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
  • C11D3/044—Hydroxides or bases
• • 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
  • C11D3/06—Phosphates, including polyphosphates
• • 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
  • C11D3/08—Silicates
• • 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
  • C11D3/10—Carbonates ; Bicarbonates

Definitions

• ABSTRACT Machine dishwashing detergents having a low condensed phosphate content and characterized by the presence therein of a metallic salt of citric acid (e.g. sodium citrate).
• An alkaline machine dishwashing detergent e.g. pH at 1% concentration above 10.5 containing less than 30 weight percent on a dry basis of sodium tripolyphosphate and at least 5 weight percent of an alkali metal citrate.
• Machine dishwashing detergents constitute a generally recognized class of detergent compositions.
• Machine dishwashing detergents are mixtures of ingredients whose purpose, in combination, is to emulsify and remove food soils, to inhibit the foam caused by certain food soils, to promote the wetting of dinnerware to -*----v-. thereby minimize or eliminate visually observable spotting, to remove stains such as those caused by coffee and tea, to prevent a buildup of soil films on dinnerware surfaces, to reduce or eliminate tarnishing of flatware, and to destroy bacteria. Additionally, machine dishwashing detergents must possess these characteristics without substantially etching or corroding or otherwise damaging the surfaces of dinnerware and flatware.
• Machine dishwashing detergents are often highly alkaline (a pH above 10.0 and frequently above 12.5 at concentrations of 1 weight in water).
• Machine dishwashing detergents are often formulated by mixing or otherwise combining alkaline detergent salts and alkaline condensed phosphate salts.
• chlorine releasing agents and low-foaming or non-foaming organic surface active agents are optionally and preferably included in such compositions.
• nitrilo triacetic acid appears to be one of the most promising candidates.
• one disadvantageous effect of nitrilo triacetic acid is its tendency to de-stabilize chlorine in use solutions of machine dishwashing detergents.
• Other disadvantages of NTA at the present time include cost, lack of general availability, and lack of a threshold effect.
• the present invention is based upon the discovery that metallic salts of citric acid (e.g. sodium citrate) are effective partial substitutes for alkaline condensed phosphates in machine dishwashing detergents.
• the i DETAILED DISCUSSION Machine dishwashing detergents of the present invention can be formulated as a solid detergent or as single or multiple package liquid detergents.
• Solid or dry detergents can be formed by blending to- 2 gether the various detergent-forming ingredients to form a powdered or granular product, or they can be agglomerated, pelletized or the like.
• Multiple package liquid detergents are those machine diswashing detergents which are formulated into two or more separate liquid components, each component being packaged separately.
• the separate components are dispensed from their separate containers into the dishwashing tank by suitable dispensing apparatus.
• the machine dishwashing detergent compositions of i the present invention will normally contain at least one 3 alkaline detergent salt other than an alkaline condensed phosphate salt, at least one alkaline condensed phosphate salt, at least one citrate, and, optionally, a
• the pH of these machine dishwashing detergents will 7 normally be at least 10.0 and generally not above about 12.8 at a concentration of 1 weight percent in water. i
• the effectiveness of the present compositions at these high pHs is unexpected since alkali metal citrates are not normally used to sequester calcium, magnesium, or
• pH values can be obtained by calculating the negative of the logarithm of the hydroxyl ion concentration but are preferably determined by pH measuring instruments which can accurately determine the negative of the logarithm of the hydroxyl ion activity, e.g. Corning Model 12, Research pH meter, with Beckman 39099 E- 3 glass electrode (OlOOC., pH 0-l4 range) and matched calomel reference electrode. Additionally, nomographs can be used for sodium ion error correction.
• a suflicient amount of the dry or liquid detergents formulations of this invention should be used to provide wash water containing at least O.l percent by weight of detergent solids in water. It is preferred that the wash water contain these solids in stable aqueous solution.
• the condensed alkali metal phosphate content is preferably near the lower end of the ranges defined herein for greater water solubility and hydrolytic stability of the liquid composition. It is permissible and even preferred for these liquid detergent compositions to contain an aqueous diluting medium which acts as a solvating phase rather than the continuous phase of an emulsion or dispersion.
