WO1997042283A1 - Compositions pour detergents en barres - Google Patents

Compositions pour detergents en barres Download PDF

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Publication number
WO1997042283A1
WO1997042283A1 PCT/US1996/006273 US9606273W WO9742283A1 WO 1997042283 A1 WO1997042283 A1 WO 1997042283A1 US 9606273 W US9606273 W US 9606273W WO 9742283 A1 WO9742283 A1 WO 9742283A1
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WIPO (PCT)
Prior art keywords
units
mixtures
alkylene
formula
alkyl
Prior art date
Application number
PCT/US1996/006273
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English (en)
Inventor
Aimee Go Dy
Shulin Zhang
Uday Narendra Sheth
Original Assignee
The Procter & Gamble Company
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Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to PCT/US1996/006273 priority Critical patent/WO1997042283A1/fr
Priority to MA24578A priority patent/MA24159A1/fr
Publication of WO1997042283A1 publication Critical patent/WO1997042283A1/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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0094—High foaming compositions
    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C11D10/042—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on anionic surface-active compounds and soap
    • 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
    • C11D17/006—Detergents in the form of bars or tablets containing mainly surfactants, but no builders, e.g. syndet bar
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • 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
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3723—Polyamines or polyalkyleneimines
    • 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
    • C11D3/37—Polymers
    • C11D3/3792—Amine oxide containing polymers
    • 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

