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
  • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
  • C11D7/02—Inorganic compounds

Definitions

• the present invention relates in general to cleaning compositions and in particular to the provision of cleaning compositions beneficially adapted for use in connection with the cleaning of substrates such as dishware and the like having a glazed surface.
• a primary object of the present invention resides in the provision of cleaning compositions substantially devoid of any tendency to attack the glazed surface of a wide variety of substrates.
• Another object of the present invention resides in the provision of cleaning compositions capable of providing superior cleaning activity e.g., bleaching, washing, etc.
• a watersoluble alkaline detergent composition for automatic dishwashing comprises a major amount of inorganic builder salts such as alkali metal phosphates, silicates, carbonates, sulfates; a bleaching agent capable of liberating hypohalite in aqueous media; and aluminum chlorhydroxide as an overglaze protector.
• inorganic builder salts such as alkali metal phosphates, silicates, carbonates, sulfates
• a bleaching agent capable of liberating hypohalite in aqueous media
• aluminum chlorhydroxide as an overglaze protector.
• the aluminum chlorhydroxide preferred in the practice of the present invention and capable of inhibiting overglaze attack is a slightly off-white powder believed to have the formula, Al (OH) Cl-2H 0 where the atomic ratio of Al to Cl is 2:1. -Its aluminum content as A1 0 is about 47% and a 15% solution of the solid has a pH of about 4.2.
• Aluminum chlorhydroxide is soluble in water in all proportions and forms stable solutions in normally used concentrations (up to about 50%). Concentrations above 50% become extremely viscous and diflicult to handle. Solutions thereof exhibit no significant change in pH even after prolonged periods of standing (2 years), with the pH varying within the range of about 4.0 to about 4.5.
• the water soluble builder salts utilized in the instant detergent compositions include the inorganic basic and neutral water soluble salts.
• the builder salt is employed in amounts ranging up to about 95% i.e., 50-95% by weight with a range of from about 70% to about by weight of the composition being preferred.
• Suitable builders include without necessary limitation,
• Trisodium phosphate Tetrasodium pyrophosphate Sodium acid pyrophosphate Sodium tripolyphosphate hexahydrate Sodium monobasic phosphate Sodium dibasic phosphate Sodium hexameta phosphate Sodium silicates, SiO /Na O of 1/1 to 3.2/1 Sodium carbonate Sodium sulfate Borax etc.
• Suitable organic builders include salts of organic acids and, in particular, the water soluble salts of aminopolycarboxylic acids.
• the alkali metal salts such as sodium potassium and lithium; ammonium and substituted ammonium salts such as methylammonium, diethanolammonium and triethanolammonium; and amine salts such as mono, diand triethanolamine methylamine, octylamino diethylenetriamine, triethylenetetramine and ethylenediamine are efiioacious.
• the acid portion of the salt can be derived from acids such as nitrilodiacetic; N-(2- hydroxyethyl) nitrilodiacetic acid, nitrilotriacetic acid (NTA), ethylenediamine tetraacetic acid '(EDTA); N- (Z-hydroxyethyl) ethylene diamine triacetic acid; Z-hydroxyethyl iminodiacetic acid; 1,2-diaminocyclohexanediacetic acid; diethylenetriamine penta-acetic acid and the like.
• the builder salt is preferably employed in amounts sufiicient to yield a pH in water of from 9.5 to 12, preferably from 10 to 11.
• Particularly preferred compositions contain for example from about 55 to about 75% sodium tripolyphosphate hexahydrate and about 15 to about 25% sodium metasilicate as alkaline builders.
• the cleaning compositions described herein may further be provided with one or more bleaching agents which may in general be defined as encompassing compounds capable of liberating a hypohalite such as hypochlorite chlorine and/r hypobromite bromine on contact with aqueous media.
• bleaching agents include the dry, particulate heterocyclic N-bromo and N- chloro imides such as trichloro-cyanuric, tribromocyanuric acid, dibromoand dichlorocyanuric acid, the salts thereof with water-solubilizing cations such as potassium and sodium.
• Such bleaching agents may be employed in admixtures comprising two or more, particularly efiicacious bleaching agent in this regard comprising the material commercially available from the Monsanto Chemical Company under the trade name designation ACL-66, ACL signifying available chlorine and the numerical designation 66, indicating the parts per pound of available chlorine.
