EP0530958B1 - Produits adoucissants pour le linge à base d'une combination d'un composé de pentaérythritol et montmorillonite - Google Patents

Produits adoucissants pour le linge à base d'une combination d'un composé de pentaérythritol et montmorillonite Download PDF

Info

Publication number
EP0530958B1
EP0530958B1 EP92306450A EP92306450A EP0530958B1 EP 0530958 B1 EP0530958 B1 EP 0530958B1 EP 92306450 A EP92306450 A EP 92306450A EP 92306450 A EP92306450 A EP 92306450A EP 0530958 B1 EP0530958 B1 EP 0530958B1
Authority
EP
European Patent Office
Prior art keywords
pentaerythritol
bentonite
pec
fabric softening
sodium
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.)
Expired - Lifetime
Application number
EP92306450A
Other languages
German (de)
English (en)
Other versions
EP0530958A2 (fr
EP0530958A3 (en
Inventor
Eduardo E. Puentes-Bravo
Jean-Paul Mhf Grandmaire
Anita M. Hermosilla
Viviane E.A. Tack
Jan R.P. Doms
Pierre M. Lambert
Marcel Jeg Gillis
Paul A. Heckles
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.)
Colgate Palmolive Co
Original Assignee
Colgate Palmolive 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 Colgate Palmolive Co filed Critical Colgate Palmolive Co
Publication of EP0530958A2 publication Critical patent/EP0530958A2/fr
Publication of EP0530958A3 publication Critical patent/EP0530958A3/en
Application granted granted Critical
Publication of EP0530958B1 publication Critical patent/EP0530958B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • C11D17/047—Arrangements specially adapted for dry cleaning or laundry dryer related applications
    • 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
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/507—Polyesters
    • 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
    • C11D1/667—Neutral esters, e.g. sorbitan esters
    • 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
    • C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
    • C11D3/1246—Silicates, e.g. diatomaceous earth
    • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
    • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2093—Esters; Carbonates

