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
  • C11D3/16—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
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
  • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
• • 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
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3942—Inorganic per-compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/04—Carboxylic acids or salts thereof
  • C11D1/06—Ether- or thioether carboxylic acids
• • 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
  • C11D1/123—Sulfonic acids or sulfuric acid esters; Salts thereof derived from carboxylic acids, e.g. sulfosuccinates
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
  • C11D1/146—Sulfuric acid esters
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/02—Anionic compounds
  • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
  • C11D1/29—Sulfates of polyoxyalkylene ethers
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3907—Organic compounds
  • C11D3/3915—Sulfur-containing compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3907—Organic compounds
  • C11D3/3917—Nitrogen-containing compounds

Definitions

• the present invention relates to a bleach detergent composition that contains a modified polyamine especially useful as a cotton soil release -and dispersant agent, and to processes for making.
• Various fabric surface modifying agents have been commercialized and are currently used in detergent compositions and fabric softener/antistatic articles and compositions.
• surface modifying agents are soil release polymers.
• Soil release polymers typically comprise an oligomeric or polymeric ester "backbone" and are generally very effective on polyester or other synthetic fabrics where the grease or similar hydrophobic stains form an attached film and are not easily removed in an aqueous laundering process.
• the soil release polymers have a less dramatic effect on "blended” fabrics, that is, on fabrics that comprise a mixture of cotton .and synthetic material, and have little or no effect on cotton articles.
• Alkoxylated polyamines are heretofore known and have been shown to provide specific cleaning benefits. Examples of alkoxylated polyamines are disclosed in U.S.
• effective soil release .agents for cotton articles and dispersants can be prepared from certain modified polyamines. This unexpected result has yielded compositions that can provide soil release benefits for cotton articles that were once available only on synthetic and synthetic-cotton blended fabric.
• bleaching agents especially peroxygen bleaches which are formulated into both liquid and granular laundry detergent compositions
• the formulator must consider the instability of a particular soil dispersant toward the bleach.
• Many successful dispersents have polyalkyleneamine or polyalkyleneimine backbones which are susceptible to oxidation at the amine functionalities and potentially to breakdown or fragmentation by bleaching agents which may be present. From another view, the interaction of bleaching agents with these polyalkyleneimine-based dispersents depletes the .amount of bleach present, therefore affecting the bleaching performance.
• the present invention is a bleach detergent composition that comprises a bleach agent, and a complexed polyamine which comprises a modified polyamine and an anionic species capable of forming a complex with the modified polyamine.
• the modified polyamine is especially useful as a cotton soil release and dispersant agent.
• the complexed polyamine is less reactive with the bleach agent in a wash solution containing the bleach detergent composition.
• the invention also relates to a process for preparing a bleach detergent composition that contains a bleach agent and a complexed polyamine which is substantially non-reactive with the bleach agent in the wash solution.
• the bleach detergent composition more particularly comprises a peroxygen bleach agent, a complexed polyamine comprising a modified polyamine and an anionic agent capable of forming a complex with the modified polyamine, and adjunct detergent ingredients.
• the process of the present invention more particularly comprises the steps of pre- mixing a modified polyamine with an anionic agent, preferably an anionic detersive surfactant, to form a complexed polyamine, and thereafter, adding adjunct detergent ingredients, such as builders and water to form the bleach detergent composition.
• an anionic agent preferably an anionic detersive surfactant
• the bleach detergent composition preferably comprises: a) at least about 0.01% to about 95%, preferably from about 0.1% to about 60%, more preferably from about 0.1% to about 30% by weight, of a detergent surfactant selected from the group consisting of anionic, nonionic, cationic, zwitterionic, and ampholytic surfactants, and mixtures thereof; b) from about 0.05% to about 30%, more preferably from about 0.5% to about 30%, most preferably from about 1% to about 20%, by weight, of a bleach agent; c) from about 0.01 to about 10% by weight, of a complexed polyamine, the complexed polyamine comprising a water-soluble alkoxylated polyamine and an anionic detersive surfactant; and d) adjunct ingredients selected from the group consisting of builders, optical brighteners, soil release polymers, dye transfer agents, dispersents, enzymes, suds suppressers, dyes, perfumes, colorants, filler salts, hydrotropes, enzymes, photoactivators, flu
• the bleaching agent preferably is a peroxygen bleaching compound which is capable of yielding hydrogen peroxide in .an aqueous liquor.
• peroxygen bleaching compounds which is capable of yielding hydrogen peroxide in .an aqueous liquor.
• These compounds are well known in the art and include hydrogen peroxide and the alkali metal peroxides, organic peroxide bleaching compounds such as urea peroxide, and inorganic persalt bleaching compounds, such as the alkali metal perborates, percarbonates, perphosphates, and the like. Mixtures of two or more such bleaching compounds can also be used, if desired.
