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
  • C11D3/16—Organic compounds
  • C11D3/36—Organic compounds containing phosphorus
  • C11D3/364—Organic compounds containing phosphorus containing nitrogen
• • 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
  • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
  • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/33—Amino carboxylic acids
• • 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
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/22—Organic compounds
  • C11D7/32—Organic compounds containing nitrogen
  • C11D7/3245—Aminoacids
• • 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
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/22—Organic compounds
  • C11D7/36—Organic compounds containing phosphorus

Definitions

• the present invention relates to a laundry detergent compositions and more particularly, to a process for improving storage stability and scoopabihty of laundry detergent compositions by incorporation of useful levels of a concentrated chelant agglomerate into a laundry detergent composition
• any useful level of a chelant agglomerate can be ad-mixed into a laundry detergent composition such that the chelant agglomerate desirably improves the solubility and storage stability of the resultant ad-mixed detergent composition formulation and at the very least, does not detrimentally affect the laundry detergent composition's fiowability and scoopabihty characteristics.
• the present invention overcomes the problems, as set forth above.
• U.S. Patent 5,108,646 discloses a process for making detergent builder agglomerates by mixing a detergent builder with a selected binder to form free flowing agglomerates.
• the invention meets the needs above by providing a process for preparation of a chelant composition by a non-spray-drying process, a process for improving one or more of storage stability, fiowability and scoopabihty of a laundry detergent composition, and a chelant agglomerate useful as an ad-mix in a particulate laundry detergent.
• a process for preparation of a chelant composition by a non-spray-drying process includes the steps of admixing a transition metal chelant and an inorganic compound to form a mixture, agglomerating the mixture in an aqueous medium to form a chelant agglomerate and drying the chelant agglomerate.
• a process for improving one or more of storage stability, fiowability and scoopabihty of a laundry detergent composition includes the steps of providing a chelant composition prepared by a non-spray-drying process and incorporating the chelant composition into a particulate laundry detergent material in a weight ratio in a range of from about 0 05 99.95 to about 2 98, chelant composition to particulate laundry detergent material
• the non-spray-drying process includes the steps of admixing a transition metal chelant and an inorganic compound to form a mixture, agglomerating the mixture in an aqueous medium to form a chelant agglomerate, and drying the chelant agglomerate.
• a chelant agglomerate useful as an ad-mix in a particulate laundry detergent has a composition including a transition metal chelant, an inorganic compound and water.
• the chelant agglomerate is formed by admixing the transition metal chelant and the inorganic compound to form a mixture, agglomerating the mixture in the water to form the chelant agglomerate, and drying the chelant agglomerate.
• the process for preparation of a chelant composition by a non-spray-drying process includes the steps of admixing a transition metal chelant and an inorganic compound to form a mixture, agglomerating the mixture in an aqueous medium to form a chelant agglomerate, and drying the chelant agglomerate.
• the transition metal chelant is sodium dit ⁇ aminepentaacetate and the inorganic compound is selected from the group consisting of sulfates, carbonates, silicates, alummosihcates and mixtures thereof.
• the inorganic compound is an aluminosilicate material and preferably, the inorganic compound is an aluminosilicate ion exchange mate ⁇ al of the formula, MnVnr(AlO- > )m(S ⁇ O 2 )yl»xH O where n is the valence of the cation M, x is the number of water molecules per unit cell, m and y are the total number of tetrahedra per unit cell, and y/m is 1 to 100, and wherein M is selected from the group consisting of sodium, potassium, magnesium, and calcium Most preferably, the inorganic compound is zeolite.
• the step of admixing includes mixing and granulating the transition metal chelant and the inorganic compound in one or more of a high-speed mixer and granulator, desirably in a weight ratio in a range of from about 10'90 to about 80:20 respectively, preferably in a weight ratio in a range of from about 15:85 to about 60 40 respectively and most preferably in a weight ratio in a range of from about 25.75 to about 35:65 respectively
• the step of agglomerating includes forming a chelant- lnorganic compound pre-mix with water before agglomerating, desirably in a weight ratio in a range of from about 10:90 to about 80:20 respectively, preferably in a weight ratio in a range of from about 15:85 to about 60-40 respectively and most preferably in a weight ratio in a range of from about 25:75 to about 35:65 respectively
• a process for improving storage stability and scoopabiht is another preferred embodiment of the present invention.
• the process includes the first step of forming a chelant agglomerate. It has very surprisingly been found that when the chelant particles are separated from the rest of the laundry detergent composition and chelant agglomerates are formed and then the chelant agglomerates are incorporated into a particulate laundry detergent composition, there is a dramatic increase in the resultant laundry detergent composition's storage stability and scoopabihty when the chelant agglomerate is eventually ad-mixed with the detergent powder in a desired weight ratio in a range of from about 0.05:99.95 to about 2:98, a preferred weight ratio m a range of from about 0.3:99.7 to about 1.5:98.5, and a most preferred weight ratio in a range of from about 0.1 :99.9 chelant agglomerate:laundry detergent composition.
• the finish product i.e., the laundry detergent composition
• the finish product i.e., the laundry detergent composition
• the detergent composition having a chelant has improved storage stability and scoopabihty
• this improvement is achieved as a result of having separated the hygroscopic transition metal chelant from the rest of the "sticky" laundry composition.
• the tern "lump cake” property is meant to include composition storage stability and powder solubility in water.
• the term “sticky” components is meant to include a mixture of one or more of surfactants, polyethylene glycol, polyacrylates and water.
• the term “builder” is intended to mean all materials which tend to remove calcium ion from solution, either by ion exchange, complexation, sequestration or precipitation.
• the term “scoopabihty” is defined on a scale of 1 to 5, 1 being the least desirable value and 5 being the most desirable value, of the ability or characteristic of a laundry composition to be scooped up in a spoon without exhibiting tackiness or dumpiness Chelants
• the chelating agents can be selected from the group consisting of ammo carboxylates, ammo phosphonates, polyfunctionally-substiruted aromatic chelating agents, sodium ditriammepentaacetate and mixtures thereof Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.
• Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylethylenediammetriacetates, nitrilo-triacetates, ethylenediamine tetraprop ⁇ onates, t ⁇ ethylenetetraaminehexacetates, diethylenet ⁇ aminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
• Ammo phosphonates are also suitable for use as chelating agents in the compositions of the invention when at lease low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.
• Polyfunctionally-substiruted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as l,2-d ⁇ hydroxy-3,5- disulfobenzene.
• EDDS ethylenediamine disuccinate
• these chelating agents will generally comprise from about 0.05% to about 10% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from about 0.05% to about 3.0% by weight of such compositions.