Definitions

  • This invention relates to fabric softening products for applications to laundry during washing and/or, rinsing cycles, to apply to the fibers of the fabrics of such laundry fabric softening amounts of fabric softening compounds of such products. More particularly, it relates to such products that include as fabric softening components higher fatty acid esters of pentaerythritol, of pentaerythritol oligomers, or of ethoxylated derivatives of such pentaerythritol or oligomer esters, and any mixtures thereof, all of which may be designated PEC (for pentaerythritol compound), together with a clay of the montmorillonite type, very preferably bentonite, and which do not necessarily contain quaternary ammonium salts.
  • PEC for pentaerythritol compound
  • Fabric softening compositions and articles have long been employed to make washed laundry items softer to the touch and more comfortable to the wearer.
  • Such compositions include solutions, emulsions and particulate and powder products.
  • the fabric softeners of choice for most commercial products have usually been quaternary ammonium salts, such as dimethyl ditallowyl ammonium chloride, and emulsions of such softener have been added to the rinse water in the washing machine to soften laundry.
  • emulsions or powder products including such fabric softener can be added to the wash water, with a detergent composition, or the detergent composition can include a fabric softening components, making it a so-called "softergent”.
  • such quaternary ammonium salt is a di-lower alkyl, di-higher alkyl ammonium halide but mono-lower alkyl tri-higher alkyl ammonium halides have also found use in some instances.
  • EP-A-494769 is citable under EPC Article 54(3). It discloses a dispersion in water of 20 parts clay (gel forming sodium bentonite), 2 parts tripentaerythritol tetralaurate, 2 parts optional emulsifier and 76 parts water.
  • the invented compositions are surprisingly effective softergents, which clean as well as detergent compositions based on the same detersive components, and they also act synergistically with respect to fabric softening in non-detersive products such as wash cycle and rinse additives, and dryer products, in all of which the combination of PEC and bentonite softens treated laundry significantly better than would be expected from the additive effective of such components.
  • fabric softenings by each of the PEC and bentonite asymptotically approach limits which are below the excellent softening that is desirable, a composition containing PEC and bentonite softens significantly better and transcends such limits.
  • a particulate fabric softening detergent composition for application to fibrous materials, so that a fabric softening component thereof is deposited on the fibrous materials and softens them comprises a PEC, which is a fabric softening component which is a C 8 -C 24 aliphatic acid ester of pentaerythritol, of an oligomer of pentaerythritol, of a lower alkylene oxide derivative, containing 1 to 10 alkylene oxide moieties, of pentaerythritol or of a lower alkylene oxide derivative, containing 1 to 10 alkylene oxide moieties, of an oligomer of pentaerythritol, or a mixture thereof, a montmorillonite clay capable of swelling in use, and a synthetic organic detergent of the anionic and/or nonionic type(s) the composition containing 1 to 35% by weight of the detergent, 2 to 20% by weight of the PEC and 10 to 30% by weight of the clay
  • the particulate composition preferably contains 2 to 15% of PEC and 10 to 25% of bentonite.
  • the synthetic organic detergent is preferably a mixture of anionic and nonionic detergents, and the proportion thereof is in the range of 3 to 25%, the composition is built with 10 to 60% of builder, and the proportions of PEC and bentonite are in the ranges of 2 to 15% and 10 to 25%.
  • the anionic detergent may be a sulfated and/or sulfonated detergent
  • the nonionic detergent may be a condensation product of a higher fatty alcohol and ethylene oxide
  • the builder may be selected from the group consisting of water soluble alkali metal polyphosphates, carbonates, silicates, borates, citrates, bicarbonates, gluconates, nitrilotriacetates and ethylene diamine tetraacetates, water insoluble water softening zeolites, and mixtures thereof
  • the PEC may be a higher aliphatic acid partial ester of pentaerythritol or of an oligomer of pentaerythritol
  • the bentonite may be sodium and/or calcium bentonite.
  • a preferred particulate composition in accordance with the invention comprises 1 to 10% of sodium higher alkylbenzene sulfonate, 1 to 10% of nonionic detergent, which is a condensation product of one mol of higher fatty alcohol and 5 to 10 mols of ethylene oxide, 2 to 10% of sodium silicate, 15 to 35% of sodium tripolyphosphate, 2 to 10% of sodium carbonate, 3 to 10% of higher aliphatic acid partial ester of pentaerythritol and 12 to 20% of sodium and/or calcium bentonite.
  • nonionic detergent which is a condensation product of one mol of higher fatty alcohol and 5 to 10 mols of ethylene oxide
  • 2 to 10% of sodium silicate 15 to 35% of sodium tripolyphosphate
  • 2 to 10% of sodium carbonate 3 to 10% of higher aliphatic acid partial ester of pentaerythritol and 12 to 20% of sodium and/or calcium bentonite.
  • the higher aliphatic acid partial ester of pentaerythritol is preferably pentaerythritol distearate and the bentonite is preferably calcium bentonite.
  • composition in liquid or gel form which comprises 3 to 20% of the synthetic organic detergent, 2 to 20% of the PEC and 10 to 30% of the bentonite, in an aqueous medium.
  • compositions in accordance with the present invention are preferably essentially free of quaternary ammonium compound fabric softener.
  • PECs those which are preferred are the pentaerythritol distearates and dipentaerythritol dilaurates, and of the montmorillonites, sodium and calcium bentonite are preferred.
  • the invention also includes processes for softening laundry with the invented products.
  • U.S. patent 3,928,212 describes various softening agents which are polyhydric alcohol esters but none of them is a pentaerythritol ester or an ester of an oligomer or ethoxylated derivative of pentaerythritol or of an oligomer thereof.
  • U.S. 4,126,562 mentions erythritol and pentaerythritol in a list of alcohols which may be reacted with higher fatty acids to produce fabric conditioning agents but no such compound is actually described and none is shown in a fabric softening composition or article. Also U.S.
  • patent 4,126,562 is for a combination of a quaternary ammonium salt fabric softener and a nonionic ester of an alcohol with a higher fatty acid, and there is no teaching that the ester would be useful alone as a fabric softener.
  • U.S. patent 4,142,978 describes sorbitan esters with phase modifying components, such as alkyl sulfates, on a dryer sheet for softening laundry while it is being tumble dried in an automatic laundry dryer. The patent does not mention any pentaerythritol esters.
  • patent 4,162,984 relates to a textile treatment emulsion of a water insoluble cationic fabric softener, which is preferably a quaternary ammonium salt or an alkylimidazolinium salt, with a water insoluble nonionic fabric softener, which is preferably a fatty acid ester of a mono- or polyhydric alcohol or an anhydride thereof, and an aromatic mono-or dicarboxylic acid.
  • a water insoluble cationic fabric softener which is preferably a quaternary ammonium salt or an alkylimidazolinium salt
  • a water insoluble nonionic fabric softener which is preferably a fatty acid ester of a mono- or polyhydric alcohol or an anhydride thereof, and an aromatic mono-or dicarboxylic acid.
  • polyhydric alcohols that may be esterified, according to the patent, is pentaerythritol, but no pentaerythritol ester is described specifically nor is any oligomer of pentaerythritol suggested, and none is shown to be a useful fabric softening agent in the absence of quaternary ammonium salt and aromatic carboxylic acid.
  • polyglycerol is a polyhydric alcohol, as is pentaerythritol, it is not the same as pentaerythritol and the patent does not suggest the use of applicants' pentaerythritol esters as fabric softeners.
  • European patent specification 276999-A mentions fabric conditioning compositions that contain a non-cationic fabric softener and a nonionic cellulose ether.
  • ester of polyhydric alcohols are mentioned as suitable conditioning agents, pentaerythritol esters are not disclosed.
  • German patent specification 3612479-A describes textile softening compositions that contain quaternary ammonium compounds with carboxylic acid esters, and among the esters are those of various alcohols and polyols, including pentaerythritol. However, no such specific ester is described or even named, and no softening composition which does not contain quaternary ammonium compound as the fabric softener is disclosed.
  • Japanese patent 90 47,370 discloses fabric softening compositions that are based on quaternary ammonium salts but may contain a higher fatty acid ester of pentaerythritol. No specific such ester is described in the abstract.
  • any pentaerythritol ester could be employed with a montmorillonite clay, such as bentonite, as a fabric softening combination, in place of a quaternary ammonium compound or quat softener and would have essentially as good or better a softening action, and none of the disclosures mentions any specific pentaerythritol ester nor does any mention an ester of an oligomer of pentaerythritol, of lower alkoxylated pentaerythritol or of an oligomer thereof as a fabric softening agent in a fabric softening composition.
  • none of the references either alone or in combination with any of the others, anticipates the present invention or makes it obvious.
  • a main component of the invented compositions of the present invention which is usually the main fabric softening compound in such products, other than the fabric softening clay, such as bentonite, which will also be present in them, is a higher fatty acid ester of a pentaerythritol compound, which term is used in this specification to described higher fatty acid esters of pentaerythritol, higher fatty acid esters of pentaerythritol oligomers, higher fatty acid esters of lower alkylene oxide derivatives of pentaerythritol and higher fatty acid esters of lower alkylene oxide derivatives of pentaerythritol oligomers.
  • Pentaerythritol compound may be abbreviated as PEC herein, which description and abbreviation may apply to any or all of pentaerythritol, oligomers, thereof and alkoxylated derivatives thereof, as such, or more preferably and more usually, as the esters, as may be indicated by the context.
  • the oligomers of pentaerythritol are preferably those of two to five pentaerythritol moieties, more preferably 2 or 3, with such moieties being joined together through etheric bonds.
  • the lower alkylene oxide derivatives thereof are preferably of ethylene oxide or propylene oxide monomers, dimers or polymers, which terminate in hydroxyls and are joined to the pentaerythritol or oligomer of pentaerythritol through etheric linkages.
  • At least one of the PEC OH groups and preferably at least two, e.g., 1 or 2 to 4 are esterified by a higher fatty acid or other higher aliphatic acid, which can be of an odd number of carbon atoms.
  • the higher fatty acid esters of the pentaerythritol compounds are preferably partial esters and more preferably there will be at least two free hydroxyls thereon after esterification (on the pentaerythritol, oligomer or alkoxyalkane groups). Frequently the number of such free hydroxyls is two or about two but sometimes it may be one, as in pentaerythritol tristearate, or as many as eight, as in pentapentaerythritol tetrapalmitate.
