CA1282296C - Mechanical dishwashing rinse composition having a low foaming sulfonic acid rinsing agent and a source of active halogen - Google Patents
Mechanical dishwashing rinse composition having a low foaming sulfonic acid rinsing agent and a source of active halogenInfo
- Publication number
- CA1282296C CA1282296C CA000473577A CA473577A CA1282296C CA 1282296 C CA1282296 C CA 1282296C CA 000473577 A CA000473577 A CA 000473577A CA 473577 A CA473577 A CA 473577A CA 1282296 C CA1282296 C CA 1282296C
- Authority
- CA
- Canada
- Prior art keywords
- rinse
- composition
- agent
- tableware
- rinse composition
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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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
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0026—Low foaming or foam regulating compositions
-
- 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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic 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
- C11D3/3956—Liquid compositions
Abstract
Abstract A low foaming rinse composition that can be used in spray warewashing machines to provide sanitation, bleaching, and rinsing can comprise in an aqueous base a sufficient bleaching-sanitizing amount of an active-halogen composition and a sulfonate rinse agent, optionally in the presence of a threshold agent. The sulfonate rinse agent is a C1-C9 hydrocarbyl diphenyl oxide sulfonic or sulfonate composition having the formula:
Description
1~82296 MECHANICAL DISHWASHING
RINSE COMPOSITION HAVING A LOW FOAMING
S~LFONIC ACID RINSING AGENT
-Field of the Invention The invention relates to aqueous, low foaming, active halogen containing rinse solutions and composi-10 tions, rinse concentrates and methods of their use andpreparation. More particularly the invention relates to stable rinse solutions and compositions having a sul-fonate rinse agent and a source of active halogen or active halogen composition which provides a rinsing 15 action and stain removal or bleaching in the substantial ~ absence of foam.
Background of the Invention In household, commercial, industrial or institu-tional warewashing or dishwashing commonly available 20 dishwashing machines have mechanical spray mechanisms in which ware are sprayed first with a cleaning solution and second with a rinsing solution. This functional design is substantially different than the design of a household laundry machine in which objects to be cleaned 25 are immersed in a cleaning medium. Typically, in spray washers both the cleaning solutions and rinsing solu-tions are held in a machine reservoir, pumped to a spray mechanism where the cleaning or rinsing solution is directed under pressure onto the ware, and after clean-30 ing or rinsing the solution returns to the reservoir.Such spray mechanical washers can operate with a variety of combinations of cleaning, rinsing and other steps.
However most machines operate with one or more steps of the following sequence: scraping, rinsing, washing, 35 rinsing, and sanitizing. Commonly machines are classi-fied by the temperature of their cleaning and rinsing.
High temperature machines use thermal energy to achieve a sanitizing action while low temperature machines use .:
1~8229~
chemical sanitizing agents. In high temperature ma-chines a minimum of two operations are required. The ware is contacted at high temperature (140-180 F.) with an alkaline low foaming cleaner solution and are then rinsed with water at a sanitizing temperature which contains a rinse aid to promote drying with a minimum of spotting or filming. In low temperature machines, the ware are contacted with hot tap water containing an alkaline low foaming cleaner solution, are then rinsed with hot tap water (120-140 F.) which contains a rinse agent, and are contacted with an active halogen compo-sition to achieve acceptable sanitization. The con-centration of active halogen required to achieve effective sanitization typically falls within the range of about 50-100 parts of available halogen or chlorine per million parts of the rinse composition.
Typically, alkaline cleaners used in mechanical spray warewashing machines can be liquid, granular or solid in form. These high performance cleaners commonly contain active cleaning agents such as alkaline ingre-dients, including alkali metal hydroxide, phosphates, silicates, chlorine yielding compounds; defoamers and organic threshold or chelating agents. See, for ex-ample, the disclosures of Mizuno et al, U.S. Pat. No.
3,166,513; Sabatelli et al, U.S. Pat. No. 3,535,285;
Sabatelli et al, U.S. Pat. No. 3,579,455; Mizuno et al, U.S. Pat. No. 3,700,599; and Copeland et al, U.S. Pat.
No. 3,899,436 for a discussion of such high performance cleaners.
The active halogen or halogen oxidant bleach compositions can be present in the alkaline cleaners or can be separately added with the alkaline cleaner to provide a bleaching sanitizing effect during a cleaning cycle. The use of active halogen compositions in high performance cleaners in the cleaning cycle suffers from certain drawbacks. First, the active halogen composi-tions often interact with the components of the highly alkaline cleaners, reducing the effective concentration ~ , ... .
, lX82296 of active halogen and the halogen-reactive cleaner components. Second, the pH of solutions containing the cleaning agents reduces the effectiveness of the active halogen composition. In a chlorine based halogen bleach, the active agent is commonly hypochlorous acid (HOCl). In an aqueous system the dissociation of hypochlorous acid is a function of pH. For example at pH 8, 21% of the hypochlorous acid is undissociated whereas at pH 11 about 0.03% is unassociated. At equal concentration of the source of halogen at pH 8 there is nearly 700 times as much hypochlorous acid available to bleach stains and sanitize surfaces than is available at pH 11. Third, in the cleaning cycle a majority of the halogen is consumed in non-stain removing or non-sani-tizing reactions. A substantial excess of the activehalogen composition is commonly present in the clean-ing composition since the active halogen comes in contact with a large concentration of readily oxidizable organic materials which can rapidly react with halogen and reduce the concentration of active halogen. A large excess of active halogen composition is used to insure that at least some active halogen remains in the cleaner solution to destain and sanitize the tableware after the majority of the active halogen interacts with and is absorbed or reduced by organic soil. The use of substantial quantities of active halogen composition in the cleaner is an uneconomic waste of the chemical.
Clearly, a clear economic and operation benefit can result from the removal of relatively large amounts of active halogen composition from the cleaning composi-tions added to the wash cycle.
In view of the above, combining a rinse agent-with an active halogen composition in a rinse cycle would prevent problems that arise during the use of active halogen compound in the cleaner solutions. One option involves separately metering the rinse agent and active halogen composition into the rinse cycle of the ware-washing machine. ~owever, this would result in an :il , 1~82296 uneconomic duplication of metering systems. Accord-ingly, for economic and practical reasons a substantial need exists for a rinse composition which combines a rinse agent and an active halogen composition.
Rinse agents or sheeting agents are low foaming compounds commonly added to rinse water to produce a rinsing or sheeting action, to insure substantial rinse water removal and to aid in the prevention of spotting.
The precise mechanism through which rinse agents cause the rinse water to form continuous sheets of water which drain cleanly from the surface is unknown. Commonly available commercial rinse agents typically comprise a low foaming surface active agent made from homopolymers or copolymers of an alkylene oxide such as ethylene oxide or propylene oxide or mixtures thereof. Typically the surfactants are formed by reacting an alcohol, a glycol, a carboxylic acid, an amine or a substituted phenol with various proportions and combinations of ethylene oxide and propylene oxide to form both random and block copolymer substituents. Rinse agents con-taining substituents formed from an alkyleneoxide are particularly sensitive to rapid degradation in the presence of active halogen compounds. Accordingly, the combination of active halogen with the majority of presently available commercial rinse compositions in the rinse cycle would result in degradation of both rinse agent and active halogen.
Rinse agents and other components of rinse com-positions desirably have certain characteristics. The rinse agent must be soluble in an aqueous solution of active halogen composition. The rinse agent must not cause the consumption or degradation of more than about 25 wt-% and preferably less than 10 wt-% of the original active halogen composition. The active halogen must not in turn degrade the rinse agent. Further, the rinse agent compositions must produce a substantial and complete sheeting effect in the final rinse. The rinse composition must be substantially resistant to the " ::
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production of large amounts of foam. Foaming is a substantial drawback in machine spray washers using a pump that transfers rinse solution from the reservoir to the spray mechanism. The pumps used in the machines are designed to efficiently move water which is substan-tially noncompressable, but cannot move foam which is substantially highly compressable air. In the presence of foam, the delivery of rinse water can be prevented, and in extreme cases the presence of foam can result in damage to the pump.
Brief Discussion of the Invention We have found a low foaming sanitizing rinse agent for low temperature and high temperature machine warewashing which comprises in an aqueous base, a sufficient bleaching-sanitizing amount of an active halogen composition and an effective low foaming rinse agent comprising an alkyl diphenyl oxide sulfonic acid compound, or sulfonate salt thereof, which provides rinsing with little foam and is both chemically and physically compatible during storage with the active-halogen composition.
Surprisingly, we have found that the alkyl diphenyl oxide sulfonic acid or sulfonate rinse aid provides all required propertles, solubility in the solution of active halogen composition, sheeting, reduced foam production, and chemical compatibility with active halogen compositions for extended periods of time in the absence of substantial degradation of either the sur-factant or the active halogen composition. In the context of this invention "rinse agent" refers to the alkyl diphenyl oxide sulfonic acid composition, ~rinse composition" refers to the concentrate composition of water, the rinse agent the active halogen compound, and ~rinse solution~ refers to the fully dilute aqueous solution sprayed on the ware within the machine spray warewasher.
