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
  • C11D3/37—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
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/08—Silicates

Definitions

• a dishwashing detergent composition for use in dishwashing machines consisting essentially of (a) about 90%5% by weight of a water soluble alkali silicate, and (b) about 5%9 0% by weight of a polyhydroxycarboxylic acid containing carboxyl or carboxylate groups and hydroxyl groups, as well as specified polymer units.
• the composition can contain various other ingredients.
• This invention relates to a dishwashing detergent composition for use in a dishwashing machine. More particularly, it relates to a dishwashing detergent composition containing a water soluble alkali silicate and a polyhydroxycarboxylic acid.
• Dishwashing detergent compositions for use in automatic dishwashing machines are usually alkaline mixtures of certain cleaning agents, such as polyphosphates, silicates, alkali carbonates or alkali hydroxides.
• the dishwashing detergents containing the phosphates generally produce aqueous solutions having an alkaline pH. These detergents have good cleansing power, but are slightly corrosive when some sensitive objects to be washed are contacted with them. Furthermore, they have not proved entirely satisfactory for cleansing objects soiled with burnt food scraps or starch-containing deposits. The burnt food scraps are generally found on pots and pans used as cooking utensils. Additionally, there presently exists uncertainty as to the environmental effects of the phosphate containing detergents. For example, it has been alleged that the use of phosphate detergents is responsible in large part for the pollution of water supplies. Although this question has not been completely resolved, a few states are considering measures to be taken to prohibit the use of phosphate-containing detergent compositions.
• strongly alkaline cleansing agents which generally contain the alkali carbonates or alkali hydroxides exhibit relatively strong cleansing power, but also exhibit an increased corrosion effect on glass and decorated utensils.
• glass or ceramic dishes, cups, plates, etc. are frequently decorated with a glaze which is subject to attack by the strongly alkaline detergents.
• dishwashing detergent composition for use in dishwashing machines having increased cleansing power and useful on the difiicult-to-remove food residues, such as burnt foods, protein containing food scraps, starches, and stains from tea leaves and coffee grounds.
• the dishwashing detergent should be less corrosive than at least some of the prior art compositions.
• the detergent should either be free of phosphates or have a greatly reduced phosphate content.
• this invention provides a dishwashing detergent composition for use in dishwashing machines wherein the composition consists essentially of about 90%-5% by weight of a water soluble alkali silicate and about 5%-90% by weight of a polyhydroxycarboxylic acid containing carboxyl or carboxylate groups and bydroxyl groups.
• the alkali silicate and polyhydroxycarboxylic acid are in a weight ratio of about l/0.5-l/ 18.
• the acid is a cross-linked or non-cross-linked polymer having predominantly CC bonds in a main polymer chain. If the polymer chain contains side chains, at least some of the side chains contain vinyl or carbonyl groups.
• the polymers are built predominantly from units of formulas I and II and/or III.
• frequency of all such units in the polymer is such that the molar ratio of carboxyl or carboxylate groups in the polymer to hydroxyl groups in the polymer is about 1.1/1-16/1, preferably about 2/1-9/1.
• the degree of polymerization of the polymer is about 3-5,000, preferably about 3-600.
• polyhydroxycarboxylic acid means a solid cross-linked or non-cross-linked hydroxycarboxylic acid polymer.
• Another preferred dishwashing detergent composition contains a polymer having a small number (relative to units of I, II and III) of units of formula IV.
• each R radical in each unit is independently selected from hydrogen or a C -C alkyl radical. Any units of formulas I, II, III and IV present in the polymer can be arranged in any desired sequence. The degree of polymerization and the molar ratio of carboxyl or carboxylate groups to hydroxyl groups is the same as that specified above.
• each R and each R in each unit is independently selected from hydrogen or a methyl radical. It is also preferred that the dishwashing detergent composition contain a polymer having at least one unit of formula I in which at least one R is chlorine.
• the units of formulas I and IV can be present as free acids or in the form of water soluble salts.
• the detergent compositions of this invention can also contain the customary detergent additives, such as alkalies, slightly foaming non-ionic surfactants, chlorine separating compounds, enzymes, complexing agents, etc.
• customary detergent additives such as alkalies, slightly foaming non-ionic surfactants, chlorine separating compounds, enzymes, complexing agents, etc.
