WO1997044434A1 - Low moisture laundry detergent bar with improved bleach stability - Google Patents
Low moisture laundry detergent bar with improved bleach stability Download PDFInfo
- Publication number
- WO1997044434A1 WO1997044434A1 PCT/US1996/007166 US9607166W WO9744434A1 WO 1997044434 A1 WO1997044434 A1 WO 1997044434A1 US 9607166 W US9607166 W US 9607166W WO 9744434 A1 WO9744434 A1 WO 9744434A1
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- bar composition
- sodium
- moisture
- bleach
- bar
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Classifications
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- 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
- C11D1/37—Mixtures of compounds all of which are anionic
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- 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
- C11D1/652—Mixtures of anionic compounds with carboxylic amides or alkylol amides
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- 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
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0069—Laundry bars
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- 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
- C11D3/39—Organic or inorganic per-compounds
- C11D3/3942—Inorganic per-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
- C11D1/146—Sulfuric acid esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—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
- C11D1/38—Cationic compounds
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/523—Carboxylic alkylolamides, or dialkylolamides, or hydroxycarboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 contain one hydroxy group per alkyl group
Definitions
- This invention relates to a laundry detergent bar composition having a low moisture content with improved bleach stability.
- the process to make such compositions is also included herein.
- laundry detergent bars comprising synthetic organic surfactants and detergency builders are used in the laundering of clothes.
- Technical developments in the field of laundry detergent bars have concerned formulating bars which are effective in cleaning clothes; which have acceptable sudsing characteristics in warm and cool water and in hard and soft water, which have acceptable in-use wear rates, hardness, durability, and feel; which have low smear, and which have a pleasing odor and appearance.
- Methods for making laundry detergent bars are also well known in the art.
- Prior art disclosing laundry bars and methods for making laundry bars include: U.S. Pat. 3,178,370, Okenfuss, issued April 13, 1995; and Philippine Pat. 13,778, Anderson, issued September 23, 1980.
- the prior ait generally discloses laundry detergent bars containing a bleach system.
- the prior art discloses laundry bars containing sodium perborate monohydrate as a preferred bleach.
- Such prior art includes Great Britain Publication 2172300, Finch, published September 17, 1986 (equivalent to Philippine Patent 21708), and Indian Patent 165353, Malawistan Lever.
- laundry bar compositions containing a low moisture content of no more than about 3.5% in the finished product composition delivers significant improvement in bleach stability in bars over time.
- the present invention relates to a laundry detergent bar composition
- a laundry detergent bar composition comprising:
- a laundry detergent bar can achieve bleach stability over time in a low moisture content bar composition.
- Anionic synthetic detergent surfactants which are suitable for use herein include the water- soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
- alkyl is the alkyl portion of acyl groups.
- examples of this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (Cg. ⁇ g carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S. Patents 2,220,099 and 2,477,383.
- linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as Ci j .i 3 LAS.
- the alkali metal salts, particularly the sodium salts of these surfactants are preferred.
- Alkylbenzene sulfonates and processes for making them are disclosed in U.S. Patent Nos. 2,220,099 and 2,477,383.
- alkyl glyceryl ether sulfonates especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates.
- Preparation of alkyl glyceryl ether sulfonates are described in detail in U.S. Pat. 3,024,273, Whyte et al., issued March 6, 1962.
- suitable synthetic anionic surfactants include the water-soluble salts of esters of alpha-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-acyloxyalkane-l-sulfonic 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 and paraffin sulfonates containing from about 12 to 20 carbon atoms; and beta-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.
- Preferred anionic surfactants are Cjo-i ⁇ linear alkyl benzene sulfonates, Ci ⁇ . j g alkyl sulfates, and mixtures thereof.
- the amount of anionic surfactant in the compositions herein is from about 0.5% to about 60%, preferably from about 10% to about 30%.
- the bleach agent in the detergent composition is preferably at a level from about 0.10% to about 60% by weight; more preferably, from about 1% to about 50%; most preferably, from about 1% to about 20%.
- the bleach agents used herein can be any of the bleach agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known. Mixtures of bleach agents can also be used.
- a useful bleach agent that can be used encompasses percarboxylic acid bleach agents and salts thereof.
- Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
- Such bleach 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 preferred bleach agents also include 6-nonylan ⁇ ino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Bums et al.
- peroxygen bleach agents can also be used. Suitable peroxygen bleach 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. Bleach agents other than oxygen bleach agents are also known in die art and can be utilized herein.
- One type of non-oxygen bleach agent of particular interest includes photoactivated bleach agents such as the sulfonated zinc and/or aluminum phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al.
- detergent compositions will typically contain from about 0.025% to about 1.25% by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
- a useful percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers.
- the percarbonate can be coated with silicate, borate or water-soluble surfactants.
- Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.
- the preferred bleach agent for the present invention are those peroxygen bleaching compounds which are capable of yielding hydrogen peroxide in an aqueous solution. These compounds are well known in the art and include hydrogen peroxide and the alkali metal peroxides, organic peroxide bleaching compounds such as urea peroxide, and inorganic persalt bleaching compounds, such as the alkali metal perborates, percarbonates, perphosphates, and the like. Mixtures of two or more such bleaching compounds can also be used, if desired.
- Preferred peroxygen bleaching compounds to be used in the present invention include sodium perborate, commercially available in the form of mono- and tetra-hydrates, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Particular preferred are sodium perborate tetrahydrate, and especially, sodium perborate monohydrate. Sodium perborate monohydrate is especially preferred because it is very stable during storage and yet still dissolves very quickly in the bleaching solution.
- the final bar composition should have no more than about 3.5% moisture.
- the bar will contain from about 0.5% to about 3.4% moisture, more preferably, 1.4% to 3%.
- the moisture level can be determined by any methods known in the art by one skilled in the area of laundry bar compositions.
- One common method is the Bidwell Sterling Distillation method.
- Another known method is the Karl Fischer Moisture Titration Method. See AOCS official method Dd2a-59 issue 93 and AOCS official method Dd2b-59 issue 89.
- the binding agent is a non-liquid at ambient temperature.
- non-liquid means having a melting point above 38° C.
- Preferred levels of the binding agent are from about 0.5% to about 5% most preferably from about 1% to about 2.5%.
- Binding agents hold the bar together in a cohesive, soluble form.
- the binding agent is non-liquid, having a moisture level of less than 0.5%, preferably 0% in the agent material.
- the binding agent has thixotrophic properties, meaning that when shear force is applied to the binding agent, the material becomes fluid and helps the binding of the bar ingredients.
- Acceptable binding agents include precipitated silica, C ⁇ -Ci8 fatty acid alkanol amides, natural and synthetic starches (plain or modified), guar gums and derivatives of guar gums, dextrin, polyethylene glycol (M.W. 1500-20,000) and mixtures thereof.
- the binding agent is a fatty acid alkanol amide, where the alkanol can be an ethanol, methanol or propanol.
