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
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3945—Organic 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
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0021—Dye-stain or dye-transfer inhibiting compositions

Definitions

• This invention relates, in general, to bleaching agents, their manufacture and use in detergent compositions, and their application to laundry operations. More specifically, the invention relates to bleaching agents, and bleaching detergent compositions containing such agent, which provide effective low-temperature bleaching of fabrics while substantially avoiding dye damage to bleach-sensitive fabrics.
• U.S. Patent Nos. 4,385,008 and 4,403,994 address themselves to the specific problems of storage stability and impact sensitivity of the magnesium salts of peroxycarboxylic acid compounds.
• the patents disclose the combination of magnesium monoperoxyphthalic, for example, with a desensitizing diluent selected from among broad classes of materials including hydrocarbon waxes, fatty acids, aromatic acids and esters, starch, cellulose and protein.
• fatty acids the patents state that "although any aliphatic acid can be used, for practical purposes, the acid normally contains from 10 to 26 carbon atoms.". Lauric acid (a 12 carbon atoms acid) is said to be especially preferred for this purpose.
• the present invention provides, in one aspect thereof, a bleaching agent particularly effective for low temperature bleaching of laundry while substantially avoiding concomitant dye damage of bleach-sensitive dyed fabrics
• a bleaching agent particularly effective for low temperature bleaching of laundry while substantially avoiding concomitant dye damage of bleach-sensitive dyed fabrics
• particles of monoperoxyphthalic acid (MPPA) and/or a water-soluble salt said particles being at least partially coated with an effective amount of a substantially aliphatic fatty acid mixture comprised of at least about 16%, and no more than about 40%, by weight, of fatty acids having a chain length of from 20 to 22 carbon atoms, said mixture being substantially free of fatty acids having less than 14 carbon atoms.
• MPPA monoperoxyphthalic acid
• the bleaching detergent composition of the invention comprises the above-defined bleaching agent in combination with one or more surface active detergent compounds and detergent builder salts.
• bleaching of stained and/or soiled materials is effected by contacting such materials with an aqueous solution of the above-­defined compositions.
• the present invention is predicated on the discovery that effective low temperature bleaching of laundry can be achieved while substantially avoiding the undersired occurrence of pin-point spotting of bleach-sensitive fabrics by providing at least a partial coating of a specifically defined fatty acid mixture to particles of MPPA bleach (or a water-soluble salt thereof).
• the chain length distribution or the fatty acid mixture is such that it contains at least 16%, and no more than about 40%, by weight of C20-C22 aliphatic fatty acids and is substantially free of fatty acids having less than 14 carbon atoms, such as, lauric acid.
• lauric acid is a preferred diluent in the prior art for MPPA bleach as per the aforementioned U.S. Patents Nos. 4,385,008 and 4,403,994.
• Monoperoxyphthalic acid and/or one or more of its water-soluble salts are the essential bleaching compounds which provide bleaching activity in the compositions of the invention.
• MPPA provides acceptable bleaching activity, it has the disadvantage of relatively poor stability when stored in admixture with other components ordinarily present in household detergent compositions.
• the magnesium salt of MPPA is preferably employed in the compositions of the invention, namely, magnesium monoperoxyphthalate.
• the alkali metal, calcium or barium alkaline earth and/or ammonium salts of MPPA may also be employed in the bleaching and laundering compositions herein described, although such salts are generally less preferred from the standpoint of stability than the aforementioned magnesium salt.
• a fatty acid mixture is used to at least partially coat the particles of MPPA or a water-soluble salt thereof as hereinafter described.
• the fatty acid mixture is predominantly, or preferably entirely, aliphatic fatty acids although a minor amount of unsaturated fatty acids may also be present in the mixture in accordance with the invention.
• At least 16%, by weight of the acid mixture is comprised of fatty acids containing from 20 to 22 carbon atoms, e.g., arachidic and behenic acids.
• the maximum percentage of C20-C22 fatty acids in the acid mixture is about 40%, and as a practical matter it has been found that a C20-C22 acid fraction of from about 22% to 34%, by weight, is generally effective for the elimination of pin-point spotting.
• a preferred fatty acid mixture has the following chain length distribution in accordance with the invention: Carbon Chain Length Distribution (Weight Percent) C12 0% C14 10.5 C15 0.8 C16 30.5 C17 1.4 C18 27.6 C19 0.9 C20 18.5 C22 9.8
• a preferred fatty acid mixture for coating particles of MPPA or a salt of MPPA in accordance with the invention is marketed by Oleofina (Belgium), Henkel (Germany) and Mira Lanza (Italy).
