WO2000005333A1 - Procede de fabrication de tablettes de detergent a lessive presentant des proprietes physiques ameliorees - Google Patents

Procede de fabrication de tablettes de detergent a lessive presentant des proprietes physiques ameliorees Download PDF

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Publication number
WO2000005333A1
WO2000005333A1 PCT/US1998/015348 US9815348W WO0005333A1 WO 2000005333 A1 WO2000005333 A1 WO 2000005333A1 US 9815348 W US9815348 W US 9815348W WO 0005333 A1 WO0005333 A1 WO 0005333A1
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WO
WIPO (PCT)
Prior art keywords
bar
divalent metal
mixtures
neutralized
bar composition
Prior art date
Application number
PCT/US1998/015348
Other languages
English (en)
Inventor
Rohan Govind Murkunde
Richard Tugao Lasap
Darius Garcia Chavez
Maricel Legaspi Villalobos
Vinay Madhav Shenai
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to PCT/US1998/015348 priority Critical patent/WO2000005333A1/fr
Priority to AU85857/98A priority patent/AU8585798A/en
Publication of WO2000005333A1 publication Critical patent/WO2000005333A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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 ; Methods for using cleaning compositions
    • C11D11/04—Special methods for preparing compositions containing mixtures of detergents ; Methods for using cleaning compositions by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
    • 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
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/044—Hydroxides or bases
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • C11D3/062—Special methods concerning phosphates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/12—Water-insoluble compounds
    • C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2