- the alkanol amide can be a di-alkanol or mono-alkanol amide.
- the binding agent is coco monoethanolamide.
- the types and amount of binder chosen can affect bar hardness.
- the amount of any particular binder should be chosen so as to provide a bar hardness (measured by the penetrometer) of about 1.1 to 2.2 mm after 24 hours of aging ofthe bar under normal atmospheric conditions.
- the detergent bars of the present invention can contain optional ingredients commonly used in detergent products.
- optional surfactants e.g. nonionic, zwitterionic and amphoteric surfactants
- optional alkaline builders such as sodium carbonate trisodium phosphate sodium silicate, etc. and other ingredients useful herein appears in U.S. Pat. No. 3,664,961, issued to Norris on May 23, 1972, and EP 550,652, published on April 16, 1992.
- optional surfactants if present, can be included at levels up to a total of about 10%, preferably about 0.5-3%.
- a hydrotrope or mixture of hydrotropes, can be present in the laundry detergent bar.
- Preferred hydrotropes include the alkali metal, preferably sodium, salts of toluene sulfonate, xylene sulfonate, cumene sulfonate, sulfosuccinate, and mixtures thereof.
- the hydrotrope is added to the linear alkyl benzene sulfonic acid prior to its neutralization.
- the hydrotrope, if present, will preferably be present at from about 0.5% to about 5% ofthe laundry detergent bar.
- Builders The laundry bars ofthe invention can contain from about 0% to about 60% preferably from about 5% to about 25% detergent builder.
- detergent builders can be, for example, water- soluble alkali-metal salts of phosphate, pyrophosphates, orthophosphates, tripolyphosphates, higher polyphosphates, and mixtures thereof.
- Preferred builders are a water-soluble alkali-metal salt of tripolyphosphate, and a mixture of tripolyphosphate and pyrophosphate.
- the builder can also be a non-phosphate detergent builder.
- Specific examples of non-phosphate, inorganic detergency builders include water-soluble inorganic carbonate and bicarbonate salts.
- the alkali metal (e.g., sodium and potassium) carbonates, bicarbonates, and silicates are particularly useful herein.
- Specific preferred examples of builders include sodium tripolyphosphates (STPP) and tetra sodium pyrophosphates (TSPP), and mixtures thereof.
- Other specifically preferred examples of builders include zeolites and polycarboxylates.
- Sodium carbonate is a particularly preferred ingredient in the subject invention compositions, since in addition to its use as a builder, it can also provide alkalinity to the composition for improved detergency, and also can serve as a neutralizing agent for acidic components added in the composition processing.
- Sodium carbonate is particularly preferred as a neutralizing inorganic salt for an acid precursor of an anionic surfactant used in such compositions, such as the alkyl ether sulfuric acid and alkylbenzene sulfonic acid.
- Co-polymers of acrylic acid and maleic acid are preferred in the subject compositions as auxiliary builders, since it has been observed that their use in combination with fabric softening clay and clay flocculating agents further stabilizes and improves the clay deposition and fabric softening performance.
- the fabric softening clay is preferably a smectite-type clay.
- the smectite-type clays can be described as expandable, three-layer clays; i.e., alumino-silicates and magnesium silicates, having an ion exchange capacity of at least about 50 meq/100 g. of clay.
- the clay particles are of a size that they can not be perceived tactilely, so as not to have a gritty feel on the treated fabric of the clothes.
- the fabric softening clay can be added to the bar to provide about 1% to about 50% by weight of the bar, more preferably from about 2% to about 20%, and most preferably about 3% to 14%.
- Gelwhite GP is an extremely white form of smectite-type clay and is therefore preferred when formulating white granular detergent compositions.
- Volclay BC which is a smectite-type clay mineral containing at least 3% iron (expressed as Fe2 ⁇ 3) in the crystal lattice, and which has a very high ion exchange capacity, is one of the most efficient and effective clays for use in the instant compositions from the standpoint of product performance.
- certain smectite-type clays are sufficiently contaminated by other silicate minerals that their ion exchange capacities fall below the requisite range; such clays are of no use in the instant compositions.
- the polymeric clay flocculating agent is selected to provide improved deposition of the fabric softening clay.
- Such materials have a high molecular weight, greater than about 100,000. Examples of such materials can include long chain polymers and copolymers derived from monomers such as ethylene oxide, acrylamide, acrylic acid, dimethylamino ethyl methacrylate, vinyl alcohol, vinyl pyrrolidone, and ethylene imine. Gums, like guar gums, are suitable as well.
- the preferred clay flocculating agent is a polyethylene oxide) polymer.
- the amount of clay flocculating agent, if any, is about 0.2-2%, preferably about 0.5-1%. Soil Suspending Agents
- Soil suspending agents can be used. In the present invention, their use is balanced with the fabric softening clay/clay flocculating agent combination to provide optimum cleaning and fabric softening performance. Soil suspending agents can also include water-soluble salts of carboxymethylcellulose and carboxyhydroxymethylcellulose.
- a preferred soil suspending agent is an acrylic/maleic copolymer, commercially available as Sokolan®, from BASF Co ⁇ .
- Other soil suspending agents include polyethylene glycols having a molecular weight of about 400 to 10,000, and ethoxylated mono- and polyamines, and quaternary salts thereof. If included, it can be at levels up to about 5%, preferably about 0.1-1%.
- a particularly preferred optional component of the present invention is a detergent chelant.
- Such chelants are able to sequester and chelate alkali cations (such as sodium, lithium and potassium), alkali metal earth cations (such as magnesium and calcium), and most importantly, heavy metal cations such as iron, manganese, zinc and aluminum.
- Preferred cations include sodium, magnesium, zinc, and mixtures thereof.
- the detergent chelant is particularly beneficial for maintaining good cleaning performance and improved surfactant mileage, despite the presence of the softening clay and the clay flocculating agent.
- the detergent chelant is preferably a phosphonate chelant, particularly one selected from the group consisting of diethylenetriamine penta(methylene phosphonic acid), ethylene diamine tetra(methylene phosphonic acid), and mixtures and salts and complexes thereof, and an acetate chelant, particularly one selected from the group consisting of diethylenetriamine penta(acetic acid), ethylene diamine tetra(acetic acid), and mixtures and salts and complexes thereof.
- Particularly preferred are sodium, zinc, magnesium, and aluminum salts and complexes of diethylenetriamine penta(methylene phosphonate) diethylenetriamine penta (acetate), and mixtures thereof.
- such salts or complexes have a molar ratio of metal ion to chelant molecule of at least 1:1, preferably at least 2:1.
- the detergent chelant can be included in the laundry bar at a level up to about 5%, preferably from about 0.1% to about 3%, more preferably from about 0.2% to about 2%, most preferably from about 0.5% to about 1.0%.
- Another preferred additional component of the laundry bar is fatty alcohol having an alkyl chain of 8 to 22 carbon atoms, more preferably from 12 to 18 carbon atoms.
