Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
  • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/65—Mixtures of anionic with cationic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/29—Sulfates of polyoxyalkylene ethers
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/40—Monoamines or polyamines; Salts thereof
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/42—Amino alcohols or amino ethers
  • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/38—Cationic compounds
  • C11D1/62—Quaternary ammonium compounds

Definitions

• This invention relates to detergent compositions containing one or more synthetic anionic detergent surfactants and specific cationic surfactants for use in washing textiles.
• the compositions can be in any form, such as granules, liquids, tablets or pastes.
• the detergent compositions within the invention contain a detergency builder and/or a nonionic surfactant and/or a fatty acid soap and/or enzymes.
• a second aspect of this invention is a laundry additive product in the form of such specific cationic surfactants in water-releasable combination with a nonparticulate flexible substrate.
• Cationic surfactants have been incorporated in detergent compositions for purposes other than cleaning; for example, for a germicidal or sanitization benefit, a fabric softening benefit or a static control benefit. More recently it has been disclosed that cationic surfactants in combination with anionic and/or nonionic surfactants are effective for cleaning purposes.
• Patent 4,235,759 discloses liquid detergent compositions that are superior in detergency containing an alkyl polyoxyalkylene ether sulfate anionic surfactant and a mono- long chain ( C 8-16 ) alkyl quaternary ammonium cationic surfactant wherein the molar ratio of anionic surfactant: cationic surfactant is from 8:1 to 1:1.
• U.S. Patent 4,321,165, Smith et al discloses solid detergent compositions containing from 2% to 60% of a surfactant system consisting of a water-soluble anionic surfactant, an alkoxylated alcohol nonionic surfactant and a water-soluble di-long chain (C8-20) quaternary ammonium cationic surfactant wherein the ratio of anionic surfactant:cationic surfactant is from 5:1 to 1:3 and the ratio of nonionic surfactant: cationic surfactant is from 100:1 to 2:3. It is disclosed that such compositions have improved greasy soil removal capabilities.
• European Patent Application 0,026,529, Spadini et al discloses detergent compositions containing from 3% to 40% of an anionic surfactant, from 0.5% to 15% of a mono- long chain (C 8-16 ) alkyl quaternary ammonium compound or an aliphatic amine and from 1.5% to 45% of an impalpable smectite-type clay wherein the molar ratio of the nitrogenous compound: anionic surfactant is less than 1. It is stated that such compositions clean well and also act as textile softeners.
• an anionic surfactant from 0.5% to 15% of a mono- long chain (C 8-16 ) alkyl quaternary ammonium compound or an aliphatic amine and from 1.5% to 45% of an impalpable smectite-type clay wherein the molar ratio of the nitrogenous compound: anionic surfactant is less than 1. It is stated that such compositions clean well and also act as textile softeners.
• U.S. Patent 4,833,862, Smith et al (June 8, 1982), discloses liquid detergent compositions containing from about 10% to about 82% of an anionic surfactant, from about 10% to about 82% of an alkoxylated alcohol nonionic surfactant and from about 4% to about 35% of a water-soluble quaternary salt cationic surfactant. It is disclosed that such combinations exhibit improved cleaning performance on greasy and oily soils.
• Another object of the present invention is to provide detergent compositions that provide such benefits over a wide range of washing temperatures, especially under cold water washing conditions.
• Still another object of this invention is to provide a laundry additive product in the form of specific cationic surfactants in water-releasable combination with nonparticulate flexible substrates.
• the present invention comprises a detergent composition containing:
• Another aspect of the present invention is a laundry additive product comprising:
• This invention comprises detergent compositions containing an essential two component detergent surfactant system consisting of a synthetic anionic detergent surfactant and specific cationic surfactants.
• This specific two component detergent surfactant system is an effective detergent and is particularly effective on organic soils, for example, lipid, greasy and oily soils.
• the detergent compositions within the invention also provide the desired superior performance over a wide range of wash water temperatures. Such temperature can range from as low as about 5°C to about 95°C. It is preferred that the initial pH of the wash liquor; i.e., the detergent composition and wash water mixture, be greater than about 8 and most preferably from about 9 to about 11.
• the detergent compositions within the invention can be in any form, such as granules, liquids, tablets or pastes, but the granular compositions are preferred.
• the granules can range in density from about .15 grams/ cubic centimeter to about .8 grams/cubic centimeter.
• the detergent compositions within the invention provide the desired superior performance on organic soils because the synthetic anionic detergent surfactant and the cationic surfactant form an electro-neutral complex.
• the mechanism of organic soil removal is believed to be based upon the surfactant adsorbing to the soil surface to reduce the soil/water interfacial tension to such an extent that the mechanical action of the washing process removes soil from the textile surface. Since the complexes formed are electrically neutral and, therefore, do not repel each other, they can pack densely when they adsorb onto the soil surface. This results in a much lower soil/water interfacial tension and thereby provides extremely effective soil removal.