Definitions

  • the present invention relates to laundry bar compositions with excellent, sudsing, cleaning and soil suspending properties.
  • Synthetic laundry bars typically comprise a synthetic anionic surfactant such as the alkali metal salt of an alkylbenzene sulfonic acid or alkali metal salt of an alkyl sulfate and one or more alkaline builders such as alkali metal polyphosphates, carbonates or silicates. It is desired to remove a broad spectrum of soils and stains, and dispersants in the bar formulation are useful in suspending polar, highly charged, hydrophilic particles such as clay. 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. It is an object ofthe invention to provide soap-based laundry bar compositions, which provide superior sudsing, cleaning and soil suspending properties.
  • the present invention is directed to laundry detergent bar compositions comprising: A. from about 1% to about 30% synthetic anionic surfactant; B. from about 10% to about 70% soap;
  • IKN-Rh+l-lN P-RhrlN ⁇ -RlrrNht having a modified polyamine formula V7 n+ i)W rn Y n Z or a polyamine backbone corresponding to the formula:
  • V units are terminal units having the formula:
  • W units are backbone units having the formula:
  • Y units are branching units having the formula:
  • Z units are terminal units having the formula: wherein backbone linking R units are selected from the group consisting of C2-C12 alkylene, C4-C12 alkenylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxy-alkylene, Cg-Ci2
  • R 1 (OCH2CH(OR 2 )CH2) w -, -C(O)(R 4 ) r C(O)-, -CH 2 CH(OR 2 )CH 2 -, and mixtures thereof;
  • R* is C2-Cg alkylene and mixtures thereof;
  • R 2 is hydrogen, and mixtures thereof;
  • R-* is Ci -Cjg alkyl
  • R 4 is C1-C12 alkylene, C4-C12 alkenylene, Cg-Ci2 arylalkylene, Q--C10 arylene, and mixtures thereof;
  • R-> is Cj-C ⁇ alkylene, C3-C12 hydroxyalkylene, C4- C12 dihydroxy-alkylene, Cg-Ci2 dialkylarylene, -C(O)-, -
  • R ⁇ is C2-C12 alkylene or C6-C12 arylene
  • E units are selected from the group consisting of hydrogen, C1-
  • alkyl means a hydrocarbyl moiety which is straight or branched, saturated or unsaturated. Unless otherwise specified, alkyl are preferably saturated or unsaturated with double bonds, preferably with one or two double bonds.
  • the term “tallow” is used herein in connection with materials with fatty acid mixtures which typically are linear and have an approximate carbon chain length distribution of 2% C14, 29% C ⁇ , 23% Cjg, 2% palmitoleic, 41% oleic, and 3% linoleic (the first three fatty acids listed are saturated). Other mixtures with similar distribution, such as those from palm oil and those derived from various animal tallow and lard, are also included within the term tallow. The tallow can also be hardened (i.e, hydrogenated) to convert part or all of the unsaturated fatty acid moieties to saturated fatty acid moieties.
  • coconut oil is used herein in connection with materials with fatty acid mixtures which typically are linear and have an approximate carbon chain length distribution of about 8% Cg, 7% C ⁇ 0 , 48% C 12 , 17% C14, 9% C ⁇ 6 , 2% Cig, 7% oleic, and 2% linoleic (the first six fatty acids listed being saturated).
  • Other sources having similar carbon chain length distribution in their fatty acids, such as palm kernel oil and babassu oil, are included within the term coconut oil.
  • Synthetic Anionic 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 (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 Cn_i3 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.
  • 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.
  • AES alkyl ethoxy ether sulfates
  • R is alkyl of from about 10 to about 20 carbon atoms. On average, R is from about 13 to about 16. R is preferably saturated and linear.
  • x is an integer from 0 to about 20 and M is a water- soluble cation, for example, an alkali metal cation (e.g., sodium, potassium, lithium), preferably sodium or potassium, especially sodium.
  • alkali metal cation e.g., sodium, potassium, lithium
  • the preferred AES surfactant has a saturated linear alkyl with an average of 14 to 15 carbon atoms, a range of from about 14 to about 15 carbon atoms, an average of about one ethoxy unit per molecule, and is a sodium salt (Ci4-i5AEiSNa).
  • 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 synthetic anionic surfactants are Ci()-i8 linear alkylbenzene sulfonates, CiO-14 alkyl glyceryl ether sulfonates, and Cjo-ig alkyl sulfates.
  • the amount of synthetic anionic surfactant in the composition herein is from about 1% to about 30%, preferably from about 2% to about 20%. Soap
  • salts of fatty acids means salts of fatty acids.
  • the fatty acids are linear or branched containing from about 8 to about 24 carbon atoms, preferably from about 10 to about 20 carbon atoms.
  • the average carbon chain length for the fatty acid soaps is from about 12 to about 18 carbon atoms, preferably from about 14 to about 16 carbon atoms.
  • Preferred salts of the fatty acids are alkali metal salts, such as sodium and potassium, especially sodium. Also preferred salts are ammonium and alkylolammonium salts.
  • the fatty acids of soaps useful in the subject invention bars are preferably obtained from natural sources such as plant or animal esters; examples include coconut oil, palm oil, palm kernel oil, olive oil, peanut oil, corn oil, sesame oil, rice bran oil, cottonseed oil, babassu oil, soybean oil, castor oil, tallow, whale oil, fish oil, grease, lard, and mixtures thereof.
  • Preferred fatty acids are obtained from coconut oil, tallow, palm oil (palm stearin oil), palm kernel oil, and mixtures thereof.
  • Fatty acids can be synthetically prepared, for example, by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fischer-Tropsch process.
  • Alkali metal soaps can be made by direct saponification of the fats and oils or by the neutralization of the free fatty acids which are prepared in a separate manufacturing process. Particularly useful are the sodium and potassium salts of the mixtures of fatty acids derived from coconut oil and tallow, i.e., sodium and potassium tallow and coconut soaps.
  • Preferred soap raw materials for the subject invention bars are soaps made from mixtures of fatty acids from tallow and coconut oil. Typical mixtures have tallowxoconut fatty acid ratios of 85: 15, 80:20, 75:25, 70:30, and 50:50; preferred ratios are about 80:20 to 65:35.
  • Preferred soap raw materials for the subject invention are neat soaps made by kettle (batch) or continuous saponification.
