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WO1999029822A1 - Peracides ramifies a mi-chaine et precurseurs de peracides - Google Patents

Peracides ramifies a mi-chaine et precurseurs de peracides Download PDF

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Publication number
WO1999029822A1
WO1999029822A1 PCT/US1998/025982 US9825982W WO9929822A1 WO 1999029822 A1 WO1999029822 A1 WO 1999029822A1 US 9825982 W US9825982 W US 9825982W WO 9929822 A1 WO9929822 A1 WO 9929822A1
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Prior art keywords
compositions
bleaching
detergent
preferred
bleach
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WO1999029822A8 (fr
Inventor
Gregory Scott Miracle
Michael Eugene Burns
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Procter and Gamble Co
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Procter and Gamble Co
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    • 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
    • C11D3/3945—Organic per-compounds

Definitions

  • the present invention relates to mid-chain branched peracids and peracid precursors such as activators.
  • Oxygen bleaching agents such as hydrogen peroxide
  • Oxygen bleaching agents have found particular acceptance in laundry products such as detergents, in automatic dishwashing products and in hard surface cleaners. Oxygen bleaching agents, however, are somewhat limited in their effectiveness. Some frequently encountered disadvantages include color damage on fabrics and surfaces.
  • oxygen bleaching agents tend to be extremely temperature rate dependent. Thus, the colder the solution in which they are employed, the less effective the bleaching action. Temperatures in excess of 60°C are typically required for effectiveness of an oxygen bleaching agent in solution.
  • bleach activators typically perhydrolyzable acyl compounds having a leaving group such as oxybenzenesulfonate, react with the active oxygen group, typically hydrogen peroxide or its anion, to form a more effective peroxyacid oxidant. It is the peroxyacid compound which then oxidizes the stained or soiled substrate material.
  • bleach activators are also somewhat temperature dependent. Bleach activators are more effective at warm water temperatures of from about 40°C to about 60°C. In water temperatures of less than about 40°C, the peroxyacid compound loses some its bleaching effectiveness.
  • TAED tetraacetyl ethylene diamine
  • NOBS non- anoyloxybenzenesulfonate
  • hydrophobic activators which generally comprise long straight-chain alkyl moieties
  • bleach additive and bleaching compositions are provided using the selected bleaching agents to remove soils and stains not only from fabrics, but also from dishware in automatic dishwashing compositions, from kitchen and bathroom hard surfaces, and the like, with excellent results.
  • the present invention involves the use of peracids and peracid precursors or bleach activators which have mid-chain branching on an otherwise straight-chain alkanoic moiety. While not wishing to be bound by theory, it is believed that this mid-chain branching results in a compound that, relative to its equal carbon straight chain analog, has nearly the same hydrophobicity yet a markedly decreased tendency to micellize. Micellization of hydrophobic peracids and precursors can be problematic, leading to an increase in the formation of diacyl peroxides, a wasteful side process that limits the formation of active bleaching species. 75 According to the present invention, a composition comprising one or more mid-chain branched bleaching agents selected from the group consisting of:
  • R, R ⁇ , and R ⁇ are each independently selected from hydrogen and C1 -C3 alkyl, provided R, Rl, and R ⁇ are not all hydrogen; w is an integer from 0 to 11 ; x is an integer from 0 to 11 ; y is an integer from 0 to 11 ; z is an integer from 0 to 11 when m is not 0 and wherein m is 0, z is an integer from 1 to l l; w + x + y + z is from 5 to 11; and EO/PO are alkoxy moieties, wherein m is within the range of
  • the total number of carbon atoms in the branched primary alkyl moiety, including the R, Rl, and R ⁇ branching, but not including the carbon atoms in the EO/PO alkoxy moiety is from 9 to 20.
  • EO/PO are alkoxy moieties selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups and m is
  • R, Rl, and R2 are each independently selected from hydrogen and methyl. Most preferred are compounds ofthe formula
  • the present invention relates to mid-chain branched peracids and peracid precursors.
  • the branched bleaching agents having a formula selected from the group consisting of:
  • R, Rl, and R ⁇ are each independently selected from hydrogen and C1-C3
  • R, R , and R ⁇ are not all hydrogen; w is an integer from 0 to 11 ; x is an integer from 0 to 11 ; y is an integer from 0 to 11 ; z is an integer from 0 to 11 when m is not 0 and when m is 0, z is an integer from 1 to 11 ; w + x + y + z is from 5 to 11; and EO/PO are alkoxy moieties, wherein m is within the range of from 0 to about 30, preferably 0 to 10, and more preferably 0 to 5.
  • m is at least 0.1.
  • the total number of carbon atoms in the branched primary alkyl moiety, including the R, Rl, and R ⁇ branching, but not including the carbon atoms in the EO/PO alkoxy moiety is from 9 to 20.
  • EO/PO are alkoxy moieties selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups and m is
  • a leaving group as used in the present invention is any group that can be displaced from the bleaching activator as a consequence of the nucleophilic attack on the bleach activator by the perhydroxide anion.
  • the perhydrolysis reaction results in the formation ofthe peroxycarboxylic acid.
