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
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
• • 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
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/378—(Co)polymerised monomers containing sulfur, e.g. sulfonate

Definitions

• Detergent compositions for mechanically cleaning hard surfaces are characterized by the presence therein of a mixture of metallic salt of citric acid (e.g. sodium citrate) and water soluble polymeric, organic polyelectrolyte (e.g. hydrolyzed maleic anhydride polymers).
• This mixture permits the reduction of or elimination of condensed phosphate salts commonly used in deter-gent compositions of this type (e.g. machine dishwashing detergents).
• Machine dishwashing detergents constitute a subclass within this broad class that is of particular importance to the present invention.
• Machine dishwashing detergents must possess these characteristics without subcombination, is to emulsify and remove food soils, to inhibit the foam caused by certain food soils, to promote the wetting of dinnerware to thereby minimize or eliminate visually observable spotting, to remove stains such as those caused by coffee and tea, to prevent a buildup of soil and hard water films on dinner and glassware surfaces, to reduce or eliminate tarnishing of (flatware, and
• machine dishwashing detergents must possess these characteirstics 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 12.0 at concentrations of 1 weight percent in water). Frequently, machine dishwashing detergents are formulated by mixing or otherwise combining alkaline condensed phosphate salts with other inorganic alkaline detergent salts or builders. Frequently, chlorine releasing agents and low foaming or defoaming organic surface active agents (e.g. non-ionic surfactants) are optionally and preferably included in such compositions.
• nitrilo tiacetic acid (or its salt) appears to be one of the most promising candidates.
• one disadvantageous effect of nitrilo t-riacetic acid (often called NTA) is its tendency to de-stabilize chlorine in use solutions of such detergent compositions.
• Other disadvantages of NTA at the present time include cost, lack of general availability, and lack of threshold effect (i.e. inability to sequester hard water metal ions beyond its stoichiometric presence).
• the present invention is based upon the discovery that mixtures of metallic salts of citric acid (e.g. sodium citrate) and water soluble polymeric organic polyelectrolytes are elfective substitutes for condensed phosphate salts (e.g. for sodium tripolyphosphate) in detergent compositions intended for use in cleaning hard surfaces.
• condensed phosphate salts e.g. for sodium tripolyphosphate
• the mixture is also effective at sequestering hard water metal ions beyond their stoichiometric presence (i.e. the combination exhibits the same threshold effect of alkaline condensed polyphosphates). Additionally, the mixture is stable toward chlorine releasing agents (e.g.
• compositions of the present invention can be formulated as either a solid detergent or as single or multiple package liquid detergent. These detergent compositions will be used, after appropriate dilution with water, for the mechanical or machine washing of hard surfaces (e.g. mechanical spray washing). They will find particular application as machine dishwashing detergents.
• Solid or dry detergents can be formed by blending together the various detergent-forming ingredients to form a powder or granular product, or they can be agglomerated, pelletized or the like.
• Multiple package liquid detergents are those machine ware-washing detergents which are formulated into two or more separate liquid components, each component being packaged separately. In the washing operation, the separate components are dispensed from their separate containers into the washing zone by suitable dispensing apparatus.
• the machine washing detergent compositions of the present invention will contain typical detergent forming ingredients plus the mixture of metallic salt of citric acid and water soluble polyelectrolyte.
• the pH of these machine dishwashing detergents will normally be at least 10.0 at a concentration of 1 weight percent in water. pHs of from 12.012.5 are particularly desirable for many machine dishwashing uses. pHs in the 10-11 range are common for home use, while pHs above 12 are desired for industrial use.
• the detergent compositions of the present invention are typically free of alkyl benzene sulfonates and, in use, produce little or no foam as contrasted to, for example, laundry detergents containing alkyl benzene sulfonates.
• the Qitrates 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 are preferred. Sodium and potassium citrate are particularly preferred.