• Preferred peroxygen bleaching compounds include sodium perborate, commercially available in the form of mono-, tri-, and tetra-hydrate, sodium pyrophosphate peroxyhydrate, urea peroxy-hydrate, sodium peroxide, peroxyphthalate and sodium percarbonate. Particularly preferred are sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate. Sodium percarbonate is especially preferred because it is very stable during storage and yet still dissolves very quickly in the bleaching liquor. It is believed that such rapid dissolution results in the formation of higher levels of percarboxylic acid and, thus, enhanced surface bleaching performance.
• bleaching agent that can be used without restriction encompasses percarboxylic acid bleaching agents .and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta- chloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid.
• Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985, Europe ⁇ Patent Application 0,133,354, Banks et al, published February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1, 1983.
• Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al.
• a preferred percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers.
• the percarbonate can be coated with silicate, borate or water-soluble surfactants.
• Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.
• Mixtures of bleaching agents can also be used.
• Bleach activators can also be added to the bleach detergent composition in addition to the peroxygen bleaching agents.
• the peroxygen bleaching agents, the perborates, the percarbonates, etc. are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator.
• Various nonlimiting examples of activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934.
• the nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used. See also U.S.
• the amount of bleach activators will typically be from about 0.1% to about 60%, more typically from about 0.5% to about 40% of the bleaching composition comprising the bleaching .agent-plus-bleach activator.
• a highly preferred activator of the benzoxazin-type is:
• Still another class of preferre g d bleach activa ⁇ torso includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formulae:
• lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including
• Another preferred bleach agent is a peroxyacid bleaching -agent, of which .an amide substituted peroxyacid precursor compound is more preferred, including one having the formula: O O O O O
• R ⁇ is C1-C14 alkyl, aryl, alkylaryl, and mixtures thereof; R ⁇ is C1-C14 alkylene, arylene, alkylarylene, and mixtures thereof; R ⁇ is hydrogen, Ci -CIQ alkyl, aryl, alkylaryl, and mixtures thereof; L is any suitable leaving group (a preferred leaving group is phenyl sulfonate).
• R* preferably contains from 6 to 12 carbon atoms.
• R ⁇ preferably contains from 4 to 8 carbon atoms.
• R may contain, where applicable, branching, substitution, or both and may be sourced from either synthetic sources or natural sources including for example, tallow fat.
• RA alogous structural variations are permissible for RA
• the substitution can include alkyl, halogen, nitrogen, sulfur .and other typical substituent groups or organic compounds.
• R is preferably H or methyl.
• R* and R* should not contain more than 18 carbon atoms in total. .Amide substituted bleach activator compounds of this type are described in EP-A- 0170386.
• bleach activators of the above formulae include (6- octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6- decanamido-caproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551, incorporated herein by reference.
• Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein.
• One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc .and/or aluminum phthalo- cyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from about 0.025% to about 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.
• the bleaching compounds can be catalyzed by means of a manganese compound.
• a manganese compound Such compounds are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S. Pat. 5,114,606; and European Pat. App. Pub. Nos.
• metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611.
• the use of manganese with various complex ligands to enhance bleaching is also reported in the following United States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.
• compositions .and processes herein can be adjusted to provide on the order of at least one part per ten million of the active bleach catalyst species in the aqueous washing liquor, and will preferably provide from about 0.1 ppm to about 700 ppm, more preferably from about 1 ppm to about 500 ppm, of the catalyst species in the laundry liquor.
• the modified polyamines used in the process invention are water-soluble or water- dispersible, especially useful for cleaning cotton-containing fabrics or as a dispersant.
• 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 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), 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 preferably substitution is accompanied by oxidation or quaternization of at least one backbone nitrogen.
• the linear or non-cyclic polyamine backbones that comprise the modified polyamines 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 of the 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 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.
• a primary amine moiety located at the end of the main polyamine backbone having the structure
• -NH 2 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
• [N-R]- is modified according to the present invention, it is thereafter defined as a W "backbone” unit, or simply a W unit.
• W backbone
• some or all of the secondary amine moieties can remain unmodified. These unmodified secondary amine moieties by virtue of their position in the backbone chain remain "backbone” units.
• 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
• —[N-R]- is modified according to the present invention, it is thereafter defined as a Y "branching" unit, or simply a Y unit.
• Y branching
• 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 of the polyamines of the present invention can be therefore represented by the general formula V( remind+l)W m Y n Z
• the polyamine backbone has the formula
• 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 polyamine according to the present invention has the formula vw m z that is, n is equal to 0. The greater the value of n (the lower the ratio of m to n), the greater the degree of branching in the molecule.
• 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 (HOCH2CH2)HN-
• 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. 11
• the polyamines 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-C12 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; Cg-Ci2 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 unit need not be 1,4-substituted, but can also be 1,2 or 1,3 substituted C2-C12 alkylene, preferably ethylene, 1,2-propylene, and mixtures thereof, more preferably ethylene.