• the ingredients and/or their proportions are selected for good water solubility so as to permit at least one part by weight of the solid formulation to be totally dissolved in 99 (and preferably no more than 1,000, typically no more than 500) parts by weight of water.
• the solid, high pH detergent compositions of this invention typically contain fairly substantial amounts of sodium carbonate and caustic soda (sodium hydroxide) or other alkali metal hydroxides, e.g. KOH.
• caustic soda sodium hydroxide
• the amount of caustic I soda should preferably not exceed about or 30 percent by weight so that the wash water will contain only a fraction of 1 percent by weight of caustic and will exhibit a pH measurement less than 12.8.
• the lower pH formulations of this invention typically contain a metasili'cate as a non-sequestering builder salt, the same or smaller amounts of caustic, and a relatively small amount of sodium carbonate.
• All the ingredients of either of the solid or liquid compositions of this invention should be selected so as to provide a detergent which produces little or no foam during machine dishwashing, even in interaction with foamable food soils such as egg or milk residues. Lowfoaming or non-foaming ingredients can be used to help provide this freedom from excessive foaming, and,
• surfactants with low foaming or even de-foaming properties can be added to reduce or control foaming.
• a realistic test for low foaming detergent compositions containing builder salts, condensed phosphates, surfactants, etc. is the commercial dishwashing machine test described in column 2, line 59 et seq. and Table III and IV of U.S. Pat. No. 3,444,242 (Rue et a1), issued May 13, I969.
• Detergent formulations of this invention do not unduly reduce either the r.p.m. of the spray arm or the wash pressure in this test.
• Alkaline detergent salts or detergent builder salts as they are sometimes called are well known to those engaged in the detergent industry and include such chemicals as di and tri-sodium orthophosphates, sodium carbonate, sodium bicarbonate, sodium silicates, sodium metasilicate, sodium borate, caustic soda, caustic potash, and the like. These salts are used primarily to adjust the pH of the wash water and/or to minimize corrosion. These salts may have a water conditioning effect, but this effect is characterized by the precipitation of hardness rather than by a sequestration or soluble complex formation or other solubilization effect.
• the combined amount of these non-sequestering detergent builder salts will generally but not always be less than 80 weight percent of the total dishwashing detergent formula (on a dry basis). More usually, the total amount of such detergent salts will range from 2 to weight percent on the same basis.
• n is an integer ranging from 1 to about 60.
• the lower numerical values of n are preferred, e.g. 1-6. It is permissible to use condensed polyphosphates wherein n is larger than 60; however, such high molecular weight phosphates are less preferred, due to their relative lack of availability and lower water solubility. Cyclic condensed phosphates (wherein a plurality of -PO M-- units join to form a ring) can also be used.
• Typical alkaline condensed phosphates include tetrasodium pyrophosphate, tetra potassium pyrophosphate, sodium tripolyphosphate, other sodium polyphosphates and the like.
• alkaline condensed phosphate salts have a number of properties which make them particularly suitable for use in machine dishwashing detergent compositions.
• Other classes of compounds investigated by detergent chemists have equal or even superior sequestering capabilities but often lack the buffering, deflocculation, solubilizing or peptizing, and other desirable effects provided by these condensed phosphate salts.
• the socalled threshold effect (the ability to sequester hard water metal ions beyond the stoichiometric presence of the sequestering agent) has already been alluded to and is observed with sodium tripolyphosphate at the levels of about 5 to about 20 parts per million. It is also known that these condensed phosphate salts are active sequestering agents in aqueous alkaline media.
• the amount of alkaline condensed phosphate in the detergent compositions will be less than 35 weight percent on a dry basis, typically less than 30 weight percent on the same basis. To provide a reasonable assurance that the threshold effect will be obtained, more than 0.5 weight percent of the alkaline condensed phosphate (dry basis) is used in the composition. Normally, the amount of alkaline condensed phosphate used in these compositions will be from 2-20 percent, e.g. 2-10 percent, on the same basis.
• any of the water soluble metal salts of citric acid can be used in the practice of the present invention. However, all salts do not serve with equal effectiveness, and the alkali metal salts, particularly the sodium and potassium citrates, are preferred.