• sodium citrate (more accurately described as trisodium citrate dihydrate) exists as white crystals or a granular powder. :It is odorless, stable in air and has a slightly saline taste. Each molecule of trisodium citrate loses two molecules of water when heated to 150 C. Potassium citrate also exists as white crystals or powder. It is commercially available as the monohydrate (as contrasted to sodium citrate which exists as the dihydrate).
• the amount of citrate employed will generally fall within the range of -6C weight percent on a dry formula basis. Water of hydration can be considered to be a part of the salt. More usually, the amount of citrate (whether hydrated or not) will be from -40 weight percent, e.g. 15-25 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.
• Citric acid is desirable when making liquid detergent compositions, but it quickly forms the corresponding salt since such liquid compositions are quite basic (i.e. pH above 10).
• the use of a pre-formed alkali metal citrate or a mixture thereof is generally preferred, particularly when making solid detergent compositions.
• the weight ratio of citrate: polyelectrolyte will generally be above 1:1, frequently within the range of 2-10:1.
• the polyelectrolytes useful in this invention are the water soluble organic polymeric polyelectrolytes.
• a wide variety of such polyelectrolytes are known as illustrated by the following US. patents:
• Suitable polyelectrolytes are the water soluble organic polymers of polycarboxylic acids (e.g. maleic acid) or of esters of ethylenically unsaturated carboxylic acids (e.g. butyl acrylate).
• Water soluble carboxyl containing polyelectrolytes having an equivalent weight (calculated on an acid basis) of about 58 to 150, more usually from about 58 to are preferred.
• One particularly useful class of polyelectrolytes consists of: (a) homopolymers of maleic anhydride; and (b) low molecular weight linear copolymers of maleic anhydride and copolymerizable ethylenically unsaturated organic compounds such as ethylene, propylene, butylene, vinyl acetate, acrylonitrile, acrylic acid, methyl acrylate, ethyl acrylate, methyl vinyl ether, sodium vinyl sulfonate, styrene and the like. Structurally, these copolymers can be represented as follows.
• R and R can each be hydrogen or an organic radical containing from 1 to 8 carbon atoms (R and R can be the same or different), Z is an organic radical containing 1 to 8 carbon atoms (note that Z is absent in the homopolymers), M is hydrogen, ammonium or an alkali metal (e.g. sodium), n is an integer, and
• x and y are terminal groups and are hydrogen or short chain organic groups.
• copolymers are preferred.
• the upper operable limit therefore, so far as the degree of polymerization is concerned is reached when it is no longer possible to get enough of the polyelectrolyte into solution or, in the case of liquid detergents, no longer possible to get enough polyelectrolyte into the liquid detergent concentrate.
• the specific viscosity of the polyelectrolyte is preferably relatively low. Since there are viscosity differences inherently associated with different polymers, the preferred specific viscosities will vary.
• the polymer that is selected should be susceptible to handling and blending with the other components of the new detergent, as well as affording satisfactory performance. For example, when using a copolymer of ethylene and maleic anhydride it is preferred that the specific viscosity be not substantially in excess of a value of 2 as determined on a one weight percent solution of the copolymer in dimethyl formamide at 25 C. Similarly, with a vinyl acetatemaleic anhydride copolymer, it is preferred that the specific viscosity range be from 1.0 to 10.0 when determined on a four percent aqueous solution at 25 C.
• polyelectrolytes Since all polyelectrolytes do not serve with equal effectiveness, it is useful to screen or select a polyelectrolyte on the basis of its apparent chelation value (ACV) as measured in milligrams of CaCO sequestered per gram of polyelectrolyte. Below 200, the polyelectrolytes are generally ineifect-ive for purposes of this invention. Desirably, the ACV will be above 350, preferably above 500.
• Apparent chelation values (ACV) for polyelectrolytes can be determined as follows. Dissolve a 0.5 to 1.0 gram sample in about 85 ml. of water, adjusting the pH to desired use value with NaOH or NH OH, add 10 ml. of 2% Na CO then readjust the pH and make up the volume to 100 ml. with water. The solution is then titrated with a standard calcium acetate solution (0.25 M) using a magnetic stirrer. The titration is carried out in a semidarkened room using a microscope spotlight until the first faint but permanent turbidity is obtained. The endpoint is not always completely sharply defined. Variations of il5% from the average are not uncommon.
• the machine washing detergents of this invention will contain detergent salts, usually alkaline detergent salts.
• alkali metal condensed phosphate salts are alkaline and are often used in detergent compositions in large amounts
• condensed phosphate salts e.g. sodium tripolyphosphate