- a preferred fatty alcohol has an alkyl chain predominantly containing from 16 to 18 carbon atoms, so-called "high-cut fatty alcohol,” which can exhibit less base odor of fatty alcohol relative to broad cut fatty alcohols.
- fatty alcohol if any, is present in the laundry bar at up to a level of 10%, more preferably from about 0.75% to about 6% most preferably from about 2% to about 5%.
- the fatty alcohol is generally added to a laundry bar as free fatty alcohol. However, low levels of fatty alcohol can be introduced into the bars as impurities or as unreacted starting material.
- laundry bars based on coconut fatty alkyl sulfate can contain, as unreacted starting material, from 0.1% to 3.5%, more typically from 2% to 3% by weight of free coconut fatty alcohol on a coconut fatty alkyl sulfate basis.
- Another preferred optional component in the laundry bar is a dye transfer inhibiting (DTI) ingredient to prevent diminishing of color fidelity and intensity in fabrics.
- DTI ingredient can include polymeric DTI materials capable of binding fugitive dyes to prevent them from depositing on the fabrics, and decolorization DTI materials capable of decolorizing the fugitives dye by oxidation.
- An example of a decolorization DTI is hydrogen peroxide or a source of hydrogen peroxide, such as percarbonate or perborate.
- Non-limiting examples of polymeric DTI materials include polyvinylpyrridine N-oxide, polyvinylpyrrolidone (PVP), PVP-polyvinylimidazole copolymer, and mixtures thereof. Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as "PVPI") are also preferred for use herein.
- the amount of DTI included in the subject compositions, if any, is about 0.05-5%, preferably about 0.2-2%.
- Another preferred optional component in the laundry bar is a secondary fabric softener component in addition to the softening clay.
- Such materials can be used, if any, at levels of about 0.1% to 5%, more preferably from 0.3% to 3%, and can include: amines of the formula R4R5R6N, wherein R4 is C5 to C22 hydrocarbyl, R5 and R$ are independently Cj to C10 hydrocarbyl.
- R4 is C5 to C22 hydrocarbyl
- R5 and R$ are independently Cj to C10 hydrocarbyl.
- One preferred amine is ditallowmethyl amine; complexes of such amines with fatty acid of the formula R7COOH, wherein R7 is C9 to C22 hydrocarbyl, as disclosed in EP No.
- Rio is alkyl having 8 to 20 carbons
- Ri 1 is alkyl having 1 to 10 carbons
- R12 and R13 are alkyl having 1 to 4 carbons, preferably methyl
- X is an anion, preferably Cl" or Br", such as Ci 2-13 alkyl trimethyl ammonium chloride.
- Sodium sulfate is a well-known filler that is compatible with the compositions of this invention. It can be a by-product of the surfactant situation and sulfonation processes, or it can be added separately.
- Other filler materials include bentonite and talc.
- Calcium carbonate (also known as Calcarb) is also a well known and often used filler component of laundry bars.
- Fillers include minerals, such as talc and hydrated magnesium silicate- containing minerals, where the silicate is mixed with other minerals, e.g., old mother rocks such as dolomite. Filler materials are typically used, if included, at levels up to 40%, preferably from about 5% to about 25%.
- Optical brighteners are also preferred optional ingredients in laundry bars of the present invention.
- Preferred optical brighteners are dian ⁇ no stilbene, distyrilbiphenyl-type optical brighteners.
- Preferred as examples of such brighteners are 4,4'-bis ⁇ [4-anilino-6-bis(2-hydoxyethyl) amino-l,3,5-trizin-2-yl]amino ⁇ stilbene-2,2'-disulfonic acid disodium salt, 4-4'-bis(2-sulfostyryl) biphenyl and 4,4'-bis[(4-anilino-6-mo ⁇ holino-l,3,5-triazin-2-yl) aminolstilbene- ⁇ '-disulfonic acid disodium salt.
- Such optical brighteners, or mixtures thereof can be used at levels in the bar of from about 0.05% - 1.0%.
- Dyes, pigments, germicides, and perfumes can also be added to the bar composition. If included, they are typically at levels up to about 0.5%.
- Another optional component of the subject invention composition is a photobleach material, particularly phthalocyanine photobleaches which are described in U.S. Patent 4,033,718 issued July 5, 1977, incorporated herein by reference.
- Preferred photobleaches are metal phthalocyanine compounds, the metal preferably having a valance of +2 or +3; zinc and aluminum are preferred metals.
- Such photobleaches are available, for example, under the tradename TTNOLUS or as zinc phthalocyanine sulfonate.
- the photobleach components, if included, are typically in the subject compositions at levels up to about 0.02%, preferably from about 0.001% to about 0.015% more preferably from about 0.002% to about 0.01%.
- detergent enzymes are preferred. Particularly preferred are lipase, protease, amylase, and mixtures thereof. Enzymes, if included, are typically at levels up to about 5%, preferably about 0.5-3%. Processing
- the detergent laundry bars ofthe present invention can be processed in conventional soap or detergent bar making equipment with some or all ofthe following key equipment: blender/mixer, mill or refining plodder, two- stage vacuum plodder, logo printer/cutter, cooling tunnel and wrapper.
- blender/mixer mill or refining plodder
- two- stage vacuum plodder two- stage vacuum plodder
- logo printer/cutter logo printer/cutter
- cooling tunnel and wrapper In a typical process the raw materials are mixed in die blender.
- the sodium salt of coco fatty alcohol sulfate and an alkaline inorganic salt preferably sodium carbonate
- alkyl benzene sulfonic acid is reacted with the mixture to complete neutralization, the amount of alkaline inorganic salt sufficient to completely neutralize the acid.
- a non-liquid, thixotrophic binder such as coco monoethanolamide (CMEA) and other optional surfactants are added, followed by any additional optional components such as chelants. It is most preferable to use as raw materials, such materials which contain little moisture.
- the mixing can take from one minute to one hour, with the usual mixing time being from about two to twenty minutes.
- the bleach agent is added to the mixture and then mixed for an additional one to five minutes. It is usually added as one of the last ingredients, right before the perfume, if any, is added.
- the blender mix is charged to a surge tank.
- the product is conveyed from the surge tank to the mill or refining plodder via a multi-worm conveyer.
- the product is then conveyed to a double vacuum plodder, operating at high vacuum, e.g. 600 to 740 mm of mercury vacuum, so that entrapped air is removed.
- high vacuum e.g. 600 to 740 mm of mercury vacuum
- the product is extruded and cut to the desired bar length, and printed with the product brand name.
- the printed bar can be cooled, for example in a cooling tunnel, before it is wrapped, cased, and sent to storage.