• the cationic surfactants that are generally used in the art for example, C 12 trimethyl ammonium chloride
• the electro-neutral complex does not provide the desired superior performance.
• the electro-neutral complex does not crystallize or become highly viscous with the cationic surfactants of the invention. This is believed to be why the detergent compositions of the invention are particularly efficacious under wash water temperatures as low as about 5°C.
• the cationic surfactant is an essential component of the compositions within the invention. Without the cationic surfactant, the electro-neutral complex cannot be formed with the synthetic anionic detergent surfactant and, therefore, the desired superior performance is not obtained. Though, theoretically, essentially any cationic surfactant within the invention can be utilized to provide such benefit, nitrogenous surfactants that are cationic or capable of existing in cationic form are the most practicable. Also, the cationic surfactants within the invention can be saturated or unsaturated and contain straight and/or branched chains.
• the cationic surfactants within the invention are selected from the group consisting of:
• nitrogenous surfactants which are described in (i) and (ii) when Q is N, (iii), (iv) and (v) are the preferred cationic surfactants.
• both [R 2 (OR 3 ) m ] groups are on the same N.
• alkyl quaternary ammonium surfactants which are described in (i) and (ii).
• the most preferred cationic surfactants are the chloride, bromide and methylsulfate salts of the alkyl quaternary ammonium surfactants which are described in (i) when each R 2 is an alkyl group containing from 4 to about 10 carbon atoms and wherein the sum of the carbon atoms of [R 2 (OR 3 ) m ] 2 is from about 10 carbon atoms to about 14 carbon atoms and preferably from about 10 to about 12 carbon atoms; each m and y are 1 or 0, preferably 0; and each R is selected from the group consisting of methyl and hydroxyethyl.
• each R is selected from the group consisting of an alkyl group containing at least one carbon atom and said R groups optionally can be joined to form ring structures containing from five to six carbon atoms and wherein the sum of the carbon atoms of [(R 3 O) m R 5 ] 2 is from about 9 to about 15 carbon atoms and preferably from about 10 to about 14 carbon atoms; each m and y are 1 or 0, preferably 0; and each R4 is selected from the group consisting of methyl and hydroxyethyl.
• the salts of the cationic surfactants can be prepared by precomplexing the cationic surfactant directly with an anionic detergent surfactant within the invention rather than having such complex be formed in the wash liquor.
• cationic surfactants derived from aliphatic amines have a pKa at least about 1/2 unit above the initial pH of the wash liquor. Otherwise, the desired superior performance is not achieved. It is believed that such a pKa and pH limitation ensures that a substantial portion of such amines are protonated and, thus, exist in cationic form and, therefore, are able to complex with the sulfonate detergent surfactant.
• the level of cationic surfactant within the invention is related to the level of the synthetic anionic detergent surfactant. Equimolar ratios of cationic surfactant and the anionic detergent surfactant form the electro-neutral complex that is essential to provide the desired superior performance. However, it is preferred that there be a molar excess of the synthetic anionic detergent surfactant for proteinaceous and particulate soil removal and the suspension in the wash liquor of the soil removed from the textiles. Such soil suspension prevents soil redeposition. Such molar excess of synthetic anionic surfactant is also desirable because it is effective at stripping fabric softeners that have been deposited on the textile surface during previous wash cycles.
• the molar ratio of cationic surfactant: synthetic anionic detergent surfactant is less than about 1, preferably less than about 0.5 and most preferably less than about 0.25.
• the detergent compositions within the invention contain a detergency builder and a nonionic surfactant.
• the level of cationic surfactant in such compositions is from about 1/4% to about 12%, preferably from about 1/2% to about 8% and most preferably from about 1% to about 6%.
• Preferred synthetic anionic detergent surfactants are water soluble salts of alkyl benzene sulfonates, alkyl sulfates, alkyl polyethoxy ether sulfates, paraffin sulfonates, alpha-olefin sulfonates, alpha-sulfocarboxylates and their esters, alkyl glyceryl ether sulfonates, fatty acid monoglyceride sulfates and sulfonates, alkyl phenol polyethoxy ether sulfates, 2-acyloxy-alkane-1-sulfonates, and beta-alkyloxy alkane sulfonates.
• alkyl benzene sulfonates have about 9 to about 15 carbon atoms in a linear or branched alkyl chain, more preferably about 11 to about 13 carbon atoms.
• Suitable alkyl sulfates have about 10 to about 22 carbon atoms in the alkyl chain, more preferably from about 12 to about 18 carbon atoms and most preferably from about 12 to about 16 carbon atoms.