• the most preferred transition metal chelant used to carry out the present invention is sodium ditriammepentaacetate (DTPA).
• DTPA is preferably used a weight ratio of from about 0.1 :99.9 to about 1.5:98.5
• DTPA agglomerate laundry detergent composition and most preferably, in a weight ratio of 0 4:99.6.
• the chelant agglomerate consists of DTPA and zeolite in a preferred weight ratio in a range of from about 15:85 to about 25:75, DTPA. zeolite.
• the structural formula of an aluminosilicate mate ⁇ al is based on the crystal unit cell, the smallest unit of structure represented by:
• n is the valence of the cation M
• x is the number of water molecules per unit cell
• m and y are the total number of terrahedra per unit cell
• y/m is 1 to 100. Most preferably, y/m is 1 to 5.
• the cation M can be Group IA and Group IIA elements, such as sodium, potassium, magnesium, and calcium
• the preferred aluminosilicate materials are zeolites.
• the most preferred zeolites are zeolite A, zeolite X, zeolite Y, zeolite P, zeolite MAP and mixtures thereof.
• the aluminosilicate ion exchange mate ⁇ als used herein for chelant agglomerates have both a high calcium ion exchange capacity and a high exchange rate. Without intending to be limited by theory, it is believed that such high calcium ion exchange rate and capacity are a function of several interrelated factors which derive from the method by which the aluminosilicate ion exchange material is produced.
• the aluminosilicate ion exchange mate ⁇ als used herein are preferably produced in accordance with Corkill et al, U.S. Patent No. 4,605,509 (Procter & Gamble), the disclosure of which is incorporated herein by reference.
• the aluminosilicate ion exchange mate ⁇ al is in "sodium" form since the potassium and hydrogen forms of the instant aluminosilicate do not exhibit the as high of an exchange rate and capacity as provided by the sodium form.
• the aluminosilicate ion exchange material preferably is m over dried form so as to facilitate production of crisp chelant agglomerates as described herein.
• the aluminosilicate ion exchange mate ⁇ als used herein preferably have particle size diameters which optimize their effectiveness as detergent builders.
• particle size diameter represents the average particle size diameter of a given aluminosilicate ion exchange material as determined by conventional analytical techniques, such as microscopic determination and scanning electron microscope (SEM).
• the preferred particle size diameter of the aluminosilicate is from about 0.1 micron to about 10 microns, more preferably from about 0.5 microns to about 9 microns. Most preferably, the particle size diameter is from about 1 microns to about 8 microns.
• the aluminosilicate has a particle size of about 0.1-10 microns in diameter.
• the laundry detergent composition has a composition including a chelant agglomerate made according to the present invention and incorporated into the laundry detergent composition
• the laundry detergent composition also comprises a builder made by agglomeration or spray dried process, sodium carbonate, sodium sulfate, sodium t ⁇ polyphosphate, anionic and nonionic surfactants and balance water.
• Laundry detergent compositions are well known in the art and various examples of various laundry detergent compositions are disclosed, for example in U.S. Patent No. 5,554,587, issued to Scott W. Capeci, and assigned to The Procter & Gamble Company. Chelant agglomerates made by agglomeration process
• the chelant agglomerates are made by an agglomeration process.
• the agglomeration process comprises the steps of: I) admixing one or more ingredients to form a mixture; and n) agglomerating the mixture to form agglomerated particles or "agglomerates", and in) drying the agglomerate.
• such an agglomeration process involves mixing the ingredients in one or more agglomerators such as a pan agglomerator, a Z-blade mixer or more preferably in-line mixers, preferably two, such as those manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1 , Elsenerstrasse 7-9, Postfach 2050, Germany.
• a high shear mixer is used, such as a Lodige CB (Trade Name).
• a high shear mixer is used in combination with a low shear mixer, such as a Lodige CB (Trade Name) and a Lodige KM (Trade name) or Schugi KM (Trade Name).
• a low shear mixer such as a Lodige CB (Trade Name) and a Lodige KM (Trade name) or Schugi KM (Trade Name).
• the agglomerates are thereafter d ⁇ ed and/ or cooled.
• An excellent desc ⁇ ption of an agglomeration process is contained in U.S. Patent No. 5,554,587, issued to Scott W. Capeci, and assigned to The Procter & Gamble Company.
• Another agglomeration process involves mixing of various components of the final agglomorate in different stages, using an fluidized bed.
• a detergent powder can be agglomerated by spraying on of surfactants and optionally a wax, or mixtures thereof, to the acid source in powdered form and other optional ingredients. Then, additional components, including the perborate bleach and optionally the alkali source or part thereof, can be added and agglomerated in one or more stages, thus forming the final agglomerate particle.
• the agglomerates may take the form of flakes, prills, marumes, noodles, ⁇ bbons, but preferably take the form of granules.
• a preferred way to process the particles is by agglomerating dry material (e g. aluminosilicate, carbonate) with high active surfactant pastes and to control the particle size of the resulting agglomerates within specified limits.
• dry material e g. aluminosilicate, carbonate
• Typical particle sizes are from 0.10 mm to 5.0 mm in diameter, preferably from 0.25 mm to 3.0 mm in diameter, most preferably from 0.40 mm to 1.00 mm in diameter.
• the "agglomerates" have a bulk density desirably .of at least 700 g 1 and preferably, in a range of from about 700 g/1 to about 900 g/1.
• Adjunct Detergent Ingredients include other detergency builders, bleaches, bleach activators, suds boosters or suds suppressers, anti-tamish and anticorrosion agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents, smectite clays, enzymes, enzyme-stabilizing agents and perfumes. See U.S. Patent 3,936,537, issued February 3, 1976 to Baskerville, Jr. et al, incorporated herein by reference.
• Bleaching agents and activators are described in U.S. Patent 4,412,934, Chung et al., issued November 1, 1983, and in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, both of which are incorporated herein by reference.
• Chelating agents are also described in U.S. Patent 4,663,071, Bush et al., from Column 17, line 54 through Column 18, line 68, incorporated herein by reference.
• Suds modifiers are also optional ingredients and are desc ⁇ bed in U.S. Patents 3,933,672, issued January 20, 1976 to Bartoletta et al., and 4,136,045, issued January 23, 1979 to Gault et al., both incorporated herein by reference.
• Suitable smectite clays for use herein are desc ⁇ bed in U.S. Patent 4,762,645, Tucker et al. issued August 9, 1988, Column 6, line 3 through Column 7, line 24, incorporated herein by reference.
• Suitable additional detergency builders for use herein are enumerated m the Baskerville patent, Column 13, line 54 through Column 16, line 16, and in U.S. Patent 4,663,071, Bush et al, issued May 5, 1987, both incorporated herein by reference.