• the preferred formulas for detergent compositions are set forth below.
• a particularly preferred dishwashing detergent composition has about the following formula:
• a slightly foaming, non-ionic surfactant selected from the group consisting of alkylene oxide adducts of higher fatty alcohols or alkyl phenols having about 10-18 carbon atoms, preferably 12-18 1.... t I. . ⁇ .M .ha.
• a complexing agent selected from the group consisting of the hydroxy polycarboxylic acids, amino polycarboxylic acids, amino polyphosphonic acids and hydroxy alkane phosphonic acids, as well as their water soluble salts and further in which the ratio of alkali silicate to polyhydroxycarboxylic acid is about l/0.5-l/l8.
• the detergent composition of this invention can be adapted to the various purposes and requirements of use.
• a composition which develops a particularly strong cleaning effect against protein containing burnt scraps of food has about the following composition:
• a slightly foaming nonionic surfactant selected from the group consisting of alkylene oxide adducts of higher fatty alcohols having about 12-18 carbon atoms, alkylene oxide adducts of alkyl phenols with 12-18 carbon atoms, or alkylene oxide adducts of polypropylene glycol having a molecular weight of about 900-4000, and
• composition particularly effective for removing starch-containing residues, the following composition is preferred:
• an enzyme or enzyme mixture selected from the group consisting of hydrolases, preferably amylases, proteases and lipases,
• a complexing agent selected from the group consisting of the hydroxypolycarboxylic acids, amino-polycarboxylic acids, amino polyphosphonic acids and hydroxy alkane phosphonic acids, as well as their water soluble salts,
• compositions of above mentioned formulas are generally solid, lumpy or powdery cleaning agents, a liquid, slurry or paste mixture which can be dosed automatically can be used.
• a preferred formula consists essentially of:
• the ratio of alkali silicate to polyhydroxycarboxylic acid is about l/0.5-1/18.
• the polyhydroxycarboxylic acids suitable for use in this invention are described in German published appli cation 1,904,941 (U.S. Application S.N. 7,251, filed Jan. 30, 1970 now U.S. Pat. No. 3,686,145).
• the polyhydroxycarboxylic acids can be produced by known methods. For example, they can be obtained by capolymerizing acrolein, acrylic acid or substituted acrylic acids in the presence of radical catalysts or redox catalysts and by subsequent conversion according to a Cannizzaro reaction. Also, they can be obtained by copolymerizing substituted or unsubstituted acrylic acids with allyl alcohol.
• They can also be produced by saponification of copolymers of acrylic acid esters and esters of vinyl alcohol or their derivatives such as acrylonitrile. Also, they can be produced by the oxidation of copolymers of acrolein with allyl alcohol or its derivatives, or with vinyl alcohol derivatives. They can also be produced by the cyclopolymerization of allyl acrylate, the cyclopolymerization of allyl acrylate with acrylic acids and simultaneous saponification, as well as the partial oxidation of polyacrolein, or its homoor copolymerizates and subsequent conversion according to a Cannizzaro reaction. Basically, all polyrnerization processes are suitable, for example, precipitation, solution polymerization, bulk polymerization, etc.
• the preferred polyhydroxycarboxylic acids are those that can be produced by theoxidative polymerization of acrolein, and subsequent treatment of the resulting polymerizate with a strong base according to a Cannizzaro reaction.
• Preferred strong bases are the alkali hydroxides.
• the preferred polyhydroxycarboxylic acids can optionally contain small quantities of units of the formulas V and VI:
• Polyhydroxycarboxylic acids containing unts of these formulas are obtained when conversion is carried out in the presence of formaldehyde and according to the Cannizzaro reaction.
• the water soluble salts of the polyhydroxycarboxylic acids can also be used in the novel dishwashing detergent of this invention.
• the preferred salts are the alkali salts. Sodium salts and ammonium salts are particularly preferred.
• the polymers can have vinyl or carbonyl groups in sidechains in minor amounts relative to the amounts of the units identified as (I), (II) and (III) above.
