WO2000005334A1 - Composition de detergent a lessive - Google Patents

Composition de detergent a lessive Download PDF

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Publication number
WO2000005334A1
WO2000005334A1 PCT/US1998/015349 US9815349W WO0005334A1 WO 2000005334 A1 WO2000005334 A1 WO 2000005334A1 US 9815349 W US9815349 W US 9815349W WO 0005334 A1 WO0005334 A1 WO 0005334A1
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WO
WIPO (PCT)
Prior art keywords
units
laundry detergent
mixtures
formula
value
Prior art date
Application number
PCT/US1998/015349
Other languages
English (en)
Inventor
Vinay Madhav Shena
Elma Quiaonza Gonzales
Original Assignee
The Procter & Gamble Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to AU85858/98A priority Critical patent/AU8585898A/en
Priority to PCT/US1998/015349 priority patent/WO2000005334A1/fr
Publication of WO2000005334A1 publication Critical patent/WO2000005334A1/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
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/37—Mixtures of compounds all of which are anionic
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing 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
    • 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 a laundry detergent composition. Specifically, the present invention relates to a laundry detergent composition containing a synthetic anionic surfactant.
  • DTIs dye transfer inhibitors'
  • the DTIs are typically polymeric materials which complex or adsorb fugitive dyes in the wash solution, and thereby prevent the fugitive dye from transferring and/or re- depositing onto the fabric.
  • DTIs include, for example, polymers and copolymers of polyvinylpyrrolidone, carboxymethyl cellulose, vinylpyrrolidone, etc.
  • laundry detergent composition takes the form of a laundry detergent bar.
  • Technical developments in the field of laundry detergent bars have concerned formulating laundry detergent 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.
  • Laundry detergent bar processes are also well known in the art. Prior art disclosing laundry detergent bars and laundry detergent bar processes include: U.S. Patent 3,178,370, Okenfuss, issued April 13, 1965; and Philippine Patent 13778 to Anderson, issued September 23, 1980.
  • Sudsing characteristics are also very important in the laundry detergent bar and hand-wash context.
  • high sudsing characteristics are highly desirable when laundry detergent bars are used for hand-washing.
  • the amount of suds and the durability of the lather formed is directly observable. Because consumers directly correlate high sudsing characteristics with high cleaning ability, a laundry detergent bar which produces both a large volume of suds and long-lasting suds, is highly preferred by consumers. While a laundry detergent bar which has inherently inferior sudsing characteristics will often include a suds booster, high levels of such a suds booster raise the formulation costs of the bar. Accordingly, the need remains for an improved laundry detergent, and especially a laundry detergent bar, which provides improved dye transfer inhibition benefits as well as high sudsing characteristics.
  • the present invention is directed to laundry detergent compositions which contain, by weight of the final composition from about 5% to about 30% of an anionic surfactant system, which includes a linear alkylbenzene sulfonate and a coconut fatty alkyl sulfate.
  • the laundry detergent bar also contains from about
  • W units are backbone units having the formula:
  • Y units are branching units having the formula:
  • backbone linking R units are selected from the group consisting of C2-C12 alkylene, C4-C12 alkenylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxy-alkylene, C8-C12 dialkylarylene, -(R 1 0) X R 1 -, -(R 1 0) X R 5 (0R1 ) ⁇ -, (CH 2 CH(OR2)CH 2 0) z (Rl ⁇ )yRl (OCH2CH(OR2)CH2)w.
  • R1 is C2-C6 alkylene and mixtures thereof
  • R2 is hydrogen, - (R 1 0) x B, and mixtures thereof
  • R 3 is C-
  • R 4 is C1-C12 alkylene, C4-C12 alkenylene, C8-C12 arylalkylene, C6-C10 arylene, and mixtures thereof
  • R5 is C-1-C12 alkylene, C3-C12 hydroxyalkylene, C4-C-J2 dihydroxy-alkylene, CQ- C-
  • R > is C2-C12 alkylene or Cg-C-
  • E units are selected from the group consisting of hydrogen, C1-C22 alkyl, C3- C22 alkenyl, C7-C22 arylalkyl, C2-C22 hydroxyalkyl, -
  • the laundry detergent bar also contains from about 0.01% to about 5% of a stilbenedisulfonate brightener, and the balance adjunct ingredients.
  • alkyl means a hydrocarbyl moiety which is straight or branched, saturated or unsaturated. Unless otherwise specified, alkyl moieties are preferably saturated or unsaturated with double bonds, preferably with one or two double bonds.
  • 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% Cs, 7% C ⁇ ⁇ o. 48% C ⁇
  • Other sources having a similar carbon chain length distribution in their fatty acids such as palm kernel oil and babassu oil, are included within the term coconut oiL
  • moisture as used herein includes both free and bound moisture, as well as free and bound water.
  • 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 ⁇
  • the laundry detergent composition of the current invention contains an anionic surfactant system including a linear alkylbenzene sulfonate and a coconut alkyl sulfate, a modified polyethyleneimine polymer, a stilbenedisulfonate brightener, and adjunct ingredients.
  • the current invention provides a number of surprising benefits.
  • the laundry detergent composition of the present invention shows improved dye transfer inhibition benefits for a wide range of dye types, such as, for example, disperse dyes, chroma dyes, rota dyes, acid dyes, and other dye types.
  • the laundry detergent composition described herein shows dye transfer inhibition benefits for a wide range of fabric types, such as, for example, cotton, polycotton, polyester, and polyrayon.
  • the laundry detergent composition of the current invention also provides high sudsing characteristics, which consumers correlate with high cleaning ability.