Definitions

  • FIELD This invention relates to a process for making a laundry detergent bar composition containing phosphate materials.
  • 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; which have the appropriate level of sudsing; which are mild to the skin; and which have a pleasing odor and appearance.
  • Such laundry detergent bars are also well known in the art. It is known in the art to use or make a structuring system in the process for making a bar, so that the resultant bar has appropriate physical properties.
  • a common material used for such structuring system includes siliceous materials, such as aluminosilicate, silica, silicates, and clays.
  • the present invention is directed to a process for making a synthetic laundry detergent bar composition having the steps of providing a neutralized synthetic detergent active; adding a divalent metal compound to the neutralized active, wherein the divalent metal compound is selected from the group consisting of divalent metal oxides, chlorides, hydroxides, and mixtures thereof; and optionally, adding other optional components, and forming into bars; wherein the bar composition is substantially free of siliceous materials, and wherein the bar composition further comprises phosphate materials.
  • the present invention is directed to a process for making a synthetic laundry detergent bar composition having the steps of providing a neutralized detergent active; adding a divalent metal compound to the neutralized active, wherein the divalent metal compound is selected from the group consisting of divalent metal oxides, chlorides, hydroxides, and mixtures thereof; and optionally, adding other optional components, and forming into bars; wherein the bar composition is substantially free of siliceous materials, and wherein the bar composition further comprises phosphate materials.
  • the laundry detergent bars produced by the process of the present invention have improved physical properties. Improved physical properties include but are not limited to the following: appropriate bar hardness, reduced smearing, reduced mushiness, and improved overall appearance of the bar when both wet and dry.
  • a bar when is exposed to the wash water forms a creamy layer on the outside of the bar, so that when the consumer uses the bar, it is smooth to the hands.
  • the bar is substantially free of siliceous materials
  • the bars made by the process of the present invention have good physical properties.
  • the bar formulation cost is decreased while still retaining good bar physical properties.
  • the detergent bars can be processed in conventional soap or detergent bar making equipment with some of all of the following key equipment: blender/mixer, mill or refining plodder, two-stage vacuum plodder, logo printer/cutter, cooling tunnel and wrapper.
  • the raw materials are mixed in the blender.
  • An acid surfactant such as alkyl benzene sulfonic acid
  • alkaline inorganic salts to complete neutralization, the amount of alkaline inorganic salt being at least sufficient to completely neutralize the acid.
  • neutralized surfactant is added in the blender.
  • the divalent metal compound is added to a neutralized detergent active.
  • the detergent active should be substantially neutralized so that any reaction between the divalent metal compound and detergent active can be minimized, or preferably, eliminated.
  • the phosphate material is also added to the mixer. If using an acid form of detergent active, substantially all of the phosphate material is preferably added before neutralization of the detergent active is substantially completed, and the divalent metal is added after neutralization. It is also acceptable to add part of the phosphate material before and part after the neutralization of the detergent active. If starting with an already neutralized detergent active, the phosphate material can be added at the same time, or after the addition of the divalent metal compound.
  • the divalent metal compound can be premixed with the phosphate material and then added to the neutralized detergent active.
  • the divalent metal compound in the form of a slurry or suspension, instead of adding it in a powder, or dry form.
  • the phosphate material and the divalent metal compound forms a complex which acts as a structurant in the bar matrix and therefore, improves the physical properties of the resultant bar composition.
  • Other optional components are then added to the mixture. Some of the optional components may be present in the mixture when the surfactant, divalent metal compound, and/or the phosphate material is added to the mixture.
  • the composition is substantially free of siliceous materials.
  • the mixing can take from one minute to one hour, with the usual mixing time being from about two to twenty 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 multiworm conveyor.
  • the product is then conveyed to a two-stage vacuum plodder, operating at high vacuum, e.g. 600 to 740 mm of mercury vacuum, so that entrapped air/gas 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.
  • Another preferred laundry bar composition is made by the following method: The raw materials are first mixed in a blender. Sodium carbonate and pre-neutralized CFAS is mixed for about 1-2 minutes, in order to make a mixed anionic LAS/Alky I Sulfate surfactant bar composition. This is followed by the addition of linear alkyl benzene sulfonic acid and sulfuric acid (if present in the formulation). The acids are then completely neutralized by the sodium carbonate in the seat of the blender. (The amount of sodium carbonate should be at least an amount sufficient to neutralize the acids.) Sodium tripolyphosphate is added before the acids are completely neutralized. The materials are mixed for an additional 1-2 minutes after dosing.
  • a chelant if present is added, followed by calcium oxide or calcium hydroxide and other optional surfactants, and any other additional optional components.
  • the mixing can take from one minute to one hour, with the usual mixing time being from about five to ten minutes.
  • bleach and enzymes are added to the mixture and then mixed for an additional one to five minutes.
  • the composition is substantially free of siliceous materials.
  • 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 conveyor.
  • the product is then conveyed to a two-stage 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.
  • the present invention employs a number of ingredients to provide a suitable laundry detergent bar product.
  • the detergent bars of the present invention contain detergent actives, or surfactants.
  • Typical detergent actives include anionic, nonionic, cationic, zwitterionic, and amphoteric surfactants.
  • Detergent actives can be included at levels of from about 5% to about 60%, preferably from about 15% to about 30%, and more preferably from about 20% to about 25%, by weight of the total bar composition.