~82~96 - 5a -The present compositions are intended for use as rinse compositions or solutions, as opposed to "detergent" compositions, which are intended to perform the primary cleaning function. Therefore, the present compositions and solutions are free of significant amounts of the alkaline components or builder salts which are necessary to the effectiveness of "high performance"
liquid or solid detergents. Therefore, the present compositions will contain no more than about 2.5% of such components, and preferably will contain less than about 1% of alkaline components such as alkali metal hydroxides, silicates, phosphates, carbonates, bicarbonates, and the like. Substantial amounts of such compounds are incompatible with the present compositions since they can inhibit sheeting, leave solid deposits on the ware and degrade or inhibit the action of the other ingredients present.
Sulfonic Acid Rinse Agent The alkyl diphenyl oxide sulfonic acid suffactants , , 1~8~96 useful in the rinse agent composition of the invention include compounds and mixtures of compounds of the formulae:
~ R) the alkali and alkaline earth metal salts thereof, wherein each x is 0 to 4, each y is 0 to 4, the sum of both x's iB at least one, the sum of both y's is at least one and the sum of all substituents x and y is less than or equal to 6; R is hydrogen or a Cl-Cg alkyl group with at least one R being alkyl. Preferably, the alkyl group is an alkyl group of about 2 to 8 carbon atoms, x is 1 or 2, and y is 1 or 2, and the sum of x and y is 4 or less. Exa~ples of typical alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, amyl, t-amyl, hexyl, 2-ethyl(hexyl), n-octyl, n-nonyl, n-decyl, n-dodecyl and the like.
Most preferably, R is an alkyl group of about 3 to 8 carbon atoms, and the sum of x and y is about 2 to 4. The alkyl group can be an aliphatic straight chain primary group, a secondary or a tertiary group. Preferred rinse agents are about 10% to 90% dialkylated and about 10%
to 100% disulfonated, most preferably about 70 to 90%
disulfonated.
A series of commercially available mono alkyl or di-alkyl diphenyl oxide mono sulfonic acid or di-sul-.
~82296 fonic acid surfactants having alkyl group with 10 or more carbon atoms are made by Dow Chemical Co. and sold under the DOWFAX R trademark. These surfactants are commonly made by alkylating diphenyl oxide and sulfon-ating the alkylate, forming a complex mixture of mono-and dialkylate and mono- and disulfonate.
Active Halo en Com~osition g ~ _ Organic and inorganic sources of the active halogen composition can be used in the rinse agents of the invention. The sources of active halogen composition or halogen-oxidant bleach must be compatible and stable in aqueous solution or suspension. Further, they must not interact with the sulfonate rinse agent of the invention producing physical separation of the rinse agent compo-nents or chemical degradation. The strength of an - aqueous solution containing the active halogen composi-tion is measured in terms of available halogen calcu-lated as X2 wherein X can be F, Cl, Br, or I, prefer-ably X is Cl or Br. Most preferably X is Cl. Available halogen, commonly means to persons skilled in the art, the ability of the solution to liberate halogen in a solution. Such ability is also called oxidizing power.
Organic sources of the active halogen composition which can be useful at dilute (1-2%) concentration include chloramines, chlorimines, chloramides, chlor-imides, such as potassium dichloroisocyanurate, sodium dichloroisocyanurate, sodium dichloroisocyanurate dihydrate, trichlorocyanuric acid, 1,3-dichloro-5,5-dimethylhydantoin, n-chlorosulfamide, chloramine-T, dichloramine-T, chloramine-B, and dichloramine-B, etc.
and mixtures thereof. Organic agents are commonly non-stable in aqueous solutions above 1-2% by weight since the HOCl generated by the organic source of active halogen can attack functional groups in the organic portion of the source.
Preferred active halogen compositions of this invention include inorganic sources of halogen such as 1~82~96 inorganics that produce halogen as X2, OX~, HOX, etc., wherein X is Br or Cl. Such inorganic bleaching agents include alkali metal hypohalite, monobasic calcium hypohalite; dibasic magnesium hypohalite;
halogenated condensed phosphates, their hydrated species, and mixtures thereof. The most preferred active halogen composition can yield hypochlorite species in aqueous solution at appropriate pH. The hypochlorite ion can be chemically represented as:
OCl-Examples of hypochlorite yielding compounds include alkali metal and alkaline earth metal hypochlorites including lithium hypochlorite, sodium hypochlorite, potassium hypochlorite, monobasic calcium hypochlorite, dibasic magnesium hypochlorite, etc. and mixtures thereof.
Preferably, the active halogen source will be employed in the present rinse compositions in relatively high concentrations, as opposed to the concentrations employed in detergent formulations in which the halogen source functions as an adjunct cleaning agent in combination with alkaline builder salts and conventional surfactants. Therefore, the present rinse compositions will comprise about 2.5-10%, most preferably about 3-7.5%, of the active halogen source, e.g., 4-6% by weight NaOCl. At these concentrations, the present rinse compositions are storage-stable but remain highly effective to sanitize and/or destain ware when diluted to form sprayable rinse solutions as described hereinbelow.
Threshold Agents Threshold agents ti.e. complexing agents, seques-tering agents), that can be used in the invention to prevent the precipitation of hardness components in - 8a -service water can be used in the novel rinse agent compositions of the invention. Commonly service water used in the rinse cycle to dilute the rinse composition to form the rinse solution can have substantial propor-tions of hardness components, commonly calcium andmagnesium ions, which in the presence of certain rinse agents can precipitate and leave unsightly deposits of mixed calcium and magnesium salts, generally in the form of a carbonate. These deposits can often include other hardness components such as ferrous or ferric compounds and other common cations. Threshold agents act to prevent or delay crystal growth of the calcium or magnesium compounds. While the threshold mechanism is unknown, the threshold agents are used at a concentra-tion substantially less than an amount that would be stoichiometric with the hardness components. However, I
~3 1'~82~96 g _ greater than trace amounts o~ threshold agent are known to thermodynamically delay crystal growth.
Such threshold agents can be both organic and inorganic but must be resistant to reaction with the halogen oxidizing compound and must not have an undesirable rinse action inhibiting interaction with the sulfonate rinse agent. The most common or widely used threshold agents are those that coordinate metal ions through oxygen or nitrogen donor atoms or groups con-taining oxygen or nitrogen atoms. Typical organiccomplexing agents include, for example, N-hydroxy-ethylaminodiacetic acid, nitrilotriacetic acid, ethylene diamine tetraacetic acid, and its mono, di, tri and tetrasodium salts, maleic anhydride, polyacrylic acid or polymethacrylic acid, homo or interpolymers, and mixtures thereof. Examples of inorganic threshold agents include condensed phosphates hav~ng the following general formula:
~ ll 1~
HO _ P ~ - P _OH
OH n OH
wherein n in greater than or equal to 1, preferably n = 1 to 4, and the alkali metal or alkaline earth metal salts thereof.
The preferred threshold agents for use in the rinse agent of the invention comprises polyacrylic homopoly-mers and interpolymers having pendent carboxyl groups 30 and a molecular weight of about 500 to about 5,000.
These threshold agents have been found to be effective in complexing hardness components of service water and have been found to be stable in the presence of strong chlorine bleaches and soluble in the presence of sub-stantial quantities of sulfonate surfactant.
In addition to the above-described active-halogen composition, sulfonate rinse agent and threshold agent, the novel rinse agent compositions of the inven-' -.' - . -: ~ . .
~8Z~96 tion can contain optional components that can enhance performance, stability, aesthetic appeal, processing, packaging, or consumer acceptance. Such materials include optional coloring agents and perfumes. These materials should be selected from dyes and perfume varieties which are stable against degradation in the presence of strong active halogen agents.
Small amounts of alkali metal hydroxides, e.g., less than about 1%, can also be used to adjust the pH of the rinse compositions. For example, about 0.1-0.5% sodium hydroxide can be used to adjust the final pH of the composition to about 11.5.
The rinse compositions of the invention can be prepared by admixing each of the above-described components in an appropriate concentration in essentially any order to form a concentrate which can be metered into the reservoir forming a rinse solution in the machine dishwasher in order to provide an effective concentration of the components to clean, sanitize, and cause sheeting action in the rinse cycle. Commonly the concentration of the active halogen composition present in the final rinse solution should range from about 1 to 200 parts of active halogen composition per million parts of rinse water for an effective sanitizing-bleaching or stain removing action. Preferably the concentration of active halogen composition ranges from about 2 to lOo parts of active halogen, and most preferably, for reasons of economy and effectiveness, a concentration of active halogen ranges from about 10 to 50 parts of active halogen in the form of hypochlorite, per million parts of rinse water.
Similarly, the concentration of sulfonate rinse agent in the final rinse water should range from about 1 to 200 parts of sulfonate rinse agent per ~illion parts of rinse water to obtain sufficient sheeting 1~8~ 29~;
- lOa -action to result in substantially complete rinsing of the tableware. Preferably, the concentration of the sulfonate rinse agent ranges from about 2 to lO0 parts of sulfonate rinse agent, and most preferably, for 5 reasons of economy and effective rinsing, the concen-tration of the sulfonate rinse agent ranges from about lO to 80 parts of the sulfonate rinse agent per million parts of the final rinse ~ater.
