | Fabric treating articles and process |
Country Status (6)
Country | Link |
---|---|
JP (1) | JPS5338796A (en) |
CA (1) | CA1112004A (en) |
DE (1) | DE2731080A1 (en) |
FR (1) | FR2358499A1 (en) |
GB (1) | GB1578951A (en) |
IT (1) | IT1079275B (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4410441A (en) | 1982-04-26 | 1983-10-18 | Lever Brothers Company | Product for treating fabrics in a washing machine |
EP0095335A1 (en) * | 1982-05-20 | 1983-11-30 | Unilever N.V. | Device for conditioning fabrics in a tumble-dryer |
US4532719A (en) * | 1983-03-08 | 1985-08-06 | Lever Brothers Company | Method and device for conditioning fabrics in a tumble-dryer |
GB2157717A (en) * | 1984-04-18 | 1985-10-30 | Procter & Gamble | Process for washing clothes in a machine with a liquid detergent and device for applying the process |
WO1987006972A1 (en) * | 1986-05-12 | 1987-11-19 | Outdoor Industries Limited | Improvements in/or relating to chlorination of water |
WO2006061143A1 (en) * | 2004-12-08 | 2006-06-15 | Unilever Plc | Dispensing device |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2944146A1 (en) * | 1979-11-02 | 1981-05-14 | Henkel KGaA, 4000 Düsseldorf | AGENT FOR TREATING WASHED TEXTILES AND METHOD FOR TREATING TEXTILES IN A LAUNDRY DRYER |
DE3326249A1 (en) * | 1983-07-21 | 1985-01-31 | Henkel Kgaa | WASHING, DISHWASHER OR DETERGENT PACKAGING |
DE3605716A1 (en) * | 1986-02-22 | 1987-09-03 | Henkel Kgaa | USE OF INSOLUBLE DIRT COLLECTORS FOR REGENERATING WASHING AND CLEANING SOLUTIONS |
GB8607832D0 (en) * | 1986-03-27 | 1986-04-30 | Caligen Foam Ltd | Fabric treatment products |
GB8823007D0 (en) * | 1988-09-30 | 1988-11-09 | Unilever Plc | Conditioning of fabrics |
JP5127166B2 (en) * | 2006-06-14 | 2013-01-23 | ユニバーサル造船株式会社 | Stern duct and ship with it |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3442692A (en) * | 1965-08-13 | 1969-05-06 | Conrad J Gaiser | Method of conditioning fabrics |
US3594212A (en) * | 1968-03-25 | 1971-07-20 | Gen Mills Inc | Treatment of fibrous materials with montmorillonite clays and polyamines and polyquaternary ammonium compounds |
US3686025A (en) * | 1968-12-30 | 1972-08-22 | Procter & Gamble | Textile softening agents impregnated into absorbent materials |
US3632396A (en) * | 1969-04-28 | 1972-01-04 | Procter & Gamble | Dryer-added fabric-softening compositions |
US3633538A (en) * | 1970-10-20 | 1972-01-11 | Colgate Palmolive Co | Spherical device for conditioning fabrics in dryer |
US3676199A (en) * | 1970-10-20 | 1972-07-11 | Colgate Palmolive Co | Fabric conditioning article and use thereof |
US3698095A (en) * | 1970-10-20 | 1972-10-17 | Colgate Palmolive Co | Fiber conditioning article |
US3822145A (en) * | 1971-11-15 | 1974-07-02 | Colgate Palmolive Co | Fabric softening |
DE7230267U (en) * | 1972-03-07 | 1974-09-05 | Economics Laboratory Inc | Dispensing device for treatment agents intended for conditioning textiles |
US3862058A (en) * | 1972-11-10 | 1975-01-21 | Procter & Gamble | Detergent compositions containing a smectite-type clay softening agent |
US3861870A (en) * | 1973-05-04 | 1975-01-21 | Procter & Gamble | Fabric softening compositions containing water-insoluble particulate material and method |
US3945936A (en) * | 1974-01-29 | 1976-03-23 | The Procter & Gamble Company | Bleaching article |
US4022938A (en) * | 1974-04-16 | 1977-05-10 | The Procter & Gamble Company | Fabric treatment compositions |
US3947971A (en) * | 1974-11-06 | 1976-04-06 | John Levey | Fabric softener and dispenser |
-
1977
- 1977-06-17 CA CA280,772A patent/CA1112004A/en not_active Expired
- 1977-07-09 DE DE19772731080 patent/DE2731080A1/en active Granted
- 1977-07-11 GB GB29004/77A patent/GB1578951A/en not_active Expired
- 1977-07-11 IT IT50216/77A patent/IT1079275B/en active
- 1977-07-11 FR FR7721357A patent/FR2358499A1/en active Granted
- 1977-07-12 JP JP8343977A patent/JPS5338796A/en active Pending
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4410441A (en) | 1982-04-26 | 1983-10-18 | Lever Brothers Company | Product for treating fabrics in a washing machine |
EP0095335A1 (en) * | 1982-05-20 | 1983-11-30 | Unilever N.V. | Device for conditioning fabrics in a tumble-dryer |
US4567675A (en) * | 1982-05-20 | 1986-02-04 | Lever Brothers Company | Device for conditioning fabrics in a tumble-dryer |
US4532719A (en) * | 1983-03-08 | 1985-08-06 | Lever Brothers Company | Method and device for conditioning fabrics in a tumble-dryer |
GB2157717A (en) * | 1984-04-18 | 1985-10-30 | Procter & Gamble | Process for washing clothes in a machine with a liquid detergent and device for applying the process |
WO1987006972A1 (en) * | 1986-05-12 | 1987-11-19 | Outdoor Industries Limited | Improvements in/or relating to chlorination of water |
GB2219579A (en) * | 1986-05-12 | 1989-12-13 | Outdoor Ind Ltd | Improvements in/or relating to chlorination of water |
WO2006061143A1 (en) * | 2004-12-08 | 2006-06-15 | Unilever Plc | Dispensing device |
Also Published As
Publication number | Publication date |
---|---|
FR2358499B1 (en) | 1981-03-20 |
DE2731080A1 (en) | 1978-01-19 |
CA1112004A (en) | 1981-11-10 |
DE2731080C2 (en) | 1989-05-18 |
IT1079275B (en) | 1985-05-08 |
FR2358499A1 (en) | 1978-02-10 |
JPS5338796A (en) | 1978-04-10 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
PS | Patent sealed [section 19, patents act 1949] | ||
PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19960711 |