• Suitable alkyl polyethoxy ether sulfates have about 10 to about 18 carbon atoms in the alkyl chain and have an average of about 1 to about 12 -CH 2 CH 2 0- groups per molecule, preferably about 1 to about 6 -CH 2 CH 2 0- groups per molecule.
• Suitable paraffin sulfonates are essentially linear and contain from about 8 to about 24 carbon atoms, more preferably from about 12 to about 18 carbon atoms.
• Suitable alphaolefin sulfonates have about 10 to about 24 carbon atoms, more preferably about 12 to about 16 carbon atoms; alpha-olefin sulfonates can be made by reaction with sulfur trioxide followed by neutralization under conditions such that any sultones present are hydrolyzed to the k corresponding hydroxy alkane sulfonates.
• Suitable alpha-sulfocarboxylates contain from about 6 to about 20 carbon atoms; included herein are not only the salts of alpha-sulfonated fatty acids but also their esters made from alcohols containing about 1 to about 14 carbon atoms.
• Suitable alkyl glyceryl ether sulfonates are ethers of alcohols having about 10 to about 18 carbon atoms, more preferably those derived from coconut oil and tallow.
• Suitable alkyl phenol polyethoxy ether sulfates have about 8 to about 14 carbon atoms in the alkyl chain and an average of about 1 to about 6 -CH 2 CH 2 0- groups per molecule.
• Suitable 2-acyloxy-alkane-l-sulfonates contain from about 2 to about 9 carbon atoms in the acyl group and about 9 to about 23 carbon atoms in the alkane moiety.
• Suitable beta-alkyloxy alkane sulfonates contain about 1 to about 3 carbon atoms in the alkyl group and about 8 to about 20 carbon atoms in the alkane moiety.
• alkyl chains of the foregoing synthetic anionic detergent surfactants can be derived from natural sources such as coconut oil or tallow, or can be made synthetically as, for example, using the Ziegler or Oxo processes. Water solubility can be achieved by using alkali metal, ammonium, or alkanol-ammonium cations; sodium is preferred.
• the level of synthetic anionic detergent surfactant within the detergent compositions of the invention when such compositions contain a detergency builder and a nonionic surfactant is from about 5% to about 60%, preferably from about 7% to about 50% and most preferably from about 10% to about 40%.
• a second aspect of this invention is a laundry additive product in the form of the cationic surfactants within the invention in water releasable combination with nonparticulatek flexible substrates.
• Such laundry additive products are of great practicality since conventional detergent compositions generally contain a synthetic anionic detergent.
• the weight ratio of cationic surfactant to substrate is from about 30 to about 0.1 and preferably from about 10 to about 0.3.
• the cationic surfactant and an anionic detergent surfactant can be present on the substrate, optionally in the form of a complex.
• the substrate may itself be water soluble or water insoluble and in the latter case it should possess sufficient structural integrity under the conditions of the wash to be recovered from the machine at the end of the laundry cycle. Structures which are water disinte- gratable, i.e., that break down in aqueous media to insoluble individual fibers or particles, are not considered satisfactory for the purposes of the present invention.
• Water soluble materials include certain cellulose ethers, polyethylene oxide alginates, polyvinyl alcohol and water soluble polyvinyl pyrrolidone polymers, which can be formed into nonwoven and woven fibrous structures.
• Suitable water insoluble materials include, but are not restricted to, natural and synthetic fibers, foams, sponges and films.
• the substrate may have any one of a number of physical forms such as sheets, blocks, rings, balls, rods or tubes. Such forms should be amenable to unit usage by the consumer, i.e., they should be capable of addition to the washing liquor in measured amounts, such as individual sheets, blocks or balls and unit lengths of rods or tubes. Certain of these substrate types can also be adapted for single or multiple uses, and can be provided with loadings of cationic surfactant up to a cationic surfactant:substrate ratio of 30:1.
• One such article comprises a sponge material releasably enclosing enough cationic surfactant to provide the desired superior performance during several washing cycles.
• This multi-use article can be made by impregnating a sponge ball or block with about 20 grams of the cationic surfactants and any adjuncts therewith. In use, the cationic surfactant leaches out through the pores of the sponge into the wash liquor and reacts with the synthetic anionic surfactant.
• Such a filled sponge can be used to treat several loads of fabrics in conventional washing machines, and has the advantage that it can remain in the washer after use.
• a highly preferred product comprises the preferred cationic surfactants, as described hereinabove, impregnated on a flexible sheet so as to make it compatible with the movement of the fabrics in the washing machine and to facilitate its handling during manufacture of the product.
• the sheet is water pervious, i.e., water can pass from one surface of the sheet to the opposite surface and, for film type substrates, perforation of the sheet is desirable.
• the most preferred form of the substrate is a sheet of woven or nonwoven fabric or a thin sheet of cellular plastics material.