  • the higher aliphatic or fatty acids that are employed as esterifying acids are those of carbon atom contents in the range of 8 to 24, preferably 12 to 22 and more preferably 12 to 18, e.g., lauric, myristic, palmitate, oleic, stearic and behenic acids. Such may be mixtures of such fatty acids, obtained from natural sources, such as tallow or coconut oil, or from such natural materials that have been hydrogenated. Synthetic acids of odd or even numbers of carbon atoms may also be employed. Of the fatty acids lauric and stearic acids are often preferred, and such preference may depend on the pentaerythritol compound being esterified.
  • the PECs utilised in this invention can have fabric softening effects but such activities are remarkably increased when a montmorillonite clay (bentonite) is also present.
  • bentonite a montmorillonite clay
  • the PEC may be substantially undispersed in wash and rinse waters, and may be less evenly and less strongly applied to laundry from softening articles. It has been found that better dispersed PEC has greater softening activity.
  • the PEC could be in solid agglomerate form when cold or in molten form when hot, in neither of which states does it act as effectively to soften fabrics (and in both of which cases it can deposit objectionably on treated materials to produce somewhat greasy spotting thereof).
  • the bentonite acts to disperse the PEC to make it more effective as a softener, and at the same time such "dispersing agent” also acts as a softener, which avoids the undersirable dilution of softening action by an ordinary dispersing agent, and it synergistically improves fabric softening.
  • the clays that are useful components of the invented products are those which cooperate synergistically with the PECs to soften laundry better than would be expected from such a combination.
  • Such clays are the montmorillonite-containing clays which have swelling properties (in water) and which are of smectite structure, so that they deposit on fibrous materials, especially cotton and cotton/synthetic blends, such as cotton/polyester, to give such fibers and fabrics made from them a surface lubricity or softness.
  • the best of these clays for use in the present invention is bentonite and the best of the bentonites are those which have a substantial swelling capability in water, such as the sodium and potassium bentonites.
  • Such swelling bentonites are also known as western or Wyoming bentonites, which are essentially sodium bentonite.
  • Other bentonites such as calcium bentonite, are normally non-swelling and usually are, in themselves, unacceptable as fabric softening agents.
  • the present inventors have found that such non-swelling bentonites exhibit even better fabric softening in combination with PECs than do the swelling bentonites, provided that there is present in the composition being tested for softness, a source of alkali metal or other solubilising ion, such as sodium (which may come from sodium hydroxide, added to the composition, or from sodium salts, such as builders and fillers, which may be functional components of the compositions).
  • normally non-swelling bentonite is surprising and the superiority of such in the invented compositions (when a source of sodium is present) over normally swelling bentonite, such as sodium bentonite, is very surprising.
  • bentonites are those of sodium and potassium, which are normally swelling, and calcium and magnesium, which are normally non-swelling. Of these it is preferred to utilise calcium (with a source of sodium being present) and sodium bentonites.
  • the bentonites employed are not limited to those produced in the United States of America, such as Wyoming bentonite, but also may be obtained from Europe, including Italy and Spain, as calcium bentonite, which may be converted to sodium bentonite by treatment with sodium carbonate, or may be employed as calcium bentonite.
  • montmorillonite-containing smectite clays of properties like those of the bentonites described may be substituted in whole or in part for the bentonites described herein and similar fabric softening results will be obtained.
  • the swellable bentonite and similarly operative clays are of ultimate particle sizes in the micron range, e.g. 0.01 to 20 microns and of actual particle sizes in the range of Nos. 100 to 400 sieves (which have openings 0.149 to 0.037 mm across), preferably 140 to 325 sieves (which have openings 0.105 to 0.044 mm across), U.S. Sieve Series. Such size ranges also apply to the zeolite builders, which will be described later herein.
  • the bentonite and other such suitable swellable clays may be agglomerated to large particle sizes too, such as 60 to 120 sieves (which have openings 0.25 to 0.125 mm across), but such agglomerates are not preferred unless they include the PEC(s) too (in any particulate products).
  • Liquid state preparations of this invention may be emulsions (which term herein is also intended to refer to dispersions and suspensions in liquid media, as well as to emulsions), and any such "emulsions" will normally be aqueous emulsions in which the aqueous phase is the continuous phase.
  • solvents and cosolvents such as ethanol, isopropanol, propylene glycol and various mono- and di-lower alkyl esters of diethylene glycol (Carbitols ®) may also be present in such emulsions and microemulsions to promote formations of more stable products, and may also be in the continuous media.
  • Suitable dispersing agents such as emulsifiers, can be employed with the mentioned clay to further help it to disperse the PEC in aqueous media. Such as useful in liquid and solid (including particulate) products.
  • emulsifiers can be employed , and many such are described in the various Detergents and Emulsifiers publications of John W. McCutcheon, issued annually, particularly those for 1969, 1973, 1980 and 1981.
  • Preferred such emulsifiers are those which are alkyl ethers or amines which contain one or more hydroalkyl substituents too.
  • alkyl dialkanolamines or alkyl trialkanolpropylenediamines wherein the alkanol moieties are of 2 to 4 carbon atoms, preferably being 2 to 4 carbon atoms, preferably 2 or 3 and more preferably being 2, and the alkyl poly(ethylene oxide) ethers are of 2 to 24 ethylene oxide units, preferably of 8 to 12 ethylene oxide units, in which emulsifiers the alkyl is of 8 to 24, preferably 12 to 18 carbon atoms. More preferred such emulsifiers are: stearyl diethanolamine, available from Hoechst A.G.
  • Genamin® S-020 tallow triethanol propylenediamine, available from CECA, S.A. as Dinoramox® S3; and R-O-(CH 2 CH 2 O) 10 H, wherein R is a mixture of C 12-15 alkyls, available from Hoechst A.G. as Genapol® OH-100.
  • the bentonite When instead of emulsion form for the invented compositions it is desired that they be in particulate, powder, solid or gel form less water or moisture or even none is present but the bentonite will still usually be of small (micron range) ultimate size.
  • the bentonite there may be present other swellable montmorillonite clays and there may also be present with the bentonite other non-functional substantially water insoluble carriers or dispersing agents, such as calcium carbonate and silica. Even water soluble carriers, such as sodium sulfate and other "filler salts" may be used, at least in part, and such can sometimes act as dispersing agents, too.
  • the bentonite employed should desirably be of a type which is gel forming in water and capable of softening fibrous materials, and should be of micron range ultimate particle size, although it may be agglomerated to larger sizes, usually in the range of 8 to 140 sieves, U.S. Sieve Series (which have openings 2.38 to 0.105 mm across).
  • the PEC will be employed without the presence of any other fabric softening material (except the clay, such as bentonite, montmorillonite or other operative smectite) but it is possible to utilise such other materials with it if in the proportions and quantities employed they are not ecologically unacceptable and if they do not interfere with the fiber softening action of the PEC.
  • the clay such as bentonite, montmorillonite or other operative smectite
  • such additions may be important because although PECs have some antistatic properties sometimes those are insufficient for the intended purposes.
  • antistats and fabric softeners include higher alkyl neoalkanamides, e.g., N-stearyl neodecanamide; isostearamides; amines, such as N,N-ditallowalkyl N-methyl amine; esterified quaternary salts or esterquats; amidoamines; amidoquats; imidazolines; imidazolinium salts; di-higher fatty acid esters of di-lower alkanolamines, such as dicoco acid ester of diethanolamine; silicones; and alkoxylated silicones; and representative examples of some of such classes of such compounds are given below (those which may cause significant ecological harm will desirably be avoided).
  • compositions include the usual adjuvants that normally are present in other fabric softening compositions (including softergents), such as perfumes, fixatives, solvents, cosolvents, hydrotropes, antioxidants, stabilisers, pH adjusters, buffers, biodegradable antimicrobials, builders, fillers, enzymes, thickeners and fluorescent brighteners, all of which are known classes of materials in the fabric softening compositions field, with examples of several of these being in the art mentioned in this specification.
  • adjuvants that normally are present in other fabric softening compositions (including softergents)
  • perfumes fixatives, solvents, cosolvents, hydrotropes, antioxidants, stabilisers, pH adjusters, buffers, biodegradable antimicrobials, builders, fillers, enzymes, thickeners and fluorescent brighteners, all of which are known classes of materials in the fabric softening compositions field, with examples of several of these being in the art mentioned in this specification.
  • the last component of the present compositions is water.
  • any clean water can be employed, such as any of a hardness in the range of 0 to 500 p.p.m., as CaCO 3 , bit it will be preferred to use water of a hardness of no more than 150 p.p.m., more preferably less than 50 p.p.m., and most preferably the water will be deionized water that has been irradiated.
  • the invention is directed to detergent compositions (softergents) that contain the described PEC and bentonite (or other suitable montmorillonite clay).
  • Such detergent compositions will contain at least one synthetic organic detergent of the anionic or nonionic type (or a mixture thereof), which may also function as a dispersing agent for the PEC.
  • the anionic detergents are normally of the water soluble sulfate and/or sulfonated lipophile type, which may be designated “sulf(on)ated", and which include lipophile and sulf(on)ate moieties, but analogous phosph(on)ates may also be utilised.
  • sulf(on)ated the water soluble sulfate and/or sulfonated lipophile type
  • phosph(on)ates may also be utilised.
  • synthetic anionic organic sulf(on)ated detergents those preferred are higher alkyl (preferably linear alkyl) benzene sulfonates, higher fatty alcohol sulfates. Higher fatty alcohol ethoxylate sulfates, olefin sulfonates and paraffin sulfonates.
  • such compounds are water soluble alkali metal salts, such as sodium salts, and include higher fatty alkyl or other aliphatic moieties, which serve as lipophilic moieties, and which increase detergency, especially against greasy soils.
  • higher alkyl or higher aliphatic moieties will normally be of 8 to 22 carbon atoms, preferably 10 or 12 or 18 carbon atoms and more preferably, especially for the alkyl sulfates and alkylbenzene sulfonates, the alkyl moieties will be of 12 to 14 carbon atoms.