• This particular product comprises a mixture of potassium dichloro-isocyanurate (4 parts) and trichloroisocyanuric acids (one part).
• N-bromo and N-chloro imides may also be used, such as N-brominated and N-chlorinated succinimide, malonimide, phthalimide and naphth alimide.
• Other compounds include the hydantoins, such as 1,3-dibromo and l,3-dichloro-5,S-dimethylhydantoin; N-monochloro 5,5- dimethylhydantoin, methylene-bis (N-bromo-5,5-dimethylhydantoin); 1,3-dibromo and 1,3-dichloro 5-isobutylhydantoin; 1,3-bromo and 1,3-dichloro S-methyI-S-n-amylhydantoin and the like.
• hpyohalite-liberating agents comprise tribromomelamine and trichloromelamine. Dry, particulate, water soluble anhydrous inorganic salts are likewise suitable for use such as lithium hypochlorite and hypobromite.
• the hypothalite-liberating agent may, if desired, be provided in the form of a stable, solid complex or hydrate, such as sodium p-toluene-sulfobromamine-trihydrate, sodium benzene-sulfo-chloroaminedihydrate, calcium hypobromite tetrahydrate, calcium hypochlorite tetrahydrate etc.
• the present invention contemplates as an additional embodiment the use of bleaching agents capable of liberating hypochlorite as well as hypobromite such as, for example, the N-brominated, N'-chlorinated heterocyclic imides, as for example the N-bromo, N- chlorocyanuric acids and salts thereof, e.g., N-monobromo N,N dichloro-cyanuric acid, N-rnono-bromo-N- monochlorocyanuric acid, sodium N monobromo-N- monochlorocyanurate, potassium-N-monobromo-N-monochlorocyanurate; and the N-brominated, N-chlorinated hydantoins, e.g., N-bromo
• hypohalite-liberating compound is employed in an amount of from 0.5 to 5% by Weight of the composition, and preferably in an amount of from about 0.5 to 3% by weight thereof.
• hypohalide material should preferably be employed in amounts sufficient to yield from about 0.5-3% available chlorine, bromine etc. in order to assure optimum results.
• efficacious cleaning compositions may be formulated in accordance with the present invention by the use of the aluminum chlorhydroxide in amounts of about 0.5 to 3% by weight of total composition and up to about 95%, i.e. from 40% to 95% by Weight of at least one compound selected from the group of watersoluble organic detergent, water soluble neutral or alkaline builder salt, bleaching agent capable of liberating hypohalite on contact with aqueous media and caustic alkali.
• the bleaching agent is essential to the implementation of those embodiments of the present invention directed to industrial bottle cleaning compositions.
• Water soluble organic detergents i.e., surface active components may be employed, such materials being well known in the prior art, the term detergent comprehending species of the anionic, cationic, amphoteric and zwitterionic types.
• suitable anionic surface active agents include those surface active or detergent compounds which contain an organic hydrophobic group and an anionic solubilizing group.
• anionic solubilizing groups are sulfonate, sulfate, carboxylate, phosphonate 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 resin 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 about 12 to 22, carbon atoms to the molecule.
• the soaps such as the water-soluble salts of higher fatty acids or resin 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 about 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 10 to 16 carbon atoms in the alkyl group in 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 sulfonates.
• the higher alkyl mononuclear aromatic sulfonates such as the higher alkyl benzen
• anionic detergents are the olefin sulfonates, including long chain alkene sulfonates, long chain hydroxyalkane sulfonates or mixtures of alkenesulfonates and hydroxyalkanesulfonates.
• paraffin sulfonates such as the reaction products of alpha olefins and bisulfites (e.g., sodium bisulfite), e.g. primary paraffin sulfonates of about 10-20, preferably about l5-20, carbon atoms, sulfates of higher alcohols; salts of oz-Slllfofatty esters (e.g., of about 10-20 carbon atoms, such as methyl a-sulfomyristate or ot-sulfotallowate).
• alpha olefins and bisulfites e.g., sodium bisulfite
• oz-Slllfofatty esters e.g., of about 10-20 carbon atoms, such as methyl a-sulfomyristate or ot-sulfotallowate.
• sulfates of higher alcohols are sodium lauryl sulfate, sodium tallow alcohol sulfate. Turkey Red Oil or other sulfated oils, or sulfates of monoor diglycerides of fatty acids (e.g.
• alkyl poly (ethenoxy) ether sulfates such as the sulfates of the condensation products of ethylene oxide and lauryl alcohol (usually having 1 to 5 ethenoxy groups per molecule); lauryl or other higher alkyl glyceryl ethersulfonates; aromatic poly (ethenoxy) ether sulfates such as the sulfates of the condensation products of ethylene oxide and nonyl phenol (usually having 1 to 20 oxyethylene groups per molecule preferably 2-12).