  • Neat soaps typically comprise from about 65% to about 75%, preferably from about 67% to about 72%, alkali metal soap; from about 24% to about 34%, preferably from about 27% to about 32%, water; and minor amounts, preferably less than about 1% total, of residual materials and impurities, such as alkali metal chlorides, alkali metal hydroxides, alkali metal carbonates, glycerin, and free fatty acids.
  • Another preferred soap raw material is soap noodles or flakes, which are typically neat soap which has been dried to a water content of from about 10% to about 20%. The other components above are proportionally concentrated.
  • Soaps are present in the compositions herein at levels of from about 10% to about 70%, preferably from about 20% to about 50%.
  • the ratio of synthetic anionic surfactant to soap is from about 1 :50 to about 1: 1, preferably from about 1:20 to about 1: 1, more preferably from about 1:20 to about 1:4.
  • the soil release agents ofthe present invention are water-soluble or dispersible, modified polyamines.
  • the amount of polyamines in the composition herein is from about 0.05% to about 3%, preferably from about 0.3% to about 2%.
  • These 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 described herein are modified in such a manner that each nitrogen ofthe polyamine chain is thereafter described in terms of a unit that is substituted, quaternized, oxidized, or combinations thereof.
  • modification is defined as replacing a backbone -NH hydrogen atom by an E unit (substitution), quaternizing a backbone nitrogen (quaternized) or oxidizing a backbone nitrogen to the N-oxide (oxidized).
  • substitution and “substitution” are used interchangeably when referring to the process of replacing a hydrogen atom attached to a backbone nitrogen with an E unit. Quaternization or oxidation may take place in some circumstances without substitution, but substitution is preferably accompanied by oxidation or quaternization of at least one backbone nitrogen.
  • linear or non-cyclic polyamine backbones that comprise the soil release agents ofthe present invention have the general formula:
  • [H ⁇ R]n+-*[ft-Rb ⁇ - ⁇ said backbones prior to subsequent modification, comprise primary, secondary and tertiary amine nitrogens connected by R "linking" units.
  • the cyclic polyamine backbones comprising the soil release agents ofthe present invention have the general formula:
  • primary amine nitrogens comprising the backbone or branching chain once modified are defined as V or Z "terminal" units.
  • V or Z "terminal" units when a primary amine moiety, located at the end ofthe main polyamine backbone or branching chain having the structure
  • H 2 N-R]- is modified according to the present invention, it is thereafter defined as a V "terminal" unit, or simply a V unit.
  • V terminal
  • some or all ofthe primary amine moieties can remain unmodified subject to the restrictions further described herein below. These unmodified primary amine moieties by virtue of their position in the backbone chain remain “terminal” units.
  • Z Z "terminal" unit, or simply a Z unit. This unit can remain unmodified subject to the restrictions further described herein below.
  • secondary amine nitrogens comprising the backbone or branching chain once modified are defined as W "backbone" units.
  • W backbone
  • tertiary amine nitrogens comprising the backbone or branching chain once modified are further referred to as Y "branching" units.
  • Y branch point of either the polyamine backbone or other branching chains or rings, having the structure
  • Tsl-Rl— is modified according to the present invention, it is thereafter defined as a Y "branching" unit, or simply a Y unit.
  • some or all or the tertiary amine moieties can remain unmodified. These unmodified tertiary amine moieties by virtue of their position in the backbone chain remain “branching" units.
  • the R units associated with the V, W and Y unit nitrogens which serve to connect the polyamine nitrogens, are described herein below.
  • the final modified structure ofthe polyamines ofthe present invention can be therefore represented by the general formula
  • V(,v.lcH)W m Y felicitYkZ for cyclic polyamine soil release polymers.
  • the polyamine backbone has the formula
  • the polyamine backbones ofthe present invention comprise no rings.
  • a fully non-branched linear modified polyamine according to the present invention has the formula
  • VW m Z that is, n is equal to 0.
  • n the lower the ratio of m to n
  • m ranges from a minimum value of 4 to about 400, however larger values of m, especially when the value ofthe index n is very low or nearly 0, are also preferred.
  • Each polyamine nitrogen whether primary, secondary or tertiary, once modified according to the present invention, is further defined as being a member of one of three general classes; simple substituted, quaternized or oxidized. Those polyamine nitrogen units not modified are classed into V, W, Y, or Z units depending on whether they are primary, secondary or tertiary nitrogens. That is unmodified primary amine nitrogens are V or Z units, unmodified secondary amine nitrogens are W units and unmodified tertiary amine nitrogens are Y units for the pu ⁇ oses ofthe present invention.
  • Modified primary amine moieties are defined as V "terminal" units having one of three forms: a) simple substituted units having the structure:
  • Modified secondary amine moieties are defined as W "backbone" units having one of three forms: a) simple substituted units having the structure:
  • Modified tertiary amine moieties are defined as Y "branching" units having one of three forms: a) unmodified units having the structure:
  • Certain modified primary amine moieties are defined as Z "terminal" units having one of three forms: a) simple substituted units having the structure.
  • a primary amine unit comprising one E unit in the form of a hydroxyethyl moiety is a V terminal unit having the formula (HOCH 2 CH 2 )HN-.
  • the Z "terminal” unit derives from a terminal primary amino moiety ofthe structure -NH2
  • Non-cyclic polyamine backbones according to the present invention comprise only one Z unit whereas cyclic polyamines can comprise no Z units.
  • the Z "terminal” unit can be substituted with any ofthe E units described further herein below, except when the Z unit is modified to form an N- oxide. In the case where the Z unit nitrogen is oxidized to an N-oxide, the nitrogen must be modified and therefore E cannot be a hydrogen.
  • the polyamines ofthe present invention comprise backbone R "linking" units that serve to connect the nitrogen atoms ofthe backbone.
  • R units comprise units that for the pu ⁇ oses ofthe present invention are referred to as “hydrocarbyl R” units and "oxy R” units.
