WO1998053040A1 - Detergents a lessive en pains ayant des proprietes de moussage et des proprietes physiques ameliorees - Google Patents

Detergents a lessive en pains ayant des proprietes de moussage et des proprietes physiques ameliorees Download PDF

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Publication number
WO1998053040A1
WO1998053040A1 PCT/US1997/008869 US9708869W WO9853040A1 WO 1998053040 A1 WO1998053040 A1 WO 1998053040A1 US 9708869 W US9708869 W US 9708869W WO 9853040 A1 WO9853040 A1 WO 9853040A1
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WIPO (PCT)
Prior art keywords
metal compound
mixtures
magnesium
synthetic detergent
surfactant
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PCT/US1997/008869
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English (en)
Inventor
Ganapathy Venkata Ramanan
Jerome Macaisa Castro
Dean Larry Duval
Teddy Go. Monroy
Eric San Jose Robles
Johannson Jimmy Tee
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The Procter & Gamble Company
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Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to PCT/US1997/008869 priority Critical patent/WO1998053040A1/fr
Priority to AU31426/97A priority patent/AU3142697A/en
Publication of WO1998053040A1 publication Critical patent/WO1998053040A1/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
    • 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
    • C11D1/16—Sulfonic acids or sulfuric acid esters; Salts thereof derived from divalent or polyvalent alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/29—Sulfates of polyoxyalkylene ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D3/16—Organic compounds
    • C11D3/168—Organometallic compounds or orgometallic complexes