• the suitable anionic detergents include also the acyl sarcosinates (e.g. sodium lauroylsarcosinate) the acyl esters (e.g. oleic acid ester) or isothionates, and the acyl N-methyl taurides (e.g. potassium N-methyl lauroylor oleyl tauride).
• acyl sarcosinates e.g. sodium lauroylsarcosinate
• the acyl esters e.g. oleic acid ester
• isothionates e.g. potassium N-methyl lauroylor oleyl tauride
• the most highly preferred water soluble anionic detergent compounds are the ammonium and substituted ammonium (such as mono, di and triethanolamine), 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, 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.
• Nonionic surface active agents include those surface active or detergent compounds which contain an organic hydrophobic group and a hydrophilic group which is a reaction product of a solubilzing group such as carboxylate, hydroxyl, amido or amino with ethylene oxide or with the polyhydration product thereof, polyethylene glycol.
• nonionic surface active agents which may be used 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 15 ethylene oxide units; condensation products of higher fatty alcohols of monoesters of hexahydric alcohols and inner ethers thereof such as sorbitan monolaurate, sorbitol mono-oleate and mannitan monopalmitate, and the condensation products of polypropylene glycol with ethylene oxide.
• 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 15 ethylene oxide units condensation products of higher fatty alcohols of monoesters of hexahydric alcohols and inner ethers thereof such as sorbitan monolaurate,
• 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.
• suitable synthetic cationic detergents there maybe noted the diamines such as those of the type RNC H NH wherein R is an alkyl group of about 12 to 22 carbon atoms such as N-Z-aminoethyl stearyl amine and N-Z-aminoethyl myristyl amine; amido-linked amines such as those of the type R CoNHC H NH wherein R is an alkyl group of about 9 to 20 carbon atoms, such as N-Z-arnino ethyl-stearyl amide and N-amino ethyl myristyl amide; quaternary ammonium compounds wherein typically one 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 anion such as halogen, acetate, methosulfate, etc.
• Typical quaternary ammonium detergents are ethyl-dimethylstearyl ammonium chloride, benzyl-dimethyl-stearyl ammonium chloride, benzyl dimethylstearyl ammonium bromide, trimethyl stearyl ammonium chloride, trimethyl-cetyl ammonium bromide, dimethyl-ethyl dilauryl ammonium chloride, dimethyl-propyl-myristyl ammonium chloride, and the corresponding methosulfates and acetates.
• amphoteric detergents are N-alkylbeta-aminopropionic acid; N-alkyl-beta-imino-dipropionic acid, and N-alkyl, N,N-dimethyl glycine; the alkyl group may be, for example, that derived from coco fatty alcohol, lauryl alcohol, myristyl alcohol (or a lauryl-myristyl mixture), hydrogenated tallow alcohol, cetyl, stearyl, or blends of such alcohols.
• the substituted aminopropionic and iminodipropionic acids are often supplied in the sodium or other salt forms, which may likewise be used in the practice of this invention.
• amphoteric detergents examples include the betaines containing a sulfonic group instead of the carboxylic group; betaines in which the long chain substitucnt is joined to the carboxylic group without an intervening nitrogen atom, e.g. inner salts of Z-trimethylarnino fatty acids such as Z-trimethylaminolauric acid, and compounds of any of the previously mentioned types but in which the nitrogen atom is replaced by phosphorus.
• the detergent material is employed in concentrations ranging from about 0.5% to about by weight of total composition with a range of 1% to 3% being particularly preferred.
• nonionic type detergent that is, about 24% is especially beneficial in asmuch as it acts as a foam depressant as well as a detersive agent in an automatic dishwashing solution.
• test samples are immersed in deionized or distilled water maintained at a temperature of 211 F. and containing the indicated percent concentration of detergent for periods of 2, 4 and 6 hours.
• the test samples are thereafter removed, hand-rubbed with cloth and compared with untreated sample of the same standard plate.
• the treated samples are visually scrutinized to determine the extent of overglaze damage with numerical indicia being assigned to indicate the extent of overglaze damage involved.
• the scale of O, 1, 2, 3 and 4 correspond, in terms of damage, to none, slight, moderate, considerable and complete, respectively.