  • the detergent active can be either an acid form, neutralized form, or mixtures thereof.
  • 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.
  • this group of synthetic surfactants are the sodium and potassium alkyl sulfates, especially those obtained by sulfating the higher alcohols (C ⁇ -i ⁇ 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 10 to 18, abbreviated as C10- 13 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. Mixtures of the above types of anionic surfactants are preferred.
  • preferred anionic surfactants are C-J O-1 8 l' near a ⁇ / ⁇ benzene sulfonates, C10-I 8 a ' kvl sulfates, and mixtures thereof.
  • One preferred composition comprises from about 10% to about 30% LAS, by weight of the total bar composition for a primarily LAS-surfactant based bar.
  • Another preferred composition comprises a mixture of LAS:alkyl sulfate in a ratio of from about 10:90 to about 50:50, preferably from about 20:80 to about 40:60.
  • anionic synthetic 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.
  • suitable anionic synthetic 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-1 -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.
  • Amine Oxides are excellent co-surfactants that may be used in alone or in addition to other detergent actives.
  • Preferred types are C12-C18 amine oxides, preferably C14. If included, the level of amine oxide in the final bar composition is from about 1 % to about 10%, preferably, from about 2% to about 5%.
  • anionic synthetic surfactants suitable for use herein are 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.
  • optional anionic synthetic 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-1 -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.
  • hydrotrope or mixture of hydrotropes, may 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% of the laundry detergent bar.
  • Divalent metal compound 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
  • the detergent bars of the present invention contain a divalent metal compound.
  • Divalent metal compounds can be included at levels of from about 0.1 % to about 50%, preferably 1 % to about 20%, more preferably from about 1 % to about 10%, by weight of the total bar composition.
  • Divalent metal compounds useful in the present invention include divalent metal oxides, chlorides, hydroxides, and mixtures thereof. Examples include calcium oxide, calcium chloride, calcium hydroxide, magnesium oxide, magnesium chloride, magnesium hydroxide, and mixtures thereof. Commercially available materials are useful for the process. Calcium oxide is a preferred divalent metal compound. Calcium oxide can be added as it is, or as calcium hydroxide. Calcium hydroxide can be either anhydrous or a hydrate. Similarly, other divalent metal oxides can be added in its hydroxide form, and can be either anhydrous or a hydrate.
  • the divalent metal compounds are preferably in a fine powder form, with preferably 95% of the material passing through Tyler 300 mesh.
  • the material preferably is white to off-white in color, free flowing and devoid of any odor.
  • Phosphate materials The detergent bars of the present invention contain a phosphate material. Phosphate materials can be included at levels of from about 5% to about 60%, preferably from about 5% to about 20%, by weight of the total bar composition. Phosphate materials useful in the present invention include phosphate, phosphonate, phosphoric acid, and mixtures thereof.
  • phosphate examples include water-soluble alkali-metal salts of phosphates, pyrophosphates, orthophosphates, tripolyphosphates, higher polyphosphates, and mixtures thereof.
  • Preferred phosphates include water- soluble alkali-metal salt of tripolyphosphate alone, or a mixture of tripolyphosphate and pyrophosphate.
  • Especially preferred examples of phosphate include sodium tripolyphosphates (STPP) and tetra sodium pyrophosphates (TSPP), and mixtures thereof.
  • Phosphoric acid can be added as orthophosphoric acid, or meta phosphoric acid or in the form of derivatives such as esters of the phosphoric acid.
  • Phosphoric anhydride can also be used as a phosphate material in the present invention.
  • Phosphonates which may be useful in the present invention include phosphonate chelants.
  • Such chelants include 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.
  • the bars of the present invention are substantially free of siliceous materials, preferably containing less than about 1 %, more preferably not containing any in the bar composition.
  • Siliceous materials include silica in finely divided form, silicates, polymeric silicates and aluminosilicates, and clays.
  • the composition can optionally contain in addition to the phosphate material, non-phosphate material, or non-phosphate detergent builder.
  • non-phosphate, inorganic detergency builders include water-soluble inorganic carbonate and bicarbonate salts.
  • the alkali metal (e.g., sodium and potassium) carbonates and bicarbonates are particularly useful herein.
  • Other specifically preferred examples of builders include polycarboxylates.
  • Sodium carbonate another optional ingredient, 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.
  • 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.
  • Soil suspending agents can be used. 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 Corp.
  • 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 %.
  • the bleach agent in the detergent composition when included, 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-nonylamino-6- oxoperoxycaproic acid as described in U.S. Patent 4,634,551 , issued January 6, 1987 to Burns 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
  • OXONE manufactured commercially by DuPont
  • Bleach agents other than oxygen bleach agents are also known in the 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.
  • An optional 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.
  • Another 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.
  • alkali cations such as sodium, lithium and potassium
  • alkali metal earth cations such as magnesium and calcium
  • heavy metal cations such as iron, manganese, zinc and aluminum.
  • Preferred cations include sodium, magnesium, zinc, and mixtures thereof.
  • 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%.
  • 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.
  • high-cut fatty alcohol 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.
  • 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 optional component in the laundry bar is a dye transfer inhibiting (DTI) ingredient to prevent diminishing of color fidelity and intensity in fabrics.
  • DTI dye transfer inhibiting
  • 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%.
  • a fabric softener component is a fabric softener component.
  • 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 R6 are independently C1 to C10 hydrocarbyl.
  • R4 is C5 to C22 hydrocarbyl
  • R5 and R6 are independently C1 to C10 hydrocarbyl.