Definitions

  • the present invention relates to detergent bars containing synthetic detergents and builder. More specifically, it relates to a synthetic laundry bar with improved sudsing and improved physical properties.
  • 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. Patent 3,178,370, Okenfuss, issued April 13, 1965; and Philippine Patent 13,778 to Anderson, issued September 23, 1980.
  • Laundry bar compositions are commonly used in countries having high humidity, such as in the Philippines, India, and Latin America. Consumers in these and other countries often launder clothes outside and therefore often store the laundry bars outside. Such bars which are stored at high humidity conditions tend to become soft and mushy when exposed from the wrapper. Although not intended to be limited by theory, the bars tend to absorb moisture in such high humidity conditions. It is therefore desired that bars maintain an acceptable hardness level at all times.
  • a common anionic surfactant used in laundry bar compositions is linear alkyl benzene sulfonate (LAS).
  • LAS linear alkyl benzene sulfonate
  • Bar compositions comprising high levels of LAS and/or other synthetic anionic surfactants are soft and do not possess desirable physical properties. Because the bar must be sufficiently hard to rub directly against clothes, soft and mushy bars are unacceptable to consumers. Soft and mushy bars also easily deform during use; such a characteristic is also unpopular with users. It is therefore also desired that bars maintain an acceptable structural integrity at all times.
  • Bars are used for more than one wash load. After one use, the bar is stored (usually outside) and subsequently reused. Bars which have been previously moistened and used in a wash may not dry adequately after use, especially in high humidity conditions. Although not intending to be limited by theory, the bars not only stay wet and mushy after use, but they may continue to absorb additional moisture from high humidity conditions of storage after use. It is therefore desired that the bars dry quickly so as to avoid this problem. Synthetic detergents are also characterized by low sudsing levels.
  • Acceptable sudsing levels are highly desired by consumers because suds are used as a visual gauge as to the amount of detergent used. Without acceptable sudsing levels in bars, the user may use too much or too little detergent. At the same time, because the consumer of this type of product usually associates good cleaning performance with high sudsing, it is desirable to maintain high sudsing characteristics when formulating laundry bars.
  • the present invention is directed to a built synthetic detergent bar containing: a. from about 0.5% to about 60% of a metal-surfactant complex, wherein, i. the metal-surfactant complex is formed by reacting an active acid surfactant with a metal compound, wherein ii. the metal compound comprises at least about 10% of a polyvalent metal compound; b. an effective amount of moisture present during the reaction of (a)(i); c. from about 3% to about 60% builder; and d. other detersive ingredients.
  • Alkali earth metals refers to metals of Group IIA of the periodic table.
  • Alkali metals refers to metals of Group IA of the periodic table.
  • Alkyl refers to the alkyl portion of acyl groups. “Comprising” as used herein means that other steps and other ingredients which do not affect the end result can be added. This term encompasses the terms “consisting of and “consisting essentially of
  • a metal-surfactant complex is formed by reacting an active acid surfactant with a metal compound in the presence of an effective amount of moisture.
  • the resulting metal-surfactant complex is stable and results in surprisingly good physical properties when used in laundry detergent bars.
  • the amount of metal-surfactant complex useful herein is from about 0.5% to about 60%, preferably from about 15% to about 30%, and more preferably from about 19% to about 25% by weight of the finished bar composition.
  • the active acid surfactant useful herein in forming the metal-surfactant complex are the acid forms of anionic synthetic surfactants.
  • Examples of such an active acid surfactant include the acid forms 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.
  • acid forms of those obtained by sulfating the higher alcohols (C8-18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; the acid forms of alkyl benzene 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. Patent 2,220,099 to Guenther et al, issued November 5, 1940, and U.S. Patent 2,477,383 to Lewis, issued July 26, 1949.
  • HLAS linear straight chain alkyl benzene sulfonates
  • LAS and other carbon chain based compounds herein are abbreviated according to the average alkyl group length.
  • LAS with an average chain length of 12 carbon atoms is abbreviated as C-12 LAS, even though it contains a distribution of LAS molecules with alkyl groups of differing lengths.
  • C- ⁇ o-18 LAS indicates that groups of LAS molecules with chain lengths averaging from 10 carbon atoms to those groups of LAS molecules with chain lengths averaging from 18 carbon atoms, inclusive, are preferred herein.
  • an active acid surfactant suitable for use herein are the acid forms of alkyl glyceryl ether sulfonates (HAES), especially those ethers of higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfonates and sulfates; and acid forms of alkyl ethylene oxide ether sulfates containing about 1 to about 10 units of ethylene oxide per molecule and wherein the alkyl group contains from about 10 to about 20 carbon atoms.
  • HAES alkyl glyceryl ether sulfonates