• Anionic Surfactant - The preferred amonic surfactants include C ⁇ ⁇ -C ⁇ g alkyl benzene sulfonates (LAS) and primary, branched-chain and random C10-C20 alkyl sulfates (AS), the
• x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubihzing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the Cio-C j g alkyl alkoxy sulfates ("AE X S"; especially EO 1-7 ethoxy sulfates), C ⁇ Q-C 1 g alkyl alkoxy carboxylates (especially the EO 1 -5 ethoxycarboxylates), the Cjrj-18 g'y cer °l ethers, the Cjo-Cj g alkyl polyglycosides and their corresponding sulfated polyglycosides, and C ⁇ 2 -Cj g alpha-sulfonated fatty acid esters
• anionic surfactants useful herein are disclosed in U.S. Patent No. 4,285,841 , Barrat et al, issued August 25, 1981 , and in U.S. Patent No. 3,919,678, Laughhn et al. issued December 30, 1975.
• Useful anionic surfactants include the water-soluble salts, particularly the alkali metal, ammonium and alkylolammonium (e.g., monoethanolammonium or t ⁇ ethanolammonium) salts, of organic sulfu ⁇ c reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfomc acid or sulfu ⁇ c acid ester group.
• the alkali metal, ammonium and alkylolammonium (e.g., monoethanolammonium or t ⁇ ethanolammonium) salts of organic sulfu ⁇ c reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfomc acid or sulfu ⁇ c acid ester group.
• alkyl is the alkyl portion of aryl groups.
• alkyl sulfates especially those obtained by sulfatmg the higher alcohols (Cg-C j carbon atoms) such as those produced by reducing the glyce ⁇ des of tallow or coconut oil.
• anionic surfactants herein are the water-soluble salts of alkyl phenol ethylene oxide ether sulfates containing from about 1 to about 4 units of ethylene oxide per molecule and from about 8 to about 12 carbon atoms in the alkyl group.
• Other useful anionic surfactants herein include the water-soluble salts of esters of a- sulfonated fatty acids containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water-soluble salts of 2-acyloxy-alkane-l- sulfon ⁇ c acids containing from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and b-alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
• alkyl polyethoxylate sulfates of the formula RO(C 2 H 4 0) x S0 3 -M + wherem R is an alkyl chain having from about 10 to about 22 carbon atoms, saturated or unsaturated. M is a cation which makes the compound water-soluble, especially an alkali metal, ammonium or substituted ammonium cation, and x averages from about 1 to about 15.
• alkyl sulfate surfactants are the non-ethoxylated C j 2- 15 primary and secondary alkyl sulfates. Under cold water washing conditions, i.e., less than abut 65°F (18.3°C), it is preferred that there be a mixture of such ethoxylated and non-ethoxylated alkyl sulfates.
• fatty acids include cap ⁇ c, lau ⁇ c, my ⁇ stic, palmitic, stea ⁇ c, arachidic, and behenic acid.
• Other fatty acids include palmitoleic, oleic, noleic, hnolenic, and ⁇ cinoleic acid.
• Nonio c Surfactant - Conventional nonio c and amphote ⁇ c surfactants include Cj -C j alkyl ethoxylates (AE) including the so-called narrow peaked alkyl ethoxylates and C ⁇ -C ⁇ alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy)
• AE alkyl ethoxylates
• C ⁇ -C ⁇ alkyl phenol alkoxylates especially ethoxylates and mixed ethoxy/propoxy
• the Cj Q - i N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C ] 2 -C ] g N- methylglucamides. See WO 9,206,154.
• sugar-de ⁇ ved surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as Cjn-Ci N-(3-methoxypropyl) glucamide.
• the N- propyl through N-hexyl C ⁇ 2 -C ⁇ g glucamides can be used for low sudsing.
• C ⁇ o-C 2 o conventional soaps may also be used.
• the branched-chain Ci Q -Ci g soaps may be used. Examples of noniomc surfactants are described in U.S. Patent No. 4,285,841, Barrat et al, issued August 25, 1981.
• surfactants also include ethoxylated alcohols and ethoxylated alkyl phenols of the formula R(OC2H4) n OH, wherein R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 15 carbon atoms and alkyl phenyl radicals in which the alkyl groups contain from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15.
• R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 15 carbon atoms and alkyl phenyl radicals in which the alkyl groups contain from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15.
• surfactants include ethoxylated alcohols having an average of from about 10 to abut 15 carbon atoms in the alcohol and an average degree of ethoxylation of from about 6 to about 12 moles of ethylene oxide per mole of alcohol. Mixtures of anionic and noniomc surfactants are especially useful. Other conventional useful surfactants are listed m standard texts, including polyhydroxy fatty acid amides, alkyl glucosides, polyalkyl glucosides, C ⁇ 2 -C ] g betames and sulfobeta es (sultames). Examples include the C ⁇ 2 -C ⁇ N-methylglucamides. See WO
• sugar-de ⁇ ved surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C j o-C j g N-(3-methoxypropyl) glucamide.
• C j -C ⁇ g glucamides can be used for low sudsing.
• cationic surfactants are the mono alkyl quaternary ammonium surfactants although any cationic surfactant useful in detergent compositions are suitable for use herein.
• the cationic surfactants which can be used herein include quaternary ammonium surfactants of the formula:
• R j and R 2 are individually selected from the group consisting of C1 -C4 alkyl, C1-C4 hydroxy alkyl, benzyl, and -(C 2 H4 ⁇ ) x H where x has a value from about 2 to about 5;
• X is an anion; and
• R3 and R4 are each a C -C 14 alkyl or (2) R3 is a C6-C ⁇ g alkyl, and R4 is selected from the group consisting of CI -C I Q alkyl, C J -C JQ hydroxyalkyl, benzyl, and -
• quaternary ammonium surfactants are the chlo ⁇ de, bromide, and methylsulfate salts.
• desirable mono-long chain alkyl quaternary ammonium surfactants are those wherein Ri , R 2 , and R4 are each methyl and R3 is a C -Cj ⁇ alkyl; or wherein R3 is Cg.