  • One preferred amine is ditallowmethyl amine; complexes of such amines with fatty acid of the formula R7COOH, wherein R7 is Cg to C22 hydrocarbyl, as disclosed in EP No.
  • 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 sulfation and sulfonation processes, or it can be added separately.
  • Calcium carbonate also known as Calcarb
  • Filler materials are typically used, if included, at levels up to 40%, preferably from about 5% to about 25%.
  • Optical brighteners are also optional ingredients in laundry bars of the present invention. Preferred optical brighteners are diamino stilbene, distyrilbiphenyl-type optical brighteners.
  • Such brighteners are 4,4'-bis ⁇ [4-anilino-6-bis(2-hydoxyethyl) amino-1 ,3,5-trizin-2- yl]amino ⁇ stilbene-2,2'-disulfonic acid disodium salt, 4-4'-bis(2-sulfostyryl) biphenyl and 4,4'-bis[(4-aniiino-6-morpholino-1 ,3,5-triazin-2-yl) amino]stilbene-2,2'-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%.
  • 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 TINOLUS 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, cellulase, amylase, and mixtures thereof. Enzymes, if included, are typically at levels up to about 5%, preferably about 0.5-3%.
  • Another useful optional component which can be used as processing aids include glycerine and coconut monoethanol amide.
  • the detergent composition can optionally contain a polyamine soil release agent related to modified polyamines. See U.S. 5,565,145 issued October 15, 1996 to Watson et al.
  • Modified polyethyleneimine polymers may also be included herein. These modified polyethyleneimine polymers comprise backbones that can be either linear or cyclic. The polyamine backbones can also comprise polyamine branching chains to a greater or lesser degree. In general, the polyamine backbones described herein are modified in such a manner that each nitrogen of the polyamine chain is thereafter described in terms of a unit that is substituted, quaternized, oxidized, or combinations thereof.
  • Preferred modified polyethyleneimine polymers are generally polyalkyleneamines (PAA's), polyalkyleneimines (PAI's), preferably polyethyleneamine (PEA's), polyethyleneimines (PEI's), or PEA's or PEI's connected by moieties having longer R units than the parent PAA's, PAI's, PEA's or PEI's.
  • a common polyalkyleneamine (PAA) is tetrabutylenepentamine. PEA's are obtained by reactions involving ammonia and ethylene dichloride, followed by fractional distillation. The common PEA's obtained are triethylenetetramine (TETA) and teraethylenepentamine (TEPA).
  • the cogenerically derived mixture does not appear to separate by distillation and can include other materials such as cyclic amines and particularly piperazines. There can also be present cyclic amines with side chains in which nitrogen atoms appear. See U.S. Patent 2,792,372, Dickinson, issued May 14, 1957, which describes the preparation of PEA's.
  • Preferred amine polymer backbones comprise R units that are C2 alkylene (ethylene) units, also known as polyethyleneimines (PEI's).
  • Preferred PEI's have at least moderate branching, that is the ratio of m to n is less than
  • PEI's having a ratio of m to n of about 2:1 are most preferred.
  • Preferred backbones, prior to modification have the general formula:
  • the polyamine soil release agents of the present invention if included in the detergent composition is included from about 0.01% to about 5%; preferably about 0.3% to about 4%; more preferably about 0.5% to about 2.5%, by weight of the detergent composition.
  • the final bar composition should have no more than about 15% moisture.
  • the moisture level of the total bar composition 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 bars of the present invention have improved physical properties, including improved in-process and aged hardness of the bar as well as reduced solubility in water during washing. In addition, the bars of the present invention have improved cleaning benefits as well as mildness benefits.
  • the bars of the present invention are sufficiently hard.
  • a preferred test method measures bar hardness after three weeks of aging. Bars are aged for three weeks at 80°F/80 relative humidity (RH). To measure the bar hardness, a needle with a point angle of 43° attached to a force gauge (Control International, Lincolnwood, IL, USA) was forced onto the plane of the bar surface to a depth of 5.8 mm. A preferred bar hardness reading of laundry bar compositions using this test method is about 55-70 lbs. Bars of the present invention fall within the range.
  • Another method to measure bar hardness is to measure the penetration of a needle through the bar surface under a standard weight for 5 seconds using a cone penetrometer.
  • One such penetrometer is made by Associated Instrument Manufacturers India Pvt. Ltd. (Model number AIM 512).
  • the weight of the rod and the cone is 149 grams and an additional 50 gram weight is placed on the cone.
  • the penetration reading of a fresh bar made as per the present invention will typically be about 20-30 (1 /10 mm) and 15-20 (1 /10 mm) after 40 minutes. Bars aged about 3 days at ambient conditions will typically have a bar penetration reading of about 5-12 (1 /10 mm).
  • Another physical property of interest is the bar solubility in water.
  • One method of determining the bar solubility is to submerge a bar having the following dimensions 75mm x 55mm in 250 ml of water in a beaker for 2 hours, drying the bar at 60 deg. C for 2 hours and then weighing the bar.
  • the difference in weight should be about 5-20 grams for a 1 25 gram bar (1 2-1 6% of the original weight of the bar), more preferably 5-15 grams (4-12% of the original weight of the bar).
  • Example 1 In order to make 100 kg of finished product, about 6 kg dry flakes of neutralized NaCFAS (sodium salt of coconut fatty alcohol sulfate), 4 kg of sodium carbonate, 18 kg of sodium tripolyphosphate and 50 kg of sodium sulfate are added to the mixer.
  • the mixer used is a ploughshear kind of mixer (trade name: KM Mixer by Littleford Inc.).
  • the KM Mixer main shaft rpm is adjusted to 130.
  • Hot oil at 60°C is circulated around the jacket of the mixer to minimize any heat loss during the process.
  • the powders added are at ambient temperature.
  • the mixer is started and at the same time, about 1 1 kg of the neutralized NaCFAS paste is added to the mixer.
  • the paste temperature is in the range of 55-60°C.
  • the mixture is mixed for about 3 minutes.
  • about 7 kg of LAS (linear alkyl benzene sulfonate acid and 2.5 kg of sulfuric acid are added to the batch.
  • the mixture is further mixed for about 3 minutes. This is followed by the addition of 1 kg of C 12 coco fatty alcohol, 40 kg of calcium carbonate, and 3 kg of calcium hydroxide.
  • the mixture is mixed for about a minute. This is followed by the addition of optional components such as brighteners, anti-redepositton agents, soil release polymers, etc.
  • Perfume 0.35 0.35 0.35 polyethyleneimines 0.1 0 0.7