  • a group to be suitable leaving group it must exert an electron attracting effect. It should also form 135 a stable entity so that the rate ofthe back reaction is negligible. This facilitates the nucleophilic attack by the perhydroxide anion.
  • the leaving group must be sufficiently reactive for the reaction to occur within the optimum time frame (e.g. a wash cycle). However, if the leaving group is too reactive, this activator will be difficult to stabilize for use in a bleaching 140 composition.
  • These characteristics are generally paralleled by the pKa ofthe conjugate acid ofthe leaving group, although exceptions to this convention are known. Ordinarily, leaving groups that exhibit such behavior are those which their conjugate acid has a pKa in the range of from about 4 to about 13, preferably from about 6 to about 11 and most preferably from about 8 to about 11.
  • Preferred leaving 145 groups are those selected from the group consisting of:
  • R ⁇ , R? and R ⁇ may be the same or different, and are selected from H, alkyl, alkaryl, aryl or aralkyl containing from about 1 to about 14 carbon atoms, halogen, hydroxyl, C ⁇ to C14 alkoxyl, amino, C to C14 alkylamino, COOR ⁇ (wherein R ⁇ is H or C ⁇ to C ⁇ 4 alkyl) and carbonyl functions.
  • Y is H or a 155 so lubilizing group.
  • the preferred solubilizing groups are -SO3" M + , CO2"M + , SO4"M + , -
  • solubilizing groups are -SO3" M + 160 and CO2"M + , with R" as hereinbefore defined.
  • M is a cation which provides solubility to bleach activator and X is an anion which provides solubility to bleach activator.
  • M is an alkali metal, alkaline earth metal, ammonium, or substituted ammonium cation, with sodium and potassium being most preferred.
  • the anion X is a halide, hydroxide, methylsulfate or acetate anion.
  • bleach activators with a leaving group that does not contain a solubilizing group should be well dispersed in the bleaching solution in order to assist in their dissolution.
  • L can also be a modified or unmodified lactam leaving group.
  • lactams which are suitable as leaving groups in the present application have the generic 170 structure:
  • R represents an optionally substituted alkenyl chain with at least two carbon atoms in the alkenyl chain.
  • This alkenyl chain forms a cyclic structure with the -N- and -C(O)-.
  • the term modified means that the alkenyl can be substituted at least
  • Suitable heterocyclic chain substitutes are O, N, and S, with O being preferred.
  • Suitable substituents include, but are not limited to, Cj-Cg alkyl, Cj-C6 alkenyl, Cj-Cg alkoxy, chloride, bromide, iodide.
  • the preferred substituents are C1 -C6 alkyl, C1-C6 alkoxy and chloride.
  • 180 preferred modified lactam leaving groups are: alpha-chlorocaprolactam, alpha- chloro-valerolactam, alpha, alpha-dichlorolactam, alpha,alpha-dichlorovalerolactam, alpha-methoxycaprolactam, alpha-methoxy-valerolactam,
  • the lactams When the lactams are unmodified, it means that they contain no substituents other hydrogen and have no heterocyclic substitution ofthe alkenyl chain of R.
  • R is preferably an alkenyl chain of two to seven carbon atoms. It is preferred that the lactam leaving group will be unmodified. It is more preferred that the unsubstituted
  • 190 lactam leaving group will be either caprolactam or valerolactam. That is:
  • compositions does not include molecules wherein the units R, R , and R ⁇ are all
  • compositions may still further comprise some amount of linear, non-branched primary chain compounds in admixture with the branched chain materials. Further, this linear non-branched primary chain compound may be present as the result of the process used to manufacture the
  • 205 may comprise some amount of the present compositions. Such materials may be present as the result of incomplete reaction of the starting alcohol (alkoxylated or non-alkoxylated) used to prepare the peracid or peracid precursor, or these alcohols may be separately added to the present invention.
  • EO/PO are alkoxy moieties, preferably selected from ethoxy, propoxy, and mixed ethoxy/propoxy groups, wherein m is defined as above.
  • the (EO/PO) m moiety may be either a distribution with average degree of alkoxylation (e.g., ethoxylation and/or propoxylation) corresponding to m, or it may be a single specific chain with alkoxylation (e.g., ethoxylation and/or propoxylation) of exactly the
  • Branched-chain peracids and precursors of the type herein can be used in all manner of cleaning compositions.
  • the detergent compositions of the invention thus may also contain additional detergent components. The precise nature of these
  • Cleaning compositions herein include, but are not limited to: granular, bar-form and liquid
  • laundry detergents liquid hand dishwashing compositions; liquid, gel and bar-form personal cleansing products; shampoos; dentifrices; hard surface cleaners, and the like.
  • Such compositions can contain a variety of conventional detersive ingredients.
  • compositions of the invention preferably contain one or more additional detergent components selected from surfactants, builders, alkalinity system, organic polymeric compounds, suds suppressors, soil suspension and anti-redeposition agents and corrosion inhibitors.
  • compositions of the present invention may contain additional conventional bleaching agents and activators in conjunction with the mid-chain branched peracids and precursors described hereinbefore.