• the alkali metal salts particularly the sodium and potassium citrates
• Commercial sodium citrate is fully neutralized and is more accurately described as trisodium citrate.
• Trisodium citrate is available as white crystals or granular powder. It is odorless, stable in air, and has a pleasant saline taste. Each molecule of trisodium citrate dihydrate loses two molecules of water of hydration when heated to 150C.
• Commercial potassium citrate also exists as white crystals or powder. It is normally available as the monohydrate (as contrasted to sodium citrate which exists as the dihydrate).
• the amount of citrate employed will be above 5 percent and will generally fall within the range of 5-60 weight percent on a dry basis (expressed as trisodium citrate). Water of hydration can be considered to be part of the salt. More usually, the amount of citrate (whether hydrated or not) employed will be from 5-40 weight percent, e.g. l-30 percent on the same basis.
• citrates can be used.
• a citrate can be formed in situ from, for example, the combination of citric acid with sodium or potassium hydroxide.
• the use of a pre-formed alkali metal citrate or a mixture thereof is particularly preferred with dry blended solid detergents.
• the combination of the citrate and the condensed phosphate salt e.g. sodium tripolyphoshate
• the total of the citrate and the condensed phosphate salt will be in the range of 7-90 weight percent on a dry basis and will generally not exceed 65 weight percent (dry basis) of the total composition.
• Excellent results can be obtained from the combination of sodium tripolyphosphate and sodium citrate when the ratio on a dry weight basis of polyphosphate to citrate is less than about 2:] but greater than about 0.05:1, i.e., 1:2 to 20:1 citratezpolyphosphate.
• One preferred method for formulating a detergent composition of this invention is to modify a conventional machine dishwashing detergent formula by replacing more than one-third of the condensed phosphate salt with citrate; provided, of course. that the condensed phosphate content is reduced below 35 percent on a dry weight basis.
• a typical elemental analysis for phosphorus in compositions of this invention shows less than 8.7% (e.g. less than by weight phosphorus.
• Orthophosphates are preferably not used as builder salts (or used in very small amounts), so that However, one-third, one-half, or even nine-tenths or more of the polyphosphate can be replaced by citrate with little or no significant loss in overall performance characteristics of the detergent composition.
• citrates are formed in situ from citric acid in compositions of the present invention, either solid or dissolved citric acid can be used.
• aqueous citric acid solutions at concentrations of about 25-40 percent by weight are suitable.
• CHLORINE RELEASING AGENTS Among the various chlorine releasing agents are chlorinated trisodium phosphate, potassium and sodium dichloroisocyanurate, trichloroisoeyanuric acid and double salts or crystalline complex salts or hydrated salts thereof (See U.S. Pat. No. 3,272,813), trichloromelamine, Chloramine T," alkali metal and alkaline earth metal hypochlorites (e.g. sodium or potassium salt). These agents are not always required for 1 good dishwashing, and, in any event, less than 5 or l0 percent by weight (e.g. 0.l3%), based on the dry solids of the total composition, is ordinarily effective.
• the preferred chlorine-releasing agents are the chlon'nated cyanurate's and their salts.
• the alkali metal hypochlorites are also particularly useful.
• surfactants are useful in many types of detergent compositions, those which have a tendency to produce'stable foam are preferably excluded or used in minimum amounts in machine dishwashing compositions.
• the preferred surfactants of this composition have a cloud point of about 45C. or less (preferably less than 35C, e.g. 2030C.) determined in distilled water at a concentration of 1 percent.
• These preferred surfactants, at 0.l weight percent concentration in water have Ross-Miles test values indicating the formation of very little stable foam after several minutes.
• the i Ross-Miles test is performed by pipetting the 0.1 percent detergent solution into a column of water, measuring the height of foam immediately after pipetting and measuring again after 5 minutes. Water hardness is preferably specified for the test, but foam height values for nonionic surfactants tend to be independent of the hardness of the test water.