  • a suitable active acid surfactant includes the water soluble acids 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 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 acids of olefin and paraffin sulfonates containing from about 12 to 20 carbon atoms; and acids of 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.
  • a preferred active acid surfactant are the acids of C ⁇ ⁇ o-18 a,k y' sulfates (AS), C- ⁇ o-18 linear alkyl benzene sulfonates (LAS), C10-14 alkyl glyceryl ether sulfonates (AES), and mixtures thereof.
  • AS C ⁇ ⁇ o-18 a,k y' sulfates
  • LAS C- ⁇ o-18 linear alkyl benzene sulfonates
  • AES C10-14 alkyl glyceryl ether sulfonates
  • the weight ratio of active acid surfactant to metal compound varies greatly according to the type of active acid surfactant, the metal compound, and their respective molecular weights.
  • Metal Compound A metal compound suitable for use herein in forming the metal-surfactant complex include water soluble polyvalent metal compounds such as alkali earth metals, water soluble monovalent metal compounds such as the alkali metal compounds, other metal compounds capable of reacting with the active acid surfactant to form a metal-surfactant complex, and mixtures thereof.
  • the active acid surfactant is substantially completely reacted with the metal compound. Therefore, the amount of metal compound is dependent upon the amount of active acid surfactant, the type of metal compound, and the reaction itself. For example, in a neutralization reaction, although excess metal compound can be used, the amount of metal compound should be at least stoichiometrically sufficient to substantially completely neutralize the active acid surfactant.
  • the reaction of the active acid surfactant with the metal compound can be for example, a neutralization type reaction, a caustic neutralization reaction, or anion exchange reaction, depending upon the type of metal compound used.
  • the types of reactions described are non-limiting.
  • the metal compound must contain at least about 10% polyvalent metal compound, preferably from about 20% to about 100%, and more preferably from about 33% to about 70% by weight of the total metal compound used to form the metal- surfactant complex.
  • a polyvalent metal compound is preferred.
  • the types of polyvalent metal compound useful herein includes water soluble salts of the alkali earth metals, water soluble alkali earth metal compounds, water soluble polyvalent metal salts, water soluble polyvalent metal compounds, and mixtures thereof.
  • the metal cation of the polyvalent metal compound possess a charge of from about +2 to about +3.
  • a preferred polyvalent metal compound of the invention include calcium chloride, calcium hydroxide, calcium sulfate, magnesium bicarbonate, magnesium carbonate, magnesium chloride, magnesium hydroxide, magnesium sulfate, and mixtures thereof.
  • the polyvalent metal compound can react with the active acid surfactant in a variety of ways so as to form the metal-surfactant complex. Compounds such as magnesium hydroxide, calcium hydroxide, and other strong reducing agents can react with the active acid surfactant via caustic neutralization.
  • Magnesium bicarbonate, magnesium carbonate, and other typical neutralizing agents can react with the active acid surfactant via common neutralization reactions, while polyvalent metal sulfates, chlorides, and others can react with the active acid surfactant via ion exchange reactions.
  • the metal compound can also optionally contain a monovalent metal compound. Accordingly, if present, the monovalent metal compound must be less than about 90% of the metal compound by weight, preferably from about 0% to about 80%, and more preferably from about 30% to about 66%.
  • a preferred monovalent metal compound useful herein is a water soluble alkali metal compound which can react with the active acid surfactant when in the presence of moisture. Preferably, the monovalent metal compound reacts with the active acid surfactant via a neutralization or a caustic neutralization reaction. Examples of a monovalent metal compound useful herein are potassium compounds, sodium compounds, and mixtures thereof. Accordingly, a preferred monovalent metal compound of the invention includes potassium bicarbonate, potassium carbonate, potassium hydroxide, sodium bicarbonate, sodium carbonate, sodium hydroxide, and mixtures thereof.
  • An effective amount of moisture should be present to enhance the reaction between the active acid surfactant and the metal compound.
  • This moisture can be present either as free water which is added to the reaction mixture or as moisture which is already present with the reactants.
  • the effective amount of moisture present during the reaction step which forms the metal-surfactant complex should be at levels less than about 5%, preferably less than about 2%, and more preferably from about 0.5% to about 1%, by weight of the finished bar composition. Additional moisture may be added to the bar formulation after the formation of the metal-surfactant complex is complete. This additional moisture may, for example, be added when other detersive ingredients are added to the formulation.
  • Examples of a builder useful herein are the water soluble alkali metal salts of phosphates, pyrophosphates, orthophosphates, tripolyphosphates, higher polyphosphates, and mixtures thereof.
  • a preferred builder is a phosphate builder such as water soluble alkali metal salts of tripolyphosphates, and a mixture of tripolyphosphates and pyrophosphates.
  • Specific preferred examples of a builder useful herein include the sodium tripolyphosphates (STPP), tetra sodium pyrophosphates (TSPP), and mixtures thereof.
  • the laundry bars of the invention contain from about 3% to about 60%, preferably from about 5% to about 50%, more preferably from about 10% to about 30% builder, by weight of the total bar composition.
