Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—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

Definitions

• the present invention relates to detergent compositions containing a fabric-softening amount of a smectite-type clay.
• the clay is present in the form of agglomerates which comprise from 0.5% to 30% of an organic humectant.
• British Patent 1,572,815 discloses a detergent composition based on soap and a curd-dispersing agent.
• the compositions comprise from 4% to 25% of a smectite-type clay.
• the clay is agglomerated with water, an aqueous electrolyte solution, a nonionic surfactant, or an aqueous solution of an organic adhesive.
• adhesives include dextrin, gelatine, carboxymethyl-cellulose, starch, carboxymethyl starch, and alkyl and hyroxy alkyl substituted celluloses and starches.
• the agglomerates are disclosed to minimize dustiness while the full softening potential of the clay is preserved.
• British Patent 1,167,037 discloses clays that have been treated with alkanolamine salts and an organic humectant.
• the treated clays are disclosed to hydrate rapidly and to develop viscosity in a short period of time as compared to untreated clays.
• British Patent 1,400,898 discloses detergent compositions comprising, as a fabric softening ingredient, a smectite-type clay.
• the present invention relates to the granular detergent compositions comprising a) conventional detergent ingredients; and b) clay agglomerates comprising from 60% to 99.5% smectite-type clay and from 30% to 0.5% of an organic humectant.
• Preferred humectants include:
• Preferred clay flocculating agents are polymers like poly(ethylene oxide), poly(acryl amide) and poly(acrylate), having a weight average molecular weight of from 100.000 to 10 million. Most preferred are poly (ethylene oxide) polymers having a molecular weight (weight average) in the range 150.000 to 5 million.
• the detergent compositions of the present invention comprise conventional detersive surfactants, conventional detergent builders and, optionally, other conventional detergent ingredients.
• the compositions further comprise a fabric-softening amount, typically from 1% to 35% by weight preferably from 3% to 15% by weight of the detergent composition, of the fabric-softening clay agglomerates herein.
• Percentages herein are percentages by weight of the detergent compositions, unless otherwise specified.
• compositions of this invention will typically contain organic surface-active agents ("surfactants”) to provide the usual cleaning benefits associated with the use of such materials.
• surfactants include well-known synthetic anionic, nonionic, amphoteric and zwitterionic surfactants. Typical of these are the alkyl benzene sulfonates, alkyl- and alkylether sulfates, paraffin sulfonates, olefin sulfonates, alkoxylated (especially ethoxylated) alcohols and alkyl phenols, amine oxides, alpha-sulfonates of fatty acids and of fatty acid esters, and the like, which are well-known from the detergency art.
• detersive surfactants contain an alkyl group in the C9-C18 range; the anionic detersive surfactants can be used in the form of their sodium, potassium or triethanolammonium salts; the nonionics generally contain from about 5 to about 17 ethylene oxide groups.
• U.S. Patent 3 995 669 the disclosures of which are incorporated herein by reference, contains detailed listings of such typical detersive surfactants.
• C11-C16 alkyl benzene sulfonates, C12-C18 paraffin-sulfonates and alkyl sulfates, and the ethoxylated alcohols and alkyl phenols are especially preferred inthe compositions of the present type.
• the surfactant are the water- soluble soaps, e.g. the common sodium and potassium coconut or tallow soaps well-known in the art.
• the surfactant component can comprise as little as 1% of the compositions herein, but preferably the composi­ tions will contain 5% to 40%, preferably 10% to 30%, of surfactant. Mixtures of the ethoxylated nonionics with anionics such as the alkyl benzene sulfonates, alkyl sulfates and paraffin sulfonates are preferred for through-the-wash cleansing of a broad spectrum of soils and stains from fabrics.
• compositions herein can contain other ingredients which aid in their cleaning performance.
• through-the-wash detergent compositions contain a detergent builder and/or metal ion sequestrant.
• detergent builders include the nitrilotriacetates, polycarboxylates, citrates, carbonates, zeolites, water-soluble phosphates such as tri-polyphosphate and sodium ortho- and pyro-phosphates, silicates, and mixtures thereof.