• R ⁇ , R 2 , and R4 are selected from methyl and hydroxyalkyl moieties Lauryl t ⁇ methyl ammonium chlo ⁇ de, my ⁇ styl t ⁇ methyl ammonium chloride, palmityl t ⁇ methyl ammonium chloride, coconut t ⁇ methylammonium chlo ⁇ de, coconut tnmethylammonium methylsulfate, coconut dimethyl-monohydroxy-ethylammonium chlonde, coconut dimethyl-monohydroxyethylammonium methylsulfate, steryl dimethyl-monohydroxy- ethylammonium chlo ⁇ de, steryl dimethyl-monohydroxyethylammonium methylsulfate, di- Cj -
• lauryl t ⁇ methyl ammonium chloride commercially available from Witco
• Other desirable surfactants are lauryl t ⁇ methyl ammonium chloride and my ⁇ styl t ⁇ methyl ammonium chloride
• Suitable cationic surfactants are the alkanol amidal quaternary surfactants of the formula
• R' can be Ci Q_ ⁇ g alkyl or a substituted or unsubstituted phenyl
• R ⁇ can be a C]_4 alkyl, H, or (EO) y , wherein y is from about 1 to about 5, Y is O or -N(R 3 )(R 4 ), R 3 can be H,
• R 5 , R 6 , R 7 are independently selected from C j _4 alkyl, H, or (EO) y , v herein > is from about 1 to about 5
• the laundry detergent compositions herein also contain amine oxide surfactants of the formula
• the structure (I) provides one long-chain moiety Rl (EO) x (PO) y (BO) z and two short chain moieties, CH R' R' is preferably selected from hydrogen, methyl and -CH 2 OH
• R ⁇ may be somewhat longer, having a chainlength in the range Ci 2 -C 4
• amme oxides are illustrated by C 12-14 alkyldimethyl amine oxide, hexadecyl dimethylamme oxide, octadecylamine oxide and their hydrates, especially the dihydrates as disclosed in U.S Patents 5,075,501 and 5,071,594, incorporated herein by reference
• the invention also encompasses amme oxides wherein x+y+z is different from zero, specifically x+y+z is from about 1 to about 10, R* is a p ⁇ mary alkyl group containing 8 to about 24 carbons, preferably from about 12 to about 16 carbon atoms, in these embodiments y + z is preferably 0 and x is preferably from about 1 to about 6, more preferably from about 2 to about 4, EO represents ethyl eneoxy, PO represents propyleneoxy, and BO represents butyleneoxy Such amine oxides can be prepared by conventional synthetic methods, e g , by the reaction of alkylethoxysulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide
• Desirable amine oxides herein are solids at ambient temperature, more preferably they have melting-points in the range 30°C to 90°C
• Amme oxides suitable for use herein are made commercially by a number of suppliers, including Akzo Chemie, Ethyl Corp , and Procter & Gamble See McCutcheon's compilation and Kirk-Othmer review article for alternate amme oxide manufacturers
• Other desirable commercially available amine oxides are the solid, dihydrate ADMOX 16 and ADMOX 18, ADMOX 12 and especially ADMOX 14 from Ethyl Corp
• R' is H
• R' is CH 2 OH, such as hexadecylb ⁇ s(2- hydroxyethyl)am ⁇ ne oxide, tallowb ⁇ s(2-hydroxyethyl)amme oxide, stearylb ⁇ s(2-hydroxyethyl)am ⁇ ne oxide and oleylb ⁇ s(2- hydroxyethyl)am ⁇ ne oxide
• Enzymes can be included in the formulations herein for a wide variety of fab ⁇ c laundering purposes, including removal of protein-based, carbohydrate-based, or t ⁇ glyce ⁇ de- based stains, for example, and for fab ⁇ c restoration
• the enzymes to be incorporated include proteases, amylases, hpases, and cellulases, as well as mixtures thereof
• Other types of enzymes may also be included They may be of any suitable o ⁇ gin, such as vegetable, animal, bacterial, fungal and yeast origin However, their choice is governed by several factors such as pH-activity and/or stability optima, thermostability, stability versus active detergents, builders and so on In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases
• Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically about 0.01 mg to about 3 mg, of active enzyme per gram of the composition.
• compositions herein will typically comprise from about 0.001% to about 5%, preferably 0.01% to 1% by weight of a commercial enzyme preparation.
• Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition.
• proteases are the subtihsins which are obtained from particular strains of B. subti s and B. hcheniforms. Another suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold by Novo Industries A/S under the registered tradename ESPERASE. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1,243,784 of Novo. Proteolytic enzymes suitable for removing protein-based stains that are commercially available include those sold under the trade names ALCALASE and SAVINASE by Novo Industries A/S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (The Netherlands).
• proteases include Protease A (see European Patent Application 130,756, published January 9, 1985) and Protease B (see European Patent Application Serial No. 87303761.8, filed April 28, 1987, and European Patent Application 130,756, Bott et al, published January 9, 1985).
• Amylases include, for example, ⁇ -amylases desc ⁇ bed in British Patent Specification No. 1 ,296,839 (Novo), RAPIDASE, International Bio-Synthetics, Inc. and TERMAMYL, Novo Indust ⁇ es.
• the cellulase usable in the present invention include both bacterial or fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5. Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al, issued March 6, 1984, which discloses fungal cellulase produced from Humicola insolens and Humicola strain DSM1800 or a cellulase 212- producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a a ⁇ ne mollusk (Dolabella Au ⁇ cula Solander).
• Suitable cellulases are also disclosed GB-A-2.075.028; GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME (Novo) is especially useful.
• Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutze ⁇ ATCC 19.154, as disclosed m B ⁇ tish Patent 1,372,034. See also hpases in Japanese Patent Application 53,20487, laid open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co.
• Amano-P Lipase P
• Other commercial hpases include Amano-CES, hpases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. hpolyticum NRRLB 3673, commercially available from Toyo Jozo Co., Tagata, Japan; and further Chromobacter viscosum hpases from U.S. Biochemical Corp., U.S.A. and Diosynth Co., The Netherlands, and hpases ex Pseudomonas gladioli.
• the LIPOLASE enzyme de ⁇ ved from Humicola lanugmosa and commercially available from Novo is a preferred lipase for use herein.
• a wide range of enzyme mate ⁇ als and means for their incorporation into synthetic detergent compositions are also disclosed m U.S. Patent 3,553,139, issued January 5, 1971 to McCarty et al Enzymes are further disclosed in U.S. Patent 4,101,457, Place et al, issued July 18, 1978, and in U.S. Patent 4,507,219, Hughes, issued March 26, 1985, both. Enzyme mate ⁇ als useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed m U S Patent 4,261,868, Hora et al, issued Ap ⁇ l 14, 1981. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S.
• Patent 3,600,319 issued August 17, 1971 to Gedge. et al, and European Patent Application Publication No. 0 199 405, Application No. 86200586.5, published October 29, 1986, Venegas Enzyme stabilization systems are also described, for example, in U.S Patent 3,519,570.