  • Bleaching agents will typically be at levels of from about 1% to about 30%, more typically from about 5% to about 20%, of the detergent composition, especially for fabric laundering. If
  • 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.
  • the bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other
  • Perborate bleaches e.g., sodium perborate (e.g., mono- or tetra-hydrate) can be used herein.
  • bleaching agent that can be used without restriction encompasses percarboxylic acid bleaching agents and salts thereof.
  • Suitable 250 examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4- oxoperoxybutyric acid and diperoxydodecanedioic acid.
  • Such 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, European Patent Application
  • 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.
  • Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching
  • 260 compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate” bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide.
  • Persulfate bleach e.g., OXONE, manufactured commercially by DuPont
  • OXONE manufactured commercially by DuPont
  • a preferred percarbonate bleach comprises dry particles having an average
  • the percarbonate can be coated with silicate, borate or water-soluble surfactants.
  • Percarbonate is available from various sources
  • 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
  • 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.
  • NOBS nonanoyloxybenzene sulfonate
  • TAED tetraacetyl ethylene diamine
  • R is an alkyl group containing from about 6 to about 12 carbon atoms
  • R 2 is an alkylene containing from 1 to about 6 carbon atoms
  • R ⁇ is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms
  • L is any suitable
  • a leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion.
  • a preferred leaving group is phenyl sulfonate.
  • bleach activators of the above formulae include (6- octanamido-caproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)oxybenzenesul-
  • Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990, incorporated herein by reference.
  • Still another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams ofthe formulae:
  • R ⁇ is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms.
  • Highly preferred 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
  • Bleaching agents other than oxygen bleaching agents are also known in the art.
  • Non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from about 0.025% to about 1.25%, by weight, of such bleaches, especially sulfonate zinc
  • 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.
  • 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, ofthe catalyst species in the laundry liquor.
  • Cobalt bleach catalysts useful herein are known, and are described, for example, in M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg. Mech., (1983), 2, pages 1-94.
  • the most preferred cobalt catalyst useful herein are cobalt pentaamine acetate salts having the formula [Co(NH3)5OAc] Ty, wherein "OAc” represents an acetate moiety and "Ty" is an
  • compositions and cleaning processes herein can be adjusted to provide on the order of at least one part per hundred million of the active bleach catalyst species in the aqueous washing medium, and will preferably provide from about 0.01 ppm to about 25 ppm, more preferably from about 0.05 ppm to about 10 ppm, and most preferably from about
  • compositions herein will comprise from about 0.0005% to about 0.2%, more preferably from about 0.004% to about 0.08%, of bleach catalyst, especially manganese or cobalt catalysts, by weight ofthe cleaning compositions.
  • Enzymes - Enzymes are preferably included in the present detergent compositions for a variety of purposes, including removal of protein-based, carbohydrate-based, or triglyceride-based stains from substrates, for the prevention of refugee dye transfer in fabric laundering, and for fabric restoration.
  • Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures
  • 365 thereof of any suitable origin such as vegetable, animal, bacterial, fungal and yeast origin.
  • Preferred selections are influenced by factors such as pH-activity and/or stability optima, thermostability, and stability to active detergents, builders and the like.
  • bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
  • Detersive enzyme means any enzyme having a cleaning, stain removing or otherwise beneficial effect in a laundry, hard surface cleaning or personal care detergent composition.
  • Preferred detersive enzymes are hydrolases such as proteases, amylases and lipases.
  • Preferred enzymes for laundry purposes include, but are not limited to, proteases, cellulases, lipases and peroxidases. Highly
  • amylases and/or proteases including both current commercially available types and improved types which, though more and more bleach compatible though successive improvements, have a remaining degree of bleach deactivation susceptibility.
  • Enzymes are normally incorporated into detergent or detergent additive
  • compositions 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, dishware and the like. In practical terms for current commercial preparations, typical amounts are up to about 5 mg by weight, more
  • 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.
  • AU Anson units
  • 390 For certain detergents, such as in automatic dishwashing, it may be desirable to increase the active enzyme content of the commercial preparation in order to minimize the total amount of non-catalytically active materials and thereby improve spotting/filming or other end-results. Higher active levels may also be desirable in highly concentrated detergent formulations.
  • proteases are the subtilisins which are obtained from particular strains of B. subtilis and B. licheniformis.
  • One suitable 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 Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous
  • proteases 400 enzymes is described in GB 1,243,784 to Novo.
  • Other suitable proteases include ALCALASE® and SAVLNASE® from Novo and MAXATASE® from International Bio-Synthetics, Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756 A, January 9, 1985 and Protease B as disclosed in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985. See also a high pH
  • protease from Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo.
  • Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 9203529 A to Novo.