• Metal ion sequestrants include all of the above, plus materials like ethylenediaminetetraacetate, the amino-­polyphosphonates (DEQUEST) and a wide variety of other poly-functional organic acids and salts too numerous to mention in detail here. See U.S. Patent 3 579 454 for typical examples of the use of such materials in various cleaning compositions. In general, the builder/sequestrant will comprise about 0.5% to 45% of the composition.
• the 1-10 micron size zeolite (e. g. zeolite A) builders disclosed in German patent 2 422 655 are especial­ly preferred for use in low-phosphate compositions.
• Particularly suitable phosphate-free builders are ether carboxylate mixtures comprising
• Typical detergent compositions contain from 5% to 35% of this builder system.
• the laundry compositions herein also preferably contain enzymes to enhance their through-the-wash cleaning performance on a variety of soils and stains.
• Amylase and protease enzymes suitable for use in detergents are well-known in the art and in commercially available liquid and granular detergents.
• Commercial detersive enzymes preferably a mixture of amylase and protease
• Detergent cellulase enzymes provide both cleaning and softening benefits, particularly to cotton fabrics. These enzymes are highly desirable in the detergent compositions of this invention.
• compositions herein can contain other ingredients which aid in their cleaning performance.
• the compositions herein can advantageously contain a bleaching agent, especially a peroxyacid bleaching agent.
• peroxyacid bleaching agent encompasses both peroxyacids per se and systems which are able to yield peroxyacids in situ .
• Peroxyacids per se are meant to include the alkaline and alkaline-earth metal salts thereof.
• Peroxyacids and diperoxyacids are commonly used; examples are diperoxydodecanoic acid (DPDA) or peroxyphthalic acid.
• Systems capable of delivering peracids in situ consist of a peroxygen bleaching agent and an activator thereof.
• the peroxygen bleaching agents are those capable of yielding hydrogen peroxide in an aqueous solution; these compounds are well-known in the art, and include hydrogen peroxide, alkali-metal peroxides, organic peroxide bleaching agents such as urea peroxide, inorganic persalt bleaching agents such as alkali metal perborates, percarbonates, perphosphates, persilicates, and the like.
• sodium perborate commercially available in the form of mono- and tetra-hydrates, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate and urea peroxyhydrate.
• the liberated hydrogen peroxide reacts with a bleach activator to form the peroxyacid bleach.
• bleach activators include esters, imides, imidazoles, oximes, and carbonates.
• preferred materials include methyl o-acetoxy benzoates; sodium-p-acetoxy benzene sulfonates such as sodium 4-nonanoxyloxybenzene sulfonate; sodium-4-octanoyloxybenzene sulfonate, and sodium-4-decanoyloxybenzenesulfonate : biophenol A diacetate; tetra acetyl ethylene diamine; tetra acetyl hexamethylene diamine; tetra acetyl methylene diamine.
• alpha-substituted alkyl or alkenyl esters such as sodium-4(2-chlorooctanoyloxy)benzene sulfonate, sodium 4-(3,5,5-trimethyl hexanoyloxy)benzene sulfonate.
• Suitable peroxyacids are also peroxygen bleach activators such as described in published European Patent Application N° 0 116 571, i.e., compounds of the general type RXAOOH and RXAL, wherein R is a hydroxcarbyl group, X is a hetero-atom, A is a carbonyl bridging group and L is a leaving group, especially oxybenzenesulfonate.
• quaternary ammonium compounds of the formula R4R5R6R7N+X ⁇ , wherein R4 is alkyl having from 8 to 20, preferably from 12-18 carbon atoms, R5 is alkyl having from 1 to 10 carbon atoms, and R6 and R7 are each C1 to C4 alkyl preferably methyl :
• X ⁇ is an anion, e.g. chloride.
• Examples of such quaternary ammonium compounds include C12-C14 alkyl trimethyl ammonium chloride and cocoalkyl trimethyl ammonium methosulfate.
• the quaternary ammonium compounds can be used at levels from 0.5% to 5%, preferably from 1% to 3%.
• Smectite-type clays are widely used as fabric softening ingredients in detergent compositions. Most of these clays have a cation exchange capacity of at least 50 meq/100g.
• Montmorrillonite clays are commonly used for this purpose. It appears, however, that certain hectorite clays provide better fabric softening performance than the more commonly used montmorillonites.
• the hectorites exhibiting this superior fabric softening performance are hectorites of natural origin having a lath-type shape.
• the fabric softening clay is present in the form of agglomerates.
• These agglomerates comprise, in addition to the clay, an organic humectant.
• the agglomerates optionally further comprise a polymeric clay flocculating agent.
• the agglomerates comprise by weight of the agglomerate, from 60% to 99.5% of the clay; from 0.5% to 30% of the humectant; and from 0% to 10% of the clay flocculating agent.
