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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
  • C11D3/38609—Protease or amylase in solid compositions only

Definitions

• ABSTRACT OF THE DISCLOSURE A detergent washing composition containing an alkali salt of a hydroperoxide and a water-soluble synthetic organic surface active agent.
• This invention relates to detergent washing compositions for cleaning soiled laundry at the boil.
• the composition is a powdery solid.
• the peroxide compound in the detergent washing composition should have certain characteristics including:
• washing detergent composition which contains an organic peroxide' which is water soluble, solid and has good storage stability and cleaning efficiency at the boil.
• this invention relates to a stable, substantially dry, washing detergent composition for cleaning soiled laundry at the boil which comprises a water-soluble synthetic organic surface active agent and an alkali salt of a hydroperoxide having the formula:
• R R and R are each hydrogen or a hydrocarbon radical, R R and R not being all simultaneously hydrogen and two of R R, and R capable of being part of the same cyclic hydrocarbon group and M is an alkali metal, such as sodium or potassium or ammonium.
• hydrocarbon radicals R R and R are not critical and they can be therefore chosen among the straight or branched chain alkyl radicals, especially alkyl radicals having 1 to 12 carbon atoms, the aryl alkyl radicals, the cycloalkyl, alkyl-c'ycloalkyl and arylcycloalkyl radicals, the unsaturated homologues of these alkyl and cycloalkyl radicals, and the aromatic radicals, especially phenyl, alkylphenyl, naphthyl, alkylnaphthyl and antracenyl.
• hydrocarbon radicals can be by other means substituted by different heteroatoms or groups of heteroatoms, such as for example halogen atoms, hydroxyl groups, nitrates, sulfonyls, ethers, carboxylic acids or esters of carboxylic acids.
• the non-salified hydroperoxides are not utilizable in washing compositions, for generally they are liquids, insoluble in water and often present a strong odor which is difficult to conceal. It has been proposed to condense these hydroperoxides with sultones, such as popane sultone, or alkylene oxides, such as ethylene oxide, however, the resulting products possess too much stability and do not efficiently release oxygen to permit effective cleaning of soiled laundry.
• alkali salts of hydroperoxides utilized in the instant invention are soluble in water, are without rehibitory odor and produce effective cleaning of soiled laundry.
• they are produced from hydroperoxides in accordance with known procedures at very low cost compared to the cost of condensing with sultones or alkylene oxides.
• the alkali salt of hydroperoxide is introduced into the composition in such amount that the amount of active oxygen in the powder is 0.2 to 4%, which corresponds to usual doses found in classical compositions of a persalt base.
• the content by weight of the composition in salt of hydroperoxide thus varies in function of the molecular weight of the latter. As a general rule this content is however from 0.5 to 10%.
• the surface active agent which may be employed may be any commonly used compound having surface active or detergent properties. Most preferable are those watersoluble surface active compounds having anionic or nonionic properties.
• Anionic surface active agents include those surface active or detergent compounds which contain an organic hydrophobic group and an anionic solubilizing group. Typical examples of anionic solubilizing groups are sulfonate, sulfate, carboxylate, and phosphate.
• Suitable anionic detergents which fall within the scope of the invention include the soaps, such as the water-soluble salts of higher fatty acids or rosin acids, such as may be derived from fats, oils and waxes of animal, vegetable or marine origin, e.g., the sodium soaps of tallow, grease, coconut oil, tall oil and mixtures thereof; and the sulfated and sulfonated synthetic detergents, particularly those having about 8 to 26, and preferably 12 to 22, carbon atoms to the molecule.
• the soaps such as the water-soluble salts of higher fatty acids or rosin acids, such as may be derived from fats, oils and waxes of animal, vegetable or marine origin, e.g., the sodium soaps of tallow, grease, coconut oil, tall oil and mixtures thereof
• the sulfated and sulfonated synthetic detergents particularly those having about 8 to 26, and preferably 12 to 22, carbon atoms to the molecule.
• suitable synthetic anionic detergents there may be cited the higher alkyl mononuclear aromatic sulfonates such as the higher alkyl benzene sulfonates containing from to 16 carbon atoms in the alkyl group on a straight or branched chain, e.g., the sodium salts of decyl, undecyl, dodecyl (lauryl), tridecyl, tetradecyl, pentadecyl, or hexadecyl benzene sulfonate and the higher alkyl toluene, xylene and phenol sulfonates; alkyl naphthalene sulfonate, ammonium diamyl naphthalene sulfonate, and sodium dinonyl naphthalene sulfonate; sulfated aliphatic alcohols such as sodium lauryl and hexadecyl sulfon
• anionic surface active agents which may be employed in the practice of this invention include olefin sulfonates, typically containing 8-25 carbon atoms.
• sulfuric acid esters of polyhydric alcohols incompletely esterified with higher fatty acids e.g. coconut oil monolyceride monosulfate, tallow diglyceride monosulfate; and the hydroxy sulfonated higher fatty acid esters such as the higher fatty acid esters of low molecular weight alkylol sulfonic acids, e.g., oleic acid ester of isethionic acid.