  • the improved sudsing characteristics include a larger volume of suds, as well as longer lasting suds than, for example, a laundry detergent formulation containing soap and an anionic surfactant. This lowers formulation costs, as less suds booster need be added into the laundry detergent formulation.
  • laundry detergent composition described herein include improved stain removal, cleaning and whitening benefits, which can potentially lower formulation costs by reducing the number of additional agents needed in laundry detergent formulations. Additionally, the benefits produced by the combination described herein also allow a reduction of the surfactant level in the laundry detergent formulation, further leading to lowered formulation costs.
  • the laundry detergent composition described herein is in the form of a laundry detergent bar.
  • the present invention provides distinct advantages in a laundry detergent bar because the direct application thereof to a fabric increases the effectiveness of the dye transfer inhibition benefits. Additionally, because laundry detergent bars are commonly used for hand washing in areas with water having a high hardness (i.e., greater than about 10 grains/gallon), the sudsing benefits (especially as compared to soap-containing laundry detergent bars) described herein are more readily observable in a laundry detergent bar/hand wash context.
  • the laundry detergent composition of the current invention contains, by weight of the final composition, from about 5% to about 30%, preferably from about 10% to about 25%, and more preferably from about 16% to about 25%, of an anionic surfactant system.
  • the anionic surfactant system of the laundry detergent bar of the current invention contains both a linear alkylbenzene sulfonate (LAS), and a coconut fatty alkyl sulfate (CFAS). Other anionic surfactants may be contained herein as well.
  • the LAS useful herein has the general formula:
  • R represents an alkyl group of from about 10 to about 20 carbon atoms
  • X * represents a cationic species, preferably an alkali metal salt or ammonium moiety.
  • alkali metal salts the sodium and potassium salts of these surfactants are particularly preferred.
  • the LAS suitable for use herein includes 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.
  • LAS and other carbon chain based compounds herein are abbreviated according to the average alkyl group length. For example, LAS with an average chain length of 12 carbon atoms is abbreviated as C-
  • the LAS raw material useful herein is typically at least 90% LAS, preferably at least 95% LAS, with the remainder comprising a combination of linear alkyl benzene, moisture, and/or sulfuric acid.
  • Unsulfonated linear alkyl benzene is available from, for example, P. T. Unggul Indah Corp. (Indonesia), Chemphil Group - L G Chemicals Corp. (Batangas, Philippines), Isu Chemical Co., Ltd. (Korea), and Formosan Union Chemical Corp. (Taiwan).
  • LAS is commercially available from, for example, Formosan Union Chemical Corp. and Isu Chemical Co., Ltd.
  • linear chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 13, abbreviated as C-
  • the amount of LAS suitable for use in the laundry detergent bar is from about 1 % to about 30%, preferably from about 2% to about 20%, and more preferably from about 3% to about 15%, by weight of the final composition.
  • the CFAS suitable for use herein corresponds to the general formula: wherein, R represents an alkyl group of from about 8 to about 18 carbon atoms, and X * represents a cationic species, preferably an alkali metal salt.
  • the CFAS suitable for use herein includes those used in detergent applications, particularly the sodium and potassium CFAS salts. These may be obtained by sulfating the higher alcohols (C ⁇ -i ⁇ carbon atoms) produced by reducing the glycerides of coconut oil.
  • CFAS suitable for use herein is commercially available, for example, from Optimus Industrial Development, Inc. (Laguna, Philippines), Colgate (Quezon, Philippines), Lever (Philippines), Chemphil Group - LMG Chemicals Corp. (Batangas, Philippines), United Coconut Chemicals, Inc. (Batangas, Philippines), Pilipinas Kao, Inc. (Philippines), and Stepan Philippines, Inc. (Batangas, Philippines).
  • CFAS is available as either a flake (dried to about 10% to about 20% moisture) and/or as a paste (typically about 20% to about 30% moisture). Both physical forms are useful herein, with a mixture thereof being preferred.
  • the actual weight ratio of flake CFAS to paste CFAS depends primarily upon the desired moisture content of the final laundry detergent form. For example, if free water and moisture are to be minimized, then a flake may be preferable. In a laundry detergent bar, the typical weight ratio of CFAS flake to CFAS paste is from about 100:0 to about 30:70.
  • Preferred CFAS is C ⁇ -i ⁇ CFAS, especially C12 CFAS.
  • CFAS is present in a laundry detergent bar at from about 1% to about 30%, preferably from about 4% to about 22%, more preferably from about 10% to about 18%, by weight of the final composition.
  • the ratio of LAS to CFAS in the anionic surfactant system is from about 19:1 to 1 :9, preferably from about 10:1 to about 1 :5, and more preferably from about 4:1 to about 1 :3, by weight, in the final composition.
  • the anionic surfactant system will further comprise a tallow alkyl sulfate.
  • the anionic surfactant system contains therein a mixture of fatty acids of tallow and coconut oil having a weight ratio of tallow:coconut fatty acid of from about 85:15 to about 50:50, preferably from about 80:20 to about 65:35.
  • anionic surfactants are optionally included in the anionic surfactant system herein.
  • the anionic surfactants useful herein may be provided in either as a pre-
  • the laundry detergent composition of the current invention be substantially free of soap (i.e., less than about 1% by weight of the final laundry detergent bar). Without intending to be limited by theory, it is believed that the addition of soap to the current invention leads to reduced sudsing characteristics, especially in hard water conditions (i.e., greater than about 10 grains/gallon).
  • the modified polyethyleneimine polymer of the present invention is a water-soluble or dispersible, modified polyamine.