• the "oxy" R units comprise -(R 1 0) x R 5 (OR 1 ) x -,
• R units are C2-C12 alkylene, C4-C12 alkenylene, C3-C12 hydroxyalkylene, C4-C12 dihydroxyalkylene, C -Cj2 dialkylarylene, - (R 1 0) x R 1 -,-CH 2 CH(OR 2 )CH2-, -(CH 2 CH(OH)CH2 ⁇ ) z (R 1 0) y R 1 (OCH2CH- (OH)CH ) w -, -(R 1 0) x R 5 (OR 1 ) x -, more preferred R units are C 2 -C 12 alkylene, C 3 -C 12 hydroxy-alkylene, C 4 -C 12 dihydroxyalkylene, -(R ⁇ R 1 -, -(R 1 0) x R 5 (OR 1 ) x -, -(CH 2 CH(OH)CH2 ⁇ ) z (R 1 0)yR 1 (OCH 2 CH-(OH)CH2)
• Rl units are C2-C6 alkylene, and mixtures thereof, preferably ethylene.
• R 2 is hydrogen, and -(R*0) x B, preferably hydrogen.
• R- is Cj-Cig alkyl, C7-C12 arylalkylene, C7-C12 alkyl substituted aryl, C6-C
• R- units serve .as part of E units described herein below.
• R ⁇ is C1-C12 alkylene, C4-C ⁇ 2 alkenylene, Cg-Cj2 arylalkylene, C6-C J arylene, preferably CJ-CJO alkylene, C -Cj2 arylalkylene, more preferably C2-Cg alkylene, most preferably ethylene or butylene. 12
• R ⁇ is C1-C12 alkylene, C3-C12 hydroxyalkylene, C4-Cj2 dihydroxyalkylene, Cg- C 12 dialkylarylene, -C(O)-, -C(0)NHR 6 NHC(0)-, -C(0)(R 4 ) r C(0)-, -R ⁇ OR 1 )-, -CH 2 CH(OH)CH2 ⁇ (R 1 0)yR 1 OCH 2 CH(OH)CH 2 -, -C(0)(R 4 ) r C(0)-, -CH 2 CH(OH)CH 2 -, R 5 is preferably ethylene, -C(O)-, -C(0)NHR 6 NHC(0)-, -R ⁇ OR 1 )-, -CH 2 CH(OH)CH 2 -, -CH 2 CH(OH)CH2 ⁇ (R 1 0) y R 1 OCH 2 CH-(OH)CH2-, more preferably - CH 2 CH(OH)CH 2 -.
• R° is C2-C12 alkylene or Cg-C ⁇ arylene.
• the preferred "oxy" R units are further defined in terms of the R , R 2 , and R ⁇ units.
• Preferred "oxy" R units comprise the preferred R*, R 2 , and R ⁇ units.
• the preferred modified polyamines comprise at least 50% R units that are ethylene.
• Preferred R% R 2 , and R ⁇ units are combined with the "oxy" R units to yield the preferred "oxy” R units in the following manner. i) Substituting more preferred R 5 into -(CH2CH 2 0) x R 5 (OCH 2 CH2) x - yields
• E units are selected from the group consisting of hydrogen, C1-C22 alkyl, C3-C22 alkenyl, C7-C22 arylalkyl, C -C 2 2 hydroxyalkyl, -(CH 2 ) p C0 2 M, -(CH 2 ) q S0 3 M, -CH(CH 2 C0 2 M)C0 2 M, -(CH 2 ) p P0 3 M, -(R! ⁇ ) m B, -C(0)R 3 , preferably hydrogen, C 2 - C 2 2 hydroxyalkylene, benzyl, ⁇ 22 alkylene, -(R ⁇ O ⁇ B, -C(0)R 3 , -(CH 2 ) p C ⁇ 2M, -(CH 2 ) q S0 3 M, -CH(CH 2 C0 2 M)C0 2 M, more preferably Ci -C 2 2 alkylene, -(R ⁇ B, -C(0)R 3 , -(CH
• E units do not comprise hydrogen atom when the V, W or Z units are oxidi.zed, 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 N-oxides. According 13
• 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 ⁇ Cg alkyl, -(CH 2 ) q S0 3 M, -(CH 2 ) p C0 2 M, -(CH 2 ) q - (CHS0 3 M)CH 2 S0 3 M, -(CH 2 ) q (CHS ⁇ 2M)CH 2 S ⁇ 3M, -(CH 2 ) p P0 3 M, -P0 3 M, preferably hydrogen, -(CH 2 ) q S0 3 M, -(CH2) q (CHS0 3 M)CH 2 S ⁇ 3M, -(CH 2 ) q - (CHS02M)CH 2 S0 3 M, more preferably hydrogen or -(CH ) q S0 3 M.
• M is hydrogen or a water soluble cation in sufficient amount to satisfy charge balance.
• a sodium cation equally satisfies -(CH2) p C02M, and -(CH2) q S ⁇ 3M, thereby resulting in -(CH2) p C ⁇ 2Na, and -(CH2) q S03Na moieties.
• More th.an 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 P03M moiety substituted with sodium atoms has the formula -(CH2) p P03Na3.
• Divalent cations such as calcium (Ca + ) 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; k is less than or equal to the value of n; 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 polyamines used in 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.
• the most preferred polyamines 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 C 2 -C ⁇ 2 alkylene, preferred is C 2 -C3 alkylene, most preferred is ethylene.