  • the "hydrocarbyl" R units are C2-C12 alkylene, C4-C12 alkenylene, C3-C12 hydroxyalkylene wherein the hydroxyl moiety may take any position on the R unit chain except the carbon atoms directly connected to the polyamine backbone nitrogens; C4-C12 dihydroxyalkylene wherein the hydroxyl moieties may occupy any two ofthe carbon atoms ofthe R unit chain except those carbon atoms directly connected to the polyamine backbone nitrogens; Cg-Ci2 dialkylarylene which for the purpose ofthe present invention are arylene moieties having two alkyl substituent groups as part ofthe linking chain.
  • a dialkylarylene unit has the formula
  • the unit need not be 1, 4-substituted, but can also be 1,2 or 1,3 substituted2- C12 alkylene, preferably ethylene, 1,2-propylene, and mixtures thereof, more preferably ethylene.
  • the "oxy" R units comprise -(R 1 O) x R 5 (OR 1 ) x -, CH 2 CH(OR 2 )CH2O) z (R 1 O) y R 1 (OCH2CH(OR 2 )CH2) w -, -CH 2 CH(OR 2 )CH 2 -, -(R-O ⁇ R 1 -, and mixtures thereof.
  • R units are C2-C12 alkylene, C3-C12 hydroxyalkylene, C4-C 12 dihydroxyalkylene, Cg-C 12 dialkylarylene, -(R 1 0) x R l -, - CH 2 CH(OR 2 )CH 2 -, -(CH 2 CH(OH)CH 2 O) z (R 1 0) y R 1 (OCH 2 CH-(OH)CH 2 ) w -, - (R ⁇ O) ⁇ R ⁇ (OR ⁇ ) x -, more preferred R units are C2-C12 alkylene, C3-C12 hydroxy ⁇ alkylene, C4-C12 dihydroxyalkylene, -(RJo ⁇ R 1 -, -(R 1 O) x R 5 (OR 1 ) x -, (CH 2 CH(OH)CH2 ⁇ ) z (R 1 O) y R 1 (OCH2CH-(OH)CH2) w -, and mixtures thereof, even more preferred R
  • R-- units are C2-C6 alkylene, and mixtures thereof, preferably ethylene.
  • R 2 is hydrogen, and -(R-O ⁇ B, preferably hydrogen.
  • R 3 is Cj-Cig alkyl, C7-C12 arylalkylene, C7-C12 alkyl substituted aryl, C ⁇ -
  • C12 aryl and mixtures thereof, preferably C1-C12 alkyl, C7-C12 arylalkylene, more preferably C- -C12 alkyl, most preferably methyl.
  • lO units serve as part of E units described herein below.
  • R 4 is C1-C12 alkylene, C4-C12 alkenylene, Cg-Cj2 arylalkylene, Cg-Cjo arylene, preferably C J-C JO alkylene, Cg-Ci2 arylalkylene, more preferably C2-Cg alkylene, most preferably ethylene or butylene.
  • R 5 is C1-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, Cg-Ci2 dialkylarylene, -C(O)-, -C(O)NHR6NHC(O)-, -C(O)(R 4 ) r C(O)-, -R OR 1 )-, -CH 2 CH(OH)CH 2 O(R 1 O) y R 1 OCH2CH(OH)CH2-, -C(O)(R 4 ) r C(O)-, - CH 2 CH(OH)CH 2 -, R 5 is preferably ethylene, -C(O)-, -C(O)NHR 6 NHC(O)-, -
  • R 6 is C2-C12 alkylene or C6-C12 arylene.
  • the preferred "oxy" R units are further defined in terms ofthe R 1 , R 2 , and R 5 units.
  • Preferred "oxy" R units comprise the preferred R', R 2 , and R-> units.
  • the preferred soil release agents ofthe present invention comprise at least 50% Rl units that are ethylene.
  • Preferred Rl, R 2 , and R-- * units are combined with the "oxy" R units to yield the preferred "oxy” R units in the following manner.
  • E units are selected from the group consisting of hydrogen, Cj-C22 alkyl, C3- C22 alkenyl, C7-C22 arylalkyl, C 2 -C 2 2 hydroxyalkyl, -(CH 2 ) p CO2M, - (CH 2 ) q SO 3 M, -CH(CH2CO 2 M)CO 2 M, -(CH 2 )pPO 3 M, -(R ⁇ B, -C(O)R 3 , preferably hydrogen, C2-C22 hydroxyalkylene, benzyl, C1-C22 alkylene, -(R ⁇ O ⁇ B, - C(O)R 3 , -(CH 2 ) p CO 2 M, -(CH 2 ) q SO 3 M, -CH(CH 2 CO 2 M)CO2M, more preferably Cl-C 2 2 alkylene, -(R ⁇ B, -C(O)R 3 , -(CH 2 ) p CO 2 M,
  • E units do not comprise hydrogen atom when the V, W or Z units are oxidized, that is the nitrogens are N-oxides.
  • the backbone chain or branching chains do not comprise units ofthe following structure:
  • E units do not comprise carbonyl moieties directly bonded to a nitrogen atom when the V, W or Z units are oxidized, that is, the nitrogens are N- oxides.
  • the E unit -C(0)R 3 moiety is not bonded to an N-oxide modified nitrogen, that is, there are no N-oxide amides having the structure
  • B is hydrogen, C ⁇ -C 6 alkyl, -(CH 2 ) q SO 3 M, -(CH 2 ) p CO 2 M, -(CH 2 ) q -
  • M is hydrogen or a water soluble cation in sufficient amount to satisfy charge balance.
  • a sodium cation equally satisfies -(CH2) p CO2M, and (CH2) q S ⁇ 3M, thereby resulting in -(CH2) p CO2Na, and -(CH2) q SO3Na moieties
  • More than one monovalent cation, (sodium, potassium, etc.) can be combined to satisfy the required chemical charge balance.
  • more than one anionic group may be charge balanced by a divalent cation, or more than one mono-valent cation may be necessary to satisfy the charge requirements of a poly-anionic radical
  • a -(CH2) ⁇ P ⁇ 3M moiety substituted with sodium atoms has the formula - (CH2)r>PO3Na3.
  • Divalent cations such as calcium (Ca 2+ ) or magnesium (Mg 2+ ) may be substituted for or combined with other suitable mono-valent water soluble cations
  • Preferred cations are sodium and potassium, more preferred is sodium.
  • X is a water soluble anion such as chlorine (Cl"), bromine (Br) and iodine
  • (I) or X can be any negatively charged radical such as sulfate (SO4 2 ”) and methosulfate (CH3SO3-).
  • indices have the following values: p has the value from 1 to 6, q has the value from 0 to 6; r has the value 0 or 1; w has the value 0 or 1, x has the value from 1 to 100; y has the value from 0 to 100; z has the value 0 or 1; m has the value from 4 to about 400, n has the value from 0 to about 200; m + n has the value of at least 5.
  • the preferred soil release agents ofthe present invention comprise polyamine backbones wherein less than about 50% ofthe R groups comprise "oxy" R units, preferably less than about 20% , more preferably less than 5%, most preferably the R units comprise no "oxy" R units.
  • the most preferred soil release agents which comprise no "oxy" R units comprise polyamine backbones wherein less than 50% ofthe R groups comprise more than 3 carbon atoms.
  • ethylene, 1,2-propylene, and 1,3-propylene comprise 3 or less carbon atoms and are the preferred "hydrocarbyl" R units. That is when backbone R units are C2-C12 alkylene, preferred is C2-C3 alkylene, most preferred is ethylene.
  • the soil release agents ofthe present invention comprise modified homogeneous and non-homogeneous polyamine backbones, wherein 100% or less of the -NH units are modified.
  • the term pu ⁇ ose ofthe present invention the term
  • homogeneous polyamine backbone is defined as a polyamine backbone having R units that are the same (i.e., all ethylene). However, this sameness definition does not exclude polyamines that comprise other extraneous units comprising the polymer backbone which are present due to an artifact ofthe chosen method of chemical synthesis. For example, it is known to those skilled in the art that ethanolamine may be used as an "initiator” in the synthesis of polyethyleneimines, therefore a sample of polyethyleneimine that comprises one hydroxyethyl moiety resulting from the polymerization "initiator" would be considered to comprise a homogeneous polyamine backbone for the pu ⁇ oses ofthe present invention.