• non-foaming or low-foaming detersodium Gimme dihydme 250 gents used in this invention have Ross-Miles foam sodium tripolyphosphate (anhydrous) 5 1 caustic soda (anhydrous) 21 height values of less than 45 mm/ 15 mm (initial value/ sod' tas'l' h d 2 5 minute value).
• Typical of these preferred surfactants y mus) 2 are nonionic surfactants containing oxyethylene and, if sodium dichloroisocyanurate desired, some oxypropylene units. See for example US.
• EXAMPLE 1 This example illustrates the preparation of a single package liquid machine dishwashing detergent concentrate having a pH above 10.0
• the aforementioned commercial machine dishwash- Ingredient Amount (5%) ing test of the Rue et al US. Pat. No. 3,444,242 provides a criterion for the low foaming characteristics of Citric acid 100 completely formulated compositions of this invention.
• zfi" g gf; 2:8 The compositions of this invention control foam to the NaOCl (added as 10-15% NaOCl extent that when used at 0.25 to 0.75 percent by weight sg 1'; (dry basis) in 6.5 liters of 140F. wash water, the rpm.
• the aforementioned surfactants are used in limited amounts, e. g. 0-5 percent by weight of the total formulation.
• Citric acid is dissolved in part or all of the water.
• KOH is added to neutralize the citric acid (i.e., form a citrate in situ). After the solution cools, the remaining ingredients are added.
• Solid detergent compositions for machine dishwashing were prepared by blending soda ash (anhydrous sodium carbonate), caustic soda (anhydrous sodium hydroxide), the low foaming nonionic surfactant described in US. Pat. No. 3,048,548, various amounts of sodium tripolyphosphate (STP) and sodium citrate (i.e. trisodium citrate dihydrate), the citrate and the ST? each being varied over the range of 0-33.40 parts by weight.
• the detergent composition containing no citrate was referred to as the Standard
• the detergent containing no STP was referred to as the All-Citrate" sample.
• the low foaming nonionic surfactant was premixed with sodium carbonate to form an 85/15 (weight/weight) Na- CO /surfactant composition hereinafter referred to as the pre-mix.”
• bases such as sodium and potassium hydroxide, filler, corrosion inhibitors, anti-caking agents, coloring agents and the like can be included in machine dishwashing detergents of this invention.
• neutral salts such as sodium sulfate and sodium chloride can be used as fillers.
• compositions of this invention are water soluble.
• water soluble is meant the ability to form at least a 10 weight percent solution in deionized water.
• EXAMPLE 1 The pH of the Standard was measured with a Corning glass electrode pH meter at 1.0 percent by weight and 0.1 percent by weight concentration in aqueous solution. The results were:
• This example illustrates the preparation of a solid or dry detergent according to this invention.
• the detergent formulations were tested and compared to the Standard" as to their performance in machine dishwashing.
• glasses were washed in a Hobart C-44 dishwasher using well water of l3 grains hardness heated to l60F.
• the glasses were cycled ten times in the dishwasher, during which time the detergent concentration was maintained at a level of 2,000 parts per million (plus or minus percent).
• the glasses were inspected for filming and spotting.
• the results reported subsequently in Table I were based upon an average rating of three glasses.
• the detergents were ranked in order of performance from the least film (l) to the heaviest film (5). Essentially no foaming was observed in the wash tank in connection with any of the detergent formulations tested.
• an alkaline condensed phosphate salt generally characterized by the structural formula 0 i ll no-p-o P-O n l OM on wherein M is hydrogen or an alkali metal, at least one i M being an alkali metal, and
• n is an integer ranging from 1 to and 2. 2 by weight, on a dry basis, of a nonsequestering, alkaline, pH-adjusting or buffering detergent builder salt;
• said detergent Composition having a pH of about 10.0 to 12.8 and a Ross-Miles foam height, determined at a concentration of 0.1 percent by weight of said detergent composition in water, of less than 45 mm initially and less than 15mm after five minutes in a column of water maintained at 50C.; the improvement which comprises:
• said salt of citric acid substitutes for part of said condensed phosphate; whereby the amount of said condensed phosphate in the resulting detergent composition is in the range of 0.5 to 35 percent by weight of the resulting detergent composition; and whereby the amount of said detergent builder salt in the resulting detergent composition is within the range of 2 80% by weight;
• said salt of citric acid substitutes for at least one-third by weight, on a dry basis, said alkaline condensed phosphate, whereby the ratio of said salt of citric acid to said condensed phosphate in said resulting detergent composition, on a dry weight basis, is in the range of from 1:3 to 20:1.