• Nonionic surface active agents are those surface active or detergent compounds which contain an organic hydrophobic group and a hydrophilic group which is a reaction product of a solubilizing group such as carboxylate, hydroxyl, amido, or amino with ethylene oxide or with the polyhydration product thereof, polyethylene glycol.
• nonionic surface active agents there may be noted the condensation products of alkyl phenols with ethylene oxide, e.g., the reaction product of isooctyl phenol with about 6 to 30 ethylene oxide units; condensation products of alkyl thiophenols with 10 to ethylene oxide units; condensation products of higher fatty alcohols such as tridecyl alcohol with ethylene oxide; ethylene oxide addends of monoesters of hexahydric alcohols and inner ethers thereof such as sorbitan monolaurate, sorbitol monooleate and mannitan monopalrnitate and the condensation products of polypropylene glycol with ethylene oxide.
• Cationic surface active agents may also be employed. Such agents are those surface active detergent compounds which contain an organic hydrophobic group and a cationic solubilizing group. Typical cationic solubilizing groups are amine and quaternary groups.
• the diamines such as those of the type RNHCfl-LNH; where R is an alkyl group of 12 to 22 carbon atoms, such as N-aminoethyl stearyl amine and N-aminoethylmyristyl amine; amide-linked amines such as those of the type R'CONHC I-LNH wherein R is an alkyl group of about 12 to 18 carbon atoms, such as N- amino ethyl-stearyl amide and N-amino ethyl myristyl amide; quaternary ammonium compounds wherein typically one of the groups linked to the nitrogen atom is an alkyl group of about 12 to 18 carbon atoms and three of the groups linked to the nitrogen atom are alkyl groups which contain 1 to 3 carbon atoms, including such 1 to 3 carbon alkyl groups bearing inert substituents, such as phenyl groups, and there is present an ani
• Typical quaternary ammonium detergents are ethyl-dimethyl-stearyl ammonium chloride, benzyl-dimethyl-stearyl ammonium chloride, trimethyl-stearyl ammonium chloride, trimethyl-cetyl ammonium bromide, methyl-ethyl-dilauryl ammonium chloride, dimethyl-propyl-myristyl ammonium chloride, and the corresponding methosulfates and acetates.
• the surface active compounds which are used in the most preferred aspects of this invention are those having anionic or nonionic properties.
• the most highly preferred water-soluble anionic detergent compounds are the ammonium and substituted ammonium (such as mono-, diand triethanolamine), alkali metal (such as sodium and potassium) and alkaline earth metal (such as calcium and mangesium) salts of the higher alkyl benzene sulfonates, the higher alkyl sulfates, and the higher fatty acid monoglyceride sulfates.
• the particular salt will be suitably selected depending upon the particular formulation and the proportions therein.
• the surface active agent is typically present in amount of about 4-95 by weight of the detergent composition, preferably about 4-40%.
• the detergent composition of the invention may include a builder for the detergent.
• the builder may be any of the watersoluble inorganic builder salts commonly known in the art, or it may be a water-soluble organic sequestering agent such as sodium nitrilotriacetate, or mixtures thereof.
• the water-soluble inorganic builder salt may be suitable alkali metal, alkaline earth metal, or heavy metal salt or combinations thereof.
• Ammonium or an ethanol-ammonium salt in a suitable amount may be added also, but generally used are the sodium and potassium phosphates, silicates, carbonates, bicarbonates, borates, sulfates, and chlorides.
• Particularly preferred builder salts are polyphosphates, silicates and borates.
• water-soluble inorganic builder salt mixtures used in the detergent compositions it is often preferred to have present a mixture of sodium tripolyphosphate and sodium or potassium bicarbonate, such as a combination or mixture of salts wherein the bicarbonate to tripolyphosphate ratio is selected from the range of about 1:1 to about 3:1.
• Phase I and Phase II sodium tripolyphosphate and mixtures thereof may be successfully used in the compositions.
• the usual commercial tripolyphosphate consists mainly of the Phase II material.
• the commercial tripolyphosphate material is usually essentially tripolyphosphate, e.g. 87-95%, with small amounts, e.g., 413% of other phosphates, e.g. pyrophosphate and orthophosphate.
• Sodium tripolyphosphate in its hydrated form may be used also.
• Trisodium orthophosphate may be used in the amounts indicated.
• the sodium or potassium bicarbonate is an effective pH buffer.
• the bicarbonate may be incorporated directly as anhydrous bicarbonate or in the form of sesquicarbonate, a hydrate containing both bicarbonate and carbonate.
• Suitable builder salts which may be present include the water-soluble sodium and potassium silicates, carbonates, borates, chlorides and sulfates.
• the builder salt is employed in amount in the range of about 20-90%, preferably at least 25% (e.g. 35 to of the detergent composition.
• the composition may also contain polymeric additives such as sodium carboxymethylcellulose or polyvinyl alcohol (e.g. in amount of about 0.15%) or other polymeric additives to inhibit redeposition of soil.