• the polyamines 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 polyamines.
• Preferred polyamines 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 (PJAA'S), polyalkyleneimines (P.Ar S), preferably polyethyleneamine (PEA's), polyethyleneimines (PEI's), or PEA's or PEI's connected by moieties having longer R units than the parent PA 's, PAI's, PEA's or PEI's.
• a common polyalkyleneamine (PAA) is tetrabutylenepent ⁇ unine. 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 15
• 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 C 2 alkylene (ethylene) units, also known as polyethylenimines (PEI's).
• 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's prior to modification, will have a molecular weight greater than about 200 daltons.
• the relative proportions of primary, secondary and tertiary amine units in the polyamine backbone will vary, depending on the manner of preparation.
• Each hydrogen atom attached to each nitrogen atom of the polyamine backbone chain represents a potential site for subsequent substitution, quaternization or oxidation.
• polyamines can be prepared, for example, by polymerizing ethyleneimine in the presence of a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.
• a catalyst such as carbon dioxide, sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid, acetic acid, etc.
• Specific methods for preparing these polyamine backbones are disclosed in U.S. Patent 2,182,306, 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.
• modified polyamines of the present invention comprising PEI's, are illustrated in Formulas I - IV:
• Formula I depicts a polymer comprising a PEI backbone wherein all substitutable nitrogens are modified by replacement of hydrogen with a polyoxyalkyleneoxy unit, - (CH 2 CH 2 0)7H, having the formula 16
• Formula I This is an example of a polymer that is fully modified by one type of moiety.
• Formula II depicts a polymer comprising a PEI backbone wherein all substitutable primary amine nitrogens are modified by replacement of hydrogen with a polyoxyalkyleneoxy unit, -(CH 2 CH 2 0)7H, the molecule is then modified by subsequent oxidation of all oxidizable primary and secondary nitrogens to N-oxides, wherein the polymer has the formula
• Foimula II Formula III depicts a polymer comprising a PEI backbone wherein all backbone hydrogen atoms are substituted and some backbone amine units are quaterni.zed.
• the substituents are polyoxyalkyleneoxy units, -(CH 2 CH 2 0)7H, or methyl groups.
• the modified PEI polymer has the formula 17
• Formula IV depicts a polymer comprising a PEI backbone wherein the backbone nitrogens are modified by substitution (i.e. by -(CH 2 CH 2 0) H or methyl), quaternized, oxidized to N-oxides or combinations thereof.
• the resulting polymer has the formula
• not all nitrogens of a unit class comprise the s-ame 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.
• the Anionic Agent can be substituted on the primary and secondary amine nitrogens, except for the restrictions described herein above.
• the anionic agent can form an ionic complex with the nitrogens of the modified polyamine.
• this ion complex can be formed and is stable at a pH value in the range from about 5, up to about 10.
• the anionic agent has anionic functionality within this pH range, whereby when mixed with the modified polyamine under conditions where the pH of the mixture is from about 5 to about 10, the anionic agent and the polyamine can complex 18
• the complexation occurs at the nitrogen sites of the polyamine, where the unshared pairs of electrons are available to complex with the anionic species of the anionic agent.
• Preferred anionic agents are detergent ingredients that are typically used in detergent products and which are capable of forming the anionic species within the pH range of about 5 to about 10.
• anionic agents include anionic detersive surfactants and inorganic salts having a buffering pH of between 7 and 10, and include polyphosphate builders, such as alkali tripolyphosphate and alkali pyrophosphate.
• Other common detergent ingredients such as sodium carbonate and sodium silicate are generally not suitable as an anionic agent, since they either do not form a suitable anionic species at such pH, or their alkalinity is sufficiently high that solutions containing these materials have a pH generally above 10.
• the modified polyamine will resist forming any kind of an ionic complex. Therefore, when mixed with agents that have high alkalinity, or when mixed with an anionic agent of the present invention but at solution conditions where the pH is above about 10, the desired complexed polyamine will not be formed. Consequently, then the mixture is processed into a bleach detergent composition, and subsequently added into a wash solution, the uncomplexed nitrogen sites of the modified polyamine can react with and destroy the bleach agent.
• Nonlimiting examples of an anionic detersive surfactant useful .as an anionic agent include the conventional C ⁇ j -C j g alkyl benzene sulfonates ("LAS") and primary, branched-chain .and random C 0"C 2 o alkyl sulfates ("AS"), the Cj ⁇ -Cig secondary (2,3) alkyl sulfates of the formula CH (CH 2 ) x (CHOS0 " M + ) CH 3 and CH 3 (CH 2 ) y (CHOS03 _ M + ) CH 2 CH 3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the Cjo-C ⁇ g alkyl alkoxy sulfates (".AExS”; especially EO 1-7 ethoxy sulfates), Cjo-C
• adjunct detergent ingredients can be incorporated in the detergent composition during subsequent steps of the present process invention.