• Woven fabric sheets can take the form of a plain weave natural or synthetic fiber of low fiber count/unit length, such as is used for surgical dressings, or of the type known as cheese cloth. Loading limitations on sheet type substrates limit the amount of cationic surfactant that can be applied to the sheet namely to a maximum represented by a cationic surfactant:substrate ratio of about 10:1.
• a very desirable attribute of the laundry additive products of the present invention is that they do not interfere with the mechanical operation of the washing machine into which they are put.
• a high proportion of domestic washing machines are of the rotating perforated drum type in which the perforations extend over the entire peripheral surface. In this type of equipment the drum construction and mode of operation obviates any problem of obstruction to liquid flow in the machine.
• Certain older types of machine utilize an agitator in a stationary vessel provided with a recirculating liquid system. In order to avoid liquid blockage in this machine type it may be necessary to provide slits or perforations in the substrate, particularly if it is in sheet form. Sheet structures of this type are disclosed in U.S. Patents 3,944,694 and 3,956,556, McQueary (March 16, 1976 and May 11, 1976, respectively).
• suitable materials which can be used as a substrate in the invention herein include, among others, sponges, paper and woven and nonwoven fabrics.
• a suitable sponge-like material that can be used in the present invention comprises an absorbent foam-like material in the form of a sheet.
• the term "absorbent foam-like material” is intended to encompass three dimensional absorptive materials such as "gas blown foams", natural sponges and composite fibrous based structures such as are disclosed in U.S. Patents 3,311,115 and 3,430,630.
• a particularly suitable material of this type is a hydrophilic polyurethane foam in which the internal cellular walls of the foam have been broken by reticulation. Foams of this type are described in detail in U.S. Patent 3,794,029, Dulle.
• a preferred example of this foam type comprises a hydrophilic polyurethane foam of density 0.596 grs per cubic inch with a cell count of between 8 and 40 cells per cm, preferably about 24 to 32 per cm available from the Scott Paper Company, Eddystone, Pennsylvania, U.S.A. under the Registered Trade Mark "Hydrofoam”.
• Preferred sheets of this type of material have thicknesses in the range from 3 to 5 mm.
• the preferred substrates of the laundry additive products of the invention are apertured and nonapertured nonwoven fabrics which 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, wood pulp, jute, hemp, cotton, linen, sisal, or ramie), synthetic (e.g., rayon, cellulose, ester, polyvinyl derivatives, polyolefins, polyamides, or polyesters) or mixtures of any of the above.
• natural e.g., wool, silk, wood pulp, jute, hemp, cotton, linen, sisal, or ramie
• synthetic e.g., rayon, cellulose, ester, polyvinyl derivatives, polyolefins, polyamides, or polyesters
• nonwoven cloths are not a part of this invention and being well known in the art, are not described in detail herein.
• such cloths are made by air or water laying processes in which the 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 polyesters, polyamides, vinyl resins, and other thermoplastic fibers can be bonded, i.e., the fibers are spun out onto a flat . surface and bonded (melted) together by heat or by chemical reactions.
• the absorbent properties desired herein are particularly easy to obtain with nonwoven cloths and are provided merely by building up the thickness of the cloth, i.e., by super-imposing a plurality of carded webs or mats to a thickness adequate to obtain the necessary absorbent properties, or by allowing a sufficient thickness of the fibers to deposit on the screen.
• Any diameter or denier of the fiber (generally up to about 10 denier) can be used, inasmuch as it is the free space between each fiber that makes the thickness of the cloth directly related to the absorbent capacity of the cloth, and which further makes the nonwoven cloth especially suitable for impregnation with a cationic surfactant by means of intersectional or capillary action.
• any thickness necessary to obtain the required absorbent capacity can be used.
• binder-resins used in the manufacture of nonwoven cloths can provide substrates possessing a variety of desirable traits.
• the absorbent capacity of the cloth can be increased, decreased, or regulated by respectively using a hydrophilic binder-resin, a hydrophobic binder-resin or a mixture thereof in the fiber bonding step.
• the hydrophobic binder-resin when used singly or as the predominant compound of a hydrophobic-hydrophilic mixture, provides nonwoven cloths which are especially useful as substrates when the cationic surfactant mixtures disclosed herein are used in an automatic washer.
• the substrate herein is a nonwoven cloth made from fibers, deposited haphazardly or in a random array on the screen, the compositions exhibit excellent strength in all directions and are not prone to tear or separate when used in the washer.
• the nonwoven cloth is water-laid or air-laid and is made from cellulosic fibers, particularly from regenerated cellulose or rayon, which are lubricated with standard textile lubricant.
• the fibers are from 4 to 50 mm in length and are from 1.5 to 5 denier (Denier is an internationally recognized unit in yarn measure, corresponding to the weight in grams of a 9,000 meter length of yarn).