• said salt of citric acid is an alkali metal citrate; the amount of said citrate is l 30 percent by weight and the amount of said alkaline condensed phosphate on the same basis is less than 30 percent by weight, all on a dry basis.
• said detergent composition consists essentially of solids including a chlorinereleasing agent selected from the group consisting of chlorinated trisodium phosphate, potassium dichloroisocyanurate, sodium dichloroisocyanurate, trichloroisoeyanuric acid, double salts or crystalline complex salts or hydrated salts of trichloroisocyanuric acid, trichloromelamine, and Chloramine T.
• a chlorinereleasing agent selected from the group consisting of chlorinated trisodium phosphate, potassium dichloroisocyanurate, sodium dichloroisocyanurate, trichloroisoeyanuric acid, double salts or crystalline complex salts or hydrated salts of trichloroisocyanuric acid, trichloromelamine, and Chloramine T.
• said detergent composition is a liquid concentrate containing a chlorine releasing agent comprising an alkali metal hypochlorite.
• a machine dishwashing detergent composition which, in 0.1 weight percent concentration in water, has Ross-Miles foam heights, using a water column maintained at 50C., of less than 45mm initially and less than mm after five minutes, and which has a pH, determined at 1 weight percent solution in water, of about 10 to 12.8, said composition consisting essentially of:
• n is an integer from I to 6, all of the said percentages being on a dry basis.
• composition according to claim 7 wherein the ratio, on a dry weight basis, of said component (0) to said component (d) is in the range of 1:2 to 20:1, and total of said components (0) and (d) does not exceed 65 percent by weight of said composition on a dry basis.
• composition according to claim 7 wherein said component (c) is the product of the in situ reaction of citric acid and an alkali metal hydroxide.
• composition according to claim 7 wherein said detergent composition consists essentially of solids including a chlorine-releasing agent selected from the group consisting of chlorinated trisodium phosphate, potassium dichloroisocyanurate, sodium dichloroisocyanurate, trichloroisocyanuric acid, double salts or crystalline complex salts or hydrated salts of trichloroisocyanuric acid, trichloromelamine, and Chloramine T.
• a chlorine-releasing agent selected from the group consisting of chlorinated trisodium phosphate, potassium dichloroisocyanurate, sodium dichloroisocyanurate, trichloroisocyanuric acid, double salts or crystalline complex salts or hydrated salts of trichloroisocyanuric acid, trichloromelamine, and Chloramine T.
• composition according to claim 7 wherein said detergent composition is a liquid concentrate containing a chlorine releasing agent comprising an alkali metal hypochlorite.
• composition according to claim 13 wherein said water soluble detergent builder salt is sodium carbonate.
• composition according to claim 14 wherein said composition comprises l0-30 percent by weight of said citrate and 2-20 percent by weight of sodium tripolyphosphate.
• wash water used in said process after addition of said composition, comprises 0. l-l percent by weight of said composition on a dry basis.
• Treated wash water useful for machine dishwashing having a pH in the range of about 10 12.8 and being substantially free of stable foam comprising:
• a machine detergent composition comprising:
• c. 2 70 percent by weight of a non-sequestering, alkaline, pH-adjusting or buffering alkali metal detergent builder salt, all on a dry basis, and

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Cited By (30)

Citations (10)

• 1971
  • 1971-06-30 CA CA117,133A patent/CA959370A/en not_active Expired
  • 1971-08-21 DE DE19712142055 patent/DE2142055A1/de active Pending
  • 1971-08-23 GB GB3938171A patent/GB1314507A/en not_active Expired
  • 1971-09-07 FR FR7132256A patent/FR2107361A5/fr not_active Expired
• 1972
  • 1972-11-10 US US305596A patent/US3899436A/en not_active Expired - Lifetime

Patent Citations (10)

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