  • the higher fatty alcohol ethoxylate sulfates that are useful will normally be of 1 to 20 ethoxy groups per mol, preferably 3 to 10 or 15, e.g. 3 to 7.
  • anionic detergents there may be mentioned sodium linear dodecylbenzene sulfonate, sodium linear tridecylbenzene sulfonate, sodium lauryl alcohol sulfate, sodium coco alcohol triethoxylate sulfate, sodium C 16 paraffin sulfonate and sodium olefin sulfonate derived from C 14 olefin.
  • ethylene oxide condensates with higher fatty alcohols or with alkyl phenols such as condensation products of 3 to 20, 5 to 15, 6 to 12 or 7 to 11 mols of ethylene oxide with higher fatty alcohols of 10 or 12 to 18 or 13 to 17 carbon atoms or with alkyl phenols of 7 to 10 carbon atoms in the alkyl groups, e.g., Dobanol® 25-7, Synperonic® A7, Neodol® 25-3, Neodol 25-7, Neodol 45-11, and C 13-17 alcohols condensed with 7 or 11 mols of ethylene oxide per mol.
  • water soluble builders for the anionic and nonionic detergents it is preferred to employ water soluble salts, such as sodium or potassium salts, more preferably sodium salts, and of these the carbonates, silicates, borates, bicarbonates and phosphates, especially the polyphosphates, are preferred, such as sodium carbonate, sodium bicarbonate, sodium silicate of Na 2 O:SiO 2 ratio in the range of 1:1.6 to 1:3, preferably 1:2 to 1:3, e.g., about 1:3, 1:2.35 or 1:2.4, sodium tripolyphosphate and tetrasodium pyrophosphate, but sodium sesquicarbonate and sodium sesquisilicate may also be used, as may be the corresponding potassium and other soluble salts, when suitable.
  • water soluble salts such as sodium or potassium salts, more preferably sodium salts
  • these the carbonates, silicates, borates, bicarbonates and phosphates, especially the polyphosphates are preferred, such as sodium carbonate, sodium bicarbonate,
  • the zeolites especially the hydrated zeolites.
  • Such zeolites include crystalline, amorphous and mixed crystalline and amorphous zeolites of both synthetic and natural origins, which are of satisfactorily quick and sufficiently effective activities in counteracting calcium hardness ions in wash waters.
  • the zeolites employed are characterised as having high exchange capacities for calcium ions, which exchange capacity is normally from about 200 to 400 milligram equivalents of calcium carbonate per gram of the zeolite.
  • exchange capacity is normally from about 200 to 400 milligram equivalents of calcium carbonate per gram of the zeolite.
  • the zeolite will be of the formula (Na 2 O) x .
  • crystalline zeolites that are useful those preferred include Zeolites A, X and Y, with A being more preferable, and the most preferred of these is Zeolite 4A. These zeolites are preferably in finely divided state when added to the crutcher with the synthetic detergent prior to drying, and are of ultimate particle diameters and actual sizes like those previously described for the bentonites.
  • Other builders that may be utilised include organic compounds, which are often sequestrants for hardness ions.
  • Such compounds include organic acids, especially hydroxy and amino polycarboxylic acids, such as citric and gluconic acids and ethylene diamine tetraacetic acid (EDTA) and nitrilotriacetic acid (NTA), all usually as their water soluble salts, e.g., sodium salts.
  • EDTA ethylene diamine tetraacetic acid
  • NTA nitrilotriacetic acid
  • Additional useful builders are the organo-phosphorus chelating agents, such as the Dequests®, e.g., Dequest 2046, which are manufactured by Monsanto Co.
  • the proportions of components of the invented compositions and articles will be those which result in stable and effective products for fabric softening applications.
  • concentrations in such liquid and gel softergent compositions will be in the range of 2 to 20%, more preferably 2 to 15% and most preferably 3 to 10%, e.g., about 5 to 6%.
  • the particulate softergents will comprise 2 to 20% of PEC, preferably 2 to 15% and more preferably 3 to 10%, e.g., 6%.
  • the bentonite or suitable clay content of the liquid or gel state softergents will be in the operative range of 10 to 30% and preferably 15 to 20%, e.g., 16% or 18%.
  • the particulate softergents such ranges are 10 to 30%, 10 to 25 %, 12 to 20% and 15 to 20%, respectively.
  • the operative percentage of synthetic organic detergent is, respectively, 3 to 20% and 1 or 2 to 35 %, preferably 3 to 25 %, more preferably 3 to 20% and most preferably 5 to 15%.
  • the synthetic organic detergent will be a mixture of anionic and nonionic detergents, with the percentages thereof being in the ranges of 1 to 10% of each, preferably 1 to 5% of each and more preferably 1 to 3% of anionic detergent and 3 to 5% of nonionic detergent, e.g., about 2% and about 4%, respectively.
  • the percentages of builder(s) will normally be in the range of 5 to 80%, preferably being in the range of 10 to 60%, more preferably 20 to 50% and most preferably 30 to 40%, with the percentages of sodium tripolyphosphate, sodium carbonate and sodium silicate, when such three builders are present, often being in the ranges of 10 to 50%, 2 to 20% and 2 to 15%, respectively, preferably 15 to 35%, 2 to 10% and 2 to 10%, and most preferably 20 to 30%, 3 to 8% and 2 to 6%, e.g., about 23%, 6% and 4%, respectively.
  • liquid softergents such ranges of contents for synthetic detergents and for builders will often be multiplied by a factor that is proportional to the solids content of the liquid composition divided by the limiting solids contents of the range for the particulate or solid product.
  • compositions that contain emulsifier(s) will normally be in the range of 0.2 to 10%, preferably 0.4 or 0.5 to 5% and more preferably 0.7 or 1 to 3%, e.g., about 1.25 or 2%.
  • the emulsifier contains both an alkyl alkanolamine and an alkyl poly(ethylene oxide) ether, as may be preferred, the proportion of the alkanolamine will usually desirably be equal to or greater than that of the alkyl poly(ethylene oxide) ether alkanol, preferably being of 2 to 5 times as much, e.g., about 4 times as much.
  • such percentages can be of 0.2 to 5% of the alkanolamine and 0.05 to 5% of the ether alkanol, preferably 0.3 to 3% and 0.1 to 2% and more preferably 0.5 to 2% and 0.2 to 1%.
  • the total adjuvants content will be no more than 25%, preferably will be no more than 15% and in many instances will be held to a limit of 5%. None of the adjuvants, in the amounts employed, will be such as to cause unacceptable levels of toxicity which could adversely affect aquatic organisms, including fish, that inhabit lakes and streams into which there are fed washing machine effluents that included the present compositions.
  • the invented compositions may be considered to consist essentially of the named components, or softergent form, with only environmentally acceptable proportions of adjuvants being allowed to be present therein.
  • the present compositions are preferably essentially free of quaternary ammonium compounds.
  • compositions and articles are not ecotoxic increasing limits of 0.1%, 0.3% and 0.5% may be imposed, which are more preferred, preferred and acceptable limits respectively, under such circumstances, and are within the broader invention.
  • emulsifiers are more often employed in aqueous compositions, they may also be present in solid or particulate products and the proportions thereof in such products will be proportionally the same as for the liquids, on a solids basis.
  • a suitable adjuvant for the described products is an acidifying agent, such as hydrochloric or other suitable acid, which is useful to adjust the pH of the emulsion or other aqueous composition to within the range of 2.5 to 5.5, preferably 2.5 to 4, e.g., 3.5.
  • an acidifying agent such as hydrochloric or other suitable acid
  • the percentage of HCl (concentrated basis) or equivalent other acidifying agent present will usually be in the range of 0.01 to 0.4%, preferably 0.05 to 0.2%.
  • a sodium-containing compound may be present to provide sodium ions (alternatively, potassium compounds can be present) to convert alkaline earth or magnesium bentonite to swelling alkali metal bentonite, in which case the proportion employed will usually be at least stoichiometric, and may be up to 20% in excess of stoichiometric.
  • Sodium hydroxide may be a suitable source of sodium ions, especially for the softergent compositions which are desirably alkaline.
  • the invented solid, particulate and gel compositions is comparatively simple, involving little more than mixings of components, (with gelling, and agglomeration steps sometimes) but to produce applicants' dispersions a particular process is followed (and that is the process of the working examples).
  • the PEC be melted before addition to the aqueous medium and the temperature to which the PEC is raised will desirably be within 10 °C of the melting point thereof.
  • the PEC be mixed with any meltable emulsifier especially one of lipophilic character (or more lipophilic character than another emulsifier present), such as the alkanolamine, when a mixed alkanolamine/ether alcohol (or alkanolamine/ethoxylated alcohol) emulsifier is employed, and melted together with it, but alternatively the two meltable materials, PEC and alkanolamine, may be separately melted and added together or simultaneously to the aqueous medium (usually water), which should also be at about the same elevated temperature, about 60 °C., for example.
  • the smectite clay may be added before, with or after the emulsifier/PEC mixture.
  • the water employed is often desirably acidified, as by addition to it of HCl or other suitable acid, to generate a final pH in the range of 2.5 to 5.5, preferably 2.5 to 4.0, e.g., about 3.5.
  • the emulsion produced may be cooled to room temperature, with the balance of emulsifier being added before or after such cooling, preferably before. The result is a stable emulsion which resists separation under normal elevated temperature conditions for periods of six months or more.
  • the PEC prefferably, the melted PEC, at elevated temperature, will be sprayed onto a tumbling mass of the particulate agglomerated smectite or montmorillonite powder (such as bentonite) or agglomerate thereof with any other particulate materials of the product, and will thereby be distributed throughout it evenly.
  • the mixer employed will include size reduction means to make sure the PEC is in small enough particles so as to be depositable evenly on the laundry being treated.
  • the bentonite or other smectite clay particles may be at room temperature when the PEC is being applied to them and the PEC will be solidified on contact with the particulate mass, usually with little agglomeration taking place, but by controlling the PEC application, the temperature and mixer speed, some agglomeration may be obtainable, when desired.
  • the softergents may be made in usual manners, with the PEC and bentonite being post-added or being added at a suitable stage of the manufacturing process, including crutching and spray drying, taking into account that they will not be subjected to destabilising or destructive temperatures.
  • the various invented compositions are employed in the same manners as are other softergents that apply fabric softener to laundry.
  • Softergents may be charged to the washing machine as if they were detergents, with the desired concentrations being in the range of 0.1 to 1%, preferably 0.1 to 0.5% e.g., about 0.15% in the U.S.A. and about 0.5% in Europe, to compensate for different washing conditions employed.