  • the bars of the present invention may optionally contain in addition to phosphate builders, non-phosphate builders.
  • a non- phosphate builder such as inorganic detergency builders, include the 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 a builder useful herein include polycarboxylates. Co-polymers of acrylic acid and maleic acid are also preferred in the subject compositions as auxiliary builders.
  • the detergent bars of the present invention can also contain among their other detersive ingredients additional optional surfactants in addition to the anionic synthetic detergent surfactants used to form the metal-surfactant complex described above.
  • additional optional surfactants can include additional anionic surfactants such as those used to form the metal- surfactant complex, as well as other anionic, cationic, nonionic, zwitterionic, and amphoteric surfactants.
  • Amine oxide surfactants can also be optionally included herein.
  • Amine oxides are excellent co-surfactants that may be used in conjunction with the present invention.
  • Preferred types are C-12- 18 amine oxides, preferably C14 amine oxides. 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%.
  • 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, if present, will preferably be present at from about 0.5% to about 5% of the laundry detergent bar.
  • 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 about 10,000, and ethoxylated mono and polyamines, and quaternary salts thereof. If included, these compounds can be at levels up to about 5%, preferably about 0.1-1%.
  • the detergent composition can optionally contain a polyamine soil release agent related to modified polyamines.
  • a polyamine soil release agent related to modified polyamines.
  • Preferred polyamines comprise backbones that can be either linear or cyclic.
  • the polyamine backbones can also comprise polyamine branching chains to a greater or lesser degree.
  • the polyamine backbones are modified in such a manner that each nitrogen of the polyamine chain is thereafter described in terms of a unit that is substituted, quatemized, oxidized, or combinations thereof.
  • the preferred polyamine soil release agents that comprise the backbone of the compounds 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 to Dickinson, issued May 14, 1957, which describes the preparation of PEA's.
  • Preferred amine polymer backbones comprise R units that are C2 alkylene
  • PEI's polyethylenimines
  • Preferred PEI's have at least moderate branching, that is the ratio of m to n is less than 4:1 , however 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: wherein m and n are the same as defined herein above.
  • Preferred PEI's, prior to modification will have a molecular weight greater than about 200 daltons.
  • the relative proportions of primary, secondary and tertiary amine units in the polyamine backbone will vary, depending on the manner of preparation.
  • Each hydrogen atom attached to each nitrogen atom of the polyamine backbone chain represents a potential site for subsequent substitution, quaternization or oxidation.
  • polyamines can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.
  • a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.
  • Specific methods for preparing these polyamine backbones are disclosed in U.S. Patent 2,182,306 to Ulrich et al., issued December 5, 1939; U.S. Patent 3,033,746 to Mayle et al., issued May 8, 1962; U.S. Patent 2,208,095 to Esselmann et al., issued July 16, 1940; U.S. Patent 2,806,839 to Crowther, issued September 17, 1957; and U.S. Patent 2,553,696 to Wilson, issued May 21 , 1951.
  • 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.
  • Bleach agents in the detergent composition when included, are 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.
  • Bleach agents useful herein are those that encompass 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 to Hartman, issued November 20, 1984, U.S. Patent Application 740,446 to Burns et al, filed June 3, 1985, European Patent Application 0,133,354 to Banks et al, published February 20, 1985, and U.S. Patent 4,412,934 to 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., OXONETM, manufactured commercially by DuPont
  • OXONETM 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 to Holcombe et al, issued July 5, 1977. 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 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, and urea peroxyhydrate. 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 the 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 copper, 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 copper, iron, manganese, zinc and aluminum.
  • Preferred cations include iron, manganese, copper, 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%, and even more preferably from about 0.5% to about 1.0%.
  • Another optional component of the laundry bar is fatty alcohol having an alkyl chain of 8 to 22 carbon atoms, 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 alcohols, if any, are present in the laundry bar at up to a level of 10%, preferably from about 0.75% to about 6%, more 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.
  • a preferred DTI ingredient includes polymeric DTI materials capable of binding fugitive dyes to prevent them from depositing on the fabrics, and decolorization DTI materials capable of decolorizing the fugitive 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 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 optional component in the laundry bar is the 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, and 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. 0,133,804 B to Burckett and Busch, issued October 18, 1989; complexes of such amines with phosphate esters of the formula RsO-P(O)(OH)-OR9 and HO-P(O)(OH)-OR9, wherein Re and Rg are independently C1 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 B to De Buzzaccarini