1~8Z296 The concentration of the threshold agent commonly depends on the concentration of hardness components (commonly less than 200 ppm) in service water provided by local water utilities. The concentration of the threshold agent should be maintained in an amount of agent to inhibit or reduce the rate of the precipitation of hardness components in the rinse solution. Commonly service water in most locales can be successfully treated if the concentration of the threshold agent is maintained at less than 150 parts of threshold agent per million parts of total final rinse water. However, should deposits of calcium and magnesium carbonate appear on tableware, the concentration of the threshold agent can be augmented. Preferably the concentration of the threshold agent in the final rinse solution for use in most available service water (hardness of 150 ppm or less) ranges from about 0.2 to 25 parts of the threshold agent, and most preferably, for reasons of high performance and economy, the concentration of the threshold agent ranges from about 0.5 to 10 parts of the threshold agent per million parts of the final rinse water.
Commonly concentrates of the components can be prepared which can be diluted at a ratio to provide a final rinse water having active components within the above concentrations by forming in an aqueous base a rinse agent concentrate containing from about 0.1 to 15 wt-% of a source of the active halogen (halogen-oxidizing bleach) composition capable of releasing active halogen into the aqueous solution, about 0.1 to 15 wt-~ of the sulfonate surfactant, and optionally about 0.1 to 20 wt-~ of the threshold agent.
Preferably, the rinse agent concentrates of the invention contain a major portion of an aqueous medium, e.g., water. Preferably, the rinse agent concentrates of the invention contain sufficient active halogen ~3 ~82'~96 - lla -compounds to provide about 0.5 to 10 wt-% of active halogen composition, in combination with about 0.5 to 12 wt % of the sulfonate surfactant and optionally about 0.5 to 15 wt-~ of the threshold agent. Most preferably, the rinse agent of 1~8Z;~96 the invention contains about 1 to 7.5 wt-~ of sodium hypochlorite, about 1 to 10 wt-% of the sulfonate surfactant, and about 1 to 10 wt-~ of a polyacrylic acid threshold ayent having a molecular weight of about 300 to 5,000.
The above-described rinse agents can be used in institutional, industrial and household dishwashing machines that have the capability of injecting con-trolled amounts of the rinse agent into a final rinse water. The rinse composition of the invention can be metered into a machine dishwasher at a ratio of one part of the rinse composition per each 4,000 or more total parts of rinse solution. Preferably the ratio is one part of rinse composition per each 5,000 to 100,000 parts of the final rinse solution, depending on the concentration of the components in the rinse composition concentrate.
In household and commercial operations, washing of dishware comprises at a minimum two stages, a washing cycle and a rinsing cycle. An optional first stage in which larger agglomerates of foods can be removed from the dishes which is commonly called a scraping or first stage cycle, water is maintained at a temperature of from about 100 to 120 F. in order to effectively remove large food agglomerates.
A washing cycle is usually performed using aqueous solutions or suspensions of highly alkaline cleaners with water at an elevated temperature. l'he washing cycle can commonly be performed at relatively low 30 temperature, i.e. 120-160 F. or at relatively high temperature, commonly 160-200 F. The rinse cycle or last stage of the dishwasher operation is usually maintained at a temperature that ranges from 120-200 F.
depending on the need to use high temperature sanitiz-ing. Typically food soil load is highest in the optional scraping or preparatory cycle, lower in the wash cycle and is negligible in the rinse cycle except for staining that is generally physically associated or chemically lX~ 96 bonded into the surface of the ware.
In order to conserve heat and water it is customary to feed back used rinse water into the wash or scraping stage. Generally, the wash or rinse water commonly contains low concentrations of rinse additive due to dilution by water.
The following Examples further provide a basis for understanding the invention and include a best mode.
Example I
Into a 2,000 ml glass beaker equipped with magnetic stirrer was placed 235.8 grams of soft water. Into the water under stirring was added 625.0 grams of an 8.0 wt-% aqueous solution of sodium hypochlorite (5.1% NaOCl) and the mixture was stirred until uniform. Into the ~5 uniform solution was added 111.2 grams of a 45 wt-% aqueous solution of a sodium dihexyl diphenyl oxide sulfonate (90% dialkylate and about 98% disulfonate). Also added was 10.0 grams of a 50 wt-% aqueous solution of sodium polyacrylate (an average polymer molecular weight of 20 2,000-5,000). After the addition was complete and the mixture was uniform, the pH was adjusted to 11.5 with 0.22 g. of 50 wt-% aqueous sodium hydroxide. During addition of the components, the temperature was maintained between 60-80 F.
ExamPle II
Into a 2,000 ml glass beaker equipped with a magnetic stirrer was placed 280 grams of soft water. Into the water under stirring was added 600 grams of an 8 wt-%
aqueous solution of sodium hypochlorite (4.8% NaOCl) and the mixture was stirred until uniform. Into the uniform ~olution was added 120 grams of DOWFAX ~ 2Al a 45 wt-%
solution of a sodium alkyl diphenyl oxide sufonate (90%
monoalkylate and greater than 90% disulfonate wherein the alkyl groups are C10 linear groups, made from an alpha olefin). After the mixture was uniform, the pH was 8x~96 - 13a -adjusted to 11.5 with 0.27g of 50 wt-% aqueous sodium hydroxide. During blending the temperature was maintained between 60 and 80 F.
D
- , : .
.
1~82~96 Exam~le III
Example II was repeated with DOWFAX ~ 3B2 a sodium alkyl diphenyl oxide sulfonate (90% monoalkylate and greater than 90~ disulfonate having C12 branched alkyl groups made from a tetrapropylene oligomer). The pH was adjusted to 11.5 with 0.34g of 50% aqueous sodium hydroxide.
Exam~le IV
Into a 2,000 milliliter glass beaker equipped with a magnetic stirrer was placed 283.3 grams of soft water.
Into the water under stirring was added 600 grams of an 8%
aqueous sodium hypochlorite ~4.8% NaOCl) solution. After the solution became uniform, 40 grams of DOWFAX ~ 2A1 was added (an alkylated diphenyl oxide sulfonate which is 90% monoalkylate and greater than 90% disulfonate having C10 linear alkyl groups formed from an alpha olefin).
After the mixture became uniform, 66.7 grams of a 45 wt-%
aqueous solution of an alkyl diphenyl oxide sulfonate 190% monoalkyl and about 98.3% disulfonate) having C6 linear alkyl groups was added. Along with the diphenyl oxide sulfonate wa~ added 10 grams of a 50 wt-% aqueous 801ution of a sodium polyacrylate having a polymer molecular weight between 2,000 and 5,000. After the ~olution was uniform the pH was adjusted to ll.S with 0.20g of 50~ aqueous sodium hydroxide. The temperature of the mixture during preparation was maintained between 60 and 80 F.
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~'~82~9~;
Sheeting Evaluation Concentration for Continuous Water Sheeting*
Product ~316 of Tempera- Stainless Example ture Glass Steel 10 I 160 F. 600 ppm (30 ppm)** 1400 ppm (70 ppm) II 160 F. 450 ppm (22.5 ppm) 1300 ppm (65 ppm) III 160 F. 550 ppm (27.5 ppm) 1400 ppm (70 ppm) IV 160 F. 500 ppm (25 ppm) 1400 ppm (70 ppm) "Pluronic"*
25R2 160 F. (90 ppm) (100 ppm) , .
* Concentration of rinse composition for continuous films of water to be formed over surface under evaluation.
** Concentration in (.) is active surfactant concentra-tion.
Foaming Evaluation (Dynamic Foam) Product of Example Concentration Foam Hei~ht Temperature I 500 ppm 0.50 inches 120 F.
I 500 ppm 0.50 inches 160 F.
30 II 500 ppm 6 inches 120 F.
II 500 ppm 6 inches 160 F.
III 500 ppm 8 inches 120 F.
III 500 ppm 8 inches 160 F.
IV 500 ppm 3 inches 120 F.
IV 500 ppm 3 inches 160 F.
* Trademark ~' 1~82'~9 TAfiLE 3 Chlorine Stability 240 Ho~rs at 100 F.
Product of Initial Final Percent 5 Example Chlorine Chlorine Remaininq I 5.0 4.65 93.0 II 4.78 4.60 96.2 III 4.85 4.67 96.3 IV 4.75 4.54 95.6 10 Co~trol* 5.0 4.75 95.0 * 5.0% NaOCl solution with pH adjusted to 11.50.