• the fibers are at least partially orientated haphazardly, particularly substantially haphazardly, and are adhesively bonded together with hydrophobic or substantially hydrophobic binder-resin, particularly with a nonionic self-crosslinking acrylic polymer or polymers.
• the cloth comprises 70% fiber and 30% binder-resin polymer by weight and has a basis weight of from 10 to 100, preferably from 24 to 72 g/m .
• a suitable example is an air-laid, nonwoven cloth comprising 70% regenerated cellulose (American Viscose Corporation) and 30% hydrophobic binder-resins (Rhoplex HA-8 on one side of the cloth, Rhoplex HA-16 on the other; Rohm & Haas, Inc.).
• the cloth has a thickness of 4 to 5 mils, a basis weight of 29 g/m 2 .
• a 30 cm length of the cloth 21 cm wide weighs 1.78 grams.
• the fibers are .10 mm in length, 1.5 denier, and are orientated substantially haphazardly.
• the fibers are lubricated with sodium oleate.
• a further exemplary substrate is a water-laid, nonwoven cloth commercially available from C. H. Dexter Co., Inc.
• the fibers are regenerated cellulose, 15 mm in length, 1.5 denier, and are lubricated with a similar standard textile lubricant.
• the fibers comprise 70% of the nonwoven cloth by weight and are orientated substantially haphazardly; the binder-resin (HA-8) comprises 30% by weight of the cloth.
• the substrate is 4 mils thick, and it has a basis weight of 29 g/m 2 .
• Apertured nonwoven substrates are also useful for the purposes of the present invention.
• the apertures which extend between opposite surfaces of the substrate, are normally in a pattern and are formed during lay-down of the fibers to produce the substrate.
• Exemplary apertured nonwoven substrated are disclosed in U.S. Patents 3,741,724, 3,930,086 and 3,750,237.
• a suitable diamond patterned apertured substrate is obtainable from Chicopee Manufacturing Co., Milltown, New Jersey, U.S.A. under the Code No. SK 650 WFX 577 and comprising a polyester-wood pulp mixture having a basis weight of 50 g/m 2 and approximately 13 apertures per square cm.
• an apertured nonwoven substrate also available from Chicopee Manufacturing Co., under the Code No. AK 30 ML 1379, comprises a regenerated cellulose sheet of 3.0 denier fibers bonded with Rhoplex RA 8 binder (fiber:binder ratio 70:30) having a basis weight of 40 g/m 2 and 17 apertures/cm 2 .
• a highly preferred square patterned apertured substrate of similar composition but fiber:binder ratio of 80:20 and basis weight 35 g/m 2 is also available from Chicopee BV Holland.
• apertured fabrics for the purposes of the invention have from 10-20 apertures/cm2, preferably 12-18 apertures/cm 2 .
• the size and shape of the substrate sheet is a matter of choice and is determined principally by factors associated with the convenience of its use. Thus the sheet should not be so small as to become trapped in the crevices of the machine or the clothes being washed or so large as to be awkward to package and dispense from the contained in which it is sold.
• sheets ranging in plan area from 130 cm 2 to 1300 cm 2 are acceptable, the preferred area lying in the range of from 520 cm 2 to 780 cm .
• the detergent compositions within the invention contain a detergency builder.
• the level of detergency builder of the detergent compositions is from about 0% to about 70%, preferably from about 10% to about 60% and most preferably from about 20% to about 50% of a detergency builder.
• the preferred detergency builders are the water-soluble sequestrants such as tripolyphosphates, hexametaphosphates and higher polymerization species, citrates, nitrilotriacetates and water-soluble polyacetals as disclosed in U.S. Patents 4,144,266 and 4,246,495, incorporated herein by reference and mixtures _ thereof.
• the most preferred detergency builders are tripolyphosphates, nitrilotriacetates and water-soluble polyacetals and mixtures thereof.
• Water-soluble inorganic or organic electrolytes are suitable builders.
• the electrolytes have an equivalent weight of less than 210, especially less than 100 and include the common alkaline polyvalent calcium ion sequestering agents.
• the builder can also be water-insoluble calcium ion exchange materials; however, nonlimiting examples of suitable water-soluble, inorganic detergent builders include: alkali metal carbonates, borates, phosphates, bicarbonates, silicates, sulfates and chlorides. Specific examples of such salts include sodium and potassium tetraborates, perborates, bicarbonates, carbonates, percarbonates, orthophosphates, pyrophosphates and sulfates.