  • a polyamine backbone comprising all ethylene R units wherein no branching Y units are present is a homogeneous backbone.
  • a polyamine backbone comprising all ethylene R units is a homogeneous backbone regardless ofthe degree of branching or the number of cyclic branches present.
  • non-homogeneous polymer backbone refers to polyamine backbones that are a composite of various R unit lengths and R unit types.
  • a non-homogeneous backbone comprises R units that are a mixture of ethylene and 1,2-propylene units.
  • a mixture of "hydrocarbyl” and “oxy” R units is not necessary to provide a non-homogeneous backbone. The proper manipulation of these "R unit chain lengths" provides the formulator with the ability to modify the solubility and fabric substantivity ofthe soil release agents ofthe present invention.
  • Preferred soil release polymers ofthe present invention comprise homogeneous polyamine backbones that are totally or partially substituted by polyethyleneoxy moieties, totally or partially quaternized amines, nitrogens totally or partially oxidized to N-oxides, and mixtures thereof.
  • polyethyleneoxy moieties totally or partially quaternized amines
  • nitrogens totally or partially oxidized to N-oxides, and mixtures thereof.
  • not all backbone amine nitrogens must be modified in the same manner, the choice of modification being left to the specific needs ofthe formulator.
  • the degree of ethoxylation is also determined by the specific requirements ofthe formulator.
  • the preferred polyamines that comprise the backbone ofthe compounds ofthe present invention 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 (TEP A).
  • 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
  • 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:
  • PEI [H ⁇ r ⁇ CrilrHI ⁇ C ⁇ 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 ofthe 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.
  • modified soil release polymers ofthe present invention comprising
  • PEI's are illustrated in Formulas I - IV:
  • Formula I depicts a soil release polymer comprising a PEI backbone wherein all substitutable nitrogens are modified by replacement of hydrogen with a polyoxyalkyleneoxy unit, -(CH2CH2 ⁇ )7H, having the formula
  • Formula I This is an example of a soil release polymer that is fully modified by one type of moiety.
  • Formula II depicts a soil release polymer comprising a PEI backbone wherein all substitutable primary amine nitrogens are modified by replacement of hydrogen with a polyoxyalkyleneoxy unit, -(CH2CH2O)7H, the molecule is then modified by subsequent oxidation of all oxidizabie primary and secondary nitrogens to N-oxides, said soil release agent having the formula
  • Formula II Formula III depicts a soil release polymer comprising a PEI backbone wherein all backbone hydrogen atoms are substituted and some backbone amine units are quaternized.
  • the substituents are polyoxyalkyleneoxy units, -(CH2CH2 ⁇ )7H, or methyl groups.
  • the modified PEI soil release polymer has the formula
  • Formula III Formula IV depicts a soil release polymer comprising a PEI backbone wherein the backbone nitrogens are modified by substitution (i.e. by -(CH2CH2O)7H or methyl), quaternized, oxidized to N-oxides or combinations thereof.
  • the resulting soil release polymer has the formula
  • not all nitrogens of a unit class comprise the same modification.
  • the present invention allows the formulator to have a portion ofthe secondary amine nitrogens ethoxylated while having other secondary amine nitrogens oxidized to N-oxides.
  • This also applies to the primary amine nitrogens, in that the formulator may choose to modify all or a portion ofthe primary amine nitrogens with one or more substituents prior to oxidation or quaternization. Any possible combination of E groups can be substituted on the primary and secondary amine nitrogens, except for the restrictions described herein above.
  • Soil suspending agents can be used. In the present invention, their use is bal ⁇ anced with the fabric softening clay/clay flocculating agent combination to provide optimum cleaning and fabric softening performance.
  • One such 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.
  • a highly preferred soil suspending agent is a water-soluble salt of carboxymethylcellulose and carboxyhydroxymethylcellulose. Soil suspending agents should be used at levels up to about 5%, preferably about 0.1-1%.
  • 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.
  • compositions of the subject invention comprise from about 5% to about 30% moisture, preferably from about 10% to about 25% moisture, more preferably from about 16% to about 25% moisture.
  • the laundry bars of the 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.
  • 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 ofthe 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 ofthe 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 poly(ethylene oxide) polymer.
  • the amount of clay flocculating agent, if any, is about 0.2-2%, preferably about 0.5-1%.
  • 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 prefe ⁇ ed 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.
  • a 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 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 Ro are independently Cj to C JO hydrocarbyl.
  • R4 is C5 to C22 hydrocarbyl
  • R5 and Ro are independently Cj to C JO hydrocarbyl.
  • One preferred amine is ditallowmethyl amine; complexes of such amines with fatty acid of the formula R7COOH, wherein R7 is Co to C22 hydrocarbyl, as disclosed in EP No.
  • the bleaching component can be a source of "OOH group, such as sodium perborate monohydrate, sodium perborate tetrahydrate and sodium percarbonate.
  • Sodium percarbonate (2Na2CO3*3H2O2) is preferred since it has a dual function of both a source of HOOH and a source of sodium carbonate.
  • Another optional bleaching component is a peracid per se, such as a formula:
  • the bleaching component can contain, as a bleaching component stabilizer, a chelating agent of polyaminocarboxylic acids, polyaminocarboxylates such as ethylenediaminotetraacetic acid, diethylenetriaminopentaacetic acid, and ethylenediaminodisuccinic acid, and their salts with water-soluble alkali metals.