- a preferred low moisture laundry bar composition is made by the following method: The raw materials are first mixed in a blender. A dry form (flakes, noodles, needles, ground powder) and a high active neutralized paste form of sodium salt of coco fatty alcohol sulfate, sodium carbonate, and sodium tripolyphosphate is mixed for three minutes. The amount of neutralized fatty alcohol sulfate paste with 25% to 35% moisture, contains an amount of water that will not translate to more than 2.5% moisture by weight in the final composition. A dose mixture of linear alkyl benzene sulfonic acid and sulfuric acid which have been pre-mixed for 1-1.5 minutes is then added to the blender, being completely neutralized by the sodium carbonate in the seat of the blender.
- the amount of sodium carbonate is at least an amount sufficient to neutralize the acids.
- the materials are mixed for an additional 1-2 minutes after dosing.
- a non-liquid, thixotrophic binder such as coco monoethanolamide (CMEA) and other optional surfactants are added, followed by any additional optional components such as chelants.
- CMEA coco monoethanolamide
- the mixing can take from one minute to one hour, with the usual mixing time being from about five to ten minutes.
- the bleach agent is added to the mixture and then mixed for an additional one to five minutes.
- the blender mix is charged to a surge tank.
- the product is conveyed from the surge tank to the mill or refining plodder via a multi-worm conveyer.
- the product is then conveyed to a double vacuum plodder, operating at high vacuum, e.g. 600 to 740 mm of mercury vacuum, so that entrapped air is removed.
- high vacuum e.g. 600 to 740 mm of mercury vacuum
- the product is extruded and cut to the desired bar length, and printed with the product brand name.
- the printed bar can be cooled, for example in a cooling tunnel, before it is wrapped, cased, and sent to storage.
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Abstract
This invention relates to a laundry detergent bar composition having a low moisture content with improved bleach stability. The process to make such compositions is also included herein.
Description
LOW MOISTURE LAUNDRY DETERGENT BAR WITH IMPROVED BLEACH STABILITY
FIELD OF THE INVENΗON This invention relates to a laundry detergent bar composition having a low moisture content with improved bleach stability. The process to make such compositions is also included herein.
BACKGROUND OF THE INVENTION
In societies where mechanical washing machines are not common, laundry detergent bars comprising synthetic organic surfactants and detergency builders are used in the laundering of clothes. Technical developments in the field of laundry detergent bars have concerned formulating bars which are effective in cleaning clothes; which have acceptable sudsing characteristics in warm and cool water and in hard and soft water, which have acceptable in-use wear rates, hardness, durability, and feel; which have low smear, and which have a pleasing odor and appearance. Methods for making laundry detergent bars are also well known in the art. Prior art disclosing laundry bars and methods for making laundry bars include: U.S. Pat. 3,178,370, Okenfuss, issued April 13, 1995; and Philippine Pat. 13,778, Anderson, issued September 23, 1980. The prior ait generally discloses laundry detergent bars containing a bleach system. In addition, the prior art discloses laundry bars containing sodium perborate monohydrate as a preferred bleach. Such prior art includes Great Britain Publication 2172300, Finch, published September 17, 1986 (equivalent to Philippine Patent 21708), and Indian Patent 165353, Hindustan Lever.
It has now been found that laundry bar compositions containing a low moisture content of no more than about 3.5% in the finished product composition delivers significant improvement in bleach stability in bars over time.
SUMMARY OF THE INVENTION
The present invention relates to a laundry detergent bar composition comprising:
(a) from about 0.5% to about 60% anionic synthetic detergent surfactant,
(b) from about 0.10% to about 60% bleach agent,
(c) no more than about 3.5% moisture in the finished bar composition, and
(d) from about 0.1% to about 10% non-liquid, thixotrophic binding agents.
All documents referenced herein are incorporated by reference.
DETAILED DESCRIPTION OF THE INVENTION
While this specification concludes with claims distinctly pointing out and particularly claiming that which is regarded as the invention, it is believed that the invention can be better understood through a careful reading of the following detailed description of the invention. In this specification all percentages are by weight, all temperatures are expressed in degrees Celsius, molecular weights are in weight average, and the decimal is represented by the point (.), unless otherwise indicated.
In accordance with the present invention it has been found that a laundry detergent bar can achieve bleach stability over time in a low moisture content bar composition.
Anionic synthetic detergent surfactants
Anionic synthetic detergent surfactants which are suitable for use herein include the water- soluble salts, preferably the alkali metal, ammonium and alkylolammonium salts of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl" is the alkyl portion of acyl groups.) Examples of this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (Cg.ι g carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the sodium and potassium alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain configuration, e.g., those of the type described in U.S. Patents 2,220,099 and 2,477,383. Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as Ci j.i 3 LAS. The alkali metal salts, particularly the sodium salts of these surfactants are preferred. Alkylbenzene sulfonates and processes for making them are disclosed in U.S. Patent Nos. 2,220,099 and 2,477,383.
Other synthetic anionic surfactants suitable for use herein are the sodium alkyl glyceryl ether sulfonates, especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates. Preparation of alkyl glyceryl ether sulfonates are described in detail in U.S. Pat. 3,024,273, Whyte et al., issued March 6, 1962.
In addition, suitable synthetic anionic surfactants include the water-soluble salts of esters of alpha-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-acyloxyalkane-l-sulfonic 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 and paraffin sulfonates containing from about 12 to 20 carbon atoms; and beta-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.
Preferred anionic surfactants are Cjo-iβ linear alkyl benzene sulfonates, Ciø.jg alkyl sulfates, and mixtures thereof.
The amount of anionic surfactant in the compositions herein is from about 0.5% to about 60%, preferably from about 10% to about 30%.
Bleach Agent
The bleach agent in the detergent composition is preferably at a level from about 0.10% to about 60% by weight; more preferably, from about 1% to about 50%; most preferably, from about 1% to about 20%. The bleach agents used herein can be any of the bleach agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known. Mixtures of bleach agents can also be used.
A useful bleach agent that can be used encompasses percarboxylic acid bleach agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleach 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 preferred bleach agents also include 6-nonylanιino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Bums et al.
Other peroxygen bleach agents can also be used. Suitable peroxygen bleach 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. Bleach agents other than oxygen bleach agents are also known in die art and can be utilized herein. One type of non-oxygen bleach agent of particular interest includes photoactivated bleach agents such as the sulfonated zinc and/or aluminum phthalocyanines. 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 phthalocyanine. A useful percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of
said particles being larger than about 1,250 micrometers. Optionally, the percarbonate can be coated with silicate, borate or water-soluble surfactants. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.
The preferred bleach agent for the present invention are those peroxygen bleaching compounds which are capable of yielding hydrogen peroxide in an aqueous solution. These compounds are well known in the art and include hydrogen peroxide and the alkali metal peroxides, organic peroxide bleaching compounds such as urea peroxide, and inorganic persalt bleaching compounds, such as the alkali metal perborates, percarbonates, perphosphates, and the like. Mixtures of two or more such bleaching compounds can also be used, if desired. Preferred peroxygen bleaching compounds to be used in the present invention include sodium perborate, commercially available in the form of mono- and tetra-hydrates, sodium carbonate peroxyhydrate, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Particular preferred are sodium perborate tetrahydrate, and especially, sodium perborate monohydrate. Sodium perborate monohydrate is especially preferred because it is very stable during storage and yet still dissolves very quickly in the bleaching solution.