• suitable organic alkaline detergency builders include: (1) water-soluble amino carboxylates and aminopolyacetates, for example, sodium and potassium glycinates, ethylenediaminetetraacetates and N-(2-hydroxyethyl)nitrilodiacetates and diethylenetriamine- pentaacetates; (2) water-soluble salts of phytic acid, for example, sodium and potassium phytates; (3) water-soluble polyphosphonates, including sodium, potassium, and lithium salts of ethane-l-hydroxy-1, 1-diphosphonic acid; sodium, potassium, and lithium salts of ethylene diphosphonic acid; and the like; (4) water-soluble polycarboxylates such as the salts of lactic acid, succinic acid, malonic acid, maleic acid, citric acid, carboxymethyloxysuccinic acid, 2-oxa-1,1,3-propane tricarboxylic acid, 1,1,2,2-ethane tetracarboxylic acid, cyclopentane
• a water-soluble material capable of forming a water-insoluble reaction product with water hardness cations preferably in combination with a crystallization seed which is capable of providing growth sites for said reaction product.
• a further class of detergency builder materials useful in the present invention are insoluble sodium aluminosilicates, particularly those described in Belgian Patent 814,874, issued November 12, 1974, incorporated herein by reference.
• This patent discloses and claims detergent compositions containing sodium aluminosilicates having the formula: wherein z and y are integers equal to at least 6, the molar ratio of z to y is in the range of from 1.0:1 to about 0.5:1, and X is an integer from about 15 to about 264, said aluminosilicates having a calcium ion exchange capacity of at least 200 milligrams equivalent/gram and a calcium ion exchange rate of at least about 2 grains/ gallon/minute/gram.
• a preferred material is:
• compositions of the invention can contain a nonionic surfactant.
• nonionic surfactants for use herein comprise those typical nonionic surfactants well known in the detergency arts.
• the preferred nonionic surfactants are fatty acid. amide surfactants, amine oxide surfactants and ethoxylated alcohols.
• Suitable fatty acid amide surfactants are ammonia amides, monoethanol amides, diethanol amides and ethoxylated amides.
• Particularly preferred amides are those where the alkyl group contains from about 10 to about 16 carbon atoms, such as coconut alkyl monoethanol or diethanol amide.
• Such compounds are commercially available under the tradenames Super-Amide L-9 and GR, from Onyx Chemical Company, Jersey City, NJ; Super-Amide F-3 from Ryco, Inc., Conshohocken, PA and Gafamide CDD-518, available from GAF Corp., New York, NY.
• the amine oxide surfactants of the present invention comprise compounds and mixtures of compounds having the formula wherein R is an alkyl, hydroxyalkyl, alkoxyhydroxy- propyl radical, alkoxyhydroxyethyl, alkyl amido or alkyl carboxylate in which the alkyl and alkoxy, respectively, contain from about 8 to about 18 carbon atoms, R 2 and R 3 are methyl, ethyl, propyl, isopropyl, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, or together are a heterocyclic, e.g., morpholino structure in which the nitrogen is part of the heterocyclic ring and n is from 0 to about 10.
• R is an alkyl, hydroxyalkyl, alkoxyhydroxy- propyl radical, alkoxyhydroxyethyl, alkyl amido or alkyl carboxylate in which the alkyl and alkoxy, respectively, contain from about 8 to about 18 carbon atoms
• amine oxide surfactants include: dimethyldodecylamine oxide, dimethyltetrade- cylamine oxide, ethylmethyltetradecylamine oxide, cetyl- dimethylamine oxide, dimethylstearylamine oxide, cetyl- ethylpropylamine oxide, diethyldodecylamine oxide, diethyltetradecylamine oxide, dipropyldodecylamine oxide, bis-(2-hydroxyethyl)dodecylamine oxide, bis(2-hydroxyethyl)-3-dodecoxy-2-hydroxypropylamine oxide, (2-hydroxypropyl)methyltetradecylamine oxide, dimethyl- oleylamine oxide, dimethyl-(2-hydroxydodecyl)amine oxide, C 8-20 alkyl(alpha-dimethylamine oxide) carboxylate, and the corresponding decyl, hexadecyl and octadecyl, cet
• the ethoxylated alcohols for use herein have the formula wherein R is an alkyl, hydroxy alkyl, alkylene, hydroxy alkylene acyl, or hydroxy acyl group containing from about 8 to about 22 carbon atoms or an alkylbenzene group wherein the alkyl group contains from about 6 to about 15 carbon atoms or mixtures thereof;
• X is a number from about 2 to about 30; and
• R is selected from the group consisting of H, alkyl groups containing from 2 to about 4 carbon atoms, acyl groups containing from 2 to about 4 carbon atoms and mixtures thereof.
• the HLB of these nonionic surfactants is preferably from about 5 to about 20, most preferably from about 8 to about 14.
• nonionic surfactants are: (1) the condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide and propylene glycol, and (2) the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. These surfactants are marketed by BASF Wyandotte under the tradenames Pluronic and Tetronic respectively.