  • Other preferred proteases include those of WO 9510591 A to Procter & Gamble . When desired, a protease having decreased adsorption and increased hydrolysis is available
  • protease D is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different
  • Amylases suitable herein, especially for, but not limited to automatic dishwashing purposes include, for example, ⁇ -amylases described in GB 1,296,839 to Novo; RAPIDASE®, International Bio-Synthetics, Inc. and TERMAMYL®,
  • amylases herein share the characteristic of being "stability- enhanced" amylases, characterized, at a minimum, by a measurable improvement in one or more of: oxidative stability, e.g., to hydrogen peroxide/tetraacetylethylenediamine in buffered solution at pH 9-10; thermal
  • Stability e.g., at common wash temperatures such as about 60°C; or alkaline stability, e.g., at a pH from about 8 to about 11, measured versus the above- identified reference-point amylase.
  • Stability can be measured using any of the art- disclosed technical tests. See, for example, references disclosed in WO 9402597. Stability-enhanced amylases can be obtained from Novo or from Genencor
  • amylases herein have the commonality of being derived using site-directed mutagenesis from one or more of the Bacillus amylases, especially the Bacillus ⁇ -amylases, regardless of whether one, two or multiple amylase strains are the immediate precursors. Oxidative stability-enhanced amylases vs. the above-identified reference amylase are preferred for use, especially
  • Such preferred amylases include (a) an amylase according to the hereinbefore incorporated WO 9402597, Novo, Feb. 3, 1994, as further illustrated by a mutant in which substitution is made, using alanine or threonine, preferably threonine, of the methionine residue located in position 197 of
  • B. licheniformis alpha-amylase known as TERMAMYL®
  • TERMAMYL® the homologous position variation of a similar parent amylase, such as B. amyloliquefaciens, B. subtilis, or B. stearothermophilus
  • stability-enhanced amylases as described by Genencor International in a paper entitled "Oxidatively Resistant alpha-Amylases" presented at the 207th American Chemical Society National Meeting, March 13-17
  • oxidative stability enhanced amylase include those described in WO 9418314 to Genencor International and WO 9402597 to Novo. Any other oxidative stability-enhanced amylase can be used, for example as derived by site-directed mutagenesis from known chimeric, hybrid or simple mutant parent forms of available amylases. Other preferred enzyme modifications
  • amylase enzymes include those described in WO 95/26397 and in copending application by Novo Nordisk PCT/DK96/00056.
  • Specific amylase enzymes for use in the detergent compositions of the present invention include ⁇ -amylases characterized by having a specific activity at least 25% higher than the specific
  • ⁇ -amylase activity assay 480 activity of Termamyl® at a temperature range of 25°C to 55°C and at a pH value in the range of 8 to 10, measured by the Phadebas® ⁇ -amylase activity assay.
  • uch Phadebas® ⁇ -amylase activity assay is described at pages 9-10, WO 95/26397.
  • ⁇ -amylases which are at least 80% homologous with the amino acid sequences shown in the SEQ ID listings in the references.
  • 485 enzymes are preferably incorporated into laundry detergent compositions at a level from 0.00018% to 0.060% pure enzyme by weight of the total composition, more preferably from 0.00024% to 0.048% pure enzyme by weight of the total composition.
  • Cellulases usable herein include both bacterial and fungal types, preferably
  • U.S. 4,435,307, Barbesgoard et al, March 6, 1984 discloses suitable fungal cellulases from Humicola insolens or Humicola strain DSM1800 or a cellulase 212-producing fungus belonging to the genus Aeromonas, and cellulase extracted from the hepatopancreas of a marine mollusk, Dolabella Auricula Solander. Suitable cellulases are also disclosed in GB-A-
  • 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. See also lipases in Japanese Patent
  • Lipase 500 Application 53,20487, laid open Feb. 24, 1978.
  • This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name 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.
  • the D96L variant of the native Humicola lanuginosa lipase improves the lard stain removal efficiency by a factor 4.4 over the wild-type lipase (enzymes compared in an amount ranging from 0.075 to 2.5 mg protein per liter).
  • Research Disclosure No. 35944 published on March 10, 1994, by Novo Nordisk discloses that the lipase variant (D96L) may be
  • the present invention provides the benefit of improved whiteness maintenance on fabrics using low levels of D96L variant in detergent compositions containing the mid-chain branched primary alkyl alkoxylated sulfate surfactants in the manner disclosed herein, especially when the D96L is used
  • Cutinase enzymes suitable for use herein are described in WO 8809367 A to Genencor.
  • Peroxidase enzymes may be used in combination with oxygen sources, e.g., percarbonate, perborate, hydrogen peroxide, etc., for "solution bleaching" or
  • peroxidases include horseradish peroxidase, ligninase, and haloperoxidases such as chloro- or bromo- peroxidase.
  • Peroxidase-containing detergent compositions are disclosed in WO 89099813 A, October 19, 1989 to Novo and WO 8909813 A to Novo.
  • Builders - Detergent builders selected from aluminosilicates and silicates are preferably included in the compositions herein, for example to assist in controlling
  • 550 mineral especially Ca and/or Mg, hardness in wash water or to assist in the removal of particulate soils from surfaces.
  • Suitable silicate builders include water-soluble and hydrous solid types and including those having chain-, layer-, or three-dimensional- structure as well as amorphous-solid or non-structured-liquid types. Preferred are alkali metal silicates,
  • layered aluminum-free ⁇ -Na2Si ⁇ 5 morphology silicate marketed by Hoechst and is preferred especially in granular laundry compositions. See preparative methods in German DE-A-3,417,649 and DE-A-3, 742,043.
