Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/2075—Carboxylic acids-salts thereof
  • C11D3/2086—Hydroxy carboxylic acids-salts thereof
• • 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
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/046—Salts
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3942—Inorganic per-compounds
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/395—Bleaching agents
  • C11D3/3953—Inorganic bleaching agents
• • 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
  • C11D3/395—Bleaching agents
  • C11D3/3955—Organic bleaching agents

Definitions

• This invention relates to inhibitors suitable for retarding the discoloration of hard surfaces and more particularly, to synthetic detergent formulations suitable for dishwashing purposes and containing discoloration inhibitors.
• Detergent compositions containing chlorinating compounds are now widely used for many cleansing applications. It has been observed that metallic surfaces such as gold, silver and platinum and non-metallic surfaces including chinaware, glass, porcelain and plastic surfaces such as are found inside automatic dishwashing machines become discolored when contacted with detergent formulations containing chlorinating agents in the presence of manganese ion (Mn++) and particularly at elevated temperatures. Since the water of most communities contains manganese ion in concentrations high enough to cause discoloration of hard surfaces, it is apparent that a serious problem exists in this regard.
• Mn++ manganese ion
• Another object is to prevent the discoloration of metallic and non-metallic hard surfaces caused by contact with aqueous detergent compositions containing halogenating agents in the presence of manganese ion.
• Still another object of this invention is to prepare dishwashing compositions suitable for washing dinner-ware decorated with a precious metal without discoloration of the metal.
• An additional object is the preparation of compositions which may be added to aqueous detergent solutions containing halogenating agents to inhibit the discoloration of hard surfaces which come in contact with the detergent solution in the presence of manganese ion.
• compositions containing discoloration inhibitors selected from the group consisting of (1) compounds furnishing gluconate ion in aqueous solution and certain combinations thereof with (2) cerium compounds or (3) certain inorganic persalts. These compositions prevent the discoloration of hard surfaces which would normally occur in the presence of halogenating agents and manganese ion.
• the materials which inhibit the discoloration of hard surfaces when the latter are exposed to halogenating agents in aqueous solutions containing manganese ion are those which produce gluconate ion in aqueous solutions as well as compositions containing these compounds and other ingredients.
• the gluconate compounds which 'are employed in this invention are those materials which supply gluconate ion in aqueous solution.
• Examples of gluconate salts which can be used are alkali metal gluconates such as sodium and potassium, ammonium gluconate, gluconic acid, alpha-sodium glucoheptonate dihydrate, glucono-delta-lacetone, etc.
• cerium ion in aqueous solutions can be utilized in combination with compounds furnishing gluconate ion to prevent or inhibit discoloration of hard surfaces.
• Any cerium compound which fulfills the aforementioned requirement c'an be used. Examples of these compounds include cerium nitrate, cerium sulfate, cerium halides such as cerium chloride, etc.
• combinations of the gluconate and cerium inhibitors rather than the gluconate alone. It has been found that combinations of these materials are particularly effective in preventing discoloration. As pointed out more particularly in the following examples, combinations of, for example, cerium nitrate and sodium gluconate are considerably more effective as discoloration inhibitors than either of these compounds alone.
• gluconate salts such as sodium gluconate
• watersoluble inorganic perborates and dipersulfates such as the alkali metal and ammonium salts thereof are also efficacious in preventing or retarding the discoloration of hard surfaces under the conditions described above.
• inorganic materials include sodium perborate and ammonium dipersulfate [(NH S O
• the proportions of discoloration inhibitor which can be employed in this invention depend upon a number of variables and can best be determined by those skilled in the ,art. Thus, the solubility of the inhibitor in aqueous solution is one factor and the level of manganese ion in the aqueous solution is still another factor in determining the requisite proportion of inhibitor to be employed.
• the amount of discoloration inhibitor which should be added to a composition is the amount which is sufiicient to give the desired inhibition when the composition is used in its normal way such as for a dishwashing formulation.
• the aforementioned materials have the following common characteristics: they are all non-alkaline, inorganic and organic halogenating agents which discolor hard surfaces in the presence of manganese ion. In the absence of manganese ion or when these halogenating materials are removed from' the aqueous solution it is observed that no discoloration occurs.
• Alkaline-reacting chlorinating compounds such as hypochlorites, e.g., calcium and sodium hypochlorite, and chlorinated trisodium phosphate do not induce discoloration when added to aqueous solutions containing manganese ion unless condensed inorganic polyphosphates such as sodium tripolyphosphate are also present. These com densed polyphosphates do not discolor hard surfaces in the absence of halogenated agents even though manganese ion is present in the solution. Although highly alkaline detergent formulations will not ordinarily cause discoloration even when halogenating materials are present, this does not hold true if the compositions contain condensed phosphates. In the latter case, it has been found necessary to add discoloration inhibitors.