The data presented in Table 1 entitled "Sheeting Evaluation" was obtained using a Champion 1-KAB machine dishwasher having wash and rinse temperatures of about 160 F. Test pieces were placed in the machine having a glass door to permit visual observation of the test pieces. For the evaluation the test pieces were washed in soft water three times on automatic cycle using 200 grams of an alkaline detergent prepared by blending 30 wt-~ sodium metasilicate, 35% sodium tripolyphospate, 20 3 wt-% PLURAFACl surfactant No. RA-43, and 32~ sodium carbonate. During the three wash cycles no rinse additive was used. To determine the sheeting effect the machine was filled with water and set on manual. Into the water was added 500 parts of "Mazola"** corn oil per million parts of rinse water, and a minimum measured amount of rinse composition of the Examples. The mixture was circulated for 3 minutes and the concentration of rinse additive was progressively increased by injecting increasing amounts of rinse composition until a substantially continuous sheeting effect of the rinse water was noted over substantially all the test pieces.
The minimum concentration for continuous sheeting was noted and recorded in Table 1.
The data recorded in Table 2 entitled "Foaming 1 Trademark * Trademark lZ82296 Evaluation (Dynamic Foam)" was generated in a foam test device which is a cylindrical container 8 liters in volume, 15 centimeters in diameter and 50 centimeters in height equipped with an electric hot plate for tempera-ture control, and a pump to recirculate the test solu-tion at 6 psi through a means to direct a spray of the test solution onto the surface of the contents of the solution to generate foam.
Three liters of a test solution prepared in soft water which contained 6.0 grams of a dry blend of 30 wt-%
sodium metasilicate, 35 wt-% sodium tripolyphosphate, 3% PLURAFAC ~ RA-43 and 32 wt-% sodium carbonate was used (200 ppm in the aqueous detergent). The rinse compositions were evaluated at 500 parts per million by adding 1.5 grams of the rinse composition of each example to 3 liters of the test detergent. The tests were performed by recirculating the detergent solution through the spray means in the dynamic foam tester for 5 minutes to verify that the initial equilibrated foam was no more than lt2 inch above the surface of the test solution. After the equilibrated foam level was established the rinse composition was added to the test solution and after 5 minutes, the foam height was measured.
The chlorine stability test was performed by placing about 400 grams of the fully compounded rinse additive composition in capped translucent polyethylene bottles which were stored for 240 hours at 100F. The chlorine concentrations were measured by a standard iodometric titration with thiosulfate.
An examination of the Tables shows that the rinse additive composition of the Examples had acceptable sheeting properties, generated 0.5-8.0 inches of foam at 120 and 160F., and contained stable chlorine.
The compositions of Examples II and III, wherein the rinse additives were C10- and C12-alkylated, respectively, generated substantially more foam than the P~
.
1'~8Z'~9G
- 17a -compositions of the other Examples. The C6-alkylated additive generated substantially less foam than the other additives, and reduced the foam generated by the C12-alkylated additive.
The above Examples, data, and specification provide a basis for understanding the invention. However, since many embodiments of the invention can be made without departing from the spirit and scope of the invention, -~282296 the invention resides wholly in the claims herelnafter appended.
;
:
RINSE COMPOSITION HAVING A LOW FOAMING
S~LFONIC ACID RINSING AGENT
-Field of the Invention The invention relates to aqueous, low foaming, active halogen containing rinse solutions and composi-10 tions, rinse concentrates and methods of their use andpreparation. More particularly the invention relates to stable rinse solutions and compositions having a sul-fonate rinse agent and a source of active halogen or active halogen composition which provides a rinsing 15 action and stain removal or bleaching in the substantial ~ absence of foam.
Background of the Invention In household, commercial, industrial or institu-tional warewashing or dishwashing commonly available 20 dishwashing machines have mechanical spray mechanisms in which ware are sprayed first with a cleaning solution and second with a rinsing solution. This functional design is substantially different than the design of a household laundry machine in which objects to be cleaned 25 are immersed in a cleaning medium. Typically, in spray washers both the cleaning solutions and rinsing solu-tions are held in a machine reservoir, pumped to a spray mechanism where the cleaning or rinsing solution is directed under pressure onto the ware, and after clean-30 ing or rinsing the solution returns to the reservoir.Such spray mechanical washers can operate with a variety of combinations of cleaning, rinsing and other steps.
However most machines operate with one or more steps of the following sequence: scraping, rinsing, washing, 35 rinsing, and sanitizing. Commonly machines are classi-fied by the temperature of their cleaning and rinsing.
High temperature machines use thermal energy to achieve a sanitizing action while low temperature machines use .:
1~8229~
chemical sanitizing agents. In high temperature ma-chines a minimum of two operations are required. The ware is contacted at high temperature (140-180 F.) with an alkaline low foaming cleaner solution and are then rinsed with water at a sanitizing temperature which contains a rinse aid to promote drying with a minimum of spotting or filming. In low temperature machines, the ware are contacted with hot tap water containing an alkaline low foaming cleaner solution, are then rinsed with hot tap water (120-140 F.) which contains a rinse agent, and are contacted with an active halogen compo-sition to achieve acceptable sanitization. The con-centration of active halogen required to achieve effective sanitization typically falls within the range of about 50-100 parts of available halogen or chlorine per million parts of the rinse composition.
Typically, alkaline cleaners used in mechanical spray warewashing machines can be liquid, granular or solid in form. These high performance cleaners commonly contain active cleaning agents such as alkaline ingre-dients, including alkali metal hydroxide, phosphates, silicates, chlorine yielding compounds; defoamers and organic threshold or chelating agents. See, for ex-ample, the disclosures of Mizuno et al, U.S. Pat. No.
3,166,513; Sabatelli et al, U.S. Pat. No. 3,535,285;
Sabatelli et al, U.S. Pat. No. 3,579,455; Mizuno et al, U.S. Pat. No. 3,700,599; and Copeland et al, U.S. Pat.
No. 3,899,436 for a discussion of such high performance cleaners.
The active halogen or halogen oxidant bleach compositions can be present in the alkaline cleaners or can be separately added with the alkaline cleaner to provide a bleaching sanitizing effect during a cleaning cycle. The use of active halogen compositions in high performance cleaners in the cleaning cycle suffers from certain drawbacks. First, the active halogen composi-tions often interact with the components of the highly alkaline cleaners, reducing the effective concentration ~ , ... .
, lX82296 of active halogen and the halogen-reactive cleaner components. Second, the pH of solutions containing the cleaning agents reduces the effectiveness of the active halogen composition. In a chlorine based halogen bleach, the active agent is commonly hypochlorous acid (HOCl). In an aqueous system the dissociation of hypochlorous acid is a function of pH. For example at pH 8, 21% of the hypochlorous acid is undissociated whereas at pH 11 about 0.03% is unassociated. At equal concentration of the source of halogen at pH 8 there is nearly 700 times as much hypochlorous acid available to bleach stains and sanitize surfaces than is available at pH 11. Third, in the cleaning cycle a majority of the halogen is consumed in non-stain removing or non-sani-tizing reactions. A substantial excess of the activehalogen composition is commonly present in the clean-ing composition since the active halogen comes in contact with a large concentration of readily oxidizable organic materials which can rapidly react with halogen and reduce the concentration of active halogen. A large excess of active halogen composition is used to insure that at least some active halogen remains in the cleaner solution to destain and sanitize the tableware after the majority of the active halogen interacts with and is absorbed or reduced by organic soil. The use of substantial quantities of active halogen composition in the cleaner is an uneconomic waste of the chemical.
Clearly, a clear economic and operation benefit can result from the removal of relatively large amounts of active halogen composition from the cleaning composi-tions added to the wash cycle.
In view of the above, combining a rinse agent-with an active halogen composition in a rinse cycle would prevent problems that arise during the use of active halogen compound in the cleaner solutions. One option involves separately metering the rinse agent and active halogen composition into the rinse cycle of the ware-washing machine. ~owever, this would result in an :il , 1~82296 uneconomic duplication of metering systems. Accord-ingly, for economic and practical reasons a substantial need exists for a rinse composition which combines a rinse agent and an active halogen composition.
Rinse agents or sheeting agents are low foaming compounds commonly added to rinse water to produce a rinsing or sheeting action, to insure substantial rinse water removal and to aid in the prevention of spotting.
The precise mechanism through which rinse agents cause the rinse water to form continuous sheets of water which drain cleanly from the surface is unknown. Commonly available commercial rinse agents typically comprise a low foaming surface active agent made from homopolymers or copolymers of an alkylene oxide such as ethylene oxide or propylene oxide or mixtures thereof. Typically the surfactants are formed by reacting an alcohol, a glycol, a carboxylic acid, an amine or a substituted phenol with various proportions and combinations of ethylene oxide and propylene oxide to form both random and block copolymer substituents. Rinse agents con-taining substituents formed from an alkyleneoxide are particularly sensitive to rapid degradation in the presence of active halogen compounds. Accordingly, the combination of active halogen with the majority of presently available commercial rinse compositions in the rinse cycle would result in degradation of both rinse agent and active halogen.