Bar Physical Properties
The final bar composition should have no more than about 3.5% moisture. Preferably, the bar will contain from about 0.5% to about 3.4% moisture, more preferably, 1.4% to 3%. The moisture level can be determined by any methods known in the art by one skilled in the area of laundry bar compositions. One common method is the Bidwell Sterling Distillation method. Another known method is the Karl Fischer Moisture Titration Method. See AOCS official method Dd2a-59 issue 93 and AOCS official method Dd2b-59 issue 89.
Although the bar has low moisture, it still has acceptable physical properties in terms of hardness and binding due to the addition of from about 0.1% to about 10% of a non-liquid, thixotrophic binding agent. The binding agent is a non-liquid at ambient temperature. As used herein, "non-liquid" means having a melting point above 38° C. Preferred levels of the binding agent are from about 0.5% to about 5% most preferably from about 1% to about 2.5%. Binding agents hold the bar together in a cohesive, soluble form. The binding agent is non-liquid, having a moisture level of less than 0.5%, preferably 0% in the agent material. The binding agent has thixotrophic properties, meaning that when shear force is applied to the binding agent, the material becomes fluid and helps the binding of the bar ingredients. Acceptable binding agents include precipitated silica, Cβ-Ci8 fatty acid alkanol amides, natural and synthetic starches (plain or modified), guar gums and derivatives of guar gums, dextrin, polyethylene glycol (M.W. 1500-20,000) and mixtures thereof. Preferably, the binding agent is a fatty acid alkanol amide, where the alkanol can be an ethanol, methanol or propanol. The alkanol amide can be a di-alkanol or mono-alkanol amide. Most preferably, the binding agent is coco monoethanolamide. The types and amount of binder chosen
can affect bar hardness. Preferably, the amount of any particular binder (within the above-described percentage ranges) should be chosen so as to provide a bar hardness (measured by the penetrometer) of about 1.1 to 2.2 mm after 24 hours of aging ofthe bar under normal atmospheric conditions.
Adjunct Ingredients
Optional Surfactants
The detergent bars of the present invention can contain optional ingredients commonly used in detergent products. A typical listing of the classes and species of optional surfactants, (e.g. nonionic, zwitterionic and amphoteric surfactants) optional alkaline builders such as sodium carbonate trisodium phosphate sodium silicate, etc. and other ingredients useful herein appears in U.S. Pat. No. 3,664,961, issued to Norris on May 23, 1972, and EP 550,652, published on April 16, 1992. Such optional surfactants, if present, can be included at levels up to a total of about 10%, preferably about 0.5-3%.
In addition, a hydrotrope, or mixture of hydrotropes, can be present in the laundry detergent bar. Preferred hydrotropes include the alkali metal, preferably sodium, salts of toluene sulfonate, xylene sulfonate, cumene sulfonate, sulfosuccinate, and mixtures thereof. Preferably, the hydrotrope is added to the linear alkyl benzene sulfonic acid prior to its neutralization. The hydrotrope, if present, will preferably be present at from about 0.5% to about 5% ofthe laundry detergent bar. Builders The laundry bars ofthe invention can contain from about 0% to about 60% preferably from about 5% to about 25% detergent builder. These detergent builders can be, for example, water- soluble alkali-metal salts of phosphate, pyrophosphates, orthophosphates, tripolyphosphates, higher polyphosphates, and mixtures thereof. Preferred builders are a water-soluble alkali-metal salt of tripolyphosphate, and a mixture of tripolyphosphate and pyrophosphate. The builder can also be a non-phosphate detergent builder. Specific examples of non-phosphate, inorganic detergency builders include water-soluble inorganic carbonate and bicarbonate salts. The alkali metal (e.g., sodium and potassium) carbonates, bicarbonates, and silicates are particularly useful herein. Specific preferred examples of builders include sodium tripolyphosphates (STPP) and tetra sodium pyrophosphates (TSPP), and mixtures thereof. Other specifically preferred examples of builders include zeolites and polycarboxylates.
Sodium carbonate is a particularly preferred ingredient in the subject invention compositions, since in addition to its use as a builder, it can also provide alkalinity to the composition for improved detergency, and also can serve as a neutralizing agent for acidic components added in the composition processing. Sodium carbonate is particularly preferred as a neutralizing inorganic salt for an acid precursor of an anionic surfactant used in such compositions, such as the alkyl ether sulfuric acid and alkylbenzene sulfonic acid.
Co-polymers of acrylic acid and maleic acid are preferred in the subject compositions as auxiliary builders, since it has been observed that their use in combination with fabric softening clay and clay flocculating agents further stabilizes and improves the clay deposition and fabric softening performance. Fabric Softening Clay
The fabric softening clay is preferably a smectite-type clay. The smectite-type clays can be described as expandable, three-layer clays; i.e., alumino-silicates and magnesium silicates, having an ion exchange capacity of at least about 50 meq/100 g. of clay. Preferably the clay particles are of a size that they can not be perceived tactilely, so as not to have a gritty feel on the treated fabric of the clothes. The fabric softening clay can be added to the bar to provide about 1% to about 50% by weight of the bar, more preferably from about 2% to about 20%, and most preferably about 3% to 14%.
While any of the smectite-type clays described herein are useful in the present invention, certain clays are preferred. For example, Gelwhite GP is an extremely white form of smectite-type clay and is therefore preferred when formulating white granular detergent compositions. Volclay BC, which is a smectite-type clay mineral containing at least 3% iron (expressed as Fe2θ3) in the crystal lattice, and which has a very high ion exchange capacity, is one of the most efficient and effective clays for use in the instant compositions from the standpoint of product performance. On the other hand, certain smectite-type clays are sufficiently contaminated by other silicate minerals that their ion exchange capacities fall below the requisite range; such clays are of no use in the instant compositions.
Clay flocculating AgSPt
It has been found that the use of a clay flocculating agent in a laundry bar containing softening clay provides surprisingly improved softening clay deposition onto the clothes and clothes softening performance, compared to that of laundry bars comprising softening clay alone. The polymeric clay flocculating agent is selected to provide improved deposition of the fabric softening clay. Typically such materials have a high molecular weight, greater than about 100,000. Examples of such materials can include long chain polymers and copolymers derived from monomers such as ethylene oxide, acrylamide, acrylic acid, dimethylamino ethyl methacrylate, vinyl alcohol, vinyl pyrrolidone, and ethylene imine. Gums, like guar gums, are suitable as well. The preferred clay flocculating agent is a polyethylene oxide) polymer. The amount of clay flocculating agent, if any, is about 0.2-2%, preferably about 0.5-1%. Soil Suspending Agents
Soil suspending agents can be used. In the present invention, their use is balanced with the fabric softening clay/clay flocculating agent combination to provide optimum cleaning and fabric softening performance. Soil suspending agents can also include water-soluble salts of carboxymethylcellulose and carboxyhydroxymethylcellulose. A preferred soil suspending agent is an
acrylic/maleic copolymer, commercially available as Sokolan®, from BASF Coφ. Other soil suspending agents include polyethylene glycols having a molecular weight of about 400 to 10,000, and ethoxylated mono- and polyamines, and quaternary salts thereof. If included, it can be at levels up to about 5%, preferably about 0.1-1%.