Abstract

L'invention concerne un procédé de fabrication d'une composition pour tablette de détergent à lessive synthétique consistant à fournir un principe actif détergent synthétique neutralisé; à ajouter un composé métallique divalent au principe actif neutralisé, composé qui est sélectionné dans le groupe formé d'oxydes, de chlorures, d'hydroxydes métalliques divalents et de leurs mélanges; à ajouter éventuellement d'autres composants facultatifs et à les transformer en tablettes. La composition est essentiellement exempte de matériaux siliceux et comprend des matériaux phosphatés. Les tablettes présentent des propriétés physiques améliorées telles qu'une dureté adéquate et des traces réduites.
PCT/US1998/015348 1998-07-23 1998-07-23 Procede de fabrication de tablettes de detergent a lessive presentant des proprietes physiques ameliorees WO2000005333A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/US1998/015348 WO2000005333A1 (fr) 1998-07-23 1998-07-23 Procede de fabrication de tablettes de detergent a lessive presentant des proprietes physiques ameliorees
AU85857/98A AU8585798A (en) 1998-07-23 1998-07-23 Process for making laundry detergent bars having improved physical properties

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1998/015348 WO2000005333A1 (fr) 1998-07-23 1998-07-23 Procede de fabrication de tablettes de detergent a lessive presentant des proprietes physiques ameliorees

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001042419A1 (fr) * 1999-12-08 2001-06-14 Unilever Plc Composition amelioree de detergent en pain et procede de production
US7022135B2 (en) 2001-08-17 2006-04-04 Medtronic, Inc. Film with highly porous vascular graft prostheses
CN100336891C (zh) * 2006-01-26 2007-09-12 哈尔滨市宏昌石油助剂有限公司 微乳胶及其制作方法

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2235205A (en) * 1989-08-10 1991-02-27 Unilever Plc Detergent laundry bars
WO1995007340A1 (fr) * 1993-09-09 1995-03-16 The Procter & Gamble Company Composition en barre contenant un tensioactif a base d'amide d'acides gras n-aryloxy polyhydroxy
WO1997036985A1 (fr) * 1996-03-29 1997-10-09 The Procter & Gamble Company Pain de detergent pour lessive, presentant une faible teneur en humidite et une stabilite d'enzyme amelioree
WO1998053040A1 (fr) * 1997-05-22 1998-11-26 The Procter & Gamble Company Detergents a lessive en pains ayant des proprietes de moussage et des proprietes physiques ameliorees

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2235205A (en) * 1989-08-10 1991-02-27 Unilever Plc Detergent laundry bars
WO1995007340A1 (fr) * 1993-09-09 1995-03-16 The Procter & Gamble Company Composition en barre contenant un tensioactif a base d'amide d'acides gras n-aryloxy polyhydroxy
WO1997036985A1 (fr) * 1996-03-29 1997-10-09 The Procter & Gamble Company Pain de detergent pour lessive, presentant une faible teneur en humidite et une stabilite d'enzyme amelioree
WO1998053040A1 (fr) * 1997-05-22 1998-11-26 The Procter & Gamble Company Detergents a lessive en pains ayant des proprietes de moussage et des proprietes physiques ameliorees

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001042419A1 (fr) * 1999-12-08 2001-06-14 Unilever Plc Composition amelioree de detergent en pain et procede de production
US6310016B1 (en) 1999-12-08 2001-10-30 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Detergent bar composition and manufacturing process comprising colloidal aluminum hydroxide phosphate complex
US7022135B2 (en) 2001-08-17 2006-04-04 Medtronic, Inc. Film with highly porous vascular graft prostheses
CN100336891C (zh) * 2006-01-26 2007-09-12 哈尔滨市宏昌石油助剂有限公司 微乳胶及其制作方法

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