• This type of fatty acid mixture has a molecular weight of about 287 a melting point of about 50°C, and the fraction of C20-C22 fatty acids is about 28% with preferably no fatty acid having less than 14 carbon atoms.
• the method of coating the particulate MPPA or MPPA salt with the fatty acid mixture is not critical.
• the fatty acid mixture is sprayed in molten form onto the heated and agitated particles of MPPA bleach.
• the process may be continous or discontinuous with the particles being agitated mechanically or in a fluidized bed. It is advantageous to spray the molten fatty acid mixture at a temperature of about 10°C above its melting point while the particulate MPPA or MPPA salt is heated to about 10°C below said melting point.
• a fatty acid mixture having the preferred chain length distribution described above has a melting point of about 50°C.
• the particle size of MPPA or its salt may suitably vary from about 16 mesh to about 170 mesh corresponding to about 1180 microns to 90 microns. A particle size of from about 18 to 140 mesh is preferred.
• the total amount of fatty acid mixture used to partially envelope or coat the monoperoxyphthalate bleach particle is desirably from about 25 to 35%, by weight, of the coated particles.
• the suitable level of coating is generally determined by the degree of color protection i.e., avoidance of pin-point spotting, required. For the majority of bleach-sensitive dyed fabrics, a coating of about 27 to 30%, by weight, of the coated particles of MPPA or its water-soluble salt, will insure maximum color or dye protection.
• the bleaching agent as herein described may be formulated as an separate bleach product, or alternatively, may be employed in a built detergent com­position.
• the bleaching agent of the invention may be incorporated into a laundering detergent compositions containing surface active agents, such as, anionic, cationic, nonionic, ampholytic and zwitterionic detergents and mixtures thereof.
• the bleaching detergent compositions herein described may include conventional additives used in the fabric washing art, such as, binders, fillers, builder salts, proteolytic enzymes, optical brighteners, perfume, dyes, corrosion inhibitors, anti-redeposition agents, foam stabilizers and the like, all of which may be added in varying quantities depending on the desired properties of the bleaching composition and their compatibility with such composition.
• the instant bleaching agents When the instant bleaching agents are incorporated into a conventional laundering composition and are thus provided as a fully formulated bleaching detergent composition, the latter compositions will comprise the following: from about 5 to 50%, by weight, of the instant bleaching agents; from about 5 to 50%, by weight, of a detergent surface active agent, preferably from about 5 to 30%, by weight; and from about 5 to 80%, by weight, of a detergent builder salt which can also function as a buffer to provide the requisite pH range when the laundering composition is added to water.
• the aqueous wash solutions will have a pH range of from about 7 to 12, preferably from about 8 to 10, and most preferably from about 8.5 to 9.
• a preferred amount of the builder salt is from about 20% to about 65%, by weight, of the composition.
• the balance of the composition will predominantly comprise water, filler salts, such as, sodium sulfate, and optionally, minor additives, such as, optical brighteners, perfumes, dyes, anti-redeposition agents and the like.
• anionic surface active agents useful in the present invention are those surface active compounds which contain an organic hydrophobic group containing from about 8 to 26 carbon atoms and preferably from about 10 to 18 carbon atoms in their molecular structure and at least one water-solubilizing group selected from the group of sulfonate, sulfate, carboxylate, phosphonate and phosphate so as to form a water-soluble detergent.
• Suitable anionic detergents include soaps, such as, the water-soluble salts (e.g., the sodium, potassium, ammonoium and alkanol-­ammonium salts) of higher fatty acids or resin salts containing from about 8 to 20 carbon atoms and preferably 10 to 18 carbon atoms.
• Suitable fatty acids can be obtained from oils and waxes of animal or vegetable origin, for example, tallow, grease, coconut oil and mixtures thereof.
• Particularly use­ful are the sodium and potassium salts of the fatty acid mixtures derived from coconut oil and tallow, for example, sodium coconut soap and potassium tallow soap.
• the anionic class of detergents also includes the water-soluble sulfated and sulfonated detergents having an aliphatic, preferably an alkyl radical containing from about 8 to 26, and preferably from about 12 to 22 carbon atoms.
• alkyl includes the alkyl portion of the higher acyl radicals.
• the sulfonated anionic detergents are the higher alkyl mononuclear aromatic sulfonates such as the higher alkyl benzene sulfonates containing from about 10 to 16 carbon atoms in the higher alkyl group in a straight or branched chain, such as, for example, the sodium, potassium and ammonium salts of higher alkyl benzene sulfonates, higher alkyl toluene sulfonates and higher alkyl phenol sulfonates.