Other Optional Adjunct Ingredients
A particularly preferred optional component of the present invention is a detergent chelant. Such chelants are able to sequester and chelate alkali cations (such as sodium, lithium and potassium), alkali metal earth cations (such as magnesium and calcium), and most importantly, heavy metal cations such as iron, manganese, zinc and aluminum. Preferred cations include sodium, magnesium, zinc, and mixtures thereof. The detergent chelant is particularly beneficial for maintaining good cleaning performance and improved surfactant mileage, despite the presence of the softening clay and the clay flocculating agent.
The detergent chelant is preferably a phosphonate chelant, particularly one selected from the group consisting of diethylenetriamine penta(methylene phosphonic acid), ethylene diamine tetra(methylene phosphonic acid), and mixtures and salts and complexes thereof, and an acetate chelant, particularly one selected from the group consisting of diethylenetriamine penta(acetic acid), ethylene diamine tetra(acetic acid), and mixtures and salts and complexes thereof. Particularly preferred are sodium, zinc, magnesium, and aluminum salts and complexes of diethylenetriamine penta(methylene phosphonate) diethylenetriamine penta (acetate), and mixtures thereof.
Preferably such salts or complexes have a molar ratio of metal ion to chelant molecule of at least 1:1, preferably at least 2:1.
The detergent chelant can be included in the laundry bar at a level up to about 5%, preferably from about 0.1% to about 3%, more preferably from about 0.2% to about 2%, most preferably from about 0.5% to about 1.0%.
Another preferred additional component of the laundry bar is fatty alcohol having an alkyl chain of 8 to 22 carbon atoms, more preferably from 12 to 18 carbon atoms. A preferred fatty alcohol has an alkyl chain predominantly containing from 16 to 18 carbon atoms, so-called "high-cut fatty alcohol," which can exhibit less base odor of fatty alcohol relative to broad cut fatty alcohols. Typically fatty alcohol, if any, is present in the laundry bar at up to a level of 10%, more preferably from about 0.75% to about 6% most preferably from about 2% to about 5%. The fatty alcohol is generally added to a laundry bar as free fatty alcohol. However, low levels of fatty alcohol can be introduced into the bars as impurities or as unreacted starting material. For example, laundry bars based on coconut fatty alkyl sulfate can contain, as unreacted starting material, from 0.1% to 3.5%, more typically from 2% to 3% by weight of free coconut fatty alcohol on a coconut fatty alkyl sulfate basis.
Another preferred optional component in the laundry bar is a dye transfer inhibiting (DTI) ingredient to prevent diminishing of color fidelity and intensity in fabrics. A preferred DTI ingredient can include polymeric DTI materials capable of binding fugitive dyes to prevent them from depositing on the fabrics, and decolorization DTI materials capable of decolorizing the fugitives dye by oxidation. An example of a decolorization DTI is hydrogen peroxide or a source of hydrogen peroxide, such as percarbonate or perborate. Non-limiting examples of polymeric DTI materials include polyvinylpyrridine N-oxide, polyvinylpyrrolidone (PVP), PVP-polyvinylimidazole copolymer, and mixtures thereof. Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (referred to as "PVPI") are also preferred for use herein. The amount of DTI included in the subject compositions, if any, is about 0.05-5%, preferably about 0.2-2%.
Another preferred optional component in the laundry bar is a secondary fabric softener component in addition to the softening clay. Such materials can be used, if any, at levels of about 0.1% to 5%, more preferably from 0.3% to 3%, and can include: amines of the formula R4R5R6N, wherein R4 is C5 to C22 hydrocarbyl, R5 and R$ are independently Cj to C10 hydrocarbyl. One preferred amine is ditallowmethyl amine; complexes of such amines with fatty acid of the formula R7COOH, wherein R7 is C9 to C22 hydrocarbyl, as disclosed in EP No. 0,133,804; complexes of such amines with phosphate esters of the formula RgO-P(0)(OH)-OR9 and HO-P(0)(OH)-OR9, wherein Rg and R9 are independently Ci to C20 alkyl of alkyl ethoxylate of the formula -alkyl-(OCH2CH2); cyclic amines such as imidazolines of the general formula 1 -(higher alkyl) amido (lower alkyl)-2- (higher alkyl)imidazoline, where higher alkyl is from 12 to 22 carbons and lower alkyl is from 1 to 4 carbons, such as described in UK Patent Application GB 2,173,827; and quaternary ammonium compounds of the formula RιoRllRl2Rl3N+X'. wherein Rio is alkyl having 8 to 20 carbons, Ri 1 is alkyl having 1 to 10 carbons, R12 and R13 are alkyl having 1 to 4 carbons, preferably methyl, and X is an anion, preferably Cl" or Br", such as Ci 2-13 alkyl trimethyl ammonium chloride. Sodium sulfate is a well-known filler that is compatible with the compositions of this invention. It can be a by-product of the surfactant situation and sulfonation processes, or it can be added separately. Other filler materials include bentonite and talc.
Calcium carbonate (also known as Calcarb) is also a well known and often used filler component of laundry bars. Fillers include minerals, such as talc and hydrated magnesium silicate- containing minerals, where the silicate is mixed with other minerals, e.g., old mother rocks such as dolomite. Filler materials are typically used, if included, at levels up to 40%, preferably from about 5% to about 25%.
Optical brighteners are also preferred optional ingredients in laundry bars of the present invention. Preferred optical brighteners are dianύno stilbene, distyrilbiphenyl-type optical brighteners. Preferred as examples of such brighteners are 4,4'-bis{[4-anilino-6-bis(2-hydoxyethyl) amino-l,3,5-trizin-2-yl]amino}stilbene-2,2'-disulfonic acid disodium salt, 4-4'-bis(2-sulfostyryl) biphenyl and 4,4'-bis[(4-anilino-6-moφholino-l,3,5-triazin-2-yl) aminolstilbene-Σ^'-disulfonic acid
disodium salt. Such optical brighteners, or mixtures thereof, can be used at levels in the bar of from about 0.05% - 1.0%.