  • 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-anilino-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%.
  • Another useful optional component of the subject compositions are detergent enzymes. Particularly preferred are lipase, protease, amylase, cellulase, and mixtures thereof. Enzymes, if included, are typically at levels up to about 5%, preferably about 0.5-3%.
  • the detergent laundry bars of the present invention can be processed in conventional soap or detergent bar making equipment with some or all of the 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 the raw materials are mixed in the blender.
  • the active acid surfactant is reacted with the metal compound in the presence of an effective amount of moisture.
  • the metal-surfactant complex easily forms when the mixture (at the time of the reaction) is substantially free of competing reactants.
  • the metal-surfactant complex can be either pre-formed and then added as an additive to the bar formulation, or it can be made in the blender seat itself
  • a builder of the phosphate and/or non-phosphate variety, can be added next in the seat before the active acid surfactant-metal compound reaction takes place, or after the other detersive ingredients. Then other detersive ingredients, such as optional surfactants, followed by any additional optional other detersive ingredients such as chelants are added.
  • 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 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/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.
  • the preferred bars of the invention have improved sudsing and physical properties such as improved hardness, low bar smear, and decreased drying time.
  • the bars which include a metal-surfactant complex created with an active acid surfactant and a metal compound with at least 10% of a polyvalent metal compound possess significantly better sudsing characteristics than conventional bars lacking this complex.
  • a preferred 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.
  • a cone 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.
  • Yet another physical property of consumer relevance is the rate of drying of the bar after usage and storage under high humidity conditions.
  • a preferred method to measure this property is to place a bar with dimensions of 75mm x 55mm with one of its large flat surface in contact with about 20 ml of water in a petri dish for 2 hours and then scraping the gel formed. This procedure is repeated for a second cycle except that the gel is not scraped off from the bar surface after the second contact with water.
  • the bar is then stored under 30 degrees C and 88% Relative Humidity for 24 hours and then the bar surface which was exposed to the water is graded for dryness on a 1-5 grading scale by experienced operators as illustrated below:
  • the desired dryness grade is typically between 3.5-5.0.
  • Preferred bars of the present invention have a dryness grade within this range.
  • a preferred laundry bar composition is made by the following method: 2.71 parts magnesium carbonate, a polyvalent metal compound, is added to a mixer containing 19.13 parts of HLAS, an active acid surfactant. To this, 1 part moisture as free water is added to the mixer and the resulting slurry is mixed for 1-5 minutes. A metal-surfactant complex is thus formed by the neutralization of the active acid surfactant (HLAS) by the polyvalent metal compound (MgCO ⁇ ). Then, a chelant, if present is added, followed by other optional surfactants, STPP, and any other detersive ingredients. The total mixing time can take up to about one hour, with the usual mixing time being from about five to twenty minutes.
  • bleach and enzymes can be 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 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.
  • Another preferred laundry bar composition is made by the following method: 1.8 parts of magnesium carbonate, a polyvalent metal compound, and
  • the bar formulation is then further processed according to the process described in Example 1.
  • Example 3 Another preferred laundry bar composition is made by the method of
  • Example 1 except that the HLAS is separately neutralized by a stoichiometric amount of caustic NaOH, instead of magnesium carbonate.
  • the resulting surfactant paste is then modified by adding STPP and/or sodium silicate and then added as a paste mixture to the blender.
  • the bar formulation is then further processed according to the process described in Example 1.
  • Another preferred laundry bar composition is made by the method of Example 1 , except that the HLAS is separately neutralized by a stoichiometric amount of caustic Mg(OH)2, instead of magnesium carbonate.
  • the resulting surfactant paste is then modified by adding STPP and/or sodium silicate and then added as a paste mixture to the blender.
  • the bar formulation is then further processed according to the process described in Example 1.
  • Another preferred laundry bar composition is made by the method of
  • Example 1 except that the HLAS is separately neutralized by a stoichiometric amount of caustic Ca(OH)2, instead of magnesium carbonate.
  • the resulting surfactant paste is then modified by adding STPP and/or sodium silicates and then added as a paste mixture to the blender.
  • the bar formulation is then further processed according to the process described in Example 1.