  • the amount of modified polyethyleneimine polymer suitable for use in the composition herein is from about 0.05% to about 5%, preferably from about 0.1% to about 3%, more preferably from about 0.3% to about 1.5%, by weight of the final composition.
  • These modified polyethyleneimine polymers comprise backbones that may be either linear or cyclic.
  • the polyamine backbones may 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 of the 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), quatemizing 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 modified polyethyleneimine polymers of the 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 when a primary amine moiety, located at the end of the main polyamine backbone or branching chain having the structure: H2N-R]- is modified according to the present invention, it is thereafter defined as a V "terminal" unit, or simply a V unit.
  • some or all of the 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.
  • -NH2 is modified according to the present invention, it is thereafter defined as a 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
  • the major constituent of the backbones and branching chains of the present invention having the structure:
  • E ⁇ - — is modified according to the present invention, it is thereafter defined as a W "backbone” unit, or simply a W unit. However, for the purposes of the present invention, some or all of the secondary amine moieties can remain unmodified.
  • tertiary amine nitrogens comprising the backbone or branching chain once modified are further referred to as Y
  • branching units.
  • a tertiary amine moiety which is a chain branch point of either the polyamine backbone or other branching chains or rings, wherein B represents a continuation of the chain structure by branching, having the structure:
  • branching unit or simply a Y unit. However, for the purposes of the present invention, some or all or the tertiary amine moieties can remain unmodified.
  • the final modified structure of the modified polyethyleneimine polymers of the present invention can be therefore represented by the general formula: V (n+1) W m Y n Z for linear modified polyethyleneimine polymers and by the general formula:
  • V(n-k+1)W m Y n y k Z for cyclic modified polyethyleneimine polymers .
  • modified polyethyleneimine polymers comprising rings, a Y' unit of the formula:
  • the polyamine backbone has the formula:
  • V n -k m Y n Y'k wherein k is the number of ring forming branching units.
  • the polyamine backbones of the present invention comprise no rings.
  • the ratio of the index n to the index m relates to the relative degree of branching.
  • a fully non-branched linear modified polyethyleneimine polymer 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
  • the degree of branching in the molecule typically the value for m ranges from a minimum value of 4 to about 400, however larger values of m, especially when the value of the 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 purposes of the 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:
  • the Z "terminal” unit derives from a terminal primary amino moiety of the 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 of the 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 modified polyethyleneimine polymers of the present invention comprise backbone R "linking" units that serve to connect the nitrogen atoms of the backbone.
  • R units comprise units that for the purposes of the 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-C-12 dihydroxyalkylene wherein the hydroxyl moieties may occupy any two of the carbon atoms of the R unit chain except those carbon atoms directly connected to the polyamine backbone nitrogens; C8-C12 dialkylarylene which for the purpose of the present invention are arylene moieties having two alkyl substituent groups as part of the linking chain.
  • a dialkylarylene unit has the formula:
  • the "oxy" R units comprise -
  • R10 X R 5 (0R1) X -, -CH2CH(OR2)CH 2 O) z (R 1 0)yR (OCH2CH(OR2)CH2)w-. - CH2CH(OR 2 )CH2-, -(R 0) X R 1 -, and mixtures thereof.
  • Preferred R units are C2-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, C8-C12 dialkylarylene, -(Rl ⁇ ) x R 1 -, -CH 2 CH(0R2)CH2-,
  • R units are C2-C12 alkylene, C3-C12 hydroxy-alkylene, C -C12 dihydroxyalkylene, -(R 1 0) x R 1 -, -(R 1 O) X R 5 (OR1) X -, (CH2CH(OH)CH2 ⁇ ) 2 (R O) y R 1 (OCH2CH-(OH)CH 2 ) -.
  • R units are C2-C12 alkylene, C3 hydroxyalkylene, and mixtures thereof, most preferred are C2-C6 alkylene.
  • the most preferred backbones of the present invention comprise at least 50% R units that are ethylene.
  • R 1 units are C2-C6 alkylene, and mixtures thereof, preferably ethylene.
  • R2 is hydrogen, and -(R 1 O) x B, preferably hydrogen.
  • R3 js C-1-C18 alkyl, C7-C12 arylalkylene, C7-C12 alkyl substituted aryl, C 6-C-12 aryl, and mixtures thereof , preferably C1-C12 alkyl, C7-C12 arylalkylene, more preferably C ⁇
  • R 3 units serve as part of E units described herein below.
  • R4 is C-
  • R5 i s C-1-C12 alkylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, Cs-C ⁇ dialkylarylene, -C(O)-, -C(O)NHR6NHC(O)-, -
  • C(O)(R4) r C(O)-, -CH 2 CH(OH)CH 2 -, R 5 is preferably ethylene, -C(O)-, - C(O)NHR6NHC(O)-, -R1 (0R1)-, -CH 2 CH(OH)CH 2 -,
  • R 6 is C2-C12 alkylene or C ⁇ -C-12 arylene.
  • the preferred "oxy" R units are further defined in terms of the R 1 , R 2 , and R5 units.
  • Preferred "oxy" R units comprise the preferred R 1 , R , and R5 units.
  • the preferred modified polyethyleneimine polymers of the present invention comprise at least 50% R 1 units that are ethylene.
  • Preferred R 1 , R , and R 5 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, C1-C22 alkyl,
  • 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 of the 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
  • the E unit -C(O)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 ⁇
  • M is hydrogen or a water soluble cation in sufficient amount to satisfy charge balance.