Rinse agents and other components of rinse com-positions desirably have certain characteristics. The rinse agent must be soluble in an aqueous solution of active halogen composition. The rinse agent must not cause the consumption or degradation of more than about 25 wt-% and preferably less than 10 wt-% of the original active halogen composition. The active halogen must not in turn degrade the rinse agent. Further, the rinse agent compositions must produce a substantial and complete sheeting effect in the final rinse. The rinse composition must be substantially resistant to the " ::
,,,.,, ,~, ~, ~
,~, -' -:
~L'~ ~ ~ Z 9 ~
production of large amounts of foam. Foaming is a substantial drawback in machine spray washers using a pump that transfers rinse solution from the reservoir to the spray mechanism. The pumps used in the machines are designed to efficiently move water which is substan-tially noncompressable, but cannot move foam which is substantially highly compressable air. In the presence of foam, the delivery of rinse water can be prevented, and in extreme cases the presence of foam can result in damage to the pump.
Brief Discussion of the Invention We have found a low foaming sanitizing rinse agent for low temperature and high temperature machine warewashing which comprises in an aqueous base, a sufficient bleaching-sanitizing amount of an active halogen composition and an effective low foaming rinse agent comprising an alkyl diphenyl oxide sulfonic acid compound, or sulfonate salt thereof, which provides rinsing with little foam and is both chemically and physically compatible during storage with the active-halogen composition.
Surprisingly, we have found that the alkyl diphenyl oxide sulfonic acid or sulfonate rinse aid provides all required propertles, solubility in the solution of active halogen composition, sheeting, reduced foam production, and chemical compatibility with active halogen compositions for extended periods of time in the absence of substantial degradation of either the sur-factant or the active halogen composition. In the context of this invention "rinse agent" refers to the alkyl diphenyl oxide sulfonic acid composition, ~rinse composition" refers to the concentrate composition of water, the rinse agent the active halogen compound, and ~rinse solution~ refers to the fully dilute aqueous solution sprayed on the ware within the machine spray warewasher.
~82~96 - 5a -The present compositions are intended for use as rinse compositions or solutions, as opposed to "detergent" compositions, which are intended to perform the primary cleaning function. Therefore, the present compositions and solutions are free of significant amounts of the alkaline components or builder salts which are necessary to the effectiveness of "high performance"
liquid or solid detergents. Therefore, the present compositions will contain no more than about 2.5% of such components, and preferably will contain less than about 1% of alkaline components such as alkali metal hydroxides, silicates, phosphates, carbonates, bicarbonates, and the like. Substantial amounts of such compounds are incompatible with the present compositions since they can inhibit sheeting, leave solid deposits on the ware and degrade or inhibit the action of the other ingredients present.
Sulfonic Acid Rinse Agent The alkyl diphenyl oxide sulfonic acid suffactants , , 1~8~96 useful in the rinse agent composition of the invention include compounds and mixtures of compounds of the formulae:
~ R) the alkali and alkaline earth metal salts thereof, wherein each x is 0 to 4, each y is 0 to 4, the sum of both x's iB at least one, the sum of both y's is at least one and the sum of all substituents x and y is less than or equal to 6; R is hydrogen or a Cl-Cg alkyl group with at least one R being alkyl. Preferably, the alkyl group is an alkyl group of about 2 to 8 carbon atoms, x is 1 or 2, and y is 1 or 2, and the sum of x and y is 4 or less. Exa~ples of typical alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, amyl, t-amyl, hexyl, 2-ethyl(hexyl), n-octyl, n-nonyl, n-decyl, n-dodecyl and the like.
Most preferably, R is an alkyl group of about 3 to 8 carbon atoms, and the sum of x and y is about 2 to 4. The alkyl group can be an aliphatic straight chain primary group, a secondary or a tertiary group. Preferred rinse agents are about 10% to 90% dialkylated and about 10%
to 100% disulfonated, most preferably about 70 to 90%
disulfonated.
A series of commercially available mono alkyl or di-alkyl diphenyl oxide mono sulfonic acid or di-sul-.
~82296 fonic acid surfactants having alkyl group with 10 or more carbon atoms are made by Dow Chemical Co. and sold under the DOWFAX R trademark. These surfactants are commonly made by alkylating diphenyl oxide and sulfon-ating the alkylate, forming a complex mixture of mono-and dialkylate and mono- and disulfonate.
Active Halo en Com~osition g ~ _ Organic and inorganic sources of the active halogen composition can be used in the rinse agents of the invention. The sources of active halogen composition or halogen-oxidant bleach must be compatible and stable in aqueous solution or suspension. Further, they must not interact with the sulfonate rinse agent of the invention producing physical separation of the rinse agent compo-nents or chemical degradation. The strength of an - aqueous solution containing the active halogen composi-tion is measured in terms of available halogen calcu-lated as X2 wherein X can be F, Cl, Br, or I, prefer-ably X is Cl or Br. Most preferably X is Cl. Available halogen, commonly means to persons skilled in the art, the ability of the solution to liberate halogen in a solution. Such ability is also called oxidizing power.
Organic sources of the active halogen composition which can be useful at dilute (1-2%) concentration include chloramines, chlorimines, chloramides, chlor-imides, such as potassium dichloroisocyanurate, sodium dichloroisocyanurate, sodium dichloroisocyanurate dihydrate, trichlorocyanuric acid, 1,3-dichloro-5,5-dimethylhydantoin, n-chlorosulfamide, chloramine-T, dichloramine-T, chloramine-B, and dichloramine-B, etc.
and mixtures thereof. Organic agents are commonly non-stable in aqueous solutions above 1-2% by weight since the HOCl generated by the organic source of active halogen can attack functional groups in the organic portion of the source.
Preferred active halogen compositions of this invention include inorganic sources of halogen such as 1~82~96 inorganics that produce halogen as X2, OX~, HOX, etc., wherein X is Br or Cl. Such inorganic bleaching agents include alkali metal hypohalite, monobasic calcium hypohalite; dibasic magnesium hypohalite;
halogenated condensed phosphates, their hydrated species, and mixtures thereof. The most preferred active halogen composition can yield hypochlorite species in aqueous solution at appropriate pH. The hypochlorite ion can be chemically represented as:
OCl-Examples of hypochlorite yielding compounds include alkali metal and alkaline earth metal hypochlorites including lithium hypochlorite, sodium hypochlorite, potassium hypochlorite, monobasic calcium hypochlorite, dibasic magnesium hypochlorite, etc. and mixtures thereof.
Preferably, the active halogen source will be employed in the present rinse compositions in relatively high concentrations, as opposed to the concentrations employed in detergent formulations in which the halogen source functions as an adjunct cleaning agent in combination with alkaline builder salts and conventional surfactants. Therefore, the present rinse compositions will comprise about 2.5-10%, most preferably about 3-7.5%, of the active halogen source, e.g., 4-6% by weight NaOCl. At these concentrations, the present rinse compositions are storage-stable but remain highly effective to sanitize and/or destain ware when diluted to form sprayable rinse solutions as described hereinbelow.
Threshold Agents Threshold agents ti.e. complexing agents, seques-tering agents), that can be used in the invention to prevent the precipitation of hardness components in - 8a -service water can be used in the novel rinse agent compositions of the invention. Commonly service water used in the rinse cycle to dilute the rinse composition to form the rinse solution can have substantial propor-tions of hardness components, commonly calcium andmagnesium ions, which in the presence of certain rinse agents can precipitate and leave unsightly deposits of mixed calcium and magnesium salts, generally in the form of a carbonate. These deposits can often include other hardness components such as ferrous or ferric compounds and other common cations. Threshold agents act to prevent or delay crystal growth of the calcium or magnesium compounds. While the threshold mechanism is unknown, the threshold agents are used at a concentra-tion substantially less than an amount that would be stoichiometric with the hardness components. However, I
~3 1'~82~96 g _ greater than trace amounts o~ threshold agent are known to thermodynamically delay crystal growth.
Such threshold agents can be both organic and inorganic but must be resistant to reaction with the halogen oxidizing compound and must not have an undesirable rinse action inhibiting interaction with the sulfonate rinse agent. The most common or widely used threshold agents are those that coordinate metal ions through oxygen or nitrogen donor atoms or groups con-taining oxygen or nitrogen atoms. Typical organiccomplexing agents include, for example, N-hydroxy-ethylaminodiacetic acid, nitrilotriacetic acid, ethylene diamine tetraacetic acid, and its mono, di, tri and tetrasodium salts, maleic anhydride, polyacrylic acid or polymethacrylic acid, homo or interpolymers, and mixtures thereof. Examples of inorganic threshold agents include condensed phosphates hav~ng the following general formula:
~ ll 1~
HO _ P ~ - P _OH
OH n OH
wherein n in greater than or equal to 1, preferably n = 1 to 4, and the alkali metal or alkaline earth metal salts thereof.
The preferred threshold agents for use in the rinse agent of the invention comprises polyacrylic homopoly-mers and interpolymers having pendent carboxyl groups 30 and a molecular weight of about 500 to about 5,000.
These threshold agents have been found to be effective in complexing hardness components of service water and have been found to be stable in the presence of strong chlorine bleaches and soluble in the presence of sub-stantial quantities of sulfonate surfactant.
In addition to the above-described active-halogen composition, sulfonate rinse agent and threshold agent, the novel rinse agent compositions of the inven-' -.' - . -: ~ . .