• adjunct ingredients include other surfactants such as cationic surfactants, other detergency builders, suds boosters or suds suppressers, anti-tarnish and anticorrosion agents, soil suspending agents, soil release agents, germicides, pH adjusting agents, non-builder alkalinity sources, chelating agents such as diethylene triamine penta acetic acid (DTP A) and diethylene triamine penta(methylene phosphonic acid), smectite clays, enzymes, enzyme-stabilizing agents, dye transfer inhibitors and 19
• DTP A diethylene triamine penta acetic acid
• smectite clays enzymes, enzyme-stabilizing agents, dye transfer inhibitors and 19
• Other builders can be generally selected from the various water-soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphorates, polyphosphonates, carbonates, borates, polyhydroxy sulfonates, polyacetates, carboxylates, and polycarboxylates.
• alkali metal especially sodium, salts of the above.
• Preferred for use herein are the phosphates, carbonates, Cirj-ig ⁇ att y acids, polycarboxylates, and mixtures thereof. More preferred are sodium tripolyphosphate, tetrasodium pyrophosphate, citrate, tartrate mono- and di-succinates, -and mixtures thereof (see below).
• crystalline layered sodium silicates exhibit a clearly increased calcium and magnesium ion exchange capacity.
• the layered sodium silicates prefer magnesium ions over calcium ions, a feature necessary to insure that substantially all of the "hardness" is removed from the wash water.
• These crystalline layered sodium silicates are generally more expensive than amorphous silicates as well as other builders. Accordingly, in order to provide an economically feasible laundry detergent, the proportion of crystalline layered sodium silicates used must be determined judiciously.
• the crystalline layered sodium silicates suitable for use herein preferably have the formula
• the crystalline layered sodium silicate has the formula
• inorganic phosphate builders are sodium and potassium tripolyphosphate, pyrophosphate, polymeric metaphosphate having a degree of polymerization of from about 6 to 21, and orthophosphates.
• polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of ethane 1 -hydroxy- 1, 1 -diphosphonic acid and the sodium and potassium salts of ethane, 1,1,2-triphosphonic acid.
• Other phosphorus builder compounds are disclosed in U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148, all of which are incorporated herein by reference.
• nonphosphorus, inorganic builders are tetraborate decahydrate and silicates having a weight ratio of SiO ⁇ to alkali metal oxide of from about 0.5 to about 4.0, preferably from about 1.0 to about 2.4.
• Water-soluble, nonphosphorus organic builders useful herein include the various alkali metal, ammonium and substituted ammonium 20
• polyacetates examples include carboxylates, polycarboxylates and polyhydroxy sulfonates.
• examples of polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, and citric acid.
• Polymeric polycarboxylate builders are set forth in U.S. Patent 3,308,067, Diehl, issued March 7, 1967, the disclosure of which is incorporated herein by reference.
• Such materials include the water-soluble salts of homo- and copolymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citraconic acid and methylene malonic acid.
• Some of these materials are useful as the water-soluble anionic polymer as hereinafter described, but only if in intimate admixture with the non-soap anionic surfactant.
• polyacetal carboxylates for use herein are the polyacetal carboxylates described in U.S. Patent 4,144,226, issued March 13, 1979 to Crutchfield et al, and U.S. Patent 4,246,495, issued March 27, 1979 to Crutchfield et al, both of which are incorporated herein by reference.
• These polyacetal carboxylates can be prepared by bringing together under polymerization conditions an ester of glyoxylic acid and a polymerization initiator. The resulting polyacetal carboxylate ester is then attached to chemically .stable end groups to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a detergent composition.
• Particularly preferred polycarboxylate builders are the ether carboxylate builder compositions comprising a combination of tartrate monosuccinate and tartrate disuccinate described in U.S. Patent 4,663,071, Bush et al., issued May 5, 1987, the disclosure of which is incorporated herein by reference.
• Suitable smectite clays for use herein are described in U.S. Patent 4,762,645, Tucker et al, issued August 9, 1988, Column 6, line 3 through Column 7, line 24, incorporated herein by reference.
• Suitable additional detergency builders for use herein are enumerated in the Baskerville patent, Column 13, line 54 through Column 16, line 16, and in U.S. Patent 4,663,071, Bush et al, issued May 5, 1987, both incorporated herein by reference.
• the process of the instant invention involves premixing a selected modified polyamine and an anionic agent to form the complexed polyamine.
• a preferred anionic -agent is an anionic detersive surfactant, preferably in the form of a neutralized sulfate or sulfonate detersive surfactant paste.
• the surfactant paste can comprise the .anionic detersive surfactant, and optionally a nonionic surfactant, but preferably will not contain a cationic 21
• the polyamine/surfactant complex typically has a higher oxidative degradation temperature as compared to the degradation temperature of the modified polyamines by themselves.
• the modified polyamine and anionic surfactant are mixed in an in-line static mixer or a conventional mixer (e.g., crutcher) for at least about 1 minute.
• the temperature at which the premixing step using the surfactant paste is performed typically is at a temperature of from about 25°C to about 80°C.