Dyes, pigments, germicides, and perfumes can also be added to the bar composition. If included, they are typically at levels up to about 0.5%. Another optional component of the subject invention composition is a photobleach material, particularly phthalocyanine photobleaches which are described in U.S. Patent 4,033,718 issued July 5, 1977, incorporated herein by reference. Preferred photobleaches are metal phthalocyanine compounds, the metal preferably having a valance of +2 or +3; zinc and aluminum are preferred metals. Such photobleaches are available, for example, under the tradename TTNOLUS or as zinc phthalocyanine sulfonate. The photobleach components, if included, are typically in the subject compositions at levels up to about 0.02%, preferably from about 0.001% to about 0.015% more preferably from about 0.002% to about 0.01%.
Another useful optional component of the subject compositions are detergent enzymes. Particularly preferred are lipase, protease, amylase, and mixtures thereof. Enzymes, if included, are typically at levels up to about 5%, preferably about 0.5-3%. Processing
The detergent laundry bars ofthe present invention can be processed in conventional soap or detergent bar making equipment with some or all ofthe following key equipment: blender/mixer, mill or refining plodder, two- stage vacuum plodder, logo printer/cutter, cooling tunnel and wrapper. In a typical process the raw materials are mixed in die blender. The sodium salt of coco fatty alcohol sulfate and an alkaline inorganic salt (preferably sodium carbonate) are mixed in the presence of a polyphosphate builder. Then alkyl benzene sulfonic acid is reacted with the mixture to complete neutralization, the amount of alkaline inorganic salt sufficient to completely neutralize the acid. Once the neutralization reaction is completed, a non-liquid, thixotrophic binder such as coco monoethanolamide (CMEA) and other optional surfactants are added, followed by any additional optional components such as chelants. It is most preferable to use as raw materials, such materials which contain little moisture. The mixing can take from one minute to one hour, with the usual mixing time being from about two to twenty minutes. The bleach agent is added to the mixture and then mixed for an additional one to five minutes. It is usually added as one of the last ingredients, right before the perfume, if any, is added. The blender mix is charged to a surge tank. The product is conveyed from the surge tank to the mill or refining plodder via a multi-worm conveyer.
After milling or preliminary plodding, the product is then conveyed to a double vacuum plodder, operating at high vacuum, e.g. 600 to 740 mm of mercury vacuum, so that entrapped air is removed. The product is extruded and cut to the desired bar length, and printed with the product brand name. The printed bar can be cooled, for example in a cooling tunnel, before it is wrapped, cased, and sent to storage.
A preferred low moisture laundry bar composition is made by the following method:
The raw materials are first mixed in a blender. A dry form (flakes, noodles, needles, ground powder) and a high active neutralized paste form of sodium salt of coco fatty alcohol sulfate, sodium carbonate, and sodium tripolyphosphate is mixed for three minutes. The amount of neutralized fatty alcohol sulfate paste with 25% to 35% moisture, contains an amount of water that will not translate to more than 2.5% moisture by weight in the final composition. A dose mixture of linear alkyl benzene sulfonic acid and sulfuric acid which have been pre-mixed for 1-1.5 minutes is then added to the blender, being completely neutralized by the sodium carbonate in the seat of the blender. (The amount of sodium carbonate is at least an amount sufficient to neutralize the acids.) The materials are mixed for an additional 1-2 minutes after dosing. Once the neutralization reaction is completed, a non-liquid, thixotrophic binder such as coco monoethanolamide (CMEA) and other optional surfactants are added, followed by any additional optional components such as chelants. It is most preferable to use as raw materials, such materials which contain little moisture, so as not to exceed 3% total moisture in the finished product. The mixing can take from one minute to one hour, with the usual mixing time being from about five to ten minutes. As one of the last ingredients, the bleach agent is added to the mixture and then mixed for an additional one to five minutes. The blender mix is charged to a surge tank. The product is conveyed from the surge tank to the mill or refining plodder via a multi-worm conveyer.
After milling or preliminary plodding, the product is then conveyed to a double vacuum plodder, operating at high vacuum, e.g. 600 to 740 mm of mercury vacuum, so that entrapped air is removed. The product is extruded and cut to the desired bar length, and printed with the product brand name. The printed bar can be cooled, for example in a cooling tunnel, before it is wrapped, cased, and sent to storage.
Examples of the invention are set forth hereinafter by way of illustration and are not intended to be in any way limiting of the invention. BAR EXAMPLES
The invention is illustrated by the following non-limiting examples. All parts and percentages herein are by weight unless otherwise stated.
Various bar compositions (Examples A through E) can be made using the method described above.
A B C
(weight percent) Linear alkyl benzene sulfonate 6.5 6.5 6.5
Coco fatty alcohol sulfate 17.6 17.6 18.6
Soda Ash 14 14 15
Sulfuric acid 2.5 2.5 2.5
Sodium Tripolyphosphate 11.6 11.6 11.6
Calcium carbonate 39 37.75 27
Zeolite 1 0 1
Coco fatty alcohol 1 1 1
Tiθ2 1 1 1
Perborate Monohydrate 2.25 4.5 10 coco monoethanolamide 1.2 2.0 4
Fluorescent agents 0.2 0.2 0.2
Substituted methyl cellulose 0.5 0.5 0.5
Perfume 0.35 0.35 0.35
Moisture (final comp.) 3.0 1.37 1.3
Diethylenetriamine penta 0.9 0.9 0.9
Other conventional ingredients Balance Balance Balance
100 100 100
(weight percent) 1
Linear alkyl benzene sulfonate 6.5 21.5
Coco fatty alcohol sulfate 18.9 0
Soda Ash 14 15
Sulfuric acid 2.5 2.5
Sodium Tripolyphosphate 11.6 12
Calcium carbonate 17 25
Sodium Sulfate 0 3
Magnesium Sulfate 0 1.5
Sodium Silicate 0 3.3
Talc 0 10
Coco fatty alcohol 1 1
Tiθ2 1 1
Perborate Monohydrate 15 5
Protease enzyme 0.0 0.08 coco monoethanolamide 0 2.0
Polyethylene Glycol(Mol. Wt. 5000) 10 0
Fluorescent agents 0.2 0.2
Substituted methyl cellulose 0.5 1.4
Perfume 0.35 0.35
Moisture (final comp.) 2.8 2.3
Other conventional ingredients Balance Balance
100 100
Claims
1. A laundry detergent bar composition comprising:
(a) from about 0.5% to about 60% anionic synthetic detergent surfactant;
(b) from about 0.10% to about 60% bleach agent;
(c) no more than about 3.5% moisture in the finished bar composition; and (d) from about 0.1% to about 10% non-liquid, thixotrophic binding agents.
2. A bar composition according to Claim 1, comprising from about 0.5% to about 3.4% moisture in the finished bar composition.
3. A bar composition according to Claim 2, wherein the binding agent is selected from the group consisting of Cg-Cig fatty acid mono- and di-alkanol amides, wherein the alkanols are methanol, ethanol, and propanol, polyethylene glycol, and precipitated silica, and mixtures thereof.
4. A bar composition according to Claim 3, wherein the bleach agent is sodium perborate monohydrate.
5. A bar composition according to Claim 4, comprising from about 0.5% to about 5% ofthe non-liquid, thixotrophic binding agent.