  • a sodium cation equally satisfies -(CH2)pCO2M, and -(CH2)qSO3M. thereby resulting in -(CH2)pCO2Na, and -
  • (CH2)qSO3Na moieties More than one monovalent cation, (sodium, potassium, etc.) can be combined to satisfy the required chemical charge balance. However, more than one anionic group may be charge balanced by a divalent cation, or more than one monovalent cation may be necessary to satisfy the charge requirements of a poly-anionic radical.
  • a -(CH2) p O3M moiety substituted with sodium atoms has the formula -(CH2)pPO3Na3.
  • Divalent cations such as calcium (Ca2 + ) or magnesium (Mg2+) may be substituted for or combined with other suitable monovalent water soluble cations.
  • Preferred cations are sodium and potassium, more preferred is sodium.
  • X is a water soluble anion such as chlorine (CI"), 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 modified polyethyleneimine polymers of the present invention comprise polyamine backbones wherein less than about 50% of the 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.
  • modified polyethyleneimine polymers which comprise no "oxy" R units comprise polyamine backbones wherein less than 50% of the 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 modified polyethyleneimine polymers of the present invention comprise modified homogeneous and non-homogeneous polyamine backbones, wherein 100% or less of the -NH units are modified.
  • 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 of the chosen method of chemical synthesis.
  • 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 purposes of the 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 of the 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 of the modified polyethyleneimine polymers of the present invention.
  • Preferred modified polyethyleneimine polymers of the 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.
  • backbone amine nitrogens must be modified in the same manner, the choice of modification being left to the specific needs of the formulator.
  • the degree of ethoxylation is also determined by the specific requirements of the formulator.
  • the preferred polyamines that comprise the backbone of the compounds of the 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 (TEPA).
  • the cogenerically derived mixture does not appear to separate by distillation and can include other materials such as cyclic amines and particularly piperazines. There can also be present cyclic amines with side chains in which nitrogen atoms appear. See U.S. Patent 2,792,372, Dickinson, issued May 14, 1957, which describes the preparation of PEA's.
  • Preferred amine polymer backbones comprise R units that are C2 alkylene
  • PEI's polyethyleneimines
  • PEI's having a ratio of m to n of about 2:1 are most preferred.
  • Preferred backbones, prior to modification have the general formula:
  • the 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.
  • modified polyethyleneimine polymers 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, Ulrich et al., issued December 5, 1939; U.S. Patent 3,033,746, Mayle et al., issued May 8, 1962; U.S. Patent 2,208,095, Esselmann et al., issued July 16, 1940; U.S. Patent 2,806,839, Crowther, issued September 17, 1957; and U.S. Patent 2,553,696, Wilson, issued May 21, 1951; all herein incorporated by reference.
  • Formula I depicts a modified polyethyleneimine polymer comprising a PEI backbone wherein all substitutable nitrogens are modified by replacement of hydrogen with a polyoxyalkyleneoxy unit, -(CH2CH2 ⁇ )7H, having the formula:
  • modified polyethyleneimine polymer that is fully modified by one type of moiety.
  • Formula II depicts a modified polyethyleneimine polymer comprising a PEI backbone wherein all substitutable primary amine nitrogens are modified by replacement of hydrogen with a polyoxyalkyleneoxy unit, -(CH2CH2 ⁇ )7H, the molecule is then modified by subsequent oxidation of all oxidizable primary and secondary nitrogens to N-oxides, said modified polyethyleneimine polymer having the formula:
  • Formula III depicts a modified polyethyleneimine polymer comprising a
  • PEI backbone wherein all backbone hydrogen atoms are substituted and some backbone amine units are quaternized.
  • the substituents are polyoxyalkyleneoxy units, -(CH2CH2O)7H, or methyl groups.
  • the modified PEI soil release polymer has the formula:
  • Formula IV depicts a modified polyethyleneimine 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 modified polyethyleneimine 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 of the 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 of the 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.
  • Stilbenedisulfonate Brightener A stilbenedisulfonate brightener is included in the laundry detergent composition of the present invention.
  • the stilbenedisulfonate brighteners are known in laundry detergent compositions as a class of florescent whitening agents and/or as optical brighteners. Such florescent whitening agents, when deposited onto a fabric, convert ultraviolet light into visible wavelength light, thus making the fabric appear brighter and more vivid to the human eye. Without intending to be limited by theory, it is believed that in addition to these brightener effects, a stilbenedisulfonate brightener and a modified polyethyleneimine polymer interact with the surfactant system to provide enhanced dye transfer inhibition effects.
  • a preferred stilbenedisulfonate brightener is a derivative of diamino stilbene.
  • a nonlimiting example of a stilbenedisulfonate brightener useful herein includes 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[(4-aniiino-6- morpholino-1 ,3,5-triazin-2-yl) amino]stilbene-2,2'-disulfonic acid disodium salt, the 4,4'-bis- (1,2,3-triazol-2-yl)-stilbenes, 2-(stilbene-4-yl)-2H-naphtho- [1,2- d]triazole, and mixtures thereof.
  • Stilbenedisulfonate brightener examples include Ciba Specialty Chemicals (Greenboro, USA; Monthey, Switzerland), Bayer Corp. (South Carolina, USA), Hilton-Davis (Italy), and 3V Inc. (Georgetown, USA).
  • Examples of a stilbenedisulfonate brightener useful in the present composition are identified in U.S. Patent 4,790,856, issued to Wixon on December 13, 1988. Mixtures of stilbenedisulfonate brighteners are preferred herein.
  • the total stilbenedisulfonate brightener level in the laundry detergent bar may be from about 0.01% to about 5%, preferably from about 0.05% to about 1.2%, and more preferably from about 0.05% to about 0.5%, by weight of the final laundry detergent.