• the mixture will typically comprise only the .anionic surfactant and the modified polyamine, other detergent adjuncts can be added with or to the mixture; such adjuncts can include, by example, sodium tripolyphosphate, water, and other detersive surfactants
• the modified polyamine is preferably present in an amount of from about 0.01% to about 10%, more preferably from about 0.05% to about 5%, and most preferably from about 0.1% to about 1.0%, by weight of the overall detergent composition.
• the detersive surfactant paste preferably comprises from about 1% to about 70%, more preferably from about 20% to about 60%, and most preferably from about 25% to about 50%, by weight of surfactant, and the balance water and other minor ingredients.
• the surfactant paste comprising the complexed polyamine can then be made into detergents products, including both granular detergent products and liquid detergent products, by processes well known to those skilled in the art.
• the premixed complexed polyamine is then further processed into detergent compositions by known methods, which include slurrying and spray drying, and agglomeration, as discussed herein below.
• the bleach detergent compositions made using the complexed polyamine when placed into wash solutions, with or without soil loads, exhibit less loss of the bleach agent present in a washing solution compared to comparable compositions made by similar processes, except that the modified polyamine is either sprayed-on to or admixed as a particle into the detergent.
• the surfactant paste containing the complexed polyamine is made into a granular detergent process via a spray drying method.
• the surfactant paste is processed into a detergent slurry along with other detergent adjuncts (including, by example, zeolite, inorganic salts such as sodium tripolyphosphate, carbonate and sulfate, silicates, optional detergent surfactants, polymeric polycarboxylate builders, silicates, optical brighteners, colorants, antiredeposition agents, fillers, and other compatible detergent ingredients, and mixtures thereof)
• the slurry is spray dried to form a spray-dried granular detergent composition.
• This step can be completed in a conventional spray drying tower operated at an inlet temperature range of from about 180°C to about 420°C.
• apparatus operates by spraying the slurry via nozzles into a counter-current (or co-current) stream of hot air which ultimately forms porous spray-dried granules.
• An alternative process comprises a) premixing an anionic surfactant paste and a modified polyamine, b) agglomerating the surfactant paste comprising the complexed polyamine with other dry detergent ingredients i) initially in a high speed mixer/densifier, and ii) subsequently in a moderate speed mixer/densifier, to form agglomerates.
• the modified polyamine and surfactant paste are mixed for at least about 5 seconds, preferably from about 5 seconds to about 1 minute in any acceptable known mixing apparatus such as an in-line static mixer, twin-screw extruder, stirred mixing tanks and the like.
• the temperature at which the premixing step using the surfactant paste is performed typically is at a temperature of from about 25°C to about 80°C.
• the pH of the premix should be maintained between a pH of about 5 to about 10, preferably at from about 8 to about 10, and preferably without other detergent ingredients present.
• the modified polyamine is preferably present in an amount of from about 0.01% to about 10%, more preferably from about 0.05% to about 5%, and most preferably from about 0.1% to about 1.0%, by weight of the overall detergent composition.
• the detersive surfactant paste preferably comprises from about 1% to about 70%, more preferably from about 20% to about 60%, and most preferably from about 25% to about 50%, by weight of a detersive surfactant the balance water and other minor ingredients.
• the premix of modified polyamine and surfactant paste is initially agglomerated in a high speed mixer/densifier followed by a moderate speed mixer/densifier.
• the high speed mixer/densifier is a Lodige CB 30 mixer or similar brand mixer.
• These types of mixers essentially consist of a horizontal, hollow static cylinder having a centrally mounted rotating shaft around which several plough-shaped blades are attached.
• die shaft rotates at a speed of from about 100 rpm to about 2500 rpm, more preferably from about 300 rpm to about 1600 rpm.
• the mean residence time of the detergent ingredients in the high speed mixer/densifier is preferably in range from about 2 seconds to about 45 seconds, and most preferably from about 5 seconds to about 15 seconds.
• the resulting detergent .agglomerates formed in the high speed mixer/densifier are then fed into a lower or moderate speed mixer/densifier during which further agglomeration and densification is carried forth.
• This particular moderate speed mixer/densifier used in the present process should include liquid distribution and agglomeration tools so that both techniques can occur simultaneously. It is preferable to have the moderate speed mixer/densifier be, for example, a Lodige KM 600 (Ploughshare) mixer, Drais® K-T 160 mixer or similar brand mixer.
• the residence time in the moderate speed mixer/densifier is preferably from about 0.5 minutes to about 15 minutes, most preferably the residence time is about 1 to about 10 minutes.
• the liquid distribution can be accomplished 23
• cutters generally smaller in size than the rotating shaft, which preferably operate at about 3600 rpm. It should be understood that while the processing described herein is relative to formation of high density .agglomerates, the same equipment and processing steps may be used to produce less or moderately dense agglomerates. Of course, agglomerates produced by the process regardless of the density can be admixed with less dense spray-dried granules in the final detergent product, if desired.
• the detergent agglomerates produced by the process preferably have a surfactant level of from about 25% to about 55%, more preferably from about 35% to about 55% and, most preferably from about 45% to about 55%.