6. A laundry detergent bar composition comprising:
(a) from about 10% to about 30% anionic synthetic surfactant selected from the group consisting of Cjo-18 linear alkyl benzene sulfonates, Ciø.jg alkyl sulfates, and mixtures thereof, (b) from about 5% to about 25% of an alkali metal polyphosphate selected from the group consisting of tripolyphosphate and pyrophosphate,
(c) from about 1% to about 20% perborate bleach,
(d) from about 0.5% to about 3.4% moisture in the finished bar composition, and
(e) from about 0.5% to about 5% of a non-liquid, thixotrophic binding agent selected from the group consisting of Cβ-C 18 fatty acid mono- and di-alkanol amides, wherein the alkanols are methanol, ethanol, and propanol, polyethylene glycol, and precipitated silica, and mixtures thereof.
7. A bar composition according to Claim 6, wherein the perborate bleach is sodium perborate monohydrate.
8. A bar composition according to Claim 7, wherein the binder is coco monoethanolamide.
9. A process for making the bar composition of Claim 1 , which comprises:
(a) mixing a dry form and a neutralized paste form of a sodium salt of fatty alcohol sulfate in the presence of sodium carbonate, and a polyphosphate builder,
(b) reacting alkyl benzene sulfonic acid with the mixture in (a), such that the acid is completely neutralized by the sodium carbonate,
(c) adding a non-liquid, thixotrophic binding agent and optional components, and
(d) milling and plodding the mixture of (c) to form bars, wherein the total amount of moisture in the components added in Steps (a) through (c) is no more than about 3.5% ofthe moisture formed in (c).
10. A process for making the bar composition of Claim 6, which comprises: (a) mixing a dry form and a neutralized paste form of a sodium salt of fatty alcohol sulfate in the presence of sodium carbonate and sodium tripolyphosphate,
(b) reacting alkyl benzene sulfonic acid with the mixture in (a), such that the acid is completely neutralized by the sodium carbonate,
(c) adding a non-liquid, thixotrophic binding agent selected from the group consisting of Cg-Cig fatty acid alkanol amide, polyethylene glycol and precipitated silica, and mixtures thereof, and optional components, and
(d) milling and plodding the mixture of (c) to form bars, wherein the total amount of moisture in the components added in Steps (a) through (c) is no more than about 3.5% ofthe moisture formed in (c).
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US1996/007166 WO1997044434A1 (en) | 1996-05-17 | 1996-05-17 | Low moisture laundry detergent bar with improved bleach stability |
CO97025771A CO5021160A1 (en) | 1996-05-17 | 1997-05-14 | DETERGENT BAR COMPOSITIONS FOR LAUNDRY WITH IMPROVED WHITENING STABILITY AND PROCESS FOR DEVELOPMENT |
IDP971635A ID17192A (en) | 1996-05-17 | 1997-05-16 | WASHING DETERGENT STEMS WITH LOW MOVEMENT LEVELS WITH IMPROVED WHITE BLEACHING STABILITY |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/US1996/007166 WO1997044434A1 (en) | 1996-05-17 | 1996-05-17 | Low moisture laundry detergent bar with improved bleach stability |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997044434A1 true WO1997044434A1 (en) | 1997-11-27 |
Family
ID=22255118
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1996/007166 WO1997044434A1 (en) | 1996-05-17 | 1996-05-17 | Low moisture laundry detergent bar with improved bleach stability |
Country Status (3)
Country | Link |
---|---|
CO (1) | CO5021160A1 (en) |
ID (1) | ID17192A (en) |
WO (1) | WO1997044434A1 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999020734A1 (en) * | 1997-10-23 | 1999-04-29 | The Procter & Gamble Company | Laundry bars having improved physical properties |
WO1999020731A1 (en) * | 1997-10-23 | 1999-04-29 | The Procter & Gamble Company | Laundry bars having improved bleach stability |
WO1999020733A1 (en) * | 1997-10-23 | 1999-04-29 | The Procter & Gamble Company | Laundry bars having improved physical properties |
WO2000017308A1 (en) * | 1998-09-23 | 2000-03-30 | The Procter & Gamble Company | Laundry detergent bar composition containing peroxygen bleach |
WO2000017312A1 (en) * | 1998-09-23 | 2000-03-30 | The Procter & Gamble Company | A laundry detergent bar composition containing a peroxygen bleach |
US6407054B2 (en) | 1999-12-01 | 2002-06-18 | Kao Corporation | Surfactant composition |
EP1405899A1 (en) * | 2002-10-02 | 2004-04-07 | Cognis Iberia, S.L. | Solid detergents |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2172300A (en) * | 1985-03-14 | 1986-09-17 | Unilever Plc | Laundry bars |
GB2205580A (en) * | 1987-06-04 | 1988-12-14 | Procter & Gamble | Detergent bars |
EP0711827A2 (en) * | 1994-11-14 | 1996-05-15 | Unilever Plc | Tablet detergent compositions |
-
1996
- 1996-05-17 WO PCT/US1996/007166 patent/WO1997044434A1/en active Application Filing
-
1997
- 1997-05-14 CO CO97025771A patent/CO5021160A1/en unknown
- 1997-05-16 ID IDP971635A patent/ID17192A/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2172300A (en) * | 1985-03-14 | 1986-09-17 | Unilever Plc | Laundry bars |
GB2205580A (en) * | 1987-06-04 | 1988-12-14 | Procter & Gamble | Detergent bars |
EP0711827A2 (en) * | 1994-11-14 | 1996-05-15 | Unilever Plc | Tablet detergent compositions |
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO1999020734A1 (en) * | 1997-10-23 | 1999-04-29 | The Procter & Gamble Company | Laundry bars having improved physical properties |
WO1999020731A1 (en) * | 1997-10-23 | 1999-04-29 | The Procter & Gamble Company | Laundry bars having improved bleach stability |
WO1999020733A1 (en) * | 1997-10-23 | 1999-04-29 | The Procter & Gamble Company | Laundry bars having improved physical properties |
WO1999020732A1 (en) * | 1997-10-23 | 1999-04-29 | The Procter & Gamble Company | Laundry bars having improved physical properties |
WO2000017308A1 (en) * | 1998-09-23 | 2000-03-30 | The Procter & Gamble Company | Laundry detergent bar composition containing peroxygen bleach |
WO2000017312A1 (en) * | 1998-09-23 | 2000-03-30 | The Procter & Gamble Company | A laundry detergent bar composition containing a peroxygen bleach |
US6407054B2 (en) | 1999-12-01 | 2002-06-18 | Kao Corporation | Surfactant composition |
EP1405899A1 (en) * | 2002-10-02 | 2004-04-07 | Cognis Iberia, S.L. | Solid detergents |
Also Published As
Publication number | Publication date |
---|---|
CO5021160A1 (en) | 2001-03-27 |
ID17192A (en) | 1997-12-11 |
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