  • Adjunct Ingredients The balance of the laundry detergent composition disclosed herein contains adjunct ingredients, some non-limiting examples of which are listed below. Unless otherwise noted, all of the percentages below are by weight of the final composition.
  • compositions of the subject invention comprise from about 0.5% to about 30% moisture, preferably from about 1% to about 10% moisture, more preferably from about 2% to about 6% moisture.
  • the moisture level may be significantly higher.
  • Examples of a builder useful herein are the phosphates, pyrophosphates, orthophosphates, tripolyphosphates, higher polyphosphates, and mixtures thereof.
  • the water soluble alkali metal salts of these builders are preferred.
  • a preferred builder is a phosphate builder such as the 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 level of builder can vary widely depending upon the end use of the laundry detergent composition and its desired physical form.
  • the laundry detergent composition will typically comprise at least about 1% builder.
  • Liquid detergent formulations typically comprise from about 5% to about 50%, more typically about 5% to about 30%, by weight, of detergent builder.
  • Granular detergent formulations typically comprise from about 10% to about 80%, more typically from about 15% to about 50% by weight, of the detergent builder.
  • the laundry detergent bar of the present invention contains 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 final composition.
  • The4aundry detergent composition 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 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.
  • a preferred adjunct ingredient in the laundry detergent composition is an other dye transfer inhibitor ("other DTI") ingredient to further prevent diminishing of color fidelity and intensity in fabrics, and the transfer of dyes.
  • other DTI ingredients may complement and further enhance the dye transfer inhibition benefits of the present invention.
  • a preferred other DTI ingredient includes a traditional polymeric dye transfer inhibition material capable of binding fugitive dyes to prevent them from depositing on the fabrics, a decolorization dye transfer inhibition material capable of decolorizing the fugitives dye by oxidation, or a combination thereof.
  • Non-limiting, preferred examples of an other DTI ingredient includes polyvinylpyrridine N-oxide (PVNO), polyvinylpyrrolidone (PVP), polyvinylimidazole, N-vinylpyrrolidone and N-vinylimidazole copolymers (referred to as "PVPI”), copolymers thereof, and mixtures thereof.
  • PVNO polyvinylpyrridine N-oxide
  • PVP polyvinylpyrrolidone
  • PVPI polyvinylimidazole
  • copolymers thereof and mixtures thereof.
  • An example of an other DTI ingredient which provides dye transfer inhibition effects via decolorization is hydrogen peroxide or a hydrogen peroxide source, such as percarbonate or perborate.
  • the amount of other DTI ingredient included in the subject compositions is less than about 5%, preferably from about 0.05% to about 3%, more preferably from about 0.1 % to about 2%, by weight of the final composition.
  • florescent whitening agent in addition to a stilbenedisulfonate brightener, other classes of florescent whitening agent, herein described as an "other brightener" may be included as an adjunct ingredient in the laundry detergent of the present invention.
  • An especially preferred other brightener useful herein includes, for example, disodium 4,4'-bis-(2 sulfostyryl)biphenyl, also known as Brightener-49, analogs thereof, and combinations thereof.
  • Brightener-49 also known as Brightener-49
  • Such an other brightener is available from, for example, Ciba Giegy, under the tradename TINOPAL CBS.
  • Soil suspending agents can also be used herein. In the present invention, their use is balanced with the fabric softening clay/clay flocculating agent combination to provide optimum cleaning and fabric softening performance.
  • One such soil suspending agent is an acrylic/maleic copolymer, commercially available as Sokolan®, from BASF Corp.
  • Other soil suspending agents include polyethylene glycols having a molecular weight of about 400 to 10,000, and ethoxylated mono- and polyamines, and quaternary salts thereof.
  • a highly preferred soil suspending agent is a water-soluble salt of carboxymethylcellulose and carboxyhydroxymethylcellulose. Soil suspending agents may be used at levels up to about 5%, preferably about 0.1% to about 1%, by weight of the laundry detergent bar
  • the laundry detergent composition of the present invention may contain an optional surfactant commonly used in detergent products, such as a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, a zwitterionic surfactant, and mixtures thereof.
  • an optional surfactant commonly used in detergent products such as a cationic surfactant, a nonionic surfactant, an amphoteric surfactant, a zwitterionic surfactant, and mixtures thereof.
  • optional surfactants can be included at levels up to a total of about 10%, preferably from about 0.5% to about 5%, by weight, of the laundry detergent bar.
  • the laundry detergent composition may optionally contain a fabric softening clay, preferably a smectite-type clay.
  • the smectite-type clays can be described as expandable, three-layer clays; i.e., alumino-silicates and magnesium silicates, having an ion exchange capacity of at least about 50 meq/100 g. of clay.
  • the clay particles are of a size that they can not be perceived tactilely, so as not to have a gritty feel on the treated fabric of the clothes.
  • the fabric softening clay can be added to provide about 1 % to about 50%, preferably from about 2% to about 20%, and more preferably about 3% to 14% by weight of the final composition.
  • Gelwhite GP is an extremely white form of smectite-type clay and is therefore preferred when formulating white granular detergent compositions.
  • Volclay BC which is a smectite-type clay mineral containing at least 3% iron (expressed as Fe2 ⁇ 3) in the crystal lattice, and which has a very high ion exchange capacity, is one of the most efficient and effective clays for use in the instant compositions from the standpoint of product performance.
  • 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.
  • Another preferred optional component in the laundry detergent composition is a secondary fabric softener component in addition to the softening clay.
  • Such materials may be used, if any, at levels of about 0.1% to 5%, more preferably from 0.3% to 3%, and include: amines of the formula R4R5R6N, wherein R4 is C5 to C22 hydrocarbyl, R5 and Re are independently C ⁇ to C10 hydrocarbyl.