• the enzymes employed herein may be stabilized by the presence of water-soluble sources of calcium and/or magnesium ions in the finished compositions which provide such ions to the enzymes (Calcium ions are generally somewhat more effective than magnesium ions and are preferred herein if only one type of cation is being used.) Additional stability can be provided by the presence of va ⁇ ous other art-disclosed stabilizers, especially borate species. See Severson, U.S. 4,537,706 Typical detergents, especially liquids, will comprise from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 5 to about 15, and most preferably from about 8 to about 12, milhmoles of calcium ion per liter of finished composition.
• the level of calcium or magnesium ions should be selected so that there is always some minimum level available for the enzyme, after allowing for complexation with builders, fatty acids, etc., m the composition.
• Any water-soluble calcium or magnesium salt can be used as the source of calcium or magnesium ions, including, but not limited to, calcium chlo ⁇ de, calcium sulfate, calcium malate, calcium maleate, calcium hydroxide, calcium formate, and calcium acetate, and the corresponding magnesium salts.
• a small amount of calcium ion generally from about 0.05 to about 0.4 milhmoles per liter, is often also present the composition due to calcium in the enzyme slurry and formula water.
• the formulation may include a sufficient quantity of a water- soluble calcium ion source to provide such amounts in the laundry liquor.
• natural water hardness may suffice.
• compositions herein will typically comp ⁇ se from about 0.05% to about 2% by weight of a water-soluble source of calcium or magnesium ions, or both The amount can vary, of course, with the amount and type of enzyme employed in the composition.
• the laundry detergent compositions herein may also optionally, but preferably, contain various additional stabilizers, especially borate-type stabilizers.
• additional stabilizers especially borate-type stabilizers.
• such stabilizers will be used at levels in the compositions from about 0.25% to about 10%, preferably from about 0.5% to about 5%, more preferably from about 0.75% to about 4%, by weight of boric acid or other borate compound capable of forming bone acid in the composition (calculated on the basis of boric acid).
• Boric acid is prefened, although other compounds such as boric oxide, borax and other alkali metal borates (e.g , sodium ortho-, meta- and pyroborate, and sodium pentaborate) are suitable.
• Substituted boric acids e.g., phenylboronic acid, butane boromc acid, and p-bromo phenylboronic acid
• any polymeric soil release agent known to those skilled in the art can optionally be employed m the compositions and processes of this invention.
• Polymeric soil release agents are charactenzed by having both hydrophihc segments, to hydrophihze the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic segments, to deposit upon hydrophobic fibers and remain adhered thereto through completion of washing and rinsing cycles and, thus, serve as an anchor for the hydrophihc segments. This can enable stains occur ⁇ ng subsequent to treatment with the soil release agent to be more easily cleaned m later washing procedures.
• polymenc soil release agents useful herein include U.S. Patent 4,721,580, issued January 26, 1988 to Gossehnk; U.S. Patent 4,000,093, issued December 28, 1976 to Nicol, et al.; European Patent Application 0 219 048, published Ap ⁇ l 22, 1987 by Kud, et al.; U.S. Patent 4,702,857, issued October 27, 1987 to Gossehnk; U.S. Patent 4,968,451, issued November 6, 1990 to J.J. Scheibel.
• Commercially available soil release agents include the SOKALAN type of mate ⁇ al, e.g., SOKALAN HP-22, available from BASF (West Germany). Also see U.S. Patent 3,959,230 to Hays, issued May 25, 1976 and U.S.
• this polymer examples include the commercially available material ZELCON 5126 (from Dupont) and MELEASE T (from ICI).
• Other suitable polyme ⁇ c soil release agents include the terephthalate polyesters of U.S. Patent 4,71 1,730, issued December 8, 1987 to Gossehnk et al, the anionic end-capped ohgome ⁇ c esters of U.S. Patent 4,721,580, issued January 26, 1988 to Gossehnk, and the block polyester ohgome ⁇ c compounds of U.S. Patent 4,702,857, issued October 27, 1987 to Gossehnk.
• Preferred polymeric soil release agents also include the soil release agents of U.S. Patent 4,877,896, issued October 31 , 1989 to Maldonado et al.
• soil release agents will generally comprise from about 0.01% to about 10.0%, by weight, of the detergent compositions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0%.
• Clay Soil Removal/Anti-redeposition Agents typically comprise from about 0.01% to about 10.0%, by weight, of the detergent compositions herein, typically from about 0.1% to about 5%, preferably from about 0.2% to about 3.0%.
• the laundry detergent compositions of the present invention can also optionally contain water-soluble ethoxylated amines having clay soil removal and antiredeposition properties.
• Liquid detergent compositions typically contain about 0.01% to about 5%.
• the most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine.
• Exemplary ethoxylated amines are further described in U S. Patent 4,597,898, VanderMeer, issued July 1 , 1986.
• Another group of preferred clay soil removal- antiredeposition agents are the cationic compounds disclosed in European Patent Application 1 1 1 ,965, Oh and Gossehnk, published June 27, 1984
• Other clay soil removal/antiredeposition agents which can be used include the ethoxylated amine polymers disclosed in European Patent Application 1 1 1 ,984, Gossehnk, published June 27, 1984; the zwitte ⁇ onic polymers disclosed in European Patent Application 1 12,592, Gossehnk, published July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985.
• Other clay soil removal and/or anti redeposition agents known m the art can also be utilized m the compositions herein.
• Another type of preferred antiredeposition agent includes the carboxy methyl cellulose (CMC) mate ⁇ als. These materials are well known m the art.
• Polymenc dispersing agents can advantageously be utilized at levels from about 0.1% to about 7%, by weight, m the compositions herein, especially m the presence of zeolite and/or layered silicate builders.
• Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known m the art can also be used. It is believed, though it is not intended to be limited by theory, that polyme ⁇ c dispersing agents enhance overall detergent builder performance, when used m combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release peptization, and anti-redeposition.
• Polymeric polycarboxylate mate ⁇ als can be prepared by polyme ⁇ zmg or copolyme ⁇ zmg suitable unsaturated monomers, preferably m their acid form.
• Unsaturated monome ⁇ c acids that can be polyme ⁇ zed to form suitable polyme ⁇ c polycarboxylates include acrylic acid, maleic acid (or maleic anhyd ⁇ de), fuma ⁇ c acid, ltaconic acid, acomtic acid, mesaconic acid, citraconic acid and methylenemalonic acid
• the presence m the polyme ⁇ c polycarboxylates herein or monome ⁇ c segments, containing no carboxylate radicals such as vinylmethyl ether, styrene, ethylene, etc is suitable provided that such segments do not constitute more than about 40% by weight.