  • a particulate built fabric softening detergent composition (a softergent) of the above formula is made by spray drying a portion of the formula to produce base beads, and then admixing such beads with a mixture of the remaining components, except for the perfume, which is sprayed onto the mixture of the beads and other materials.
  • the spray dried beads are made by spray drying a crutcher mix of various heat stable components of the product, including sodium sulfate, sodium linear dodecylbenzene sulfonate, stearyl hydroxyethyl imidazoline, nonionic detergent, sodium silicate, sodium tripolyphosphate, sodium carbonate, ethylenediamine tetra(methylene phosphonic acid) sodium salt, optical brightener, silicone, sodium hydroxide, PEC and water, with the solids content of the crutcher mix being about 55%, to base beads of particle sizes in the range of 10 to 100, U.S. Sieve Series which has openings 2.00 to 0.149 mm across.
  • various heat stable components of the product including sodium sulfate, sodium linear dodecylbenzene sulfonate, stearyl hydroxyethyl imidazoline, nonionic detergent, sodium silicate, sodium tripolyphosphate, sodium carbonate, ethylenediamine tetra(methylene phospho
  • the bentonite is agglomerated to the same particle size range and the agglomerated bentonite and the other components (usually those which are heat sensitive), including the sodium perborate tetrahydrate, the enzyme, the hydroxylamine sulfate and the sodium aluminosilicate, are admixed with the base beads, after which the siliconate and perfume are sprayed onto the mixture resulting, to make the final softergent.
  • the PEC may be post-added to the composition in powdered form or as a co-agglomerate with bentonite.
  • the softergent In tests against various oily and clayey soils the softergent is found to be an effective and commercially acceptable detergent, using visual observations of the cleaning of soiled laundry and test swatches as well as reflectometer reading comparisons with controls.
  • the invented composition of the formula given above is as good as such "ultimate" composition or better in fabric softening effect, using 60 °C washing machine laundering of ordinary wash loads of dirty laundry or test swatches, whether the washing machines and procedures are of the American or European type, and whether the materials of the items washed are natural, such as cotton, synthetic, such as polyester, or blends thereof.
  • a panel of experienced evaluators usually at least four, compares washed swatched (or identical items), one of which was washed by a control detergent composition and the other of which was washed using a softergent that is being evaluated.
  • the difference in softness is judged and a number is assigned to indicate such difference with 1 being for a slight difference, 2 being for a moderate difference and 3 being for a great difference.
  • the swatches washed with the softergent will be softer than the control, which was washed in wash water that contained a detergent composition from which the softening bentonite-PEC combination has been omitted.
  • curve 11 shows the increase in fabric softening action on the washed laundry as the bentonite content is increased from 0 to 25%, with the dots on the curve representing specific bentonite contents. The best softening obtained is rated at about 2.7, which is about the best ever obtained with a softergent.
  • Curve 13 illustrates fabric softening action as the bentonite content is increased, with the PEC being omitted from the formula. It is notable that the curve heads downwardly, indicating less softening, when the bentonite content is over 25%.
  • Phantom curve 15 shows the expected additive effect on fabric softening action of the 6% of PEC plus the indicated percentages of bentonite. Because curve 15 is substantially lower than curve 11 for most of its length it proves that a synergistic fabric softening effect attends the presence of both bentonite and PEC in the described softergents composition.
  • FIG. 2 is similar to FIG. 1 except that in the FIG. 2 experiments it is the clay (bentonite) content that is being held constant while that of the PEC is being varied, from 0 to 20%.
  • Curve 17 shows the increase in fabric softening action of softergents of the invention which contain 16% of clay and from 1 to 10% of PEC, while curve 19 shows that when the clay content is 0% the increase in softening action as the PEC content is increased is at a lower rate, and softening actually decreases at higher PEC contents.
  • Curve 21 plots the expected (additive) effect of 16% of clay plus the indicated percentages of PEC. Because such curve is substantially lower than the actual curve 17 it is established that the combination of bentonite and PEC synergistically improves fabric softening of laundry washed with such softergents.
  • Another significant advantage of the invented softergents of this invention is in the breaking through of a perceived "softening barrier" by the invention. From FIGs. 1 and 2 it is evident that increasing the contents of either bentonite or PEC alone will not result in a superior softergent because the softening effect asymptotically approach limits less than or about 1 and even the additive effects which could be predicted are less than 2, and in all cases the fabric softenings are diminished as greater proportions of the mentioned softening agents are employed. Yet, with the invented compositions this apparent limit on softening power is transcended and less total quantities of the combination of PEC and bentonite yield superior results, with the fabric softening effects approaching those for rinse cycle additive compositions, which had previously been considered to be "an impossible dream".
  • Such effects are obtainable with other types of softergents, including those based on nonionic detergents only, anionic detergents only, water insoluble binders, such as zeolites, non-phosphate formulas, in which the builder composition can be a combination of zeolite, carbonate and silicate, and softergents built with organic builders, such as polyacetal carboxylates, NTA, EDTA, citric acid and gluconic acid.
  • the particulate product of this example is made by a procedure described in Example 1, and, when tested for detergency and fabric softening properties according to the procedures set forth in that example, exhibits good detergency and synergistic fabric softening, due to its contents of PEC and bentonite.
  • the synergistic improvement in fabric softening, compared to the expectable effects of the individual PEC and bentonite in such composition, is not as striking as in Example 1 (wherein 6% of PEC and 16% of bentonite were present) but is significant.
  • the PEC content is increased to 6% and the sodium sulphate content is decreased to 1.5%, with a corresponding increase in sodium sulfate content to 20.57%, and synergistic fabric softening is still noted, but to a lesser extent.
  • the PEC content is decreased to 16.07% to compensate, the synergistic fabric softening effect is even more pronounced.
  • Nonionic detergent 12.00 Sodium silicate (Na 2 O:SiO 2 1:2) 5.50 Zeolite 4A 23.00 Sodium maleate methacrylate copolymer 1.50 Sodium carboxymethyl cellulose 0.55 Sodium carbonate, anhydrous 13.00 Ethylenediamine tetra(methylene phosphonic acid) sodium salt 0.65 Stilbene optical brightener 0.30 Sodium hydroxide 0.15 Sodium perborate tetrahydrate 9.00 Proteolytic enzyme (Alcalase 2T) 0.70 Calcium bentonite 18.00 Hydroxylamine sulfate 0.50 Tetraacetylethylenediamine 3.86 Sodium aluminosilicate 0.50 Pentaerythritol distearate 3.50 Water 6.54 Perfume 0.75 100.00
  • the zeolite-built, non-phosphate, nonionic particulate detergent composition of this example is made by the process or processes of Examples 1 and 2 and is tested for detergency and fabric softening properties in the same manner. It is a good nonionic detergent and does not have the ecologically disadvantageous properties of phosphates or non-biodegradable anionic detergents. Also, due to its content of calcium bentonite and PEC it is of excellent fabric softening properties, synergistically better than would have been expected from the additive effects of the fabric softening agents present in the formula (and PEC is biodegradable).
  • an anionic detergent of the biodegradable type such as 5% of sodium lauryl sulfate or 10% of sodium C 14-15 paraffin sulfonate, and in some instances such anionic detergents may replace the nonionic detergent, with the total detergent content being about the same as in the formula of this example.
  • anionic detergents such as 5% of sodium lauryl sulfate or 10% of sodium C 14-15 paraffin sulfonate, and in some instances such anionic detergents may replace the nonionic detergent, with the total detergent content being about the same as in the formula of this example.
  • Such products also exhibit the excellent fabric softening properties of the formula of this example and such fabric softening is synergistically improved over the additive effects of the fabric softening components of the product.
  • This basic liquid softergent formula yields an excellent cleaner and fabric softener, which exhibits the synergism of the fabric softening components, previously described in Examples 1-3.
  • cotton terrycloth swatches are washed in an automatic washing machine in a 60 °C wash water containing 0.5% of a softergent composition of the formula of Example 1, rinsed and dried.
  • Other such swatches are washed in conventional detergent compositions, which may be of the same formula except for the omission of the bentonite and PEC, which are replaced by inert filler (sodium sulfate), and are then rinsed (in the last rinse), with rinse water to which any quaternary ammonium or amine salt rinse cycle fabric softening composition has been added, such as dimethyl distearyl ammonium chloride, so that the rinse water contains about 0.05% (or more) of the fabric softening quat or amine, and such swatches are dried.
  • conventional detergent compositions which may be of the same formula except for the omission of the bentonite and PEC, which are replaced by inert filler (sodium sulfate), and are then rinsed (
  • Strips are cut of swatches subjected to these different treatments and are tested for water absorption, by dipping lower ends of such vertical strips into an aqueous solution of water soluble dye (red Iragon) and measuring the heights to which the water rises, after 30 seconds, 1 minute, 3 minutes and 5 minutes.
  • the strips washed with the invented softergent absorb water to heights that are about twice those for the strips from the swatches that are washed, as described, and then treated with the rinse cycle softener.
  • the invented softergents soften the cotton (and other fabrics) about as well as the best of comparable softening compositions, which is an exceptional result.
  • compositions and articles of the invention may be employed and various adjuvants and active components may be included in the compositions and articles of the invention, and so long as the combination of the acceptable clay and PEC is present the synergistic fabric softening action is obtainable. Such is also the case when proportions are varied within the ranges mentioned and when different concentrations of the products are employed, within the ranges given.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Detergent Compositions (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Materials For Medical Uses (AREA)
  • Saccharide Compounds (AREA)
  • Dental Preparations (AREA)
  • Medicines Containing Material From Animals Or Micro-Organisms (AREA)
  • Medicines That Contain Protein Lipid Enzymes And Other Medicines (AREA)
  • Hydrogenated Pyridines (AREA)
  • Peptides Or Proteins (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Woven Fabrics (AREA)