• oxidation agents peroxides or peracids may be used. Preferred is the oxidation with H 0
• the oxidation polymerization it is possible to adjust the ratio of carboxyl to carbonyl groups by the ratio of oxidizing agent to amount of acrolein. The higher this ratio, the larger will be the number of carboxyl groups in the final polymer, and conversely. Since the peroxide compound also acts as chain-regulating agent, it will be understood that the degree of polymerization will be controlled also by the amount of oxidizing agent. The degree of polymerization decreases with an increasing amount of oxidizing agent and conversely.
• the oxidation polymerization of the acrolein can also be carried out in the presence of other copolymerizable monomers in virtually any desired amounts.
• the use of acrylic acid is preferred since this will directly influence the contents of carboxyl groups in the polymer.
• the acrylic acid content in the starting product also affects the degree of polymerization in that this degree increases with the content of acrylic acid.
• the homoor copolymerization of the acrolein can be carried out, depending on the desired contents of carboxyl groups in the final polymer, both in solution and as precipitation polymerization and, preferably, in an aqueous medium. If peroxy compounds are used as oxidation agents, it is preferred, first, to introduce these compounds and, if desired, the comonomer or a part thereof into an aqueous solution or suspension, and to add the acrolein and, if desired, the residual comonomer only at an increased temperature of, for instance, between 50 and 100 C.
• the polymers obtained can be used, if desired, directly for further reactions preferably after concentration of the solution. It is advisable in this case to destroy any residual amounts of oxidizing agent that may be present in the solution, for instance by addition of small amounts of MnO or activated carbon. It is, however, also possible to precipitate the solution polymers from the mass by means of a dilute acid, for instance hydrochloric acid. In this operation the remaining monomers can be recovered, for instance by distillation, directly from the reaction mass. The distillation residue in this case constitutes a highly con centrated, aqueous solution of the polymer which can be used for further reaction.
• the polymerization is carried out as a precipitation polymerization, it is easy to separate the polymers by filtration.
• the residual monomers in the filtrate can then be used for further purposes in the form in which they are present in the filtrate.
• the precipitation polymer can be purified with water or, if desired, by passing air therethrough.
• the thus-obtained polyaldehydro-carboxylic acids can be further reacted in an aqueous solution or suspension with a strong base, in the presence of formaldehyde if desired.
• This can be carried out by using the formaldehyde in about the stoichiometric amount relative to the aldehyde groups which are present in the polymer and by stirring for an extended period of time at room temperature or at an elevated temperature up to about 100 C. After 2 hours, the yield is already about 60-70%, and within 24 hours will increase to 90l00%.
• the Cannizzaro reaction may be carried out much more rapidly by selecting suitable conditions, and this particularly in the case of the reaction with water-soluble polyaldehydocarboxylic acids.
• the reaction in solution results in solutions which, in addition to the salts of the hydroxycarboxylic acid polymers, contain an excess of a base. They can be concentrated by evaporation to dryness.
• the thus-obtained salt can be used directly as complexing agent.
• the salts are obtained in a particularly pure form.
• the solution may also be neutralized prior to evaporation with a dilute acid such as hydrochloric acid, or the free acid may be precipitated.
• the course of the Cannizzaro reaction may be controlled in such a manner that eventually virtually neutral salt solutions are ob tained. This can be accomplinhed by selecting the amount of added base in such a manner that the excess of base decreases with continuing reaction, and finally, at the end of the reaction, just reaches zero.
• the neutralization of the excess base should be ef fected only with a type of acid of which the salts do not interfere in the use of the polymers.
• a type of acid of which the salts do not interfere in the use of the polymers is, for instance, carbon dioxide.
• the hydroxycarboxylic acids which are used for the neutralization can, for instance, be precipitation polymers obtained as described above. They can easily be precipitated from the solutions obtained in the reactions by means of a dilute acid.
• the polymers of the invention predominantly have carbon-to-carbon bonds in the main chain.
• the polymers predominantly consist of the aboveidentified units (I) and (II) and/or (III). These units are the main portion of the main chain which is predominantly formed by carbon-to-carbon bonds. They are in part formed when the polyaldehydrocarboxylic acid is sub jected to the Cannizzaro reaction. In this reaction, there may however also be formed intermolecular aldol condensation between the active CH groups which are uorientcd relative to the aldehyde groups in the polyaldehydrocarboxylic acid and, on the other hand, the carbonyl groups of one or several adjacent chains. In this way there result cross-linking connections.