• Particularly suitable polyme ⁇ c polycarboxylates can be derived from acrylic acid.
• acrylic acid-based polymers which are useful herein are the water-soluble salts of polyme ⁇ zed acrylic acid
• the average molecular weight of such polymers in the acid form preferably ranges from about 2,000 to 10,000, more preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000
• Water-soluble salts of such acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts
• Soluble polymers of this type are known materials Use of polyacrylates of this type in detergent compositions has been disclosed, for example, in Diehl, U.S Patent 3,308,067, issued march 7, 1967.
• Acrylic/maleic-based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent.
• Such materials include the water-soluble salts of copolymers of acrylic acid and maleic acid
• the average molecular weight of such copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from about 5,000 to 75,000, most preferably from about 7,000 to 65,000
• the ratio of acrylate to maleate segments in such copolymers will generally range from about 30: 1 to about 1 : 1, more preferably from about 10: 1 to 2: 1.
• Water-soluble salts of such acrylic acid/maleic acid copolymers can include, for example, the alkali metal, ammonium and substituted ammonium salts
• Soluble acrylate/maleate copolymers of this type are known mate ⁇ als which are desc ⁇ bed in European Patent Application No. 66915, published December 15, 1982, as well as in EP 193,360, published September 3, 1986, which also describes such polymers comp ⁇ sing hydroxypropylacrylate
• Still other useful dispersing agents include the maleic/acrylic/vinyl alcohol terpolymers.
• Such mate ⁇ als are also disclosed m EP 193,360, including, for example, the 45/45/10 terpolymer of acryhc/maleic/vmyl alcohol.
• PEG polyethylene glycol
• PEG can exhibit dispersing agent performance as well as act as a clay soil removal-antiredeposition agent.
• Typical molecular weight ranges for these purposes range from about 500 to about 100,000, preferably from about 1,000 to about 50,000, more preferably from about 1,500 to about 10,000.
• Polyaspartate and polyglutamate dispersing agents may also be used, especially m conjunction with zeolite builders.
• Dispersing agents such as polyaspartate preferably have a molecular weight (avg.) of about 10,000.
• any optical b ⁇ ghteners or other b ⁇ ghten g or whitening agents known m the art can be incorporated at levels typically from about 0.05% to about 1.2%, by weight, into the detergent compositions herein.
• Commercial optical b ⁇ ghteners which may be useful m the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazohne, couma ⁇ n, carboxyhc acid, methmecyanmes, d ⁇ benzoth ⁇ phene-5,5-d ⁇ ox ⁇ de, azoles, 5- and 6-membered- ⁇ ng heterocycles, and other miscellaneous agents
• subgroups include, but are not necessarily limited to, derivatives of stilbene, pyrazohne, couma ⁇ n, carboxyhc acid, methmecyanmes, d ⁇ benzoth ⁇ phene-5,5-d ⁇ ox ⁇ de, azoles, 5- and 6-membered- ⁇ ng heterocycles, and other miscellaneous agents
• optical b ⁇ ghteners which are useful in the present compositions are those identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988. These b ⁇ ghteners include the PHOR WHITE series of b ⁇ ghteners from Verona Other b ⁇ ghteners disclosed in this reference include Tmopal UNPA, Tmopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artie White CC and Artie White CWD, available from Hilton-Davis, located in Italy, the 2-(4-stryl-phenyl)-2H-napthol[l,2-d]t ⁇ azoles; 4,4'-b ⁇ s- (l,2,3-t ⁇ azol-2-yl)-st ⁇ l- benes, 4,4'-b ⁇ s(stryl)b ⁇ sphenyls; and the aminocouma ⁇ ns.
• b ⁇ ghteners include 4-methyl-7-d ⁇ ethyl- ammo couma ⁇ n; l,2-b ⁇ s(-venz ⁇ m ⁇ dazol-2-yl)ethylene; 1 ,3-diphenyl-phrazohnes; 2,5-b ⁇ s(benzoxazol-2-yl)th ⁇ ophene; 2-stryl-napth-[l,2-d]oxazole; and 2-(st ⁇ lbene-4-yl)-2H-naphtho- [l,2-d]t ⁇ azole. See also U.S. Patent 3,646,015, issued February 29, 1972 to Hamilton. Anionic b ⁇ ghteners are preferred herein. Suds Suppressors
• suds suppressors A wide va ⁇ ety of materials may be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979).
• One category of suds suppressor of particular interest encompasses monocarboxyhc fatty acid and soluble salts therein. See U.S. Patent 2,954,347, issued September 27, 1960 to Wayne St. John.
• the monocarboxyhc fatty acids and salts thereof used as suds suppressor typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms.
• Suitable salts include the alkali metal salts such as sodium, potassium, and lithium salts, and ammonium and alkanolammomum salts.
• the laundry detergent compositions herein may also contain non-surfactant suds suppressors These include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C ⁇ -C4 Q ketones (e.g., stearone), etc
• Other suds inhibitors include N-alkylated amino t ⁇ azines such as t ⁇ - to hexa-alkylmelamines or di- to tetra-alkyldiamine chlort ⁇ azmes formed as products of cyanu ⁇ c chlo ⁇ de with two or three moles of a p ⁇ mary or secondary amme containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphates such as monostearyl alcohol phosphate ester and monostearyl di-alkah metal (e.g., K, Na, and Li) phosphates and
• hydrocarbons preferably having a melting point below about 100°C.
• the hydrocarbons constitute a preferred category of suds suppressor for detergent compositions
• Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al.
• the hydrocarbons thus, include aliphatic, alicychc, aromatic, and heterocychc saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms.
• the term "paraffin,” as used in this suds suppressor discussion, is intended to include mixtures of true paraffins and cyclic hydrocarbons.
• sihcone suds suppressors comp ⁇ ses sihcone suds suppressors
• This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica.
• Sihcone suds suppressors are well known in the art and are, for example, disclosed in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al and European Patent Application No. 89307851.9, published February 7, 1990, by Starch, M.
• sihcone and silanated silica are desc ⁇ bed, for instance, in German Patent Application DOS 2, 124,526.
• the solvent for a continuous phase is made up of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol.
• the p ⁇ mary sihcone suds suppressor is branched/crosshnked and preferably not linear.