• hypochlorites e.g., calcium and sodium hypochlorite
• chlorinated trisodium phosphate do not induce discoloration when added to aqueous solutions containing manganese ion unless condensed inorganic
• the inhibitors of the invention can be admixed with the aforementioned halogenating agents and this combination added to aqueous solutions containing manganese ion to prevent discoloration of hard surfaces coming in contact with the solutions.
• the inhibitors can be utilized in various detergent formulations.
• the inhibitors are particularly useful when added to conventional synthetic detergent compositions of the type which contain one or more condensed polyphosphates as builders and one or more synthetic anionic and nonionic detergents.
• the inhibitor either alone or in admixture with an inert filler such as sodium sulfate may be packaged separately and introduced into the aqueous detergent solution prior to use thereof. Since local water conditions determine the extent of discoloration, this embodiment offers a more practical solution to the problem.
• detergents which may be present in formulations in which the inhibitors of the invention are compatible include alkyl aryl sulfonates, alkyl aromatic sulfonic acids, esters of sulfuric acids with aliphatic alcohols of about -18 carbon atoms, sulfonated fatty oils, sulfated and sulfonated alkoxy derivatives and sulfuric acid esters of monoglycerides and glyceryl monoethers.
• the salts of these materials are ordinarily employed.
• the inhibitors are also useful with nonionic detergents such as for example: alkylolamides of fatty acids, ethoxylated alcohols and thioalcohols, the nonionic detergents known as Pluronics which are polyoxypropylene polymers containing varying amounts of ethylene oxide present as polyoxyethylene chains, etc.
• nonionic detergents such as for example: alkylolamides of fatty acids, ethoxylated alcohols and thioalcohols, the nonionic detergents known as Pluronics which are polyoxypropylene polymers containing varying amounts of ethylene oxide present as polyoxyethylene chains, etc.
• the detergent compositions can also contain builders, fillers, soil-suspending agents and other conventional detergent ingredients.
• the compositions may also be prepared by conventional methods, such as by blending the ingredients in aqueous solution or slurry and then spraydrying the mixture at elevated temperatures.
• the invention is not concerned with the preparation of detergent compositions and that the particular detergent formulations to which the inhibitors of the invention can be added are not critical. Some surfactants may be subject to attack by the halogen-releasing agents when the compositions are stored. However, those skilled in the art can readily ascertain by sirnple trial whether the detergent and the halogenating agent are compatible.
• the sample to be tested was weighed into a marked 250 ml. Pyrex beaker, a platinum strip approximately mm. x 15 mm. x 0.003 inch was suspended therein and about 200 ml. of water containing manganese ion preheated to 145 F. was added.
• the beaker containing the test solution and the platinum strip was then put into a water bath maintained at a temperaure of about 143 F. After vigorous initial stirring to dissolve the sample, the test solution was agitated at frequent intervals.
• Several samples and a control were tested simultaneously and test solutions and platinum strips were observed closely for discoloration and other changes. Fifteen minutes after the addition of the water containing manganese ion, the platinum strips were removed from the solutions and examined.
• the strips were compared and graded against a control and were reintroduced into the solutions for an additional fifteen minute period. After a total exposure period of about thirty minutes, the platinum strips were again removed from the solution and examined, compared and graded. In certain cases, this procedure was varied to extend the total exposure period of the strips to more than thirty minutes.
• Example I The following dishwashing formulation of a conventional type was employed in the test described above:
• Example I Combinations of cerium nitrate and sodium gluconate were considerably more effective as inhibitors than either of these components used alone. Thus, while 0.1% cerium nitrate was ineffective as an inhibitor and 5% sodium gluconate was only moderately effective, a combination of both agents at the stated concentrations pre vented discoloration completely during a l5-minute contact. The behavior of combinations of these ingredients under the test conditions described in Example I is set forth in the following table.
• the combination of gluconate and cerium salt can be employed within the following range based on the results obtained with water containing 5 p.p.m. manganese ion: about 0.3% of cerium nitrate and sodium gluconate based on the total formula weight with the respective ratios varying from about 1:2 to 1:50.
• Example III It has been observed that cerium compounds are ineffective as platinum discoloration inhibitors in the absence of pyrophosphates. The data below shows that such is not the case when a combination of a gluconate and a cerium compound is employed.