~8Z~96 tion can contain optional components that can enhance performance, stability, aesthetic appeal, processing, packaging, or consumer acceptance. Such materials include optional coloring agents and perfumes. These materials should be selected from dyes and perfume varieties which are stable against degradation in the presence of strong active halogen agents.
Small amounts of alkali metal hydroxides, e.g., less than about 1%, can also be used to adjust the pH of the rinse compositions. For example, about 0.1-0.5% sodium hydroxide can be used to adjust the final pH of the composition to about 11.5.
The rinse compositions of the invention can be prepared by admixing each of the above-described components in an appropriate concentration in essentially any order to form a concentrate which can be metered into the reservoir forming a rinse solution in the machine dishwasher in order to provide an effective concentration of the components to clean, sanitize, and cause sheeting action in the rinse cycle. Commonly the concentration of the active halogen composition present in the final rinse solution should range from about 1 to 200 parts of active halogen composition per million parts of rinse water for an effective sanitizing-bleaching or stain removing action. Preferably the concentration of active halogen composition ranges from about 2 to lOo parts of active halogen, and most preferably, for reasons of economy and effectiveness, a concentration of active halogen ranges from about 10 to 50 parts of active halogen in the form of hypochlorite, per million parts of rinse water.
Similarly, the concentration of sulfonate rinse agent in the final rinse water should range from about 1 to 200 parts of sulfonate rinse agent per ~illion parts of rinse water to obtain sufficient sheeting 1~8~ 29~;
- lOa -action to result in substantially complete rinsing of the tableware. Preferably, the concentration of the sulfonate rinse agent ranges from about 2 to lO0 parts of sulfonate rinse agent, and most preferably, for 5 reasons of economy and effective rinsing, the concen-tration of the sulfonate rinse agent ranges from about lO to 80 parts of the sulfonate rinse agent per million parts of the final rinse ~ater.
1~8Z296 The concentration of the threshold agent commonly depends on the concentration of hardness components (commonly less than 200 ppm) in service water provided by local water utilities. The concentration of the threshold agent should be maintained in an amount of agent to inhibit or reduce the rate of the precipitation of hardness components in the rinse solution. Commonly service water in most locales can be successfully treated if the concentration of the threshold agent is maintained at less than 150 parts of threshold agent per million parts of total final rinse water. However, should deposits of calcium and magnesium carbonate appear on tableware, the concentration of the threshold agent can be augmented. Preferably the concentration of the threshold agent in the final rinse solution for use in most available service water (hardness of 150 ppm or less) ranges from about 0.2 to 25 parts of the threshold agent, and most preferably, for reasons of high performance and economy, the concentration of the threshold agent ranges from about 0.5 to 10 parts of the threshold agent per million parts of the final rinse water.
Commonly concentrates of the components can be prepared which can be diluted at a ratio to provide a final rinse water having active components within the above concentrations by forming in an aqueous base a rinse agent concentrate containing from about 0.1 to 15 wt-% of a source of the active halogen (halogen-oxidizing bleach) composition capable of releasing active halogen into the aqueous solution, about 0.1 to 15 wt-~ of the sulfonate surfactant, and optionally about 0.1 to 20 wt-~ of the threshold agent.
Preferably, the rinse agent concentrates of the invention contain a major portion of an aqueous medium, e.g., water. Preferably, the rinse agent concentrates of the invention contain sufficient active halogen ~3 ~82'~96 - lla -compounds to provide about 0.5 to 10 wt-% of active halogen composition, in combination with about 0.5 to 12 wt % of the sulfonate surfactant and optionally about 0.5 to 15 wt-~ of the threshold agent. Most preferably, the rinse agent of 1~8Z;~96 the invention contains about 1 to 7.5 wt-~ of sodium hypochlorite, about 1 to 10 wt-% of the sulfonate surfactant, and about 1 to 10 wt-~ of a polyacrylic acid threshold ayent having a molecular weight of about 300 to 5,000.
The above-described rinse agents can be used in institutional, industrial and household dishwashing machines that have the capability of injecting con-trolled amounts of the rinse agent into a final rinse water. The rinse composition of the invention can be metered into a machine dishwasher at a ratio of one part of the rinse composition per each 4,000 or more total parts of rinse solution. Preferably the ratio is one part of rinse composition per each 5,000 to 100,000 parts of the final rinse solution, depending on the concentration of the components in the rinse composition concentrate.
In household and commercial operations, washing of dishware comprises at a minimum two stages, a washing cycle and a rinsing cycle. An optional first stage in which larger agglomerates of foods can be removed from the dishes which is commonly called a scraping or first stage cycle, water is maintained at a temperature of from about 100 to 120 F. in order to effectively remove large food agglomerates.
A washing cycle is usually performed using aqueous solutions or suspensions of highly alkaline cleaners with water at an elevated temperature. l'he washing cycle can commonly be performed at relatively low 30 temperature, i.e. 120-160 F. or at relatively high temperature, commonly 160-200 F. The rinse cycle or last stage of the dishwasher operation is usually maintained at a temperature that ranges from 120-200 F.
depending on the need to use high temperature sanitiz-ing. Typically food soil load is highest in the optional scraping or preparatory cycle, lower in the wash cycle and is negligible in the rinse cycle except for staining that is generally physically associated or chemically lX~ 96 bonded into the surface of the ware.
In order to conserve heat and water it is customary to feed back used rinse water into the wash or scraping stage. Generally, the wash or rinse water commonly contains low concentrations of rinse additive due to dilution by water.
The following Examples further provide a basis for understanding the invention and include a best mode.
Example I
Into a 2,000 ml glass beaker equipped with magnetic stirrer was placed 235.8 grams of soft water. Into the water under stirring was added 625.0 grams of an 8.0 wt-% aqueous solution of sodium hypochlorite (5.1% NaOCl) and the mixture was stirred until uniform. Into the ~5 uniform solution was added 111.2 grams of a 45 wt-% aqueous solution of a sodium dihexyl diphenyl oxide sulfonate (90% dialkylate and about 98% disulfonate). Also added was 10.0 grams of a 50 wt-% aqueous solution of sodium polyacrylate (an average polymer molecular weight of 20 2,000-5,000). After the addition was complete and the mixture was uniform, the pH was adjusted to 11.5 with 0.22 g. of 50 wt-% aqueous sodium hydroxide. During addition of the components, the temperature was maintained between 60-80 F.
ExamPle II
Into a 2,000 ml glass beaker equipped with a magnetic stirrer was placed 280 grams of soft water. Into the water under stirring was added 600 grams of an 8 wt-%
aqueous solution of sodium hypochlorite (4.8% NaOCl) and the mixture was stirred until uniform. Into the uniform ~olution was added 120 grams of DOWFAX ~ 2Al a 45 wt-%
solution of a sodium alkyl diphenyl oxide sufonate (90%
monoalkylate and greater than 90% disulfonate wherein the alkyl groups are C10 linear groups, made from an alpha olefin). After the mixture was uniform, the pH was 8x~96 - 13a -adjusted to 11.5 with 0.27g of 50 wt-% aqueous sodium hydroxide. During blending the temperature was maintained between 60 and 80 F.
D
- , : .
.
1~82~96 Exam~le III
Example II was repeated with DOWFAX ~ 3B2 a sodium alkyl diphenyl oxide sulfonate (90% monoalkylate and greater than 90~ disulfonate having C12 branched alkyl groups made from a tetrapropylene oligomer). The pH was adjusted to 11.5 with 0.34g of 50% aqueous sodium hydroxide.
Exam~le IV
Into a 2,000 milliliter glass beaker equipped with a magnetic stirrer was placed 283.3 grams of soft water.
Into the water under stirring was added 600 grams of an 8%
aqueous sodium hypochlorite ~4.8% NaOCl) solution. After the solution became uniform, 40 grams of DOWFAX ~ 2A1 was added (an alkylated diphenyl oxide sulfonate which is 90% monoalkylate and greater than 90% disulfonate having C10 linear alkyl groups formed from an alpha olefin).
After the mixture became uniform, 66.7 grams of a 45 wt-%
aqueous solution of an alkyl diphenyl oxide sulfonate 190% monoalkyl and about 98.3% disulfonate) having C6 linear alkyl groups was added. Along with the diphenyl oxide sulfonate wa~ added 10 grams of a 50 wt-% aqueous 801ution of a sodium polyacrylate having a polymer molecular weight between 2,000 and 5,000. After the ~olution was uniform the pH was adjusted to ll.S with 0.20g of 50~ aqueous sodium hydroxide. The temperature of the mixture during preparation was maintained between 60 and 80 F.
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~'~82~9~;
Sheeting Evaluation Concentration for Continuous Water Sheeting*
Product ~316 of Tempera- Stainless Example ture Glass Steel 10 I 160 F. 600 ppm (30 ppm)** 1400 ppm (70 ppm) II 160 F. 450 ppm (22.5 ppm) 1300 ppm (65 ppm) III 160 F. 550 ppm (27.5 ppm) 1400 ppm (70 ppm) IV 160 F. 500 ppm (25 ppm) 1400 ppm (70 ppm) "Pluronic"*
25R2 160 F. (90 ppm) (100 ppm) , .