  • the bleach components if any, can be added to the bar, if any, at a level up to 20%, preferably from about 1% to about 10%, more preferably from about 2% to about 6%.
  • 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. 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%.
  • Binding agents for holding the bar together in a cohesive, soluble form can also be used, and include natural and synthetic starches, gums, thickeners, and mixtures thereof. Such materials, if included, are typically at levels up to about 3%, preferably about 0.5-2%.
  • Glycerine is commonly inco ⁇ orated in laundry bar compositions. If included, it is typically at concentrations up to about 3%, preferably about 0.5-1.5%. Glycerine can affect bar brittleness.
  • optical brighteners are also preferred optional ingredients in laundry bars of the present invention.
  • Preferred optical brighteners are diamino stilbene, distyrilbiphenyl-type optical brighteners.
  • Preferred as examples of 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-mo ⁇ holino-l,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, inco ⁇ orated 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 cellulase, lipase, protease, amylase, and mixtures thereof. Enzymes, if included, are typically at levels up to about 5%, preferably about 0.5-3%. The following are non-limiting examples ofthe synthesis of preferred soil release agents:
  • EXAMPLE I Preparation of PEI 1800 E7 The ethoxylation is conducted in a 2 gallon stirred stainless steel autoclave equipped for temperature measurement and control, pressure measurement, vacuum and inert gas purging, sampling, and for introduction of ethylene oxide as a liquid.
  • a -20 lb. net cylinder of ethylene oxide (ARC) is set up to deliver ethylene oxide as a liquid by a pump to the autoclave with the cylinder placed on a scale so that the weight change ofthe cylinder could be monitored.
  • PEI polyethyleneimine
  • the autoclave is then sealed and purged of air (by applying vacuum to minus 28" Hg followed by pressurization with nitrogen to 250 psia, then venting to atmospheric pressure).
  • the autoclave contents are heated to 130 _C while applying vacuum.
  • the autoclave is charged with nitrogen to about 250 psia while cooling the autoclave to about 105 _C.
  • Ethylene oxide is then added to the autoclave incrementally over time while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate.
  • the ethylene oxide pump is turned off and cooling is applied to limit any temperature increase resulting from any reaction exothermic.
  • the temperature is maintained between 100 and HO C while the total pressure is allowed to gradually increase during the course ofthe reaction.
  • After a total of 750 grams of ethylene oxide has been charged to the autoclave (roughly equivalent to one mole ethylene oxide per PEI nitrogen function), the temperature is increased to HO C and the autoclave is allowed to stir for an additional hour. At this point, vacuum is applied to remove any residual unreacted ethylene oxide.
  • vacuum is continuously applied while the autoclave is cooled to about 50 _C while introducing 376 g of a 25% sodium methoxide in methanol solution (1.74 moles, to achieve a 10% catalyst loading based upon PEI nitrogen functions).
  • the methoxide solution is sucked into the autoclave under vacuum and then the autoclave temperature controller setpoint is increased to 130 _C.
  • a device is used to monitor the power consumed by the agitator.
  • the agitator power is monitored along with the temperature and pressure. Agitator power and temperature values gradually increase as methanol is removed from the autoclave and the viscosity ofthe mixture increases and stabilizes in about 1 hour indicating that most ofthe methanol has been removed.
  • the mixture is further heated and agitated under vacuum for an additional 30 minutes. Vacuum is removed and the autoclave is cooled to 105 _C while it is being charged with nitrogen to 250 psia and then vented to ambient pressure. The autoclave is charged to 200 psia with nitrogen. Ethylene oxide is again added to the autoclave incrementally as before while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate while maintaining the temperature between 100 and 110 _C and limiting any temperature increases due to reaction exothermic. After the addition of 4500 g of ethylene oxide (resulting in a total of 7 moles of ethylene oxide per mole of PEI nitrogen function) is achieved over several hours, the temperature is increased to 110 _C and the mixture stirred for an additional hour.
  • reaction mixture is then collected in nitrogen purged containers and eventually transferred into a 22 L three neck round bottomed flask equipped with heating and agitation.
  • the strong alkali catalyst is neutralized by adding 167 g methanesulfonic acid (1.74 moles).
  • the reaction mixture is then deodorized by passing about 100 cu. ft. of inert gas (argon or nitrogen) through a gas dispersion frit and through the reaction mixture while agitating and heating the mixture to 130 _C.
  • inert gas argon or nitrogen
  • Example IA Quaternization of PEI I8OO E7 To a 500 mL Erlenmeyer flask equipped with a magnetic stirring bar is added polyethyleneimine having a molecular weight of 1800 which is further modified by ethoxylation to a degree of approximately 7 ethyleneoxy residues per nitrogen (PEI 1800, E7) (207.3g, 0.590 mol nitrogen, prepared as in Example I) and acetonitrile (120 g). Dimethyl sulfate (28.3g, 0.224 mol) is added in one portion to the rapidly stirring solution, which is then stoppered and stirred at room temperature overnight.
  • PEI 1800, E7 polyethyleneimine having a molecular weight of 1800 which is further modified by ethoxylation to a degree of approximately 7 ethyleneoxy residues per nitrogen (PEI 1800, E7) (207.3g, 0.590 mol nitrogen, prepared as in Example I) and acetonitrile (120 g).
  • Dimethyl sulfate 28.3g, 0.224 mol
  • the acetonitrile is removed by rotary evaporation at about 60 C, followed by further stripping of solvent using a Kugelrohr apparatus at approximately 80 C to afford 220 g ofthe desired partially quaternized material as a dark brown viscous liquid.
  • the 1 3 C-NMR (D2O) spectrum obtained on a sample ofthe reaction product indicates the absence of a carbon resonance at ⁇ 58ppm corresponding to dimethyl sulfate.
  • the *H- NMR (D2O) spectrum shows a partial shifting ofthe resonance at about 2.5 ppm for methylenes adjacent to unquatemized nitrogen has shifted to approximately 3.0 ppm. This is consistent with the desired quaternization of about 38% ofthe nitrogens.
  • Example II Formation of amine oxide of PEI 1800 E7