• the level of nonionic surfactant that can be present is from about 0% to about 50%, preferably from about .5% to about 10% and most preferably from about 1% to about 5%.
• Preferred detergent compositions comprise:
• compositions can be in any form, including granules, liquids, tablets or pastes. However, liquid compositions are highly preferred since the compositions herein are especially effective when applied directly to soils and stains in a pretreatment step.
• the compositions herein must have a molar ratio of the anionic synthetic surfactant to the cosurfactant of at least one, preferably from about 2:1 to about 20:1, and are formulated to provide an initial pH of from about 6.0 to about 8.5 at a concentration of from about 0.1% to about 2% by weight in water at 20°C. It has been found that the addition of the cosurfactant to the fatty acid containing detergents herein provides important greasy/ oily soil removal benefits only at the near-neutral wash pH.
• the wash pH is preferably from about 7.0 to about 8.5, more preferably from about 7.5 to about 8.0.
• compositions of the present invention contain from about 5% to about 40%, preferably from about 7% to about 30%, most preferably from about 10% to -about 20%, by weight of a fatty acid containing from about 10 to about 22 carbon atoms.
• the fatty acid can also contain from about 1 to about 10 ethylene oxide units in the hydrocarbon chain.
• Suitable fatty acids are saturated and/or unsaturated and can be obtained from natural sources such as plant or animal esters (e.g., palm kernel oil, palm oil, coconut oil, babassu oil, safflower oil, tall oil, castor oil, tallow and fish oils, grease, and mixtures thereof) or synthetically prepared (e.g., via the oxidation of petroleum or by hydrogenation of carbon monoxide via the Fisher-Tropsch process).
• suitable saturated fatty acids for use in the compositions of this invention include: palmitoleic, oleic, linoleic, linolenic and ricinoleic acid.
• Examples of preferred fatty acids are saturated C 10 -C 14 (coconut) fatty acids, from about 5:1 to 1:1 (preferably about 3:1) weight ratio mixtures of lauric and myristic acid, and mixtures of the above lauric/myristic blends with oleic acid at a weight ratio of about 4:1 to 1:4 mixed lauric/myristic: oleic.
• compositions of this invention can contain all of the usual components of detergent compositions including the ingredients set forth in U.S. Patent 3,936,537, Baskerville et al, incorporated herein by reference.
• Such components include color speckles, bleaching agents, bleach activators, suds boosters, suds suppressors, antitarnish and/or anticorrosion agents, soil- suspending agents, soil-release agents, dyes, fillers, optical brighteners, germicides, pH adjusting agents, alkalinity sources, hydrotropes, antioxidants, enzymes, enzyme stabilizing agents, perfumes, etc.
• water soluble salts of fatty acids can be added as part of the surfactant system. Surprisingly, they are most effective under cold water wash conditions. Suitable water soluble salts of fatty acids have from about 8 to about 18 carbon atoms. The preferred water soluble salts of fatty acids are the sodium, potassium and magnesium salts of C12-l4 fatty acids. They can be present at levels up to about 10%.
• Enzymes are believed to be particularly effective in the detergent compositions of this invention.
• the enzyme-containing detergent compositions are particularly effective on enzyme sensitive stains such as grass and blood while maintaining greasy and oily soil detergency.
• Suitable enzymes are those, for example, disclosed in U.S. Patent 4,176,079, Guerry et al (November 27, 1979), incorporated herein by reference.
• the enzymes are included at a level of from about .02% to about 3%, preferably from about .1% to about 1%.
• Nonlimiting examples of bleaching agents are sodium perborate (as the monohydrate or tetrahydrate), sodium percarbonate and other perhydrates, at levels from about 5% to 35% by weight of the composition, and activators therefor, such as tetraacetylethylenediamine, tetra- acetylglycouril and others known in the art, and stabilizers therefor, such as magnesium silicate, and ethylenediaminetetraacetate.
• activators therefor such as tetraacetylethylenediamine, tetra- acetylglycouril and others known in the art
• stabilizers therefor such as magnesium silicate, and ethylenediaminetetraacetate.
• Peroxy carboxylic acids for example, such as those disclosed in U.S. Patent 4,091,544, Hutchins (May 30, 1975), are especially useful.
• Preferred optional ingredients include suds modifiers particularly those of suds suppressing types, exemplified by silicones, and silica-silicone mixtures.
• silicone suds controlling agents can be represented by alkylated polysiloxane materials such as silica aerogels and xerogels and hydrophobic silicas of various types.
• the silicone material can be described as siloxane having the formula: wherein x is from about 20 to about 2,000 and R and R are each alkyl or aryl groups, especially methyl, ethyl, propyl, butyl and phenyl.
• the polydimethylsiloxanes (R and R 1 are methyl) having a molecular weight within the range of from about 200 to about 2,000,000, and higher, are all useful as suds controlling agents.