* Concentration of rinse composition for continuous films of water to be formed over surface under evaluation.
** Concentration in (.) is active surfactant concentra-tion.
Foaming Evaluation (Dynamic Foam) Product of Example Concentration Foam Hei~ht Temperature I 500 ppm 0.50 inches 120 F.
I 500 ppm 0.50 inches 160 F.
30 II 500 ppm 6 inches 120 F.
II 500 ppm 6 inches 160 F.
III 500 ppm 8 inches 120 F.
III 500 ppm 8 inches 160 F.
IV 500 ppm 3 inches 120 F.
IV 500 ppm 3 inches 160 F.
* Trademark ~' 1~82'~9 TAfiLE 3 Chlorine Stability 240 Ho~rs at 100 F.
Product of Initial Final Percent 5 Example Chlorine Chlorine Remaininq I 5.0 4.65 93.0 II 4.78 4.60 96.2 III 4.85 4.67 96.3 IV 4.75 4.54 95.6 10 Co~trol* 5.0 4.75 95.0 * 5.0% NaOCl solution with pH adjusted to 11.50.
The data presented in Table 1 entitled "Sheeting Evaluation" was obtained using a Champion 1-KAB machine dishwasher having wash and rinse temperatures of about 160 F. Test pieces were placed in the machine having a glass door to permit visual observation of the test pieces. For the evaluation the test pieces were washed in soft water three times on automatic cycle using 200 grams of an alkaline detergent prepared by blending 30 wt-~ sodium metasilicate, 35% sodium tripolyphospate, 20 3 wt-% PLURAFACl surfactant No. RA-43, and 32~ sodium carbonate. During the three wash cycles no rinse additive was used. To determine the sheeting effect the machine was filled with water and set on manual. Into the water was added 500 parts of "Mazola"** corn oil per million parts of rinse water, and a minimum measured amount of rinse composition of the Examples. The mixture was circulated for 3 minutes and the concentration of rinse additive was progressively increased by injecting increasing amounts of rinse composition until a substantially continuous sheeting effect of the rinse water was noted over substantially all the test pieces.
The minimum concentration for continuous sheeting was noted and recorded in Table 1.
The data recorded in Table 2 entitled "Foaming 1 Trademark * Trademark lZ82296 Evaluation (Dynamic Foam)" was generated in a foam test device which is a cylindrical container 8 liters in volume, 15 centimeters in diameter and 50 centimeters in height equipped with an electric hot plate for tempera-ture control, and a pump to recirculate the test solu-tion at 6 psi through a means to direct a spray of the test solution onto the surface of the contents of the solution to generate foam.
Three liters of a test solution prepared in soft water which contained 6.0 grams of a dry blend of 30 wt-%
sodium metasilicate, 35 wt-% sodium tripolyphosphate, 3% PLURAFAC ~ RA-43 and 32 wt-% sodium carbonate was used (200 ppm in the aqueous detergent). The rinse compositions were evaluated at 500 parts per million by adding 1.5 grams of the rinse composition of each example to 3 liters of the test detergent. The tests were performed by recirculating the detergent solution through the spray means in the dynamic foam tester for 5 minutes to verify that the initial equilibrated foam was no more than lt2 inch above the surface of the test solution. After the equilibrated foam level was established the rinse composition was added to the test solution and after 5 minutes, the foam height was measured.
The chlorine stability test was performed by placing about 400 grams of the fully compounded rinse additive composition in capped translucent polyethylene bottles which were stored for 240 hours at 100F. The chlorine concentrations were measured by a standard iodometric titration with thiosulfate.
An examination of the Tables shows that the rinse additive composition of the Examples had acceptable sheeting properties, generated 0.5-8.0 inches of foam at 120 and 160F., and contained stable chlorine.
The compositions of Examples II and III, wherein the rinse additives were C10- and C12-alkylated, respectively, generated substantially more foam than the P~
.
1'~8Z'~9G
- 17a -compositions of the other Examples. The C6-alkylated additive generated substantially less foam than the other additives, and reduced the foam generated by the C12-alkylated additive.
The above Examples, data, and specification provide a basis for understanding the invention. However, since many embodiments of the invention can be made without departing from the spirit and scope of the invention, -~282296 the invention resides wholly in the claims herelnafter appended.
;
:
Claims (27)
1. A method for cleaning tableware in a mechanical dishwasher which comprises:
(a) contacting stained and soiled tableware with an aqueous alkaline cleaning composition for a sufficient time at a sufficient temperature to remove soil to produce washed tableware; and (b) contacting the washed tableware with an aqueous rinse solution containing a low foaming, bleaching and sanitizing rinse composition to produce washed, bleached, and rinsed tableware, the rinse composition comprising:
(i) a major proportion of aqueous medium;
(ii) about 0.1 to 15 wt-% of an active halogen composition;
(iii) about 0.1 to 15 wt-% of a low foaming sulfonate rinse agent having the formula:
and the alkali metal and alkaline earth metal salts thereof, wherein x is 0 to 4, y is 0 to 4, the sum of both x's is at least one, the sum of both y's is at least one, and the sum of all substituents x and y is less than or equal to 6; and each R is a hydrogen or a C1-C9 alkyl group, at least one R
being alkyl.
(a) contacting stained and soiled tableware with an aqueous alkaline cleaning composition for a sufficient time at a sufficient temperature to remove soil to produce washed tableware; and (b) contacting the washed tableware with an aqueous rinse solution containing a low foaming, bleaching and sanitizing rinse composition to produce washed, bleached, and rinsed tableware, the rinse composition comprising:
(i) a major proportion of aqueous medium;
(ii) about 0.1 to 15 wt-% of an active halogen composition;
(iii) about 0.1 to 15 wt-% of a low foaming sulfonate rinse agent having the formula:
and the alkali metal and alkaline earth metal salts thereof, wherein x is 0 to 4, y is 0 to 4, the sum of both x's is at least one, the sum of both y's is at least one, and the sum of all substituents x and y is less than or equal to 6; and each R is a hydrogen or a C1-C9 alkyl group, at least one R
being alkyl.
2. The method of claim 1 wherein the rinse composition further comprises an effective amount of a threshold agent to prevent or delay the precipitation of alkaline earth metal hardness components.
3. The method of claim 2 wherein the threshold agent comprises about 0.1 to 15 wt-% of the rinse composition.
4. The method of claim 2 wherein the threshold agent comprises an inorganic or organic polyelectrolyte.
5. The method of claim 1 wherein the active-halogen composition comprises an alkali metal hypohalite composition.
6. The method of claim 1 further comprising maintaining the temperature of the rinse cycle between 120-200°F.
7. The method of claim 1 further comprising metering the rinse composition into a reservoir to form the rinse solution in the dishwater.
8. The method of claim 1 further comprising diluting the rinse composition with service water to form the rinse solution.
9. The method of claim 1 wherein the rinse composition causes continuous sheeting action to produce substantially complete rinsing of the tableware.
10. The method of claim 1 further comprising feeding used rinse water back into the washing stage (a).
11. The method of claim 1 further comprising a scraping stage of removing larger agglomerates of foods from the tableware prior to step (a).
12. A low foaming and sanitizing or bleaching rinse composition for machine warewashing which comprises:
(a) a major proportion of an aqueous medium;
(b) about 2.5-15% of an active halogen compound;
and (c) an effective amount of a low foaming sulfonate rinse agent of the formula:
and the alkali metal or alkaline earth metal salts thereof, wherein x is 0 to 4, y is 0 to 4, the sum of both x's is at least one, the sum of both y's is at least one, and the sum of all substituents x and y is less than or equal to 6; and each R is independently a hydrogen or a C1-C9 alkyl group, at least one R being alkyl;
(d) an amount of a threshold agent effective to prevent or delay the precipitation of alkaline earth metal hardness components; and wherein the rinse composition is free of significant amounts of alkaline detergent builder salts.
(a) a major proportion of an aqueous medium;
(b) about 2.5-15% of an active halogen compound;
and (c) an effective amount of a low foaming sulfonate rinse agent of the formula:
and the alkali metal or alkaline earth metal salts thereof, wherein x is 0 to 4, y is 0 to 4, the sum of both x's is at least one, the sum of both y's is at least one, and the sum of all substituents x and y is less than or equal to 6; and each R is independently a hydrogen or a C1-C9 alkyl group, at least one R being alkyl;
(d) an amount of a threshold agent effective to prevent or delay the precipitation of alkaline earth metal hardness components; and wherein the rinse composition is free of significant amounts of alkaline detergent builder salts.
13. The rinse composition of claim 12 which contains less than about 1% of said alkaline detergent builder salts.
14. The rinse composition of claim 12 wherein R is an alkyl group having an average of 2-8 carbon atoms, x and y are independently 1 or 2, and x + y is less than or equal to 4.
15. The rinse composition of claim 14 wherein the alkyl group has about 3 to 8 carbon atoms.
16. The rinse composition of claim 12 wherein the rinse agent comprises about 0.1 to 15 wt-% of the threshold agent.
17. The rinse composition of claim 16 wherein the threshold agent comprises an inorganic or organic polyelectrolyte.
18. The rinse composition of claim 17 wherein the polyelectrolyte comprises an acrylic homopolymer or interpolymer having pendant carboxyl groups.