• Chloritnating agent 0.001375% potassium dichloroisocyanurate in aqueous so u ion.
• Mn++ concentration 5 p.p.m.
• Example V It was discovered that combinations of dipersulfate salts and gluconates were only effective inhibitors when used with non-alkaline materials such as chlorinating agents alone rather than admixed with dishwasher compositions containing alkaline builders.
• the procedure described above for testing discoloration was varied in the case of dipersulfates by employing a test solution containing only potassium dichloroisocyanurate rather than a conventional detergent formula containing alkaline builders. The results of the tests were:
• Composition D would be effective only in the absence of alkaline materials. As explained above, dispersulfates do not inhibit discoloration when alkaline phosphates, silicates, soda ash, etc. are present. However, Composition D would be efiective in retarding discoloration in situations where non-alkaline chlorinating solution were employed to sterilize clean dishes or other surfaces which are normally subject to discoloration under the conditions discussed above.
• Example VII In another test a dishwasher product consisting of 8 Example VIII A. A sterling silver knife was exposed for 1 hr. in a 0.25% solution of a chlorinated dishwasher detergent of the type described in Example I above. The solution contained 5 p.p.m. Mn++ ion. Within 15 minutes of exposure a yellow coating became noticeable on the knife; after 1 hour of exposure the coating had turned to a deep brownish-orange. An identical knife, exposed for one hour to a corresponding dishwasher solution to which 0.065%
• the calcium hypochlorite was incorporated in the following dishwasher detergent:
• This formula contains 1.75% available chlorine.
• ⁇ No discoloration B Percentage figures shown pertain to percent detergent, inhibitor, etc. in the test solution.
• Example I 98.9% of the detergent composition shown in Example I plus 1.0% sodium gluconate+0.l% Ce(NO -6H O was employed to wash platinum trimmed dinnerware in an automatic dishwasher. After fifteen washes with this formula, the platinum trimmings showed very slight discoloring. Identical dinnerware washed the same number of times with a control containing no inhibitors discolored heavily after six washes. The glassware spotting tendencies and lipstick removal properties of the formula containing the inhibitor were practically identical to those of the control.
• Example II Another product consisting of 99% of the composition shown in Example I plus 1% sodium gluconate was emloyed to wash platinum trimmed dinnerware. After ten washes in the automatic dishwasher no discoloring occurred. Moderate discoloring of the platinum trimmings became noticeable after twenty-one washes. A control caused severe discoloration after only six washes.
• Chlorine gas bub-bled through a solution containing Mn++ (to pH 3.5) also produced severe discoloration of platinum and the presence of 0.05% sodium gluconate vastly reduced the discoloration. Furthermore, the presence of 0.05%0.075% sodium gluconate in a Mn++-containing solution prevented the discoloration of platinum induced by 0.0375% Dichloroamine T (58.5% av. Cl).
• a composition consisting essentially of a halogenating agent which normally discolors hard surfaces in the presence of manganese ions, said halogenating agent being selected from the group consisting of chlorinating agents and elemental bromine, and a discoloration inhibiting amount of a material selected from the group consisting of compounds furnishing gluconate ion in aqueous solution, combinations of compounds furnishing said gluconate ion with compounds furnishing cerium ion in aqueous solution and combinations of compounds furnishing said gluconate ion with a material selected from the group consisting of ammonium dipersulfate and sodium perborate, the composition being free of alkaline materials when ammonium dipersulfate is employed.
• composition defined in claim 1 in combination with a synthetic non-soap detergent.
• composition defined in claim 1 in combination with a condensed inorganic polyphosphate.
• composition defined in claim 1 in combination with a synthetic non-soap detergent and a condensed inorganic .polyphosphate.
• composition according to claim 1 in which the gluconate ion furnishing compound is selected from the group consisting of alkali metal gluconates, ammonium gluconate, gluconic acid, alpha-sodium glucoheptonate dihydrate and glucono delta-lactone.
• cerium compound is selected from the group consisting of cerium nitrate, cerium chloride and cerium sulfate.
• composition according to claim 1 in which the inhibiting material is a combination of a compound furnishing gluconate ions in aqueous solution and a cerium compound.
• halogenating agent is a chlorine-containing agent selected from the grou consisting of potassium dichloroisocyanurate, sodium dichlorocyanurate, dichloroisocyanuric acid, trichloroisocyanuric acid, dichlorodimethylhydantoin, N, N-dichloro p-toluenesulfonamide, sodium chlorite, chlorine, chlorinated trisodium phosphate and carcium and sodium hypochlorites.