• Representative detergent salts are sodium carbonate, sodium bicarbonate, sodium hydroxide, sodium metasilicate, sodium borate, sodium per-borate, diand tri-sodium orthophosphates, sodium sesquicarbonate, potassium carbonate, sodium sesquisilicate, sodium orthosilicate, potassium bicarbonate, potassium silicates, potassium hydroxide, alkaline con-
• Some polyelectrolytes having an ACV below 200 are ef fective (e.g. certain styrene/maleic anhydride copolymers and carboxy methyl cellulose).
• densed phosphate salts i.e. polyphosphates
• polyphosphates such as tetrasodium pyrophosphate, tetrapotassium pyrophosphate and sodium tripolyphosphate, and glassy water soluble polyphosphates as known in the art.
• Chlorine releasing agents are usually and preferably included in the detergent compositions of the present invention.
• chlorine releasing agents are chlorinated trisodium phosphate, polychloroisocyanuric acids and their salts or double salts, tri-chloromelamine, chloramine T, alkali metal and alkaline earth metal hypochlorites (e.g. sodium hypochlorite), mono, di, and trichloroisocyanuric acid, dichlorodimethyl hydantoin, solid chlorinated caustic soda, succinchlorimide, and the like.
• alkali metal and alkaline earth metal hypochlorites e.g. sodium hypochlorite
• mono, di, and trichloroisocyanuric acid e.g. sodium hypochlorite
• dichlorodimethyl hydantoin e.g. sodium hypochlorite
• solid chlorinated caustic soda e.g. sodium hypochlorite
• succinchlorimide e.g. sodium hypochlorite
• ingredients or additives which can be included in the machine washing detergent compositions of the present invention include low foaming or non-foaming nonionic surfactants such as various polyoxyalkylene polymers, bases such as sodium and potassium hydroxide, fillers, corrosion inhibitors, coloring agents, and the like.
• a machine dishwashing detergent was prepared from the following ingredients in the amounts indicated:
• Chlorine bleach sodium dichloroisocyanaurate
• Defoaming non-ionic surfactant 1 2.0
• the concentrate was formed by dissolving the citric acid in water, then adding the KOH, and finally adding the olyelectrolyte (all with agitation). The resulting mixture (which had become hot) was cooled below 90 F. and then the sodium hypochlorite was added.
• EXAMPLE 3 A liquid machine dishwashing concentrate (less expensive than Example 2) was prepared from the following ingredients by the procedure of Example 2.
• DO-97 A polyoxyalkyleue known as DO-97, a product of Economlcs Laboratory, Inc.. USA.
• the product is made by pouring the polyelectrolyte (a 50% active aqueous slurry) and the organic defoamer onto the ash with mixing until a dry product is obtained.
• the remaining ingredients can be admixed with the powder in any order.
• compositions suitable for machine dish- Washing consisting essentially of:
• alkaline detergent salt which may include not more than 10% alkali metal polyphosphates
• Detergents of claim 1 which are solid machine dishwashing detergents, wherein said salt of citric acid is sodium citrate and wherein said detergent contains, in addition to the listed ingredients, a chlorine releasing agent selected from the group consisting of polychloroisocyanuric acids and their salts.
• Improved detergents of claim 1 which are solid detergents, wherein the polyelectrolyte has an apparent chelation value of at least 350, and wherein the weight ratio of citrate to polyelectrolyte is between about 2:1 and 10:1.
• Detergents of claim 2 which are solid machine dishwashing detergents, which have a pH at a 1% concentration in water of at least 10.0, and which contain less than 5% by weight of alkali metal polyphosphate.
• alkaline detergent salt which may include not more than 10% by weight of alkali metal polyphosphate
• chlorine releasing agent selected from the group consisting of polychlorisocyanuric acids and their salts
• compositions being free of alkyl benzene sulfonates.
• said citric acid salt is sodium citrate
• said detergent salt includes soda ash
• said chlorine releasing agent is sodium dichloroisocyanuate
• said detergent includes a defoaming polyoxyalkylene polymer
• composition is free of alkali metal polyphosphates.
• Liquid detergent compositions which consist essentially of:
• ⁇ (c) about 35% of a 50% aqueous solution of sodium hydroxide

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

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Cited By (33)

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• 1970
  • 1970-09-25 US US75676A patent/US3700599A/en not_active Expired - Lifetime
• 1971
  • 1971-09-03 CA CA122,113A patent/CA942153A/en not_active Expired
  • 1971-09-14 GB GB4282271A patent/GB1344157A/en not_active Expired
  • 1971-09-16 DE DE19712146276 patent/DE2146276A1/de active Pending
  • 1971-09-20 SE SE7111898A patent/SE382225C/sv unknown
  • 1971-09-24 FR FR7134540A patent/FR2108564A5/fr not_active Expired
  • 1971-09-25 JP JP46074947A patent/JPS523409B1/ja active Pending

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