  • One preferred amine is ditallowmethyl amine; complexes of such amines with fatty acid of the formula R7COOH, wherein R7 is C9 to C22 hydrocarbyl, as disclosed in EP No. 0,133,804; complexes of such amines with phosphate esters of the formula R8 ⁇ -P(O)(OH)-ORg and HO- P(O)(OH)-ORg, wherein Re and R9 are independently Ci to C20 alkyl of alkyl ethoxylate of the formula -alkyl-(OCH2CH2); cyclic amines such as imidazolines of the general formula 1 -(higher alkyl) amido (lower alkyl)-2-(higher alkyl)imidazoline, where higher alkyl is from 12 to 22 carbons and lower alkyl is from 1 to 4 carbons, such as described in UK Patent Application GB 2,173,827; and quaternary ammonium compounds of the formula R10 11 12R13N +
  • the polyme ⁇ c clay flocculating agent provides improved deposition of the fabric softening clay, and typically, have a molecular weight greater than about 100,000.
  • examples of such materials 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(ethyleoe oxide) polymer.
  • the amount of clay flocculating agent, if any, is about 0.2-2%, preferably about 0.5-1%.
  • a particularly preferred adjunct ingredient herein is a detergent chelant.
  • Such chelants 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. This is especially preferred in the laundry detergent bars of the current invention.
  • 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 may be included herein at a level up to about 5%, preferably from about 0.1% to about 3%, more preferably from about 0.2% to about 2%, even more preferably from about 0.5% to about 1.0%.
  • Another preferred additional component of the laundry detergent composition 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 about 12 carbon atoms.
  • fatty alcohol if any, is present in the laundry detergent composition 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 detergent composition as free fatty alcohol. However, low levels of fatty alcohol may be introduced into the bars as impurities or as unreacted starting material.
  • laundry detergent compositions 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 highly preferred adjunct ingredient herein is a bleach component.
  • the bleaching component may 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 ger se, such as represented by the formula: CH3(CH2)w-NH-C(O)-(CH2)zCO3H wherein z is from 2 to 4 and w is from 4 to 10.
  • 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 may be added, if any, at a level up to 20%, preferably from about 1% to about 10%, more preferably from about 2% to about 6%.
  • additional bleach activators useful herein are to be found in U.S. 4,915,854 to Baker, et al., issued April 10, 1990, U.S. 4,412,934 to Chung and Spadini, issued November 1 , 1983 and 4,634,551 to Hardy and Ingram, issued January 6, 1987.
  • the hydrophobic activator nonanoyloxybenzene sulfonate (NOBS) and the hydrophilic tetraacetyl ethylene diamine (TAED) activator are typical, and mixtures thereof can also be used.
  • photobleach material particularly the phthalocyanine photobleaches which are described in U.S. Patent 4,033,718 issued July 5, 1977, incorporated herein by reference.
  • Preferred photobleaches are metal phthalocyanine compounds, the metal preferably having a valance of +2 or +3; zinc and aluminum are preferred metals.
  • Such photobleaches are available, for example, 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%.
  • Calcium carbonate (also known as Calcarb) is also a well known and often used filler component, especially in a laundry detergent bar.
  • Fillers include minerals, such as talc, bentonite, and hydrated magnesium silicate-containing minerals, where the silicate is mixed with other minerals, e.g., old mother rocks such as dolomite.
  • Sodium sulfate is a well-known filler useful herein. It may be a by-product of the surfactant sulfation and sulfonation processes, or it can be added separately. Filler materials are typically used, if included, at levels up to 40%, preferably from about 5% to about 25%.
  • Binding agents are especially useful in a laundry detergent bar, for holding it together in a cohesive, yet soluble form. Binding agents include natural and synthetic starches, gums, thickeners, and mixtures thereof. An example of a preferred binding agent is coconut monoethylene amide, and related materials. Such materials, if included, are typically at levels up to about 3%, preferably about 0.5-2%.
  • hydrotrope or mixture of hydrotropes
  • 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 alkylbenzene sulfonic acid prior to its neutralization.
  • the hydrotrope, if present, will preferably be present at from about 0.5% to about 5% of the laundry detergent bar.
  • the enzyme useful herein has an enzymatic activity, and includes an amylase, a cellulase, a cutinase, a lipase, a peroxidase, a protease, and mixtures thereof. Preferred selections are influenced by factors such as pH- activity and/or stability optima, thermostability, and stability to active detergents, builders and the like. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
  • An enzyme is typically incorporated into a laundry detergent composition at levels sufficient to provide a "cleaning-effective amount.”
  • cleaning effective amount refers to any amount capable of producing a cleaning, stain removal, soil removal, whitening, deodorizing, or freshness-improving effect on substrates such as fabrics, and the like.
  • typical amounts are up to about 5 mg by weight, more typically 0.01 mg to 3 mg, of active enzyme per gram of the detergent composition.
  • the compositions herein will typically comprise from 0.001% to 5%, preferably 0.01 %-1% by weight of a commercial enzyme preparation.
  • Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0.1 Anson units (AU) of activity per gram of composition. Higher active levels may also be desirable in highly concentrated detergent formulations.
  • Amylases are particularly suitable for automatic dishwashing purposes.
  • An amylase useful herein includes, for example, -amylases described in GB 1,296,839 to Outtrup H, et al., published November 22, 1972 to Novo Industries A/S of Denmark (hereinafter, "Novo”); RAPIDASE® from International Bio- Synthetics, Inc.; TERMAMYL® from Novo; FUNGAMYL® from Novo; and DURAMYL® from Novo.