• the higher alkyl mononuclear aromatic sulfonates such as the higher alkyl benzene sulfonates containing from about 10 to 16 carbon atoms in the higher alkyl group in a straight or branched chain, such as, for example, the sodium, potassium and ammonium salts of higher alkyl benzene sulfonates, higher alkyl toluene sulfonates and higher alkyl phenol
• Suitable anionic detergents are the olefin sulfonates including long chain alkene sulfonates, long chain hydroxyalkane sulfonates or mixtures of alkene sulfonates and hydroxyalkane sulfonate.
• the proportion of ethylene oxide in the polyethoxylated higher alkanol sulfate is preferably 2 to 5 moles of ethy­lene oxide groups per mole of anionic detergent, with three moles being most preferred, especially when the higher alkanol is of 11 to 15 carbon atoms.
• the ethylene oxide content of the detergent may be reduced to about two moles per mole whereas when the higher alkanol is of 16 to 18 carbon atoms in the higher part of the range, the number of ethylene oxide groups may be increased to 4 to 5 and in some cases to as high as 8 or 9.
• the most highly preferred water-soluble anionic detergent compounds are the ammonium and substituted ammonium (such as mono, di and tri-­ethanol-amine), alkali metal (such as, sodium and potassium) and alkaline earth metal (such as, calcium and magnesium) salts of the higher alkyl benzene sulfonates, olefin sulfonates and higher alkyl sulfates.
• alkali metal such as, sodium and potassium
• alkaline earth metal such as, calcium and magnesium
• the most preferred are the sodium linear alkyl benzene sulfonates (LABS), and especially those wherein the alkyl group is a straight chain alkyl radical of 12 or 13 carbon atoms.
• the nonionic synthetic organic detergents are characterized by the presence of an organic hydrophobic group and an organic hydrophilic group and are typically produced by the condensation of an organic aliphatic or alkyl aromatic hydrophobic compound with ethylene oxide (hydrophilic in nature).
• any hydrophobic compound having a carboxy, hydroxy, amido or amino group with a free hydrogen attached to the nitrogen can be condensed with ethylene oxide or with the polyhydration product thereof, polyethylene glycol, to form a nonionic detergent.
• the length of the hydrophilic or polyoxyethylene chain can be readily adjusted to achieve the desired balance between the hydrophobic and hydrophilic groups.
• the nonionic detergent employed is preferably a poly-lower alkoxy­lated higher alkanol wherein the alkanol is of 10 to 18 carbon atoms and wherein the number of moles of lower alkylene oxide (of 2 or 3 carbon atoms) is from 3 to 12.
• the higher alkanol is a higher fatty alcohol of 11 to 15 carbon atoms and which contain from 5 to 9 lower alkoxy groups per mole.
• lower alkoxy is ethoxy but in some instances it may be desirably mixed with propoxy, the latter, if present, usually being a minor (less than 50%) constituent.
• Tergitol® 15-S-7 and Tergitol 15-S-9 are linear secondary alcohol ethoxylates made by Union Carbide Corporation.
• the former is a mixed ethoxylation product of an 11 to 15 carbon atom linear secondary alkanol with seven moles of ethylene oxide and the latter is a similar product but with nine moles of ethylene oxide being reacted.
• Also useful in the present compositions are the higher molecular weight nonionics, such as Neodol 45-11, which are similar ethylene oxide condensation products of higher fatty alcohols, the higher fatty alcohol being of 14 to 15 carbon atoms and the number of ethylene oxide groups per mole being about 11.
• Such products are also made by Shell Chemical Company.
• Zwitterionic detergents such as the betaines and sulfobetaines having the following formula are also useful: wherein R is an alkyl group containing from about 8 to 18 carbon atoms, R2 and R3 are each an alkyl or hydroxyalkyl group containing about 1 to 4 carbon atoms, R4 is an alkylene or hydroxyalkylene group containing 1 to 4 carbon atoms, and X is C or S:O.
• the alkyl group can contain one or more intermediate linkages such as amido, ether, or polyether linkages or non-­functional substituents such as hydroxyl or halogen which do not substantially affect the hydrophobic character of the group.
• X is C
• the detergent is called a betaine
• X is S:O
• the detergent is called a sulfobetaine or sultaine.
• Cationic surface active agents may also be employed. They comprise surface active detergent compounds which contain an organic hydrophobic group which forms part of a cation when the compound is dissolved in water, and an anionic group. Typical cationic surface active agents are amine and quaternary ammonium compounds.
• Ampholytic (or amphoteric) detergents are also suitable for the invention.