19. The rinse composition of claim 12 wherein the concentration of the sulfonate rinse agent is about 0.1-20 wt-% of the composition.
20. The rinse composition of claim 12 wherein the concentration of the active-halogen composition is about 3.0 to 7.5 wt-% of the composition.
21. The rinse composition of claim 20 wherein the active-halogen composition comprises an alkali metal hypohalite composition.
22. The rinse composition of claim 21 wherein the alkali metal hypohalite is lithium hypochlorite, sodium hypochlorite, potassium hypochlorite, or mixtures thereof.
23. A dilute aqueous rinse solution which comprises an amount of the rinse composition of claim 12 effective to produce about 1 to 200 parts of the active-halogen compound and about 1 to 200 parts of the sulfonate rinse agent each per million parts of the dilute aqueous rinse solution.
24. A method for cleaning tableware in a mechanical dishwasher which comprises:
(a) contacting stained and soiled tableware with an aqueous alkaline cleaning composition for a sufficient time at a sufficient temperature to remove soil to produce washed tableware; and (b) contacting the washed tableware with a rinse solution comprising the rinse composition of claim 12 to produce washed, bleached, and rinsed tableware.
(a) contacting stained and soiled tableware with an aqueous alkaline cleaning composition for a sufficient time at a sufficient temperature to remove soil to produce washed tableware; and (b) contacting the washed tableware with a rinse solution comprising the rinse composition of claim 12 to produce washed, bleached, and rinsed tableware.
25. A low foaming, bleaching and sanitizing rinse composition for machine warewashing which consists essentially of:
(a) a major proportion of water:
(b) about 2.5 to 20 wt-% of an alkali metal hypohalite;
(c) about 0.1 to 20 wt-% of a low foaming rinse agent of the formula:
and alkali metal and alkaline earth metal salts thereof, wherein the agent is about 10-90%
dialkylate, about 10-100% disulfonate, and R is an alkyl group of 3 to 8 carbon atoms;
(d) about 0.1 to 10 wt-% of a polyacrylic acid polymer having a molecular weight of about 500 to 5,000; and (e) less than about 1% of an alkali metal hydroxide.
(a) a major proportion of water:
(b) about 2.5 to 20 wt-% of an alkali metal hypohalite;
(c) about 0.1 to 20 wt-% of a low foaming rinse agent of the formula:
and alkali metal and alkaline earth metal salts thereof, wherein the agent is about 10-90%
dialkylate, about 10-100% disulfonate, and R is an alkyl group of 3 to 8 carbon atoms;
(d) about 0.1 to 10 wt-% of a polyacrylic acid polymer having a molecular weight of about 500 to 5,000; and (e) less than about 1% of an alkali metal hydroxide.
26. A rinse solution for use in the rinse cycle of a mechanical warewashing machine which comprises a major proportion of water and a sufficient amount of the composition of claim 25 to provide about 1 to 200 parts of the alkali metal hypohalite and about 1 to 200 parts of the rinse agent per million parts of rinse solution.
27. A method of operating a mechanical warewashing machine which comprises cleaning soiled dishes with an aqueous alkaline cleaner to produce washed dishes and rinsing the washed dishes with the rinse solution of claim 26 to produce washed, bleached and rinsed ware.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US64625784A | 1984-08-29 | 1984-08-29 | |
| US646,257 | 1984-08-29 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1282296C true CA1282296C (en) | 1991-04-02 |
Family
ID=24592363
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000473577A Expired - Fee Related CA1282296C (en) | 1984-08-29 | 1985-02-05 | Mechanical dishwashing rinse composition having a low foaming sulfonic acid rinsing agent and a source of active halogen |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US4711738A (en) |
| EP (1) | EP0177109A3 (en) |
| JP (1) | JPS6164795A (en) |
| AU (1) | AU568902B2 (en) |
| CA (1) | CA1282296C (en) |
| NZ (1) | NZ210848A (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5358653A (en) * | 1990-06-25 | 1994-10-25 | Ecolab, Inc. | Chlorinated solid rinse aid |
| US5273677A (en) * | 1992-03-20 | 1993-12-28 | Olin Corporation | Rinse aids comprising ethoxylated-propoxylated surfactant mixtures |
| EP0916719A3 (en) * | 1992-11-03 | 1999-07-14 | The Procter & Gamble Company | Cleaning with short-chain surfactants |
| JP2521630B2 (en) * | 1992-12-10 | 1996-08-07 | 花王株式会社 | Cleaning composition for hard surfaces |
| US5474710A (en) * | 1993-08-27 | 1995-12-12 | Ofosu-Asanta; Kofi | Process for preparing concentrated surfactant mixtures containing magnesium |
| US5417893A (en) * | 1993-08-27 | 1995-05-23 | The Procter & Gamble Company | Concentrated liquid or gel light duty dishwashing detergent compositions containing calcium ions and disulfonate surfactants |
| US5415814A (en) * | 1993-08-27 | 1995-05-16 | The Procter & Gamble Company | Concentrated liquid or gel light duty dishwashing detergent composition containing calcium xylene sulfonate |
| US5876514A (en) * | 1997-01-23 | 1999-03-02 | Ecolab Inc. | Warewashing system containing nonionic surfactant that performs both a cleaning and sheeting function and a method of warewashing |
| US6423280B1 (en) * | 1998-10-29 | 2002-07-23 | Ecolab Inc. | Hydraulic control of detergent concentration in an automatic warewashing machine |
| US20040102348A1 (en) * | 2002-11-22 | 2004-05-27 | Schneider David J. | Process for stain removal |
| US9752105B2 (en) | 2012-09-13 | 2017-09-05 | Ecolab Usa Inc. | Two step method of cleaning, sanitizing, and rinsing a surface |
| US20140308162A1 (en) | 2013-04-15 | 2014-10-16 | Ecolab Usa Inc. | Peroxycarboxylic acid based sanitizing rinse additives for use in ware washing |
| CA2933458A1 (en) | 2013-12-16 | 2015-06-25 | 3M Innovative Properties Company | Detergent and rinse-aid compositions and methods |
| US10865367B2 (en) | 2017-06-26 | 2020-12-15 | Ecolab Usa Inc. | Method of dishwashing comprising detergent compositions substantially free of polycarboxylic acid polymers |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3248334A (en) * | 1961-04-24 | 1966-04-26 | Dow Chemical Co | Corrosion inhibited aqueous nonoxidizing acid compositions |
| US3248335A (en) * | 1965-04-01 | 1966-04-26 | Dow Chemical Co | Detergent composition for hard surfaces |
| US3579455A (en) * | 1968-08-02 | 1971-05-18 | Grace W R & Co | Machine dishwashing compositions containing sodium polyacrylate |
| US3700599A (en) * | 1970-09-25 | 1972-10-24 | Economics Lab | Composition for mechanically cleaning hard surfaces |
| US3793212A (en) * | 1971-07-23 | 1974-02-19 | Colgate Palmolive Co | Detergent composition and method of preparing same |
| JPS565800B2 (en) * | 1973-12-11 | 1981-02-06 | ||
| US4071463A (en) * | 1975-09-11 | 1978-01-31 | The Dow Chemical Company | Stable cleaning agents of hypochlorite bleach and detergent |
| DE2750528A1 (en) * | 1976-11-15 | 1978-05-24 | Procter & Gamble | METHOD OF KEEPING A TOILET BASIN CLEAN |
| US4174289A (en) * | 1977-07-27 | 1979-11-13 | Basf Wyandotte Corporation | Liquid detergent-bleach concentrates having high alkalinity |
| US4390448A (en) * | 1981-10-22 | 1983-06-28 | International Flavors & Fragrances Inc. | Perfumed stable aqueous hypochlorite bleach compositions containing 2-methyl-2-octanol and thickened variation thereof |
| US4552680A (en) * | 1983-11-04 | 1985-11-12 | The Procter & Gamble Company | Hypochlorite bleach containing surfactant and organic antifoamant |
-
1985
- 1985-01-16 AU AU37712/85A patent/AU568902B2/en not_active Ceased
- 1985-01-16 NZ NZ210848A patent/NZ210848A/en unknown
- 1985-01-23 EP EP85300426A patent/EP0177109A3/en not_active Withdrawn
- 1985-02-01 JP JP60016698A patent/JPS6164795A/en active Pending
- 1985-02-05 CA CA000473577A patent/CA1282296C/en not_active Expired - Fee Related
-
1986
- 1986-01-21 US US06/821,412 patent/US4711738A/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| NZ210848A (en) | 1988-06-30 |
| AU3771285A (en) | 1986-03-06 |
| US4711738A (en) | 1987-12-08 |
| EP0177109A3 (en) | 1989-06-07 |
| EP0177109A2 (en) | 1986-04-09 |
| AU568902B2 (en) | 1988-01-14 |
| JPS6164795A (en) | 1986-04-03 |
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| Date | Code | Title | Description |
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| MKLA | Lapsed |