• the particle porosity of the resulting detergent agglomerates produced according to the process of the invention is preferably in a range from about 5% to about 20%, more preferably at about 10%.
• an attribute of dense or densified agglomerates is the relative particle size.
• the present process typically provides detergent agglomerates having a median particle size of from about 400 microns to about 700 microns, and more preferably from about 400 microns to about 600 microns.
• the phrase "median particle size” refers to individual agglomerates and not individual particles or detergent granules.
• the combination of the above-referenced porosity and particle size results in agglomerates having density values of 650 g/l and higher.
• the particle size and porosity can be adjusted to produce agglomerates having lower densities, as well (e.g., 300 g/l to 500 g/l).
• Such features are especially useful in the production of low as well as high or conventional dosage laundry detergents as well as other granular compositions such as dishwashing compositions.
• the detergent agglomerates formed by the above process are then optionally dried in a fluid bed dryer and/or further conditioned by cooling the agglomerates in a fluid bed cooler or similar apparatus as are well known in the art.
• Another optional process step involves adding a coating agent to improve flowability and/or minimize over agglomeration of the detergent composition in one or more of the following locations of the instant process: (1) the coating agent can be added directly after the fluid bed cooler or dryer; (2) the coating agent may be added between the fluid bed dryer and the fluid bed cooler; (3) the coating agent may be added between the fluid bed dryer and the mixer/densifier(s); and/or (4) the coating agent may be added directly to one or more of the mixer/densifiers.
• the coating .agent is preferably selected from the group consisting of aluminosilicates, silicates, carbonates and mixtures thereof.
• the coating agent not only enhances the free flowability of the resulting detergent composition which is desirable by consumers in that it permits easy scooping of detergent during use, but also serves to control agglomeration by preventing or minimizing over agglomeration, especially when added directly to the mixer/densifier(s). As those skilled in the art are well aware, over agglomeration can lead to very undesirable flow properties and aesthetics of the final detergent product. 24
• the process can comprises the step of spraying an additional binder in the mixer/densifier(s).
• a binder is added for purposes of enhancing .agglomeration by providing a "binding" or "sticking" agent for the detergent components.
• the binder is preferably selected from the group consisting of water, anionic surfactants, nonionic surfactants, polyethylene glycol, polyvinyl pyrrolidone polyacrylates, citric acid and mixtures thereof.
• suitable binder materials including those listed herein are described in Beerse et al, U.S. Patent No. 5,108,646 (Procter & Gamble), the disclosure of which is incorporated herein by reference.
• Another optional step of the instant process entails finishing the resulting detergent agglomerates by a variety of processes including spraying and/or admixing other conventional detergent ingredients.
• the finishing step encompasses spraying on perfumes, and the addition of brighteners and enzymes to the finish-sd agglomerates to provide a more complete detergent composition.
• Such techniques and ingredients are well known in the art.
• This Example illustrates a method by which one of the selected modified polyamines is made.
• 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 of the 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 25
• 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 of the 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.
• 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. .
• 4500 g of ethylene oxide resulting in a total of 7 moles of ethylene oxide per mole of PEI nitrogen function
• the temperature is increased to 110 °C and the mixture stirred for an additional hour.
• the reaction mixture is then collected in nitrogen purged containers and eventually transferred into a 22 L three neck round bottomed fl-ask equipped with heating and agitation.
• the strong alkali catalyst is neutralized by adding 167 g methanesulfonic acid (1J4 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.
• the final reaction product is cooled slightly and collected in glass containers purged with nitrogen. In other preparations the neutralization and deodorization is accomplished in the reactor before discharging the product.
• This Example illustrates another method by which one of the selected modified polyamines is made.
• 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 mole nitrogen, prepared as in Example I), and hydrogen peroxide (120 g of a 30 wt % solution in water, 1.06 mole).
• PI-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 mole
• 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.
• This Example illustrates yet another method by which one of the selected modified polyamines is made.
• 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 of the cylinder could be monitored.
• PEI polyethyleneimine
• 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 of the 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.
• 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.
• 4500 g of ethylene oxide resulting in a total of 7 moles of ethylene oxide per mole of PEI nitrogen function
• the temperature is increased to 110 °C and the mixture stirred for an additional hour.
• the 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.
• the final reaction product is cooled slightly and collected in glass containers purged with nitrogen. In other preparations the neutralization and deodorization is accomplished in the reactor before discharging the product.
• a modified polyamine is made in accordance with Example I ("PEI 1800 E7") and used in the process of the current invention to form spray dried laundry granules for a bleach detergent composition.
• a bleach-containing spray-dried detergent composition is made into which the PEI 1800 E7 is not premixed, but is instead added after other adjunct detergent ingredients in the detergent slurry.
• Tthe detergent-making process illustrated herein is executed in a conventional pilot scale system.
• the system contains a batch mixer (called a "crutcher") in which the premixing and slurry mixing steps are completed, followed by a conventional spray drying tower (“tower").