  • polyethyleneimine having a molecular weight of 1800 and ethoxylated to a degree of about 7 ethoxy groups per nitrogen (PEI- 1800, E7) (209 g, 0.595 mol nitrogen, prepared as in Example I), and hydrogen peroxide (120 g of a 30 wt % solution in water, 1.06 mol).
  • PEI- 1800, E7 polyethyleneimine having a molecular weight of 1800 and ethoxylated to a degree of about 7 ethoxy groups per nitrogen
  • hydrogen peroxide 120 g of a 30 wt % solution in water, 1.06 mol
  • the resonances ascribed to methylene protons adjacent to unoxidized nitrogens have shifted from the original position at -2.5 ppm to -3.5 ppm.
  • To the reaction solution is added approximately 5 g of 0.5% Pd on alumina pellets, and the solution is allowed to stand at room temperature for approximately 3 days. The solution is tested and found to be negative for peroxide by indicator paper.
  • the material as obtained is suitably stored as a 51.1% active solution in water.
  • Example III Formation of amine oxide of quaternized PEI 1800 E7 To a 500 mL Erlenmeyer flask equipped with a magnetic stirring bar is added polyethyleneimine having a molecular weight of 1800 which is further modified by ethoxylation to a degree of about 7 ethyleneoxy residues per nitrogen (PEI 1800 E7) and then further modified by quaternization to approximately 38% with dimethyl sulfate (130 g, -0.20 mol oxidizeable nitrogen, prepared as in Example II), hydrogen peroxide (48 g of a 30 wt % solution in water, 0.423 mol), and water (-50 g). The flask is stoppered, and after an initial exotherm the solution is stirred at room temperature overnight.
  • PEI 1800 E7 polyethyleneimine having a molecular weight of 1800 which is further modified by ethoxylation to a degree of about 7 ethyleneoxy residues per nitrogen (PEI 1800 E7) and then further modified by quaternization to approximately 38% with dimethyl
  • EXAMPLE IV Preparation of PEI 1200 E7
  • the ethoxylation is conducted in a 2 gallon stirred stainless steel autoclave equipped for temperature measurement and control, pressure measurement, vacuum and inert gas purging, sampling, and for introduction of ethylene oxide as a liquid.
  • a -20 lb. net cylinder of ethylene oxide (ARC) is set up to deliver ethylene oxide as a liquid by a pump to the autoclave with the cylinder placed on a scale so that the weight change ofthe cylinder could be monitored.
  • PEI polyethyleneimine
  • the autoclave is then sealed and purged of air (by applying vacuum to minus 28" Hg followed by pressurization with nitrogen to 250 psia, then venting to atmospheric pressure).
  • the autoclave contents are heated to 130 °C while applying vacuum.
  • the autoclave is charged with nitrogen to about 250 psia while cooling the autoclave to about 105 °C.
  • Ethylene oxide is then added to the autoclave incrementally over time while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate.
  • the ethylene oxide pump is turned off and cooling is applied to limit any temperature increase resulting from any reaction exotherm.
  • the temperature is maintained between 100 and 110 °C while the total pressure is allowed to gradually increase during the course ofthe reaction.
  • the temperature is increased to 110 °C and the autoclave is allowed to stir for an additional hour. At this point, vacuum is applied to remove any residual unreacted ethylene oxide.
  • the mixture is further heated and agitated under vacuum for an additional 30 minutes. Vacuum is removed and the autoclave is cooled to 105 °C while it is being charged with nitrogen to 250 psia and then vented to ambient pressure. The autoclave is charged to 200 psia with nitrogen. Ethylene oxide is again added to the autoclave incrementally as before while closely monitoring the autoclave pressure, temperature, and ethylene oxide flow rate while maintaining the temperature between 100 and 110 ° C and limiting any temperature increases due to reaction exotherm. After the addition of 4500 g of ethylene oxide (resulting in a total of 7 moles of ethylene oxide per mole of PEI nitrogen function) is achieved over several hours, the temperature is increased to 110 °C and the mixture stirred for an additional hour.
  • reaction mixture is then collected in nitrogen purged containers and eventually transferred into a 22 L three neck round bottomed flask equipped with heating and agitation.
  • the strong alkali catalyst is neutralized by adding 167 g methanesulfonic acid (1.74 moles).
  • the reaction mixture is then deodorized by passing about 100 cu. ft. of inert gas (argon or nitrogen) through a gas dispersion frit and through the reaction mixture while agitating and heating the mixture to 130 °C.
  • inert gas argon or nitrogen
  • the final reaction product is cooled slightly and collected in glass containers purged with nitrogen.
  • PEI 1200 El 5 and PEI 1200 E20 can be prepared by the above method by adjusting the reaction time and the relative amount of ethylene oxide used in the reaction.
  • acetonitrile is evaporated on the rotary evaporator at ⁇ 60°C, followed by a Kugelrohr apparatus (Aldrich) at ⁇ 80°C to afford ⁇ 220g ofthe desired material as a dark brown viscous liquid.
  • a - ⁇ 3 C-NMR (D2O) spectrum shows the absence of a peak at ⁇ 58ppm corresponding to dimethyl sulfate.
  • a * H-NMR (D2O) spectrum shows the partial shifting ofthe peak at 2.5 ppm (methylenes attached to unquaternized nitrogens) to -3. Oppm.
  • 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.
  • the raw materials are mixed in the blender.
  • Alkylbenzene sulfonic acid (when used) is added into a mixture of alkaline inorganic salts, strong electrolyte salts, and fillers (preferably including sodium carbonate) and the resulting partly neutralized mixture is mechanically worked to effect homogeneity and to complete the neutralization of the mixture.
  • the soap, alkoxylated polymers, and any optional surfactants are added, followed by the builder and any additional optional components.
  • polyphosphate can be used as an alkaline salt in the neutralization.
  • 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 conveyer
  • the product is then conveyed to a double vacuum plodder, operating at high vacuum, e.g. 400 to 740 mm of mercury vacuum, so that entrapped air is removed.
  • high vacuum e.g. 400 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.
  • Soap/synthetic laundry bars of the present invention having the following compositions are prepared by conventional blending, milling and plodding procedures.
  • the bars have excellent cleaning and soil suspending properties and has better sudsing than a comparable bar that only contains synthetic anionic surfactant and no alkali metal soap of a fatty acid.