• the agglomerates further contain a heavy metal sequestering agent. Examples include heavy metal chelators, like EDTA and ethylenediamine tetramethylene phosphonic acid (EDTP).
• the agglomerates typically contain from 0.1% to 10% of the chelator.
• the organic humectant employed in the clay agglomerates may be any of the various water soluble materials utilized for such a purpose.
• the organic humectant is preferably selected from the group consisting of a) aliphatic hydrocarbon polyols having from 2 to 9 carbon atoms; b) ether alcohols derived from the polyols of a); c) ester alcohols derived from the polyols of a); d) mono- and oligosaccharides; and mixtures thereof.
• Highly preferred humectants include glycerol, ethylene glycol, propylene glycol and the dimers and trimers of glycerol, of ethylene glycol and of propylene glycol.
• the clay agglomerates comprise from 0.5% to 30%, preferably from 2% to 15%, of the humectant.
• the optional clay flocculating agent is selected from the optional clay flocculating agent
• Clay-flocculating agents are not commonly used in detergent compositions. On the contrary, one is inclined to use clay dispersants, which aid in removing clay stains from fabrics. Flocculating agents are, however, very well known in other industries like oil well drilling, and for ore flotation in metallurgy. Most of these materials are fairly long chain polymers and copolymers derived from such monomers as ethylene oxide, acrylamide, acrylic acid, dimethylamino ethyl methacrylate, vinyl alcohol, vinyl pyrrolidone, ethylene imine. Gums, like guar gum, are suitable as well.
• polymers of ethylene oxide, acryl amide, or acrylic acid are preferred. It has been found that these polymers dramatically enhance the deposition of a fabric softening clay if their molecular weights (weight average) are in the range of from 100,000 to 10 million. Preferred are such polymers having a (weight average) molecular weight of from 150.000 to 5 million.
• the most preferred polymer is poly (ethylene oxide).
• Molecular weight distributions can be readily determined using gel permeation chromatography, against standards of poly (ethylene oxide) of narrow molecular weight distributions.
• the clay agglomerates herein comprise, by weight of the clay, from 0% to 20% clay flocculating agent, preferably from 0.05% to 20% by weight of the clay if the molecular weight is 150.000 - 800.000 and from 0.005% to 2% by weight of the clay if its molecular weight is from 800.000 to 5 million.
• the detergent compositions of the present invention may further contain, in addition to the clay material, other softening ingredients.
• Suitable examples include amines of the formula R1R2R3N, wherein R1 is C6 to C20 hydrocarbyl, R2 is C1 to C20 hydrocarbyl, and R3 is C1 to C10 hydrocarbyl or hydrogen.
• a preferred amine of this type is ditallowmethylamine.
• the softening amine is present as a complex with a fatty acid of the formula RCOOH, wherein R is a C9 to C20 alkyl or alkenyl. It is desirable that the amine/fatty acid complex be present in the form of microfine particles, having a particle size in the range of from, e.g. , 0.1 to 20 micrometers. These amine/fatty acid complexes are disclosed more fully in European Patent Application N° 0 133 804, the disclosures of which are incorporated herein by reference. Preferred are compositions that contain from 1% to 10% of the amine.
• Suitable are also complexes of the above described amine and phosphate esters of the formula wherein R8 and R9 are C1-C20 alkyl, or ethoxylated alkyl groups of the general formula alkyl-(OCH2CH2) y , wherein the alkyl substituent is C1-C20, preferably C8-C16, and y is an integer of 1 to 15, preferably 2-10, most preferably 2-5.
• Amine/phosphate ester complexes of this type are more fully disclosed in European Patent Application N° 0 168 889, the disclosures of which are incorporated herein by reference.
• optional softening ingredients include the softening amides of the formula R10R11NCOR12, wherein R10 and R11 are independently selected from C1-C22 alkyl, alkenyl, hydroxy alkyl, aryl, and alkyl-aryl groups; R12 is hydrogen, or a C1-C22 alkyl or alkenyl, an aryl or alkyl-aryl group.
• R10 and R11 are independently selected from C1-C22 alkyl, alkenyl, hydroxy alkyl, aryl, and alkyl-aryl groups
• R12 is hydrogen, or a C1-C22 alkyl or alkenyl, an aryl or alkyl-aryl group.
• Preferred examples of these amides are ditallow acetamide and ditallow benzamide. Good results are obtained when the amides are present in the composition in the form of a composite with a fatty acid or with a phosphate ester, as described hereinbefore for the soft
• the amides are present in the composition at 1%-10% by weight.