• Ampholytic detergents are well known in the art and many operable detergents of this class are disclosed by Schwartz, Perry and Berch in the aforementioned "Surface Active Agents and Detergents.”
• suitable ampholytic detergents include: alkyl betaiminodipropionates, RN(C2H4COOM)2; alkyl beta-amino propionates, RN(H)2C2H4COOM; and long chain detergents having the general formula: wherein in each of the above formulae R is an acyclic hydrophobic group containing from about 8 to 18 carbon atoms and M is a cation to neutralize the charge of the anion.
• inorganic phosphates builders include sodium and potassium tripolyphosphates, pyrophosphates and hexametaphosphates.
• the organic polyphosphates specifically include, for example, the sodium and potassium salts of ethane 1-hydroxy-1,1-diphosphonic acid, ethane-1,1,2-triphosphonic acid and diethylene triamine pentamethylene phosphonic acid. Examples of these and other phosphorous builder compounds are disclosed in U.S. Patent Nos. 3,213,030; 3,422,021; 3,422,137 and 4,225,452. Pentasodium tripolyphosphate and tetrasodium pyrophosphate are especially preferred water-soluble inorganic builders.
• fatty acid HMW For a 28% coating, 78 grams of the fatty acid mixture selected is weighed and then heated to about 10°C above its melting point (for fatty acid HMW this corresponds to a temperature of about 60°C). Two hundred grams (200 g) of MMPP are preheated separately in a one liter beaker to a temperature about 10°C below the melting point of said fatty acid mixture (for fatty acid HMW this corresponds to a temperature of about 40°C).
• Coating consists of pouring slowly and continuously the melted fatty acid mixture onto the particles of MMPP while agitating the MMPP particles with a mechanical agitator such as an axial flow impeller at a speed of about 250-300 rpm. During the coating operation, the temperature of the MMPP particles are maintained at about 10°C below the melting point of the fatty acid mixture. The coating procedure is carried out in a period of less than 30 minutes.
• a bleaching detergent composition was prepared by mixing the bleaching agent of Example 1 with a granular detergent composition prepared by con­ventional spray-drying, the resultant mixture having the following approximate composition: TABLE 1 COMPONENT Weight Percent Sodium linear C10-C12 alkyl benzene sulfonate 5 Ethoxylated C11-C18 alcohol (11 moles of EO per mole alcohol) 3 Soap (sodium salt of C12-C22 carboxylic acids) 2 Sodium silicate (1 Na2O:2 Sio2) 3 Pentasodium tripolyphosphate (TPP) 40 Sodium Salt of diethylene triamine pentamethylene phosphonic acid (DTPMP) 0.5 Enzyme (a) 0.4 Optical brighteners 0.2 Coated Mg salt of MPPA (b) 7.0 Perfume 0.18 Sodium Sulfate 22 Water q.s. (a) A proteolytic enzyme purchased as Alcalase 2M (2 anson unit/gram) or as Maxatase P. (b
• Bleaching detergent compositions as described in Table 1 were prepared with different bleaching agents, each bleaching agent consisting of particles of MMPP coated with a different fatty acid mixture.
• the bleaching agents prepared with the Radiacid 60, Radiacid 161, tallow/coco and coco/palm fatty acid mixtures are not in accordance with the invention because of the chain length distribution of such fatty acid mixtures.
• test procedure was as follows: A powder dose of 180 grams of the bleaching detergent composition to be tested was added to a European washing machine (Thomson T59-44), such dosage being calculated to deliver about 0.44% available oxygen (Avox.) to the wash water. Washes were run at 30°C for 24 consecutive cycles. To magnify dye-damage effects, three blue tracer cloths which are extremely sensitive to MMPP were introduced at the beginning of each cycle and distributed in the washload by placing one at the top, the second in the middle and the third at the bottom. After each of the 24 wash test cycles, the blue tracer cloths were visually inspected and assigned a rating depending on the level of pin-point spotting observed.
• Radiacid 60 and Rediacid 160 contain a percentage of C20-C22 fatty acids above 40%, by weight, are also not in accordance with the invention. They too provided markedly inferior results with regard to being able to completely prevent pin point spotting (Class I) relative to fatty acid HMW.

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• 1988
  • 1988-06-18 EP EP19880109752 patent/EP0297373A3/fr not_active Withdrawn
  • 1988-06-22 AU AU18268/88A patent/AU604924B2/en not_active Ceased
  • 1988-06-23 MX MX012023A patent/MX169906B/es unknown
  • 1988-06-24 CA CA000570385A patent/CA1307991C/fr not_active Expired - Lifetime
  • 1988-06-24 DK DK352188A patent/DK352188A/da not_active Application Discontinuation
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