• typical liquid laundry detergent compositions with controlled suds will optionally comprise from about 0.001 to about 1 , preferably from about 0 01 to about 0.7, most preferably from about 0 05 to about 0.5, weight % of said sihcone suds suppressor, which comp ⁇ ses (1) a nonaqueous emulsion of a p ⁇ mary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a sihcone resm-producmg sihcone compound, (c) a finely divided filler material, and (d) a catalyst to promote the reaction of mixture components (a), (b) and (c), to form silanolates; (2) at least one noniomc sihcone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than about 2 weight %
• the sihcone suds suppressor herein preferably comprises polyethylene glycol and a copolymer of polyethylene glycol/polypropylene glycol, all having an average molecular weight of less than about 1,000, preferably between about 100 and 800.
• the polyethylene glycol and polyethylene/polypropylene copolymers herein have a solubility in water at room temperature of more than about 2 weight %, preferably more than about 5 weight %.
• the preferred solvent herein is polyethylene glycol having an average molecular weight of less than about 1,000, more preferably between about 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol/polypropylene glycol, preferably PPG 200/PEG 300. Preferred is a weight ratio of between about 1 : 1 and 1 :10, most preferably between 1 :3 and 1 :6, of polyethylene glycol: copolymer of polyethylene -polypropylene glycol.
• the preferred sihcone suds suppressors used herein do not contain polypropylene glycol, particularly of 4,000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, like PLURONIC L101.
• suds suppressors useful herein comp ⁇ se the secondary alcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with sihcone oils, such as the sihcones disclosed in U.S. 4,798,679, 4,075,1 18 and EP 150,872.
• the secondary alcohols include the C 6 -C 16 alkyl alcohols having a Cj-C j g chain.
• a preferred alcohol is 2-butyl octanol, which is available from
• suds should not form to the extent that they overflow the washing machine.
• Suds suppressors when utilized, are preferably present in a "suds suppressing amount.
• Suds suppressing amount is meant that the formulator of the composition can select an amount of this suds controlling agent that will sufficiently control the suds to result in a low-sudsing laundry detergent for use in automatic laundry washing machines.
• the laundry detergent compositions herein will generally comprise from 0% to about 5% of suds suppressor When utilized as suds suppressors, monocarboxyhc fatty acids, and salts therein, will be present typically in amounts up to about 5%, by weight, of the detergent composition
• Sihcone suds suppressors are typically utilized in amounts up to about 2.0%, by weight, of the detergent composition, although higher amounts may be used This upper limit is practical in nature, due p ⁇ ma ⁇ ly to concern with keeping costs minimized and effectiveness of lower amounts for effectively controlling sudsing
• these weight percentage values include any silica that may be utilized in combination with polyorganosiloxane, as well as any adjunct mate ⁇ als that may be utilized.
• Monostearyl phosphate suds suppressors are generally utilized in amounts ranging from about 0.1 % to about 2%, by weight, of the composition
• Hydrocarbon suds suppressors are typically utilized in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used.
• the alcohol suds suppressors are typically used at 0.2%-3% by weight of the finished compositions.
• the laundry detergent compositions of the present invention may also include one or more mate ⁇ als effective for inhibiting the transfer of dyes from one fabric to another du ⁇ ng the cleaning process
• dye transfer inhibiting agents include polyvmyl pyrrohdone polymers, polyamme N-oxide polymers, copolymers of N-vmylpyrrohdone and N- vinyhmidazole, manganese phthalocya ne, peroxidases, and mixtures thereof. If used, these agents typically comprise from about 0.01% to about 10% by weight of the composition, preferably from about 0.01% to about 5%, and more preferably from about 0.05% to about 2%.
• the polyamme N-oxide polymers preferred for use herein contain units having the following structural formula: R-A x -P; wherem P is a polymenzable unit to which an
• N-0 group can be attached or the N-0 group can form part of the polymenzable unit or the N-0 group can be attached to both units;
• Preferred polyamme N-oxides are those wherein R is a heterocychc group such as pyndine, py ⁇ ole, lmidazole, pyrrohdine, pipendine and derivatives thereof.
• the N-0 group can be represented by the following general structures:
• R3 wherein R j , R 2 , R3 are aliphatic, aromatic, heterocychc or alicychc groups or combinations thereof; x, y and z are 0 or 1 ; and the nitrogen of the N-0 group can be attached or form part of any of the aforementioned groups.
• the amine oxide unit of the polyamme N-oxides has a pKa ⁇ 10, preferably pKa ⁇ 7, more prefened pKa ⁇ 6.
• Any polymer backbone can be used as long as the amme oxide polymer formed is water- soluble and has dye transfer inhibiting properties
• suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amme N-oxide and the other monomer type is an N-oxide.
• the amine N-oxide polymers typically have a ratio of amine to the amme N-oxide of 10: 1 to 1 : 1 ,000,000.
• the number of amme oxide groups present in the polyamme oxide polymer can be va ⁇ ed by approp ⁇ ate copolyme ⁇ zation or by an appropnate degree of N-oxidation.
• the polyamme oxides can be obtained in almost any degree of polyme ⁇ zation.
• the average molecular weight is within the range of 500 to 1,000,000; more prefened 1,000 to 500,000; most prefened 5,000 to 100,000. This prefened class of materials can be refened to as "PVNO".
• the most prefened polyamme N-oxide useful m the detergent compositions herein is poly(4-vmylpyndme-N-ox ⁇ de) which as an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1 :4.
• Copolymers of N-vinylpynohdone and N-vinyhmidazole polymers are also prefened for use herein.
• the PVPVI has an average molecular weight range from 5,000 to 1,000,000, more preferably from 5,000 to 200,000, and most preferably from 10,000 to 20,000. (The average molecular weight range is determined by light scatte ⁇ ng as desc ⁇ bed in Barth, et al., Chemical Analysis, Vol 113.
• the PVPVI copolymers typically have a molar ratio of N-vinyhmidazole to N-vmylpynohdone from 1 : 1 to 0 2: 1 , more preferably from 0.8: 1 to 0.3: 1, most preferably from 0.6: 1 to 0.4: 1. These copolymers can be either linear or branched.
• the laundry detergent compositions also may employ a polyvmylpynohdone ("PVP") having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and more preferably from about 5,000 to about 50,000 PVP's are known to persons skilled in the detergent field; see, for example, EP-A-262,897 and EP-A- 256.696, incorporated herein by reference.
• Compositions containing PVP can also contain polyethylene glycol (“PEG”) having an average molecular weight from about 500 to about 100,000, preferably from about 1,000 to about 10,000.
• PEG polyethylene glycol
• the ratio of PEG to PVP on a ppm basis delivered in wash solutions is from about 2: 1 to about 50: 1, and more preferably from about 3: 1 to about 10: 1.
• the laundry detergent compositions herein may also optionally contain from about 0.005% to 5% by weight of certain types of hydrophihc optical b ⁇ ghteners which also provide a dye transfer inhibition action. If used, the compositions herein will preferably comprise from about 0.01 % to 1 % by weight of such optical b ⁇ ghteners.