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  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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Abstract

Cette invention se rapporte à un détergent en pain synthétique avec adjuvant, qui contient un complexe métal/tensioactif. On forme ce complexe métal/tensioactif en faisant réagir un tensioactif acide avec un composé métallique en présence d'une quantité suffisante d'eau.
PCT/US1997/008869 1997-05-22 1997-05-22 Detergents a lessive en pains ayant des proprietes de moussage et des proprietes physiques ameliorees WO1998053040A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/US1997/008869 WO1998053040A1 (fr) 1997-05-22 1997-05-22 Detergents a lessive en pains ayant des proprietes de moussage et des proprietes physiques ameliorees
AU31426/97A AU3142697A (en) 1997-05-22 1997-05-22 Laundry bars with improved sudsing and improved physical properties

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1997/008869 WO1998053040A1 (fr) 1997-05-22 1997-05-22 Detergents a lessive en pains ayant des proprietes de moussage et des proprietes physiques ameliorees

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WO1998053040A1 true WO1998053040A1 (fr) 1998-11-26

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000005333A1 (fr) * 1998-07-23 2000-02-03 The Procter & Gamble Company Procede de fabrication de tablettes de detergent a lessive presentant des proprietes physiques ameliorees
WO2000005334A1 (fr) * 1998-07-23 2000-02-03 The Procter & Gamble Company Composition de detergent a lessive
WO2001042418A1 (fr) * 1999-12-08 2001-06-14 Unilever Plc Composition de detergent en pain ameliore
WO2001042419A1 (fr) * 1999-12-08 2001-06-14 Unilever Plc Composition amelioree de detergent en pain et procede de production
US6352966B1 (en) 2000-05-19 2002-03-05 Albemarle Corporation Cleansing bars
US6660699B2 (en) 2001-09-28 2003-12-09 Unilever Home & Personal Care Usa Toilet bar having a latent acidifier
US6809070B2 (en) 2001-09-28 2004-10-26 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Toilet bar having a latent acidifier
US7662761B2 (en) 2005-05-31 2010-02-16 Conopco, Inc. Soap bars comprising insoluble multivalent ion soap complexes

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US3178370A (en) * 1963-02-27 1965-04-13 Procter & Gamble Milled detergent bar
PH13778A (en) * 1975-05-30 1980-09-23 Procter & Gamble Synthetic detergent laundry composition
US4705644A (en) * 1986-03-06 1987-11-10 Colgate Palmolive Company Alpha-sulfo-higher fatty acid-lower alcohol ester- and amide-based detergent laundry bars and process for manufacture thereof
DE3640541A1 (de) * 1986-11-27 1988-06-01 Henkel Kgaa Stueckfoermiges waschmittel
US4806273A (en) * 1986-03-06 1989-02-21 Colgate-Palmolive Company Breakage resistant higher fatty alcohol sulfate detergent laundry bars
US5089174A (en) * 1989-01-19 1992-02-18 The Procter & Gamble Company Laundry detergent bars free of C12 -C18 fatty acids and containing an alkylbenzene sulfonate, an alkyl sulfonate and a fatty alcohol
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

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3178370A (en) * 1963-02-27 1965-04-13 Procter & Gamble Milled detergent bar
PH13778A (en) * 1975-05-30 1980-09-23 Procter & Gamble Synthetic detergent laundry composition
US4705644A (en) * 1986-03-06 1987-11-10 Colgate Palmolive Company Alpha-sulfo-higher fatty acid-lower alcohol ester- and amide-based detergent laundry bars and process for manufacture thereof
US4806273A (en) * 1986-03-06 1989-02-21 Colgate-Palmolive Company Breakage resistant higher fatty alcohol sulfate detergent laundry bars
DE3640541A1 (de) * 1986-11-27 1988-06-01 Henkel Kgaa Stueckfoermiges waschmittel
US5089174A (en) * 1989-01-19 1992-02-18 The Procter & Gamble Company Laundry detergent bars free of C12 -C18 fatty acids and containing an alkylbenzene sulfonate, an alkyl sulfonate and a fatty alcohol
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

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000005333A1 (fr) * 1998-07-23 2000-02-03 The Procter & Gamble Company Procede de fabrication de tablettes de detergent a lessive presentant des proprietes physiques ameliorees
WO2000005334A1 (fr) * 1998-07-23 2000-02-03 The Procter & Gamble Company Composition de detergent a lessive
WO2001042418A1 (fr) * 1999-12-08 2001-06-14 Unilever Plc Composition de detergent en pain ameliore
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
US6492321B2 (en) 1999-12-08 2002-12-10 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Detergent bar comprising amorphous silica and salt of carboxylic and/or sulphonic acid
US6352966B1 (en) 2000-05-19 2002-03-05 Albemarle Corporation Cleansing bars
US6660699B2 (en) 2001-09-28 2003-12-09 Unilever Home & Personal Care Usa Toilet bar having a latent acidifier
US6809070B2 (en) 2001-09-28 2004-10-26 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. Toilet bar having a latent acidifier
EP1900802A2 (fr) 2001-09-28 2008-03-19 Unilever Plc Savon de toilette renfermant un acidifiant latent
US7662761B2 (en) 2005-05-31 2010-02-16 Conopco, Inc. Soap bars comprising insoluble multivalent ion soap complexes

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