• Units of the type (V) and (VI) form if the reaction of the polyaldehydrocarboxylic acids is carried out with a strong base by the Cannizzaro method in the presence of formaldehyde.
• the amount of aldehyde in this case will control the degree of cross-linking.
• the polyhydroxycarboxylic acids used in the detergent composition of this invention are substitutes for the phosphates used in conventional detergents. It will, of course, be understood that the polyhydroxycarboxylic acids can be replaced in part by alkali phosphates or alkali poly phosphates to reduce the cost of the detergent composition. Sodium hexametaphosphate or pentasodium-triphos phate are typical of the phosphate substitutes which can be used in the composition of this invention These phosphates are customarily used in detergents.
• the detergent composition of this invention also core tains a water soluble alkali silicate.
• Sodium or potassium metasilicates are preferred water soluble alkali silicates. When using sodium or potassium metasilicates, it is par ticularly preferred that the ratio of alkali oxides to silicon dioxide is of l/0.5-1/3.5.
• Alkali hydroxide or alkali carbonates can be used along with or in place of some of the soluble alkali silicates. Sodium hydroxide, potassium hydroxide and their corresponding carbonates are preferred. However, not more than 30 percent by weight of the alkali silicate is to be replaced by an alkali hydroxide since the more strongly alkaline solutions obtained exhibit a more corrosive effect on the objects being cleaned.
• the wetting effect of the detergent composition can be improved by the addition of a slightly foaming nonionic surfactant.
• Examples of compounds suitable for the addition reaction are the adduct of l%-30% by weight ethylene oxide and a polypropylene glycol having a molecular weight of about 1,750, the adduct of moles ethylene oxide or 9 moles ethylene oxide and 10 moles propylene oxide with nonyl phenol, the adduct of S-l2 moles ethylene oxide and a fatty alcohol mixture having chain lengths of C -Cu containing about by weight oleoyl alcohol, and the like.
• chlorine releasing compounds include the alkali salts of iso'cyanuric acids, for example potassium dichloroisocyanurate, the alkali hypochlorites, for example lithium or sodium hypochlorite, and complex salts containing hypochlorite, for example, the so-called chlorinated phosphates.
• enzymes suitable for use in the detergent composition are those derived from animal or plant materials, especially digestive ferments, yeasts and strains of bacteria. In most instances they represent a complex mixture of various enzymatic agents. Enzymes or enzyme mixtures selected from the group of hydrolases are preferred. Particularly preferred are the amylases, protease and lipases which cleave starch, albumin or fats.
• the enzymes can be produced from strains of bacterial fungi, yeasts, or animal organs by methods well-known in the art. Enzyme mixtures have been found to be particularly effective against starch and albumin-containing food deposits. Enzymes obtained from Bacillus sublilis are particularly suitable for use in the dishwashing detergents.
• Such enzymes are relatively stable in the presence of al- -kalis, and retain their activity at temperatures between Complexing agents can be used as buffering agents and water softening agents.
• Typical of the complexing agents which can be used are hydroxycarboxylic acids, such as citric acid and tartaric acid, the amino polycarboxylic 'acids, such as amino triacetic acid, ethylene diamino tetracetic acid, amino tri-(methylene phosphonic acid), ethylene diaminotetra-(methylene phosphonic acid), 1- hydroxyethane-l,l-diphosphonic acid as well as the higher homologues of the above-mentioned polyphosphonic acids.
• the water soluble salts such as the potassium and sodium salts, can be used instead of the free acids.
• the detergent composition can contain other components, especially inorganic salts such as sodium sulphate or sodium chloride which act as detergent agents.
• inorganic salts such as sodium sulphate or sodium chloride which act as detergent agents.
• Other possible additives include substances which have a buffering effect, dyes, perfumes, enzyme activating additives, such as ammonium chloride, etc.
• the dishwashing detergent composition of this invention When the dishwashing detergent composition of this invention is in the form of a solid or powder, it can be finished by grinding or mixing the various components by methods well known in the art. In order to obtain an intimate mixture of powdery components, it is preferable to spray the powder during or after the mixing process with an aqueous solution of crystallizing salts. For example, sodium sulphate or one of the aforementioned nonionic surfactants can be used. Such a treatment also improves the dusting characteristics of the powdery detergent composition.