  • Other layered silicates such as those having the general formula NaMSi x ⁇ 2 x + ⁇ -yH2 ⁇ wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20,
  • Layered silicates from Hoechst also include NaSKS-5, NaSKS-7 and NaSKS-11, as the ⁇ , ⁇ and ⁇ layer-silicate forms.
  • Other silicates may also be useful, such as magnesium silicate, which can serve as a crispening agent in granules, as a stabilising agent for bleaches, and as a component of suds control systems.
  • crystalline ion exchange materials or hydrates thereof having chain structure and a composition represented by the following general formula in an anhydride form: xM 2 O-ySiO 2 .zM'O wherein M is Na and/or K, M' is Ca and/or Mg; y/x is 0.5 to 2.0 and z/x is 0.005 to 1.0 as taught in U.S. 5,427,711, Sakaguchi et al, June 27, 1995. 575
  • Aluminosilicate builders are especially useful in granular detergents, but can also be incorporated in liquids, pastes or gels.
  • Suitable for the present purposes are those having empirical formula: [M z (Al ⁇ 2) z (Si ⁇ 2) v ]'xH2 ⁇ wherein z and v are integers of at least 6, the molar ratio of z to v is in the range from 1.0 to 0.5, and x is an integer from 15 to 264.
  • Aluminosilicates can be crystalline or amorphous,
  • Zeolite A has
  • the aluminosilicate has a particle size of 0.1-10 microns in diameter.
  • Detergent builders in place of or in addition to the silicates and aluminosilicates described hereinbefore can optionally be included in the
  • compositions herein for example to assist in controlling mineral, especially Ca and/or Mg, hardness in wash water or to assist in the removal of particulate soils from surfaces.
  • Builders can operate via a variety of mechanisms including forming soluble or insoluble complexes with hardness ions, by ion exchange, and by offering a surface more favorable to the precipitation of hardness ions than are the surfaces of
  • Builder level can vary widely depending upon end use and physical form of the composition.
  • Built detergents typically comprise at least about 1% builder.
  • Liquid formulations typically comprise about 5% to about 50%, more typically 5% to 35% of builder.
  • Granular formulations typically comprise from about 10% to about 80%, more typically 15% to 50% builder by weight of the
  • Suitable builders herein can be selected from the group consisting of phosphates and polyphosphates, especially the sodium salts; carbonates, bicarbonates, sesquicarbonates and carbonate minerals other than sodium carbonate
  • organic mono-, di-, tri-, and tetracarboxylates especially water- soluble nonsurfactant carboxylates in acid, sodium, potassium or alkanolammonium salt form, as well as oligomeric or water-soluble low molecular weight polymer carboxylates including aliphatic and aromatic types; and phytic acid.
  • organic mono-, di-, tri-, and tetracarboxylates especially water- soluble nonsurfactant carboxylates in acid, sodium, potassium or alkanolammonium salt form, as well as oligomeric or water-soluble low molecular weight polymer carboxylates including aliphatic and aromatic types
  • phytic acid may be complemented by borates, e.g., for pH-buffering purposes, or by sulfates, especially
  • Builder mixtures sometimes termed “builder systems” can be used and typically comprise two or more conventional builders, optionally complemented by chelants, pH-buffers or fillers, though these latter materials are generally accounted for
  • preferred builder systems are typically formulated at a weight ratio of surfactant to builder of from about 60:1 to about 1 :80.
  • Certain preferred laundry detergents have said ratio in the range 0.90:1.0 to 4.0:1.0, more preferably from 0.95:1.0 to 3.0:1.0.
  • P-containing detergent builders often preferred where permitted by legislation include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates exemplified by the tripolyphosphates, pyrophosphates, glassy polymeric meta-phosphates; and phosphonates.
  • Suitable carbonate builders include alkaline earth and alkali metal carbonates
  • 630 aragonite and vaterite, especially forms having high surface areas relative to compact calcite may be useful, for example as seeds or for use in synthetic detergent bars.
  • Suitable organic detergent builders include polycarboxylate compounds, including water-soluble nonsurfactant dicarboxylates and tricarboxylates. More typically builder polycarboxylates have a plurality of carboxylate groups, preferably
  • Carboxylate builders can be formulated in acid, partially neutral, neutral or overbased form. When in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
  • Polycarboxylate builders include the ether polycarboxylates, such as oxydisuccinate, see Berg, U.S. 3,128,287, April 7, 1964, and Lamberti et al, U.S. 3,635,830, January 18, 1972;
  • TMS/TDS "TMS/TDS" builders of U.S. 4,663,071, Bush et al, May 5, 1987; and other ether carboxylates including cyclic and alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
  • Suitable builders are the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether; 1, 3, 5-trihydroxy benzene-2,
  • 6-trisulphonic acid carboxymethyloxysuccmic acid
  • carboxymethyloxysuccmic acid the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid; as well as mellitic acid, succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccmic acid, and soluble salts thereof.