Claims (9)

  1. Composition particulaire de détergent, adoucissante pour le linge, pour application sur des matériaux fibreux, de telle sorte qu'un de ses composants adoucissants pour le linge est déposé sur les matériaux fibreux et les adoucit, comprenant un PEC, qui est un composant adoucissant pour le linge, qui est un ester d'acide aliphatique en C8-C24 du pentaérythritol, d'un oligomère du pentaérythritol, d'un dérivé d'oxyde d'alcoylène inférieur, contenant 1 à 10 parties d'oxyde d'alcoylène, du pentaérythritol, ou d'un dérivé d'oxyde d'alcoylène inférieur, contenant 1 à 10 parties d'oxyde d'alcoylène, d'un oligomère du pentaérythritol, ou un mélange de ceux-ci, une argile montmorillonite capable de gonfler lors de l'utilisation, et un détergent organique synthétique des types anionique et/ou non ionique, la composition contenant 1 à 35% en poids de détergent, 2 à 20% en poids de PEC et 10 à 30% en poids de l'argile.
  2. Composition particulaire suivant la revendication 1, contenant 2 à 15% de PEC et 10 à 25% de bentonite.
  3. Composition particulaire suivant la revendication 1 ou 2, dans laquelle le détergent organique synthétique est un mélange de détergents anioniques et non ioniques, et dans laquelle leur proportion se situe dans l'intervalle de 3 à 25%, la composition est préparée avec 10 à 60% d'adjuvant pour détergent, et les proportions de PEC et de bentonite se situent dans les intervalles de 2 à 15% et de 10 à 25%.
  4. Composition particulaire suivant la revendication 1, 2 ou 3, dans laquelle le détergent anionique est un détergent sulfaté et/ou sufonaté, le détergent non ionique est un produit de condensation d'un alcool gras en C10-C18 et d'oxyde d'éthylène, l'adjuvant pour détergent est sélectionné dans le groupe composé des polyphosphates de métal alcalin solubles dans l'eau, des carbonates, des silicates, des borates, des citrates, des bicarbonates, des gluconates, des nitrilotriacétates et des éthylènediaminetétraacétates, des zéolites adoucissantes de l'eau insolubles dans l'eau, et de leurs mélanges, dans laquelle le PEC est un ester partiel d'acide aliphatique en C8-C24 du pentaérythritol ou d'un oligomère du pentaérythritol, et dans laquelle la bentonite est la bentonite de sodium et/ou de calcium.
  5. Composition particulaire suivant l'une quelconque des revendications 1 à 4, comprenant 1 à 10% d'(alcoyle supérieur)benzène sulfonate de sodium, 1 à 10% de détergent non ionique, qui est un produit de condensation d'une mole d'alcool gras supérieur et de 5 à 10 moles d'oxyde d'éthylène, 2 à 10% de silicate de sodium, 15 à 35% de tripolyphosphate de sodium, 2 à 10% de carbonate de sodium, 3 à 10% d'ester partiel d'acide aliphatique en C8-C24 du pentaérythritol et 12 à 20% de bentonite de sodium et/ou de calcium.
  6. Composition particulaire suivant l'une quelconque des revendications 1 à 5, dans laquelle l'ester partiel d'acide aliphatique en C8-C24 du pentaérythritol est le distéarate de pentaérythritol et dans laquelle la bentonite est la bentonite de calcium.
  7. Composition de détergent, adoucissante pour le linge, sous forme liquide ou de gel, pour application sur des matériaux fibreux, de telle sorte qu'un de ses composants adoucissants pour le linge est déposé sur les matériaux fibreux et les adoucit, comprenant un PEC, une argile montmorillonite et un détergent organique synthétique suivant la revendication 1, laquelle composition comprend 3 à 20% du détergent organique synthétique, 2 à 20% du PEC et 10 à 30% de bentonite dans un milieu aqueux.
  8. Composition suivant l'une quelconque des revendications 1 à 7, caractérisée en ce qu'elle est essentiellement exempte de composé d'ammonium quaternaire adoucissant pour le linge.
  9. Procédé d'adoucissement de lessive, comprenant l'application à cette lessive d'un produit adoucissant pour le linge suivant l'une quelconque des revendications 1 à 7, de manière telle et dans des conditions telles qu'un de ses composants adoucissants pour le linge est déposé sur la lessive et l'adoucit.
EP92306450A 1991-09-06 1992-07-14 Produits adoucissants pour le linge à base d'une combination d'un composé de pentaérythritol et montmorillonite Expired - Lifetime EP0530958B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US75603091A 1991-09-06 1991-09-06
US756030 1991-09-06