• Minor amounts of optical brighteners may be present, as in proportions in the range of about 0.01 to 0.15%; examples of such brighteners are the stilbene brighteners such as sodium-2- sulfo 4 (2-naphtho-1,2-triazole) stilbene; disodium 4,4 -bis (4-anilino-6-morpholino s triazin-Z-yl-amino) stilbene disulfonate or disodium 4,4 -bis (4,6-dianilino-striazin-Z-yl-a-mino) stilbene disulfonate; and the oxazole brighteners, having for example a l-phenyl-Z-benzoxazole ethylene structure. Perfumes, coloring agents and preservatives may also be included.
• the washing detergent composition there is also included in the washing detergent composition a minor amount of water-soluble copper salt such as copper sulfate or other highly, soluble inorganic copper salts such as the nitrate or acetate.
• water-soluble copper salt such as copper sulfate or other highly, soluble inorganic copper salts such as the nitrate or acetate.
• the detergent composition contains about 20 to 4000 parts of copper atom per million parts of detergent composition (that is, about 0.1 to 20 p.p.m. in a typical 5 g./l. in use solution of the detergent composition) the cleaning efficiency at the boil is markedly increased.
• a preferred amount of copper salt provides about 10-200 p.p.m. of copper to the detergent composition (that is, about 05-10 p.p.m. in a typical 5 g./ l. in use solution).
• the cleaning efficiency is further augmented when a minor amount of water-soluble copper salt is present when a sequestering agent is also present in such amount that for each atom of copper, about 0.05-10 molecules, and preferably about 0.1-5 molecules of sequestering agent are present.
• the sequestering agent may comprise a portion of the builder in admixture with additional salts such as sodium tripolyphosphate.
• the sequestering agent when employed in accordance with this aspect of the invention is stable in the presence of the organic peroxide and typically forms a complex with copper having a dissociation constant, the common logarithm of which is between about 11 and -22.
• Illustrative of the sequestering agents which form such complexes with copper are methylaminodiacetic acid, nitrilotriacetic acid (NTA), also called amino triacetic acid, hydroxyethylaminodiacetic acid, ethylenediamine tetraacetic acid (EDTA) and diethylenetriamine pentaacetic acid (DTPA) and their Water soluble salts. These agents form complexes with copper having the following dissociation constants expressed in -logarithms.
• Dissociation constant Agent of copper complexes Methylaminodiacetic acid 11.09 Nitrilotn'acetic acid 12.68 Hydroxyethylaminodiacetic acid 11.90 Ethylenediamine tetraacetic acid 18.5 Diethylenetriamine pentaacctic acid 21.3
• the washing detergent composition of this invention can have the following general formulation by weight:
• compositions of this invention can be prepared in any suitable manner such as, e.g. by spray drying the surface active agent, mineral salt if present, and copper salt if present, and then adding, by dry mixture, the organic peroxide and, if present, the sequestering agent. Constituents which are sensitive to heat, such as perfume, are also added at this time.
• Composition I Percent Sodium dodecyl benzene sulfonate 28 Sodium tripolyphosphate 34 Sodium silicate 6 Salt of sodium hydroperoxide: q.s. for 1% of active oxygen in Composition I.
• EXAMPLE 2 In the composition defined in Example 1, but to which different copper levels are added, sodium salt of hydroperoxides (corresponding to 0.4% active oxygen in the composition) and dyed swatches are introduced in the 5 g./l. detergent solutions at the boil as in Example 1.
• composition III which contains 1.5% of active oxygen
• composition IV which then contains 0.4% of active oxygen (or about four times less than Composition III).
• the washed pieces of each batch are subjected to a visual examination, and the results of this examination expressed by means of a cipher code.
• EXAMPLE 4 There is added to 93.5 parts in weight of each of the following Composition V and VI.
• compositions according to the invention are perfectly stable.
• a stable, substantially dry, washing detergent composition for cleaning soiled laundry at the boil which consists essentially of about 4-95% by weight of a watersoluble synthetic surface active agent selected from the group consisting of anionic, nonionic and cationic surface active agents and about 05-10% by weight of an alkali salt of a hydroperoxide having the formula:
• R R and R are each selected from the group consisting of hydrogen, straight or branched chain alkyl containing 1-12 carbon atoms, cycloalkyl and aromatic radicals, R R and R not being all simultaneously hydrogen and two of R R, and R, capable of being part of the same cyclic hydrocarbon group and M is an alkali metal.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
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• Inorganic Chemistry (AREA)
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ID=27446058

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• 1970
  • 1970-04-22 FR FR7014628A patent/FR2088715A5/fr not_active Expired
  • 1970-04-22 FR FR7014629A patent/FR2088716A5/fr not_active Expired
• 1971
  • 1971-03-20 DE DE19712113635 patent/DE2113635A1/de active Pending
  • 1971-03-26 CH CH446571A patent/CH552668A/xx not_active IP Right Cessation
  • 1971-04-16 US US00134894A patent/US3746646A/en not_active Expired - Lifetime
  • 1971-04-16 US US00134893A patent/US3753915A/en not_active Expired - Lifetime
  • 1971-04-19 GB GB990371*[A patent/GB1324302A/en not_active Expired
  • 1971-04-20 CA CA110,868A patent/CA946248A/en not_active Expired
  • 1971-04-20 CA CA110,869A patent/CA957629A/en not_active Expired

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