  • Citrates e.g., citric acid and soluble salts thereof are important carboxylate builders e.g., for heavy duty liquid detergents, due to availability from renewable resources and biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicates. Oxydisuccinates are also especially useful in such compositions and combinations.
  • alkali metal phosphates such as sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used.
  • Phosphonate builders such as ethane- l-hydroxy-l,l-diphosphonate and other known phosphonates, e.g., those of U.S. 3,159,581; 3,213,030; 3,422,021; 3,400,148 and
  • 660 3,422,137 can also be used and may have desirable antiscaling properties.
  • detersive surfactants or their short-chain homologs also have a builder action. For unambiguous formula accounting purposes, when they have surfactant capability, these materials are summed up as detersive surfactants.
  • Preferred types for builder functionality are illustrated by: 3,3-dicarboxy-4-oxa-l,6-
  • Succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof.
  • Succinate builders also include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2- pentadecenylsuccinate, and the like. Lauryl-succinates are described in European
  • Fatty acids e.g., C12- 18 monocarboxylic acids
  • surfactant/builder materials especially citrate and/or the succinate builders, to provide additional builder activity.
  • Other suitable polycarboxylates are disclosed in U.S.
  • inorganic builder materials which can be used have the formula (M x )j Cay (CO3) 2 ; wherein x and i are integers from 1 to 15, y is an integer from 1 to 10, z is an integer from 2 to 25, Mj are cations, at least one of which is a water-
  • a water-soluble cation selected from the group consisting of hydrogen, water-soluble metals, hydrogen, boron, ammonium, silicon, and mixtures thereof, more preferably, sodium, potassium, hydrogen, lithium, ammonium and mixtures thereof, sodium and potassium being highly preferred.
  • noncarbonate anions include those selected
  • Preferred builders of this type in their simplest forms are selected from the group consisting of Na2Ca(CO3)2, K 2 Ca(CO 3 ) 2 , Na 2 Ca 2 (CO3)3, NaKCa(CO 3 ) 2 , NaKCa 2 (CO 3 ) 3 , K 2 Ca2(CO 3 )3, and combinations thereof.
  • Suitable builders of the above-defined type are further illustrated by, and include, the natural or synthetic forms of any one or combinations of the following minerals: aceaite, Andersonite, AshcroftineY, Beyerite, Borcarite, Burbankite, Butschliite, Cancrinite, Carbocernaite, Carletonite, Davyne, DonnayiteY, Fairchildite, Ferrisurite,
  • compositions of the present invention may include a detersive surfactant.
  • the detersive surfactant may comprise from about 1%, to about 99.8%, by weight of the composition depending upon the particular surfactants used and the effects
  • More typical levels comprise from about 5% to about 80% by weight ofthe composition.
  • the detersive surfactant can be nonionic, anionic, ampholytic, zwitterionic, or cationic. Mixtures of these surfactants can also be used.
  • Preferred detergent compositions comprise anionic detersive surfactants or mixtures of anionic
  • Nonlimiting examples of surfactants useful herein include the conventional l l"Ci8 alkyl benzene sulfonates and primary, secondary and random alkyl sulfates, the Cg-Cjg alkyl alkoxy sulfates, the Cg-Cjg alkyl polyglycosides and their corresponding sulfated polyglycosides, Cg-C g alpha-sulfonated fatty acid
  • esters Cg-C ⁇ g alkyl and alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), Cg-C g betaines and sulfobetaines ("sultaines"), Cg-Cjg amine oxides, such as branched or unbranched aliphatic N,N-dimethyl-N-oxides and the like.
  • Cg-C g betaines and sulfobetaines Cg-Cjg amine oxides, such as branched or unbranched aliphatic N,N-dimethyl-N-oxides and the like.
  • sultaines Cg-Cjg amine oxides
  • One class of nonionic surfactant particularly useful in detergent compositions ofthe present invention is condensates of ethylene oxide with a hydrophobic moiety to provide a surfactant having an average hydrophilic-lipophilic balance (HLB) in
  • hydrophobic (lipophilic) moiety may be aliphatic or aromatic in nature.
  • the length of the polyoxyethylene group which is condensed with any particular hydrophobic group can be readily adjusted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic
  • nonionic surfactants of this type are the C -Cj5 primary alcohol ethoxylates containing 3-12 moles of ethylene oxide per mole of alcohol, particularly the C14-C15 primary alcohols containing 6-8 moles of ethylene oxide per mole of alcohol, the C12-C15 primary alcohols containing 3-5 moles of ethylene
  • Suitable ethoxylated fatty alcohol nonionic surfactants for use in the present invention are commercially available under the tradenames DOBANOL and NEODOL available from the Shell Oil Company of Houston, Texas.
  • Another suitable class of nonionic surfactants comprises the polyhydroxy fatty acid amides ofthe formula:
  • R 2 C(0)N(R!)Z wherein: Rl is H, C ⁇ -Cg hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, or a mixture thereof, preferably C1 -C4 alkyl, more preferably C ⁇ or C2 alkyl, most
  • R 2 is a C5-C32 hydrocarbyl moiety, preferably straight chain C7-C19 alkyl or alkenyl, more preferably straight chain C9- C17 alkyl or alkenyl, most preferably straight chain C1 1-C19 alkyl or alkenyl, or mixture thereof; and Z is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with at least 2 (in the case of glyceraldehyde) or at least 3
  • Z preferably will be derived from a reducing sugar in a reductive amination reaction; more preferably Z is a glycityl moiety.
  • Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose, and xylose, as well as glyceraldehyde.
  • Z preferably will be selected from the group consisting of -CH -(CHOH) n -CH 2 OH, -CH(CH2OH)-
  • R can be, for example, N-methyl, N-ethyl, N-propyl, N-
  • R isopropyl, N-butyl, N-isobutyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl.
  • R is preferably methyl or hydroxyalkyl. If lower sudsing is desired, R is preferably C2-C alkyl, especially n-propyl, iso-propyl, n-butyl, iso- butyl, pentyl, hexyl and 2-ethyl hexyl.
  • R 2 -CO-N ⁇ can be, for example, cocamide, stearamide, oleamide, lauramide,
  • compositions herein A wide variety of other ingredients useful in detergent compositions can be included in the compositions herein, including other active ingredients, carriers, hydrotropes, fabric softeners, grease removal agents, processing
  • alkanolamides can be incorporated into the compositions, typically at 1%-10% levels.
  • the Cj ⁇ "Ci4 monoethanol and diethanol amides illustrate a typical class of such suds boosters.
  • Use of such suds boosters with high sudsing adjunct surfactants such as the amine oxides, betaines and sultaines noted above is also advantageous.
  • water-soluble magnesium and/or calcium salts such as MgCl2, MgSO4,
  • CaCl2, CaSO4 and the like can be added at levels of, typically, 0.1%-2%, to provide additional suds and to enhance grease removal performance.
  • compositions optionally can be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating.
  • the detersive ingredient is admixed with a surfactant before being absorbed into the porous substrate.
  • the detersive ingredient is released from the substrate into the aqueous washing liquor, where it performs its intended detersive function.
  • ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected” for use in detergents, including liquid laundry detergent compositions.
  • Liquid detergent compositions can contain water and other solvents as carriers.
  • Low molecular weight primary or secondary alcohols exemplified by methanol, ethanol, propanol, and isopropanol are suitable.
  • Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing from 2 to about 6 carbon atoms and from 2 to about 6 hydroxy groups (e.g., 1,3-propanediol,
  • compositions may contain from 5% to 90%, typically 10% to 50% of such carriers.
  • the detergent compositions herein will preferably be formulated such that, during use in aqueous cleaning operations, the wash water will have a pH of between about 6.5 and about 11, preferably between about 7.5 and 10.5.
  • product formulations preferably have a pH between about 6.8 and about 9.0.
  • Laundry products are typically at pH 9-11.
  • Techniques for controlling pH at recommended usage levels include the use of buffers, alkalis, acids, etc., and are well known to those skilled in the art. Form ofthe compositions
  • compositions in accordance with the invention can take a variety of physical forms including granular, tablet, bar and liquid forms.
  • the compositions are particularly the so-called concentrated granular detergent compositions adapted to be added to a washing machine by means of a dispensing device placed in the machine drum with the soiled fabric load.
  • the mean particle size of the components of granular compositions in accordance with the invention should preferably be such that no more that 5% of particles are greater than 1.7mm in diameter and not more than 5% of particles are less than 0.15mm in diameter.
  • mean particle size as defined herein is calculated by sieving a
  • 840 present invention typically have a bulk density of at least 600 g/litre, more preferably from 650 g/litre to 1200 g/litre. Bulk density is measured by means of a simple funnel and cup device consisting of a conical funnel molded rigidly on a base and provided with a flap valve at its lower extremity to allow the contents of the funnel to be emptied into an axially aligned cylindrical cup disposed below the
  • the funnel is 130 mm high and has internal diameters of 130 mm and 40 mm at its respective upper and lower extremities. It is mounted so that the lower extremity is 140 mm above the upper surface of the base.
  • the cup has an overall height of 90 mm, an internal height of 87 mm and an internal diameter of 84 mm. Its nominal volume is 500 ml.
  • the funnel is filled with powder by hand pouring, the flap valve is opened and powder allowed to overfill the cup.
  • the filled cup is removed from the frame and excess powder removed from the cup by passing a straight edged implement e.g.; a knife, across its upper edge.
  • the filled cup is then weighed and the value obtained for the weight of powder doubled to provide a
  • mid-chain branched peracids or precursors herein are preferably present in granular compositions in the form of agglomerate particles, which may take the form of flakes, prills, marumes, noodles, ribbons, but preferably take the form of
  • the most preferred way to process the particles is by agglomerating powders (e.g. aluminosilicate, carbonate) with high active mid-chain branched peracid or precursor pastes and to control the particle size of the resultant agglomerates within specified limits.