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  • Detergent Compositions (AREA)

Abstract

L'invention porte sur des compositions pour détergents en barres comportant un système de tensio-actifs incluant des tensio-actifs anioniques de synthèse, des savons d'acides gras et certains agents d'élimination des salissures de type polyamine renforcent l'efficacité d'élimination des salissures tout en conservant un fort pouvoir moussant.
PCT/US1996/006273 1996-05-03 1996-05-03 Compositions pour detergents en barres WO1997042283A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/US1996/006273 WO1997042283A1 (fr) 1996-05-03 1996-05-03 Compositions pour detergents en barres
MA24578A MA24159A1 (fr) 1996-05-03 1997-05-02 Compositions de barres de lavage

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/US1996/006273 WO1997042283A1 (fr) 1996-05-03 1996-05-03 Compositions pour detergents en barres

Publications (1)

Publication Number Publication Date
WO1997042283A1 true WO1997042283A1 (fr) 1997-11-13

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MA (1) MA24159A1 (fr)
WO (1) WO1997042283A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000005334A1 (fr) * 1998-07-23 2000-02-03 The Procter & Gamble Company Composition de detergent a lessive
EP1174494A1 (fr) * 2000-07-20 2002-01-23 Beiersdorf Aktiengesellschaft Pain de savon comprenant du talc, un ou plusieurs acides gras d'alkali et un ou plusieurs agents tensioactifs anioniques en absence d'oligoglycosides d'alkyl
US6677289B1 (en) 1999-07-16 2004-01-13 The Procter & Gamble Company Laundry detergent compositions comprising polyamines and mid-chain branched surfactants
US6696402B2 (en) 1999-11-09 2004-02-24 The Procter & Gamble Company Laundry detergent compositions comprising zwitterionic polyamines
US7163985B2 (en) 2002-09-12 2007-01-16 The Procter & Gamble Co. Polymer systems and cleaning compositions comprising the same
US9540596B2 (en) 2013-08-26 2017-01-10 The Procter & Gamble Company Compositions comprising alkoxylated polyamines having low melting points

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0269169A2 (fr) * 1986-11-21 1988-06-01 The Procter & Gamble Company Compositions détergentes contenant de la cellulose
WO1995032272A1 (fr) * 1994-05-25 1995-11-30 The Procter & Gamble Company Compositions de dispersion des salissures a base de polymeres du type polyalkyleneamine ethoxylee/propoxylee

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0269169A2 (fr) * 1986-11-21 1988-06-01 The Procter & Gamble Company Compositions détergentes contenant de la cellulose
WO1995032272A1 (fr) * 1994-05-25 1995-11-30 The Procter & Gamble Company Compositions de dispersion des salissures a base de polymeres du type polyalkyleneamine ethoxylee/propoxylee

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000005334A1 (fr) * 1998-07-23 2000-02-03 The Procter & Gamble Company Composition de detergent a lessive
US6677289B1 (en) 1999-07-16 2004-01-13 The Procter & Gamble Company Laundry detergent compositions comprising polyamines and mid-chain branched surfactants
US6903059B2 (en) 1999-07-16 2005-06-07 The Procter & Gamble Company Laundry detergent compositions comprising polyamines and mid-chain branched surfactants
US6696402B2 (en) 1999-11-09 2004-02-24 The Procter & Gamble Company Laundry detergent compositions comprising zwitterionic polyamines
EP1174494A1 (fr) * 2000-07-20 2002-01-23 Beiersdorf Aktiengesellschaft Pain de savon comprenant du talc, un ou plusieurs acides gras d'alkali et un ou plusieurs agents tensioactifs anioniques en absence d'oligoglycosides d'alkyl
DE10035208A1 (de) * 2000-07-20 2002-01-31 Beiersdorf Ag Geformtes Seifenprodukt, enthaltend Talkum, eine oder mehrere Fettsäuren in Form ihrer Alkaliseifen und ein oder mehrere anionische Tenside bei gleichzeitiger Abwesenheit von Alkyl-(oligo)-glycosiden
US7163985B2 (en) 2002-09-12 2007-01-16 The Procter & Gamble Co. Polymer systems and cleaning compositions comprising the same
US7442213B2 (en) 2002-09-12 2008-10-28 The Procter & Gamble Company Methods of cleaning a situs with a cleaning composition comprising a polymer system
US9540596B2 (en) 2013-08-26 2017-01-10 The Procter & Gamble Company Compositions comprising alkoxylated polyamines having low melting points
US9540595B2 (en) 2013-08-26 2017-01-10 The Procter & Gamble Company Compositions comprising alkoxylated polyalkyleneimines having low melting points

Also Published As

Publication number Publication date
MA24159A1 (fr) 1997-12-31

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