• the dishwashing detergent composition can be used in liquid form by dissolving the individual components in water and mixing the resulting solution. Dissolution of some components, particularly the organic components, can be aided by the use of other solvents, such as ethanol, propynol or isopropynol.
• the viscosity can be adjusted with water soluble polymeric compounds, such as methyl cellulose, carboxymethylcellulose, or polyacrylates.
• the liquid or paste-like detergent compositions are preferably sold as commercial concentrates having about 14%- 70% by weight solid substances, preferably about 20%- 50% by weight.
• the dishwashing detergent composition can be used in domestic dishwashers as well as in commercial dishwashing machines. Addition of the detergent to the machine can be made by hand or by means of suitable dosing devices. Liquid concentrates are particularly suitable for use in automatic liquid dosing devices conventionally used. When a solid or powdery detergent composition is used, the concentration of detergent in water during the washing cycle should be about 0.5-10 g./liter, preferably 2-5 g./ liter. When liquid detergent compositions are used, the amount employed should be sufficient to provide about 6-10 g./liter. The cleaning liquors should have a pH of about 7-12, preferably about 8-11.
• the machine washing cycle is generally followed by a few rinsing cycles using clear water. During the rinsing cycle, conventional rinsing agents can be used. After drying, clean dishes and utensils having excellent hygienic qualities are obtained.
• the dishwashing detergent composition of this inven tion exhibits excellent cleaning capacity. It i particularly suitable for removing protein-containing burnt scraps of food, traces of lipstick, tea stains, and coffee grounds.
• the compositions containing enzymes or enzyme mixtures are excellent for removing starch from the surfaces of dishes and cooking utensils, and prevent the development of starch coatings.
• the low corrosive effect of the composi tions of this invention make them particularly suitable for use on utensils having a porcelain glaze.
• water pollution problems attributable to the use of phosphates in detergents are minimized because of the greatly reduced, or in some cases the total absence, of phosphates.
• the detergent compositions contain polyhydroxycarboxylic acids, which can be prepared according to Preparatron I or analogous methods.
• the carboxyl and hydroxyl content of the acids is expressed as a percentage, and refers to the number of COOH or OH groups per monomer units in the polymer molecule.
• Example 1 To check the cleaning results of the cleaning mixtures claimed, glass dishes with burnt scraps of food, milk, chocolate pudding and minced meat are treated in a household dishwasher with 3 g. detergent per liter of washing liquor in the cleaning cycle.
• the food deposits are selected in such a way that their removal is possible only with detergents which have an especially high cleaning power. Washing is accomplished with a detergent having the following composition:
• Example 2 Washing is accomplished under the conditions of Example 1 with 3 g./ liter of the following cleaning mixture:
• Example 3 Washing is accomplished as in Example 1 with 3 g./liter of the following composition:
• Example 4 Washing is accomplished as in Example 1 with 3 g./ liter of the following cleaning composition:
• Example A cleaning mixture of the following composition is used in a household dishwasher at a concentration of 3 g./literi (a) 30% sodium metasilicate having a ratio of sodium oxide to silicon dioxide of 1:135,
• Example 6 The following cleaning mixture is used in a commercial dishwasher in a concentration of 3 g./ liter:
• Example 7 The washing is accomplished with 3 g./liter of the following cleaning composition:
• the cleaning performance must be considered excellent.
• Example 8 Washing is accomplished with 3 g./liter of the following cleaning composition:
• Example 11 A cleaning experiment is made with 9 g./liter of a liquid cleaner having the following composition:
• the cleaning result must be designated as optimum.
• Example 12 Pattern tests are conducted according to German Standard DIN 51035.
• dishwashing agents do not attack too strongly the glazed patterns and colors on dishes.
• the determination of effectiveness of washing agents is made according to German Standard 51035, Determination of the Resistance of Fired Glazed Pattern Colors and Decorations to Alkaline Cleaning Agents. The test is accomplished by treatment with a 1% trisodium phosphate solution at boiling temperature and for 30 minutes. The attack on glazed pattern colors achieved with this test can be considered to be equivalent to about 5000 wash cycles in a dishwasher.