• the PEI 1800 E7 is added to the crutcher along with a sodium linear alkylbenzene sulfonate ("LAS") surfactant paste (30% LAS and balance water) and is premixed at 25°C for about 5 minutes, wherein the pH of the premix is maintained at about 8 to 10. Thereafter, silicate, optical brightener, carboxymethyl cellulose (“CMC”), sodium carbonate, and water are added to the crutcher which is then mixed. Steam at a temperature of about 120°C, sodium sulfate and sodium tripolyphosphate are added to the crutcher as the contents are continuously mixed. The crutcher is operated in a batch mode, and contains 180 kg of wet crutcher mix per batch.
• LAS sodium linear alkylbenzene sulfonate
• the wet crutcher mix is pumped under high pressure through atomizing nozzles to form a finely divided mist.
• a counter-current flow of hot air (210°C) is impinged upon the atomized mist, causing the drying of the mixture ultimately resulting in spray dried granules which are collected at the exit of the tower.
• Continuous operation of the spray drying tower is accomplished by using an intermediate tank which accumulates multiple batches from the crutcher and feeds in a continuous manner the spray drying tower.
• the spray-dried granules may be further processed, by adding additional detergent ingredients, if desired, to form a fully formulated laundry detergent composition.
• compositions Band C The following spray-dried bleach-containing granular detergent compositions are made in accordance with the process invention (i.e. Compositions Band C) and processes outside the scope of the invention (i.e. Compositions A).
• Composition A is made via a process in which PEI 1800 E7 is added as the last wet ingredient into the crutcher, without a premixing step with LAS.
• the pH of the crutcher slurry is substantially higher than 10 (about 10.5-11.0).
• the order of addition to the crutcher is LAS paste / Silicate / Optical brightener / CMC / PEI 1800 E7 / Sodium Carbonate / Water; Steam / Sodium Sulphate / Sodium Tripolyphosphate ("STPP"). 29
• the bleach agent is a 2:1 weight ratio of sodium perborate monohydrate and sodium nonanoyloxybenzene sulfonate bleach activator.
• the bleach detergent compositions B and C made by premixing the PEI 1800 E7 with LAS, exhibits less loss of the bleach agent in a wash solution compared to composition A made by same process, except wherein the PEI 1800 E7 is the last wet ingredient added to the slurry.
• a modified poly.amine is made in accordance with Example I ("PEI 1800 E7") and used in the process of the current invention to form an agglomerated detergent composition.
• An in-line static mixer is used into which the PEI 1800 E7 is added continuously along with a sodium linear alkylbenzene sulfonate (“LAS") surfactant paste (60% LAS and balance water) at about 60°C in order to completely mix the ingredients, wherein the pH of the premix is maintained at about 7 to 10. Thereafter, the premix are continuously fed to a high speed mixer/densifier (Lodige CB-30, commercially available from Lodige) along with sodium aluminosilicate (zeolite) and sodium carbonate.
• LAS sodium linear alkylbenzene sulfonate
• the rotational speed of the shaft in the Lodige CB-30 mixer/densifier is about 1400 rpm .and the mean residence time is about 10 seconds.
• the contents from the Lodige CB-30 mixer/densifer are continuously fed into a Lodige KM 600 mixer/densifer for further agglomeration during which the mean residence time is about 6 minutes.
• the detergent agglomerates are then screened with conventional screening apparatus 30
• a bleach agent is then admixed with the detergent agglomerates to form the bleach detergent product, having the set forth below: Component % Weight
• Polyethylene glycol (MW 4000) 1.3
• the bleach agent is a 2:1 weight ratio of sodium perborate monohydrate and sodium nonanoyloxybenzene sulfonate bleach activator.
• the agglomerated detergent composition made by premixing the PEI 1800 E7 with LAS in the premixer exhibits less loss of the bleach agent in a wash solution, compared to a composition made by same process, except wherein the PEI 1800 E7 is sprayed-on to the detergent agglomerates after agglomeration.

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• 1999
  • 1999-02-03 WO PCT/US1999/002394 patent/WO1999042551A1/en active IP Right Grant
  • 1999-02-03 JP JP2000532492A patent/JP2002504590A/ja not_active Withdrawn
  • 1999-02-03 EP EP99904576A patent/EP1056827B1/en not_active Expired - Lifetime
  • 1999-02-03 ES ES99904576T patent/ES2200498T3/es not_active Expired - Lifetime
  • 1999-02-03 BR BR9908117-2A patent/BR9908117A/pt not_active Application Discontinuation
  • 1999-02-03 CA CA002320250A patent/CA2320250A1/en not_active Abandoned
  • 1999-02-03 AT AT99904576T patent/ATE246725T1/de not_active IP Right Cessation
  • 1999-02-03 CN CNB998052639A patent/CN1167783C/zh not_active Expired - Fee Related
  • 1999-02-03 DE DE69910178T patent/DE69910178T2/de not_active Expired - Fee Related
  • 1999-02-16 MA MA25467A patent/MA24824A1/fr unknown
  • 1999-02-23 AR ARP990100646A patent/AR014582A1/es unknown
• 2000
  • 2000-08-18 MX MXPA00008149 patent/MX228344B/es not_active IP Right Cessation

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