• Suitable softening ingredients are also the amines disclosed in U.K. Patent Application GB 2 173 827, the disclosures of which are incorporated herein by reference, in particular the substituted cyclic amines disclosed therein.
• Suitable are imidazolines of the general formula 1-(higher alkyl) amido (lower alkyl)-2-(higher alkyl)imidazoline wherein higher alkyl is alkyl having from 12 to 22 carbon atoms, and lower alkyl is alkyl having from 1 to 4 carbon atoms.
• a preferred cyclic amine is 1-tallowamidoethyl-2-tallowimidazoline.
• Preferred compositions contain from 1% to 10% of the substituted cyclic amine.
• the amine and amide softening ingredients may be added as a dry powder to a detergent granule, or may be sprayed onto the detergent granule or onto a carrier, either in melted or in dissolved form.
• a suitable carrier is perborate monohydrate.
• compositions herein can contain, in addition to ingredients already mentioned, various other optional ingredients typically used in commercial products to provide aesthetic or additional product performance benefits.
• Typical ingredients include pH regulants, perfumes, dyes, bleach, optical brighteners, soil suspending agents, hydrotropes and gel-control agents, freeze-thaw stabilizers, bactericides, preservatives, suds control agents, bleach activators and the like.
• compositions are typically used at a concentration of at least 400 ppm, preferably 0.05% to 1.5%, in an aqueous laundry bath at pH 7-11 to launder fabrics.
• the laundering can be carried out over the range from 5°C to the boil, with excellent results.
• the agglomeration process itself may be performed using any of the techniques and apparatus which are conventional in the art (see e.g. "A review of Detergent Agglomeration” - M.J. DOLAN, HAPPI, April 1987 p 64-85). It can be batchwise or continuous. The optimum operating conditions (preferred granule size and moisture level) can be found by trial adjustments of process parameters such as the liquid spray-on level, rate and droplet size, the residence time, etc.
• a reference agglomerate i.e. no glycerol was made in the same way.
• Both agglomerates were dry mixed with a spray-dried granular detergent to yield the following compositions: A B LAS 7 7 STPP 24 24 EDTA 0.2 0.2 Brightener 0.2 0.2 Sodium silicate 6.0 6.0 Suds suppressor 0.4 0.4 NA2CO3 10.0 10.0 PB4 (*) 20.0 20.0 Proteolytic enzyme (*) 0.5 0.5 Na2SO4 + H2O balance 93.5 93.5 Clay/ glycerol agglomerates 6.5 -- Clay Reference agglomerate -- 6.5 100.0 100.0 (*) Dry mixed
• compositions A and B were then used to wash 4 Kg clean fabric loads in a MIELE washing machine.
• the water hardness was 3.0 mmol (Ca++ + Mg ++)/l and the detergent concentration was 10 g/l.
• Clean terry towel tracers were added to permit evaluation of 1 cycle and cumulative (4 cycles) softening performance.
• Softness tracers were line dried prior to assessment by expert judges.
• a 0 ⁇ 4 panel score units (p.s.u.) scale was used for grading, in which 0 means no difference and 4 stands for a very big difference.
• Composition A was rated better for softness than B : 1 cycle tracers 0.6 p.s.u. (s) 4 cycle tracers 0.8 p.s.u. (s) (s) Differences are statistically significant at 95% confidence level.
• composition A in accordance with the invention is superior in fabric softening performance to the prior art composition A.
• the clay agglomerates may also be incorporated in a laundry additive, as such or with the aid of a water soluble and/or insoluble carrier such as e.g. a sheet or a pouch. These agglomerates, as such or with a suitable carrier, can then be added to the wash liquor on top of a conventional detergent composition.
• the laundry additive preferably also contains one or more of the additional softening ingredients specified before. The additive may thus be used in conjunction with detergent compositions that themselves do not contain such a clay and/or these other softening ingredients.

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

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Cited By (34)

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Citations (10)

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• 1988
  • 1988-10-10 EP EP88202253A patent/EP0313146B2/fr not_active Expired - Lifetime
  • 1988-10-10 DE DE19883881329 patent/DE3881329T3/de not_active Expired - Lifetime
  • 1988-10-17 IN IN894DE1988 patent/IN174322B/en unknown
  • 1988-10-19 DK DK581988A patent/DK581988A/da not_active Application Discontinuation
  • 1988-10-19 MX MX1348288A patent/MX169939B/es unknown
  • 1988-10-19 JP JP63263826A patent/JP2620338B2/ja not_active Expired - Lifetime
  • 1988-10-19 IE IE316188A patent/IE61345B1/en not_active IP Right Cessation
• 1993
  • 1993-05-27 GR GR920403265T patent/GR3007979T3/el unknown

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