• EXAMPLE 1 This example illustrates the applicability of the present invention to the preparation and use of cleaning compositions specifically adapted for use in connection with dishwashing operations.
• compositions is prepared:
• Example 1 is repeated except that th econcentration of aluminum chlorhydroxide is reduced to 1% by weight and the sodium sulfate is increased to 13% by weight.
• the results obtained are as follows:
• Example 1 is repeated except that the concentration of aluminum chlorhydroxide is reduced to 0.5% by weight and the sodium sulfate content increased to 13.5% by weight. The results obtained are shown below.
• compositions provided in accordance with the present invention are capable of superior cleaning activity i.e., displaying an outstanding capacity to readily remove stain deposits from a wide variety of glazed dishware.
• Effective industrial bottle cleaning compositions may be provided in accordance with the present invention by merely admixing with caustic alkali whereby to provide a highly alkaline composition preferably having a pH of about 12.
• Such compositions may be readily formulated in accordance with the parameters hereinbefore described.
• the detergent composition of the present invention finds most efficacious utilization in connection with the washing of the dishes and the like in automatic dishwashers, naturally, the detergent may be utilized in other fashions as desired. Usually, however, the best mode of use will be in connection with automatic dishwashers which have the ability of dispensing the detergent of the present invention in one or more separate wash cycles. Accordingly, the detergent compositions of the present invention is added to the two receptacles, if such are present, in an automatic dishwasher. When the dishwasher is set into operation, after the dishes have been suitably positioned therein, the automatic devices of the dishwasher permit the addition of sufiicient water to produce a concentration of the detergent composition of approximately 0.3% by weight.
• the operation of the dishwasher results in treating, that is, washing of the dishes With the aqueous solution of the detergent composition.
• sequence of operation in utilizing an automatic dishwasher results in one or more rinsing steps following the one or more washing cycles.
• the detergent composition of the present invention it will be noted that even after use in considerable number of washings there will be little or no attack on the overglaze on china or little or no tarnishing of silver or silver plate as a result of the use of the detergent composition.
• a water-soluble alkaline detergent composition capable of inhibiting overglaze attack consisting essentially of about 50-85% by weight of at least one inorganic builder salt selected from the group of alkali metal phosphates, silicates, carbonates and sulfates, and at least 0.5% by weight of aluminum chlorhydroxide having an aluminum to chlorine ratio of 2.
• composition in accordance with claim 1 which also includes about 0.5% to 5% by weight of a water soluble bleaching agent capable of liberating hypohalite in in aqueous media.
• a composition in accordance with claim 2 which also includes about 0.5 to 5% by weight of water soluble organic detergent selected from the group consisting of non-ionic, anionic, cationic and amphoteric detergents.
• composition in accordance with claim 1 wherein the inorganic builder is about 55-75% by weight of sodium tripolyphosphate hexahydrate and about 15-25% by weight of sodium metasilicate.
• a method for treating glases, dishes and like glazed surfaces to remove foreign bodies from the surfaces thereof without modifying the substrata comprising treating said substrata with a dilute aqueous solution of the composition defined in claim 1.

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

Applications Claiming Priority (2)

Publications (1)

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ID=26718270

Family Applications (1)

Country Status (7)

Cited By (14)

• 1970
  • 1970-05-28 US US41551A patent/US3696041A/en not_active Expired - Lifetime
• 1971
  • 1971-04-29 CA CA111,765A patent/CA945032A/en not_active Expired
  • 1971-04-29 CA CA111,764A patent/CA970646A/en not_active Expired
  • 1971-05-19 GB GB1199573A patent/GB1348140A/en not_active Expired
  • 1971-05-19 GB GB1580471*[A patent/GB1348139A/en not_active Expired
  • 1971-05-19 FR FR7118134A patent/FR2091781A5/fr not_active Expired
  • 1971-05-25 BE BE767602A patent/BE767602A/fr unknown
  • 1971-05-26 DE DE19712126103 patent/DE2126103A1/de active Pending
  • 1971-05-26 DK DK255471AA patent/DK139758B/da not_active IP Right Cessation

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