• Example 9 Washing is accomplished with 3 g./liter of the following cleaning composition:
• Cups with dried tea leaves and coffee grounds are washed with 2 g./liter of a mixture of 2 parts sodium salt of polyhydroxycarboxylic acid A and one part sodium metasilicate having a ratio of sodium oxide to silicon dioxide of 1:1.25.
• a dishwashing detergent composition for use in dishwashing machines said composition consisting essentially of:
• polyhydroxycarboxyh ic acid or a water soluble sodium salt thereof containing carboxyl or carboxylate groups and hydroxyl groups
• said polyhydroxycarboxylic acid being a cross-linked or noncross-linked polymer having predominantly CC bonds in the main polymer chain and vinyl or carbonyl groups in at least some of any side chains, said polymer consisting essentially of predominantly units of formulas I and II or I and III or I and II and III:
• each R and each R, in each unit is independently selected from hydrogen and a.
• C -C alkyl radical, or at least one R is a chlorine atom
• any units of formulas I, II and Ill present in the polymer are arranged in any desired sequence, the average frequency of all said units in the polymer corresponding to a molar ratio .of carboxyl or carboxylate groups in the polymer to hydroxyl groups in the polymer of about 1.1/1-16/1, said polymer having a degree of in which each R radical in each unit is independently selected from hydrogen or a C -C alkyl radical, and any units of formulas I, II, III and IV present in the polymer are arranged in any desired sequence, and the frequency of all units in the polymer corresponds to a molar ratio of carboxyl or carboxylate groups in the polymer to
• Dishwashing detergent composition of claim 3 in which the molar ratio of carboxyl or carboxylate groups to hydroxyl groups is about 2/1-9/1 and the degree of polymerization is about 3-600.
• Dishwashing detergent composition of claim 4 in which the molar ratio of carboxyl or carboxylate groups to hydroxyl groups is about 2/1-9/1 and the degree of polymerization is about 3-600.
• Dishwashing detergent composition of claim 1 consisting essentially of:
• a slightly foaming nonionic surfactant selected from the group consisting of the adduct of lO%-30% by weight ethylene oxide and a polypropylene glycol having a molecular weight of about 1,750, the adduct of 20 moles ethylene oxide or 9 moles ethylene oxide and 10 moles propylene oxide with nonyl phenol, the adduct of -12 moles ethylene oxide and a fatty alcohol mixture having chain lengths of C -C containing about 30% by weight oleoyl alcohol, an adduct of 30 mole percent of ethylene oxide with a polypropylene glycol having a molecular weight of 900, and an adduct of 5 moles ethylene oxide with an unsaturated fatty alcohol mixture with chain lengths of C -C (e) about 0-10% by weight of an active chlorine releasing compound selected from the group consisting of alkali salts of isocyanuric acid, alkali hypochlorites and chlor
• ratio of alkali silicate to polyhydroxycarboxylic acid is about 1/0.5-1/18.
• Dishwashing detergent composition of Claim 8 con sisting essentially of:
• Dishwashing detergent composition of claim 9 in which the composition is a solid or powder.
• a solid or powdery dishwashing detergent composition of claim 8 consisting essentially of:
• ratio of alkali silicate to polyhydroxycarboxlyic acid is about l/4-l/l8.
• Dishwashing detergent composition of claim 12 containing an enzyme with amylolytic or proteolytic activity, said enzyme obtained from Bacillus subtilis.
• a liquid dishwashing detergent composition of claim 8 consisting essentially of:
• Dishwashing detergent composition of claim 1 in which the soluble alkali silicate contains an alkali oxide and silicon dioxide in a weight ratio of about l/0.5-l/3.5.
• Dishwashing detergent composition of claim I. which produces a pH value of about 7-12 in a dilute aqueous solution

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• Chemical & Material Sciences (AREA)
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• Engineering & Computer Science (AREA)
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• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
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Cited By (19)

Families Citing this family (2)

• 1971
  • 1971-01-14 DE DE2101508A patent/DE2101508C3/de not_active Expired
• 1972
  • 1972-01-13 GB GB165672A patent/GB1357826A/en not_active Expired
  • 1972-01-13 US US00217649A patent/US3825498A/en not_active Expired - Lifetime

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