  • Cellulases usable herein include both bacterial and fungal types, preferably having a pH optimum between 5 and 9.5.
  • Suitable cellulases are also disclosed in GB-B-2,075,028 to Barbesgaar, et al., issued March 28, 1984; GB-B-2,095,275 to Murata, et al., issued August 7, 1985 and DE-OS-2,247,832 to Horikoshi and Ikeda, issued June 27 1974. CAREZYME® and CELLUZYME® (Novo) are especially useful. See also WO 91/17243 to Hagen, et al., published November 14, 1991. Cutinase enzymes suitable for use herein are described in WO 8809367A to Kolattukudy, et al., published December 1 , 1988.
  • Suitable lipase enzymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB 1,372,034 to Dijk and Berg, published October 30, 1974. See also lipases in Japanese Patent Application 53,20487 to Inugai, published February 24, 1978. This lipase is available from Amano Pharmaceutical Co., Ltd., Nagoya, Japan, under the tradename LIPASE P "AMANO,” or "AMANO-P.”
  • Other suitable commercial lipases include Amano- CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var.
  • lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., the Netherlands, and lipases ex Pseudomonas gladioli.
  • LIPOLASE® enzyme derived from Humicola lanuginosa and commercially available from Novo, see also EP 341 ,947 to Cornelissen, et al., issued August 31 , 1994, also describes a preferred lipase for use herein.
  • Lipase and amylase variants stabilized against peroxidase enzymes are described in WO 9414951 to Halkier, et al., published July 7, 1994 A to Novo. See also WO 9205249 to Clausen, et al., published April 2, 1992.
  • Peroxidase enzymes may be used in combination with oxygen sources, e.g., percarbonate, perborate, hydrogen peroxide, etc., for "solution bleaching" or prevention of transfer of dyes or pigments removed from substrates during the wash to other substrates present in the wash solution.
  • oxygen sources e.g., percarbonate, perborate, hydrogen peroxide, etc.
  • Known peroxidases include horseradish peroxidase, ligninase, and haloperoxidases such as chloro- or bromo-peroxidase.
  • Peroxidase-containing detergent compositions are disclosed in WO 8909813 A to Damhus, et al., published October 19, 1989.
  • a suitable example of a protease is a subtilisin, which is obtained from particular strains of S. subtilis and B. licheniformis.
  • protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE® by Novo.
  • a suitable protease includes ALCALASE® and SAVINASE® from Novo and MAXATASE® from International Bio-Synthetics, Inc., the Netherlands; as well as Protease A and Protease B as disclosed in EP 130,756 A to Bott, published January 9, 1985.
  • An especially preferred protease referred to as "Protease D," as described in U.S. Patent 5,679,630 to A. Baeck, et al, issued October 21, 1997, entitled “Protease-Containing Cleaning Compositions," and U.S. Patent 5,677,272 to C. Ghosh, et al, issued October 14, 1997, entitled “Bleaching Compositions Comprising Protease Enzymes.”
  • Glycerine is commonly incorporated in a laundry detergent compositions, especially a liquid detergent composition and a laundry detergent bar composition. If included, it is typically at concentrations up to about 3%, preferably about 0.5-1.5%. 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%.
  • Laundry detergent processes are known.
  • granular laundry detergent compositions may be manufactured by methods such as blow drying, granulation, and agglomeration.
  • exposure of the modified polyethyleneimine polymer and the stilbenedisulfonate brightener to acid are minimized, as extended exposure to acidic conditions may cause these compounds to degrade.
  • the modified polyethyleneimine polymer and the stilbenedisulfonate brightener be added to the laundry detergent composition after the neutralization of the anionic surfactant system (if pre-neutralized anionic surfactants are not used), and homogenized therein.
  • the laundry detergent bars of the present invention may 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.
  • a blender mixes the raw materials.
  • Linear alkylbenzene sulfonic acid is added into a mixture of alkaline inorganic salts, strong electrolyte salts, CFAS, builder, and filler (preferably including sodium carbonate).
  • the resulting partly-neutralized mixture is mechanically worked to effect homogeneity and to complete the neutralization of the mixture.
  • pre-neutralized LAS paste is available, and economically feasible, it may be used herein.
  • the modified polyethyleneimine polymer, and any optional surfactants are added, followed by the stilbenedisulfonate brightener, other DTIs (if present), and any additional adjunct ingredients.
  • the mixing takes 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, and 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 may be cooled, for example in a cooling tunnel, before it is wrapped, cased, and sent to storage.
  • the modified polyethyleneimine polymer and the stilbenedisulfonate brightener are added after neutralization of the LAS.
  • the modified polyethyleneimine polymer and the stilbenedisulfonate brightener may be added in any order.
  • polyphosphate can be used as an alkaline salt in the neutralization.
  • This test determines the Dye Transfer Inhibition capability of test compositions versus a given dye.
  • Test fabrics are typically cotton or polycotton fabrics.
  • Control product swatch is definitely much less stained.
  • -3 Control product swatch is noticeably less stained.
  • Control product swatch is slightly less stained. -1 Control product swatch may be less stained. 0 There is no difference between the control and the test product swatches. 1 Test product swatch may be less stained.
  • Test product swatch is slightly less stained.
  • Test product swatch is noticeably less stained.
  • Test product swatch is definitely much less stained.
  • Laundry detergent bars of the present invention having the following compositions are prepared by conventional blending, milling and plodding procedures.
  • Laundry detergent composition F is in the form of spray dried granules made by a tower process.