Publications (3)

Publication Number Publication Date
EP0530958A2 EP0530958A2 (fr) 1993-03-10
EP0530958A3 EP0530958A3 (en) 1993-12-15
EP0530958B1 true EP0530958B1 (fr) 1998-10-14

Family

ID=25041736

Family Applications (1)

Application Number Title Priority Date Filing Date
EP92306450A Expired - Lifetime EP0530958B1 (fr) 1991-09-06 1992-07-14 Produits adoucissants pour le linge à base d'une combination d'un composé de pentaérythritol et montmorillonite

Country Status (18)

Country Link
EP (1) EP0530958B1 (fr)
JP (1) JPH05140869A (fr)
KR (1) KR100230557B1 (fr)
AT (1) ATE172237T1 (fr)
AU (1) AU657118B2 (fr)
BR (1) BR9202088A (fr)
CA (1) CA2076718A1 (fr)
DE (1) DE69227292D1 (fr)
FI (1) FI921148A (fr)
GR (1) GR1002282B (fr)
IE (1) IE922303A1 (fr)
MX (1) MX9201444A (fr)
MY (1) MY128049A (fr)
NO (1) NO300384B1 (fr)
NZ (1) NZ242021A (fr)
PT (1) PT100303B (fr)
TR (1) TR28408A (fr)
ZA (1) ZA921989B (fr)