  • agglomerating powders e.g. aluminosilicate, carbonate
  • Such a process involves mixing an effective amount of powder with a high active mid-chain branched peracid or precursor paste
  • agglomerators such as a pan agglomerator, a Z-blade mixer or more preferably an in-line mixer such as those manufactured by Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, Netherlands, and Gebruder Lodige Maschinenbau GmbH, D-4790 Paderborn 1, Elsenerstrasse 7-9, Postfach 2050, Germany.
  • a high shear mixer is used, such as a Lodige CB (Trade Name).
  • a high active mid-chain branched peracid or precursor paste comprising from 50% by weight to 95% by weight, preferably 70% by weight to 85% by weight of mid-chain branched compounds is typically used.
  • the paste may be pumped into the agglomerator at a temperature high enough to maintain a pumpable viscosity, but low enough to avoid degradation of the active used.
  • an effective amount of the detergent composition it is meant from 20g to 300g of product dissolved or dispersed in a wash solution of volume from 5 to 65 litres, as are typical product dosages and wash solution volumes commonly employed in conventional machine laundry methods.
  • mid-chain branched peracids or precursors are used herein in
  • a preferred machine dishwashing method comprises treating soiled articles
  • an effective amount of a machine dishwashing composition in accord with the invention.
  • an effective amount ofthe machine dishwashing composition it is meant from 8g to 60g of product dissolved or dispersed in a wash solution of volume from 3 to 10 litres, as
  • 900 are typical product dosages and wash solution volumes commonly employed in conventional machine dishwashing methods.
  • Bleaching compositions having the form of granular laundry detergents are exemplified by the following formulations.
  • This Example illustrates bleaching compositions, more particularly, liquid bleach additive compositions in accordance with the invention.
  • compositions are used as bleach boosting additive (to be used in ADDITION to a bleach OR non-bleach detergent such as TIDE®) in a wash test otherwise similar to that used in Example V.
  • the additive is used at 1000 ppm, and the commercial detergent is used at 1000 ppm.
  • EXAMPLE V This Example illustrates cleaning compositions having bleach additive form, more particularly, liquid bleach additive compositions without a hydrogen peroxide source in accordance with the invention.
  • ADDITION to a bleach detergent such as TIDE® WITH BLEACH in a wash test otherwise similar to that used in Example V.
  • the additive is used at 1000 ppm, and the commercial detergent is used at 1000 ppm.
  • a granular automatic dishwashing detergent composition comprises the following.
  • Cleaning compositions having liquid form especially useful for cleaning bathtubs and shower tiles without being harsh on the hands are as follows:
  • Liquid bleaching compositions for cleaning typical household surfaces are as follows.
  • the hydrogen peroxide is separated as an aqueous solution from the other
  • a laundry bar suitable for hand-washing soiled fabrics is prepared by standard extrusion processes and comprises the following: Component Weight % Bleach Activator* 4 Sodium Perborate Tetrahydrate 12 1005 C12 linear alkyl benzene sulfonate 30
  • Phosphate (as sodium tripolyphosphate) 10 Sodium carbonate 5 Sodium pyrophosphate 7 coconut monoethanolamide 2 1010 Zeolite A (0.1 - 10 micron) 5

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Abstract

L'invention concerne des peracides ramifiés à mi-chaîne et des précurseurs de peracides utiles dans des compositions de lessive et de lavage, notamment des compositions de détergents granulaires et liquides. Ces peracides et précurseurs sont aptes à une formulation avec une large gamme d'adjuvants de détergents afin de produire des systèmes de nettoyage améliorés, destinés notamment à être utilisés dans des compositions de détergents utilisées dans des processus de lavage mettant en oeuvre des conditions de lavage à basse température d'eau. La présente invention concerne également de nouveaux peracides et précurseurs ramifiés à mi-chaîne utilisés dans les compositions de la présente invention.
PCT/US1998/025982 1997-12-09 1998-12-08 Peracides ramifies a mi-chaine et precurseurs de peracides Ceased WO1999029822A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2061456A1 (fr) * 1969-12-22 1971-07-22
EP0120591A1 (fr) * 1983-02-23 1984-10-03 The Procter & Gamble Company Ingrédients de détergents et leur utilisation dans des compositions de nettoyage et des procédés de lavage
US4486327A (en) * 1983-12-22 1984-12-04 The Procter & Gamble Company Bodies containing stabilized bleach activators
EP0447553A1 (fr) * 1989-09-11 1991-09-25 Kao Corporation Composition de blanchiment
US5637755A (en) * 1993-06-16 1997-06-10 Kao Corporation Sulfonate compound process for producing the same, and bleach composition comprising the same

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2061456A1 (fr) * 1969-12-22 1971-07-22
EP0120591A1 (fr) * 1983-02-23 1984-10-03 The Procter & Gamble Company Ingrédients de détergents et leur utilisation dans des compositions de nettoyage et des procédés de lavage
US4486327A (en) * 1983-12-22 1984-12-04 The Procter & Gamble Company Bodies containing stabilized bleach activators
EP0447553A1 (fr) * 1989-09-11 1991-09-25 Kao Corporation Composition de blanchiment
US5637755A (en) * 1993-06-16 1997-06-10 Kao Corporation Sulfonate compound process for producing the same, and bleach composition comprising the same

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