• Additional suitable silicone materials wherein the side chain groups R and R are alkyl, aryl, or mixed alkyl or aryl hydrocarbyl groups exhibit useful suds controlling properties. Examples of the like ingredients include diethyl-, dipropyl-, dibutyl-, methyl-, ethyl-, phenyl- methylpoly-siloxanes and the like.
• Additional useful silicone suds controlling agents can be represented by a mixture of an alkylated siloxane, as referred to hereinbefore, and solid silica.
• a preferred silicone suds controlling agent is represented by a hydrophobic silanated (most preferably trimethylsilanated) silica having a particle size in the range from about 10 millimicrons to 20 millimicrons and a specific surface area above about 50 m2/gm. intimately admixed with dimethyl silicone fluid having a molecular weight in the range from about 500 to about 200,000 at a weight ratio of silicone to silanated silica of from about 19:1 to about 1:2.
• the silicone suds suppressing agent is advantageously releasably incorporated in a water-soluble or water-dispersible, substantially non- surface-active detergent-impermeable carrier.
• Particularly useful suds suppressors are the self- emulsifying silicone suds suppressors, described in U.S. Patent 4,073,118, Gault et al, issued February 21, 1978, incorporated herein by reference.
• An example of such a compound is DB-544, commercially available from Dow Corning, which is a siloxane/glycol copolymer.
• Suds modifiers as described above are used at levels of up to approximately 2%, preferably from about 0.1 to about 1.5% by weight of the surfactant.
• Microcrystalline waxes having a melting point in the range from 35°C-115°C and a saponification value of less than 100 represent additional examples of preferred suds control components for use in the subject compositions, and are described in detail in U.S. Patent 4,056,481, Tate, issued November 1, 1977, incorporated herein by reference.
• the microcrystalline waxes are substantially water-insoluble, but are water-dispersible in the presence of organic surfactants.
• Preferred microcrystalline waxes have a melting point from about 65°C to 100°C, a molecular weight in the range from 400-1,000; and a penetration value of at least 6, measured at 77°F by ASTM-D1321.
• Suitable examples of the above waxes include: microcrystalline and oxidized microcrystalline petroleum waxes; Fischer-Tropsch and oxidized Fischer-Tropsch waxes; ozokerite; ceresin; montan wax; beeswax; candelilla; and carbauba wax.
• Alkyl phosphate esters represent an additional preferred suds control agent for. use herein. These preferred phosphate esters are predominantly monostearyl phosphate which, in addition thereto, can contain di-and tristearyl phosphates and monooleyl phosphate, which can contain di- and trioleyl phosphate.
• alkyl phosphate esters frequently contain some trialkyl phosphate. Accordingly, a preferred phosphate ester can contain, in addition to the monoalkyl ester, e.g., monostearyl phosphate, up to about 50 mole percent of dialkyl phosphate and up to about 5 mole percent of trialkyl phosphate.
• Laundry loads were prepared containing half swatches representing at least three and as many as six types of grease/oil soil. The remainder of the loads were soiled laundry consisting of T-shirts, dish towels, pillow cases and terry cloth bundles. The fabric load was 3-1/2% of the wash solution.
• Each load was then washed with a quantity of an individual composition that corresponds to detergent concentrations utilized in conventional automatic wash processes.
• the mini-wash system with such a load simulates a conventional automatic washing process.
• the wash water had a temperature of 60°F and contained 5 grains/gallon water hardness.
• Each of the half swatches was then comparison graded against its identical counterpart that had been washed with a different detergent composition to determine relative soil removal.
• a grading scale of -4 to 4 was used, with -4 indicating much less soil removal, 0 indicating no difference and 4 indicating much more soil removal.
• the treatment grades for each replicate are averaged across all greasy/oily stain types and then the replicate averages are averaged to give a treatment mean for each detergent composition. This average is known as the Cleaning Index.
• compositions representing the invention (B, D, F and H) containing the specific quaternary surfactant of this invention provided significantly more cleaning than the corresponding compositions A, C, E and G containing C 12 TMAC.
• the Cleaning Index was determined by the same procedure as described in Example I with A, B and C being one test and A, D and E being another test. All quaternary surfactants were compared on an equal molar basis. The results were as follows:
• B and C provided significantly more cleaning than the base composition containing C 12 TMAC.
• D and E were poorer although D was not significantly poorer than A.
• composition within the invention that contains a water soluble salt of a fatty acid:
• Solid compositions especially granular compositions, are preferred since the specific cationic cosurfactants herein provide the greatest improvement over other similar cationic cosurfactants in solid compositions.
• This composition provides the desired superior performance on conventional soils in addition to being extremely effective on enzyme-sensitive stains.
• composition within the invention that contains a water soluble salt of a fatty acid:

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