• hydrophihc optical b ⁇ ghteners useful in the present invention are those having the structural formula:
• R ⁇ is selected from amhno, N-2-b ⁇ s-hydroxyethyl and NH-2-hydroxyethyl
• R 2 is selected from N-2-b ⁇ s-hydroxyethyl, N-2-hydroxyethyl-N-methylammo, morphihno, chloro and amino
• M is a salt-forming cation such as sodium or potassium.
• Rj is amhno
• R is N-2-b ⁇ s-hydroxyethyl and M is a cation such as sodium
• the b ⁇ ghtener is 4,4',-b ⁇ s[(4-an ⁇ lmo-6-(N-2-b ⁇ s-hydroxyethyl)-s-tnaz ⁇ ne-2- yl)am ⁇ no]-2,2'-st ⁇ lbened ⁇ sulfomc acid and disodium salt.
• This particular b ⁇ ghtener species is commercially marketed under the tradename Tinopal-UNPA-GX by Ciba-Geigy Corporation.
• Tinopal-UNPA-GX is the prefened hydrophihc optical bnghtener useful in the detergent compositions herein
• Rj is amhno
• R 2 is N-2-hydroxyethyl-N-2-methylam ⁇ no and
• M is a cation such as sodium
• the b ⁇ ghtener is 4,4'-b ⁇ s[(4-an ⁇ hno-6-(N-2-hydroxyethyl-N- methylam ⁇ no)-s-t ⁇ azme-2-yl)am ⁇ no]2.2'-st ⁇ lbened ⁇ sulfon ⁇ c acid disodium salt.
• This particular bnghtener species is commercially marketed under the tradename Tinopal 5BM-GX by Ciba- Geigy Corporation.
• R j is amhno
• R 2 is morphihno
• M is a cation such as sodium
• the bnghtener is 4,4'-b ⁇ s[(4-an ⁇ hno-6-morph ⁇ hno-s-t ⁇ az ⁇ ne-2-yl)am ⁇ no]2,2'- stilbenedisulfo c acid, sodium salt
• Tinopal AMS-GX is commercially marketed under the tradename Tinopal AMS-GX by Ciba Geigy Corporation.
• the specific optical bnghtener species selected for use in the present invention provide especially effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents hereinbefore described
• selected polymenc materials e.g., PVNO and/or PVPVI
• selected optical b ⁇ ghteners e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX
• Tinopal UNPA-GX Tinopal 5BM-GX
• Tinopal AMS-GX Tinopal AMS-GX
• the extent to which b ⁇ ghteners deposit on fabrics in the wash solution can be defined by a parameter called the "exhaustion coefficient".
• the exhaustion coefficient is in general as the ratio of a) the b ⁇ ghtener mate ⁇ al deposited on fabnc to b) the initial bnghtener concentration the wash liquor.
• Bnghteners with relatively high exhaustion coefficients are the most suitable for inhibiting dye transfer in the context of the present invention.
• other, conventional optical bnghtener types of compounds can optionally be used in the present compositions to provide conventional fabnc "b ⁇ ghtness" benefits, rather than a true dye transfer inhibiting effect. Such usage is conventional and well-known to detergent formulations.
• the laundry detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators.
• bleaching agents will typically be at levels of from about 1% to about 30%, more typically from about 5% to about 20%, of the detergent composition, especially for fabric laundering If present, the amount of bleach activators will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.
• the bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known These include oxygen bleaches as well as other bleaching agents.
• Perborate bleaches e.g.. sodium perborate (e.g., mono- or tetra-hydrate) and percarbonate bleaches can be used herein.
• bleaching agent that can be used without restriction encompasses percarboxyhc acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylam ⁇ no-4-oxoperoxybuty ⁇ c acid and diperoxydodecanedioic acid.
• Such bleaching agents are disclosed in U.S Patent 4,483,781 , Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al, published February 20, 1985, and U.S.
• Patent 4,412,934, Chung et al issued November 1, 1983.
• Highly prefened bleaching agents also include 6-nonylam ⁇ no-6- oxoperoxycaproic acid as described in U.S. Patent 4,634,551 , issued January 6, 1987 to Burns et al.
• Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used. Mixtures of bleaching agents can also be used.
• Peroxygen bleaching agents, the perborates, the percarbonates, etc. are preferably combined with bleach activators, which lead to the in situ production aqueous solution (i.e., du ⁇ ng the washing process) of the peroxy acid conespondmg to the bleach activator.
• bleach activators Various nonhmiting examples of activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934.
• the nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used. See also U.S 4,634,551 for other typical bleaches and activators useful herein.
• Highly prefened armdo-de ⁇ ved bleach activators are those of the formulae:
• R* is an alkyl group containing from about 6 to about 12 carbon atoms
• R 2 is an alkylene containing from 1 to about 6 carbon atoms
• R ⁇ is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms
• L is any suitable leaving group
• a leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophihc attack on the bleach activator by the perhydrolysis anion.
• a prefened leaving group is phenyl sulfonate.
• bleach activators of the above formulae include (6- octanam ⁇ docaproyl)oxybenzenesulfonate, (6-nonanam ⁇ docaproyl)oxybenzenesul-fonate, (6- decanam ⁇ docaproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S Patent 4,634,551 , incorporated herein by reference.
• bleach activators comprises the benzoxazm-type activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990, incorporated herein by reference.
• Still another class of prefened bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams
• Highly prefened lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-t ⁇ methylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5- t ⁇ methylhexanoyl valerolactam and mixtures thereof See
• Bleaching agents other than oxygen bleaching agents are also known m the art and can be utilized herein.
• One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zmc and or aluminum phthalocyamnes. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from about 0.025% to about 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyamne.
• the bleaching compounds can be catalyzed by means of a manganese compound. Such compounds are well known the art and include, for example, the manganese-based catalysts disclosed in U.S. Pat.
• compositions and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 0.1 ppm to about 700 ppm, more preferably from about 1 ppm to about 500 ppm, of the catalyst species m the laundry liquor.
• the laundry detergent compositions can also comp ⁇ se anti-static agents as illustrated in U S Pat. 4,861 ,502.
• anti-static agents include alkyl amine-anio c surfactant ion pairs, such as distearyl amine-cumene sulfonate ion pairs. If present, anti-static agents are present in an amount of from about 0.5% to about 20%, preferably from about 1% to about 10%, more preferably from about 1% to about 5%, by weight of the detergent composition.
• Example A an embodiment of the present invention of a chelant agglomerate is exemplified:

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