Families Citing this family (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI921147A (fi) * 1991-09-06 1993-03-07 Colgate Palmolive Co Tygmjukgoerande kompositioner baserade pao en pentaerytritolfoerening ochett dispergermedel foer en saodan foerening
AU660101B2 (en) * 1992-08-07 1995-06-08 Colgate-Palmolive Company, The Heavy duty laundry detergent compositions of reduced dye transfer properties
KR20000073182A (ko) * 1999-05-07 2000-12-05 마이클 디. 오브라이언 반도체패키지 및 그 제조 방법
GB9911434D0 (en) * 1999-05-17 1999-07-14 Unilever Plc Fabric softening compositions
KR20000074351A (ko) * 1999-05-20 2000-12-15 마이클 디. 오브라이언 반도체패키지 및 그 제조방법
EP1149893B1 (fr) * 2000-04-26 2010-12-15 Colgate-Palmolive Company Ensemble doseur pour une composition adoucissante utilisable dans un cycle de lavage
US6258767B1 (en) * 2000-04-26 2001-07-10 Colgate-Palmolive Co. Spherical compacted unit dose softener
EP1276838B1 (fr) * 2000-04-26 2006-09-27 Colgate-Palmolive Company Adoucissant a dose unitaire pour un cycle de lavage
WO2001081520A1 (fr) * 2000-04-26 2001-11-01 Colgate-Palmolive Company Adoucissant en dose unitaire pour cycle de lavage
WO2001081521A2 (fr) * 2000-04-26 2001-11-01 Colgate-Palmolive Company Adoucissant en dose unitaire compactee spherique
US6670320B1 (en) * 2002-06-11 2003-12-30 Colgate-Palmolive Wash cycle unit dose softener containing a disintegrating agent
US6664222B1 (en) * 2002-06-13 2003-12-16 Colgate-Palmolive Co. Wash cycle unit dose softener
US6746995B2 (en) * 2002-06-13 2004-06-08 Colgate-Palmolive Company Wash cycle unit dose softener containing a controlled amount of moisture
CN100554398C (zh) * 2003-12-26 2009-10-28 花王株式会社 柔软洗涤剂组合物
TWI350309B (en) * 2003-12-26 2011-10-11 Kao Corp Softening detergent composition
US7754004B2 (en) * 2005-07-06 2010-07-13 Resource Development, L.L.C. Thickened surfactant-free cleansing and multifunctional liquid coating compositions containing nonreactive abrasive solid particles and an organosilane quaternary compound and methods of using
US8034760B2 (en) 2005-08-01 2011-10-11 Kao Corporation Softening detergent composition
CN101331220B (zh) 2005-12-28 2012-06-13 花王株式会社 柔软洗净剂组合物
EP2003192B8 (fr) 2006-03-31 2012-08-08 Kao Corporation Composition detergente adoucissante
DE102006016575A1 (de) * 2006-04-06 2007-10-11 Henkel Kgaa Feste, textil- und/oder hautpflegende Zusammensetzung
JP5197974B2 (ja) * 2007-03-09 2013-05-15 花王株式会社 繊維の残香性付与剤
CN103911225B (zh) * 2013-01-04 2017-12-12 艺康美国股份有限公司 固体片剂单位剂量炉清洁剂

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0530959A1 (fr) * 1991-09-06 1993-03-10 Colgate-Palmolive Company Compositions adoucissantes pour le linge à base d'un composé de pentaérythritol et d'un agent dispersant pour un tel composé

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU510901B2 (en) * 1976-01-09 1980-07-17 Procter & Gamble Company, The Fabric softening method and device
GB1599171A (en) * 1977-05-30 1981-09-30 Procter & Gamble Textile treatment composition
JPH0247370A (ja) * 1988-08-03 1990-02-16 Kao Corp 柔軟仕上剤
US5126060A (en) * 1991-01-09 1992-06-30 Colgate-Palmolive Co. Biodegradable fabric softening compositions based on pentaerythritol esters and free of quaternary ammonium compounds

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0530959A1 (fr) * 1991-09-06 1993-03-10 Colgate-Palmolive Company Compositions adoucissantes pour le linge à base d'un composé de pentaérythritol et d'un agent dispersant pour un tel composé

Also Published As

Publication number Publication date
ATE172237T1 (de) 1998-10-15
JPH05140869A (ja) 1993-06-08
IE922303A1 (en) 1993-03-10
GR920100112A (el) 1993-06-21
NO921036D0 (no) 1992-03-17
AU1300792A (en) 1993-03-11
KR100230557B1 (ko) 1999-11-15
CA2076718A1 (fr) 1993-03-07
PT100303A (pt) 1993-06-30
NO921036L (no) 1993-03-08
TR28408A (tr) 1996-06-14
EP0530958A2 (fr) 1993-03-10
PT100303B (pt) 1999-06-30
MX9201444A (es) 1993-03-01
MY128049A (en) 2007-01-31
EP0530958A3 (en) 1993-12-15
FI921148A (fi) 1993-03-07
BR9202088A (pt) 1993-04-06
NZ242021A (en) 1995-04-27
NO300384B1 (no) 1997-05-20
AU657118B2 (en) 1995-03-02
GR1002282B (el) 1996-05-02
DE69227292D1 (de) 1998-11-19
KR930006244A (ko) 1993-04-21
ZA921989B (en) 1993-09-20
FI921148A0 (fi) 1992-03-17

Similar Documents

Publication Publication Date Title
US5358647A (en) Fabric softening products based on a combination of pentaerythritol compound and bentonite
EP0530958B1 (fr) Produits adoucissants pour le linge à base d'une combination d'un composé de pentaérythritol et montmorillonite
CA1074966A (fr) Compositions adoucissantes et antistatiques compatibles avec les detergents
US5290459A (en) Biodegradable fabric softening compositions based on pentaerythritol esters and free of quaternary ammonium compounds
US5332513A (en) Particulate fabric softening and detergent compositions
FI77468B (fi) Tvaettmedelkomposition foer rengoering och uppmjukning av textiler.
GB2092610A (en) Laundry detergent substrate articles
EP0530959B1 (fr) Compositions adoucissantes pour le linge à base d'un composé de pentaérythritol et d'un agent dispersant pour un tel composé
US5593614A (en) Fabric softening composition based on higher fatty acid ester and dispersant for such ester
EP0004121A1 (fr) Compositions détergentes pour le linge à faible teneur en phosphate
US4968443A (en) Antistatic laundry detergent composition and processes therefor
US6194374B1 (en) Biodegradable fabric softening compositions based on a combination of pentaerythritol esters, bentonite and a polyphosphonate compound
EP0767826B1 (fr) Composition d'assouplisseur contenant du pentaerythritol
AU767194B2 (en) Fabric softening compositions containing pentaerythritol esters, bentonite and polyphosphonate
AU2004200424B2 (en) Fabric softening compositions containing pentaerythritol esters, bentonite and polyphosphonate
GB2207144A (en) Detergent compositions comprising a softening clay and an amphoteric material
MXPA01003077A (en) Fabric softening compositions containing pentaerythritol esters, bentonite and polyphosphonate
EP0612841A2 (fr) Utilisation de compositions pour le traitement du tissu
JPH03172399A (ja) 布帛柔軟化重質洗濯洗剤組成物

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19920803

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL SE

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL SE

17Q First examination report despatched

Effective date: 19960617

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19981014

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19981014

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 19981014

Ref country code: ES

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19981014

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19981014

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19981014

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19981014

REF Corresponds to:

Ref document number: 172237

Country of ref document: AT

Date of ref document: 19981015

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 69227292

Country of ref document: DE

Date of ref document: 19981119

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19990114

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19990114

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 19990115

ET Fr: translation filed
NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990714

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990714

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19990714

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20110727

Year of fee payment: 20