  • Laundry detergent composition G is a granular composition made in an agglomerator.
  • Laundry detergent composition H is a liquid detergent composition.
  • Laundry detergent composition I is a paste detergent composition.
  • Laundry detergent composition J is a tablet detergent composition.

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Abstract

L'invention concerne une composition de pastille de détergent à lessive comprenant un système tensioactif anionique comprenant un sulfonate alcoylbenzène linéaire et un sulfate d'alkyle et la combinaison d'un certain polymère de poyléthylènéimine modifié et d'un éclaircissant de disulfonate de stilbène afin d'améliorer l'inhibition du transfert colorant.
PCT/US1998/015349 1998-07-23 1998-07-23 Composition de detergent a lessive WO2000005334A1 (fr)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001059054A1 (fr) * 2000-02-10 2001-08-16 The Procter & Gamble Company Compositions de detergents a lessive possedant une combinaison d'un polymere d'amine cyclique et d'un inhibiteur de transfert de couleurs
WO2005059079A1 (fr) * 2003-12-16 2005-06-30 Unilever Plc Composition de lessive
EP2135934A1 (fr) 2008-06-16 2009-12-23 Unilever PLC Utilisation d'une composition de détergent de blanchisserie
EP2202290A1 (fr) 2008-12-23 2010-06-30 Unilever PLC Composition de lavage fluide et son conditionnement
WO2011100667A1 (fr) 2010-02-14 2011-08-18 Ls9, Inc. Tensio-actif et compositions nettoyantes comprenant des alcools gras ramifiés produits par voie microbienne
WO2011120799A1 (fr) 2010-04-01 2011-10-06 Unilever Plc Procédé de structuration de liquides détergents à l'aide d'huile de ricin hydrogénée
DE212009000119U1 (de) 2008-09-12 2011-12-30 Unilever N.V. Spender und Vorbehandlungsmittel für viskose Flüssigkeiten
EP2495300A1 (fr) 2011-03-04 2012-09-05 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Structuration de liquides détergents avec de l'huile de ricin hydrogénée
WO2018224379A1 (fr) 2017-06-09 2018-12-13 Unilever Plc Système de distribution de lessive liquide
WO2019038187A1 (fr) 2017-08-24 2019-02-28 Unilever Plc Perfectionnements se rapportant au nettoyage de tissus
WO2019038186A1 (fr) 2017-08-24 2019-02-28 Unilever Plc Perfectionnements se rapportant au nettoyage de tissus
WO2019144372A1 (fr) * 2018-01-26 2019-08-01 The Procter & Gamble Company Granulés détergents ayant une teneur en tensioactif anionique élevée

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WO1995027038A1 (fr) * 1994-03-30 1995-10-12 The Procter & Gamble Company Pains de detergent a lessive a blanchiment ameliore et inhibition du transfert des colorants
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
WO1997042283A1 (fr) * 1996-05-03 1997-11-13 The Procter & Gamble Company Compositions pour detergents en barres
WO1998053040A1 (fr) * 1997-05-22 1998-11-26 The Procter & Gamble Company Detergents a lessive en pains ayant des proprietes de moussage et des proprietes physiques ameliorees

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WO1995027038A1 (fr) * 1994-03-30 1995-10-12 The Procter & Gamble Company Pains de detergent a lessive a blanchiment ameliore et inhibition du transfert des colorants
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
WO1997042283A1 (fr) * 1996-05-03 1997-11-13 The Procter & Gamble Company Compositions pour detergents en barres
WO1998053040A1 (fr) * 1997-05-22 1998-11-26 The Procter & Gamble Company Detergents a lessive en pains ayant des proprietes de moussage et des proprietes physiques ameliorees

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001059054A1 (fr) * 2000-02-10 2001-08-16 The Procter & Gamble Company Compositions de detergents a lessive possedant une combinaison d'un polymere d'amine cyclique et d'un inhibiteur de transfert de couleurs
WO2005059079A1 (fr) * 2003-12-16 2005-06-30 Unilever Plc Composition de lessive
EP2135934A1 (fr) 2008-06-16 2009-12-23 Unilever PLC Utilisation d'une composition de détergent de blanchisserie
DE212009000119U1 (de) 2008-09-12 2011-12-30 Unilever N.V. Spender und Vorbehandlungsmittel für viskose Flüssigkeiten
EP2202290A1 (fr) 2008-12-23 2010-06-30 Unilever PLC Composition de lavage fluide et son conditionnement
WO2011100667A1 (fr) 2010-02-14 2011-08-18 Ls9, Inc. Tensio-actif et compositions nettoyantes comprenant des alcools gras ramifiés produits par voie microbienne
WO2011120799A1 (fr) 2010-04-01 2011-10-06 Unilever Plc Procédé de structuration de liquides détergents à l'aide d'huile de ricin hydrogénée
EP2495300A1 (fr) 2011-03-04 2012-09-05 Unilever Plc, A Company Registered In England And Wales under company no. 41424 of Unilever House Structuration de liquides détergents avec de l'huile de ricin hydrogénée
WO2018224379A1 (fr) 2017-06-09 2018-12-13 Unilever Plc Système de distribution de lessive liquide
WO2019038187A1 (fr) 2017-08-24 2019-02-28 Unilever Plc Perfectionnements se rapportant au nettoyage de tissus
WO2019038186A1 (fr) 2017-08-24 2019-02-28 Unilever Plc Perfectionnements se rapportant au nettoyage de tissus
WO2019144372A1 (fr) * 2018-01-26 2019-08-01 The Procter & Gamble Company Granulés détergents ayant une teneur en tensioactif anionique élevée

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