• a chlorine-containing agent selected from the grou consisting of potassium dichloroisocyanurate, sodium dichlorocyanurate, dichloroisocyanuric acid, trichloroisocyanuric acid, dichlorodimethylhydantoin, N, N-dichloro p-toluenesulfonamide, sodium chlorite, chlorine, chlorinated trisodium phosphate and carcium and sodium hypochlorites.
• composition according to claim 1 in which the inhibitor is a combination of a compound furnishing gluconate ions in aqueous solution and sodium perborate.
• composition according to claim 1 in which the inhibitor is a combination of a compound furnishing gluconate ions in aqueous solution and ammonium dipersulfate.
• a detergent formulation consisting essentially a condensed inorganic polyphosphate, a synthetic non-soap detergent, an alkaline reacting chlorinating agent which normally discolors hard surfaces in the presence of manganese ions and said polyphosphate, and a discoloration inhibiting amount of a compound selected from a group consisting of compounds furnishing 'gl-uconate ion in aqueous solution, combinations of compounds furnishing said gluconate ion with compounds furnishing cerium ion in aqueuos solution and combinations of compounds furnishing said gluconate ion with sodium .perborate.
• a composition consisting essentially of at least one compound which furnishes gluconate ion in aqueous solution and at least one compound which furnishes cerium ion in aqueous solution, said composition being effective in retarding the discoloring of hard surfaces when added to solutions containing manganese ion and a halogenating agent which normally discolors hard surfaces in the presence of manganese ions, said halogenating agent being selected from the group consisting of chlorinating agents and elemental bromine.
• a composition consisting essentially of a combination of at least one compound which furnishes gluconate ion in aqueous solution and at least one watersoluble salt of a material selected from the group consisting of ammonium dipersulfate and sodium perborate, said combination being effective in retarding the discoloration of hard surfaces when added to solutions containing manganese ion and a halogenating agent which normally discolors hard surfaces in the presence of manganese ions, said halogenating agent being selected from the group consisting of chlorinating agents and elemental bromine, the compositions being free of alkaline materials when ammonium dipersulfate is employed.
• a method of inhibiting the discoloration of hard surfaces resulting from exposure of the surface to a solution containing manganese ions and a halogenating agent which normally discolors hard surfaces in the presence of manganese ions selected from the group consisting of chlorinating agents and elemental bromine which comprises adding to the solution a discoloration inhibiting amount of a material selected from the group consisting of compounds furnishing g-luconate ions in aqueous solutions, combinations of compounds furnishing gluconate ions with com-ponds furnishing cerium ions in aqueous solutions and combinations of compounds furnishing gluconate ions 'with a material selected from the group consisting of ammonium dipersulfate and sodium perborate, said solution being free of alkaline materials when ammonium dipersulfate is employed.
• a method of inhibiting the discoloration of nonmetallic hard surfaces resulting from exposure of the surfaces to a solution containing manganese ions and a halogenating agent which normally discolors hard surfaces in the presence of manganese ions selected from the group consisting of chlorinating agents and elemental bromine which comprises adding to the solution a discoloration inhibiting amount of a material selected from the group consisting of compounds furnishing gluconate ions in aqueous solution, combinations of compounds furnishing cerium ions in aqueous solution, and combinations of compounds furnishing gluconate ions with a material selected from the group consisting of ammonium dipersulfate and sodium perborate, said solution being free of alkaline materials when ammonium dipersulfate is employed.
• a composition effective in retarding the discoloration of hard surfaces exposed to solutions containing manganese ions and halogenating agents selected from the group consisting of chlorinating agents and elemental bromide which normally discolor hard surfaces in the presence of manganese ions said composition consisting essentially of an inert filler and a compound selected from the group consisting of compounds furnishing gluconate ion in aqueous solution, combinations of said gluconate with compounds furnishing cerium ion in aqueous References Cited by the Examiner UNITED STATES PATENTS 2,689,225 9/1954 Anderson et al. 252-135 XR 3,049,495 8/1962 Jenkins et al.

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• Life Sciences & Earth Sciences (AREA)
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• Wood Science & Technology (AREA)
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• Inorganic Chemistry (AREA)
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Cited By (6)

Citations (3)

• 1963
  • 1963-12-12 US US329958A patent/US3303104A/en not_active Expired - Lifetime
• 1964
  • 1964-12-10 ES ES0306970A patent/ES306970A1/es not_active Expired
  • 1964-12-11 NL NL6414413A patent/NL6414413A/xx unknown
  • 1964-12-14 BE BE657110A patent/BE657110A/xx unknown

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