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
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
  • C11D3/38618—Protease or amylase in liquid compositions only
• • 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
  • C11D1/29—Sulfates of polyoxyalkylene ethers
• • 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
  • C11D1/37—Mixtures of compounds all of which are anionic
• • 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
  • C11D1/66—Non-ionic 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/83—Mixtures of non-ionic with anionic 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
  • C11D3/16—Organic compounds
  • C11D3/38—Products with no well-defined composition, e.g. natural products
  • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
  • C11D3/38663—Stabilised liquid enzyme compositions

Definitions

• ..Clld l/37, c1 1d l/83 about 2 percent to about 30 percent of an othoxylated alcohol [58] Field of Search ..252/D1G. 12, 532, 533, 536, or alkyl Phenol of sulfate thereof; and fmm 0.001 P"- cent to about 5.0 percent of enzyme.
• the detergent compositions have desirable enzyme activity upon storage and exhibit desirable levels of soil-removal performance.
• compositions can; among others, be in liquid state but in that event, they contain alcohol in admixture with nonionics as stabilizing agent for the amylolytic activity.
• alcohols if desired, in admixture with nonionics as stabilizing agents for certain enzymes is also known from Dutch Pat. application No. 68.16356. 7
• inventive liquid detergent compositions can be prepared having an unexpected storage stability and an unforeseeable soil-removal performance versus what can be obtained from enzyme-containing liquid detergent compositions currently known.
• inventive liquid detergent compositions comprise a mixture of a. from about 2 percent to about 35 percent by weight of alkane sulfonates or alpha-olefin sulfonates or mixtures thereof, both having from about 10 about 26 carbon atoms in the hydrocarbon chain;
• A represents an alkyl chain with from eight to 30 carbon atoms or an alkyl phenyl with from three to 22 carbon atoms in the alkyl chain;
• B an alkyleneoxy radical, n an integer from one to 30 and
• X represents either hydroxyl, or a sulfate radical;
• Ingredient AE,,X should be present in an amount from about 2 percent to about 30 percent by weight and preferably from about 5 percent to about percent by weight.
• the lower limit reflects'minimum perceptible performance while the 30 percent upper limit has been set so that any additional incorporation of AE,,X is only likely to result in an expected performance increase.
• the radical A can be an alkyl chain with from about eight to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms.
• A is an alkyl phenyl radical
• the alkyl group should contain from about three to about 22 carbon atoms, and preferably from about six to about 12 carbon atoms.
• E represents a poly(alkyleneoxy) radical preferably derived from ethylene oxide or propylene oxide or mixtures of both, while n stands for an integer in the range from one to 30, preferably two to 18.
• X represents either a hydroxyl or a sulfate radical.
• the preferred surface-active agents suitable for being used in the compositions claimed are derived from the condensation products of fatty alcohols with from about two to about 18 moles of ethylene oxide, either bearing a terminal hydroxyl radical or being present in its sulfated form. Particularly preferred are the alkali metal and ammonium salts of the sulfated condensation product of one mole of a mixture of straight chain C to C alcohols with three moles of ethylene oxide.
• the percent compositions should contain from about 2 percent to about 35 percent by weight, preferably from about 10 percent to about 25 percent by weight, of alkane sulfonates or alpha-olefin sulfonates or mixtures thereof, both having from about 10 to about 26 carbon atoms, preferably from about 12 to about 20 carbon atoms in the hydrocarbon chain.
• alkane sulfonates paraffin sulfonates
• the reaction product obtained from that process after neutralization and purification steps at temperatures in the range from 200 C to 300 C is present as an anhydrous melt having about the following compositions: alkane mono-sulfonates, from 81 to 83 percent; alkane disulfonates, from 10 to 12 percent; non-reacted paraffin, 1 percent; sodium sulfate, about 6 percent.
• the preferred alkane sulfonate of this invention has the following chain distribution: C alkane sulfonate: 5 percent; C alkane sulfonate: 16 percent; C alkane sulfonate: 30 percent; C alkanesulfonate: 30 percent; C alkane sulfonate: 15 percent; C alkane sulfonate: 4 percent.
• the alkane sulfonates used in all the Examples correspond to this composition.
• the preferred olefin sulfonate actives are described in detail in U.S. Pat. No. 3,332,880 issued July 25, 1967 to Kessler et a1. They consist of a mixture of from about 30 to 70 percent of Component A, preferably 35 to 65 percent; about 20 to 70 percent of Component B, preferably 25 to 60 percent; and about 2 to 15 percent of Component C, preferably 3 to 12 percent.
• Component A is a mixture of double-bond positional isomers of water-soluble salts of alkene-l-sulfonic acids containing from about 10 to about 24 carbon atoms, said mixture of positional isomers including about 10 percent to about 25 percent of an alpha-beta unsaturated isomer, about 30 percent to about 70 percent of a beta-gamma unsaturated isomer, about 5 percent to about 25 percent of a gamma-delta unsaturated isomer, and about 5 percent to about 10 percent of a delta-epsilon unsaturated isomer.
• Component B is a mixture of water-soluble salts of bifunctionally-substituted sulfur-containing saturated aliphatic compounds containing from about 10 to about 24 carbon atoms, the functional units being hydroxy and sulfonate radicals with the sulfonate radical always being on the terminal carbon and the hydroxyl radical being attached to a carbon atom at least two carbon atoms removed from the terminal carbon atom, at least percent of the hydroxy radical substitutions being in the 3, 4-, and 5-- positions.
• Component C is a mixture comprising from about 30 percent to percent water-soluble salts of alkene disulfonates containing from about 10 to about 24 carbon atoms, and from about 5 percent to about 70 percent watersoluble salts of hydroxy disulfonates containing from about 10 to about 24 carbon atoms, said alkene disulfonates containing a sulfonate group attached to a terminal carbon atom and a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, the alkene double bond being distributed between the terminal carbon atom and about the seventh carbon atom, said hydroxy disulfonates being saturated aliphatic compounds having a sulfonate radical attached to a terminal carbon, a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, and a hydroxy group attached to a carbon atom which is not more than about four carbon atoms removed from the
• the enzymes suitable for being incorporated into the inventive compositions can be of any origin, although they are mostly of animal and vegetable and particularly of bacterial origin.
• the enzyme preparations considered are mostly constituted by a mixture of different active substances all of which are characterized by a very specific enzymatic activity. They can be classified according to their activity. Examples of such sub-classes of enzymes are proteases, carbohydrases, esterases, oxydo-reductases, catalysases, peroxydases, ureases, demolases, isomerases, nucleases and so on.
• commercial enzyme preparations are seldom pure but constitute a mixture of different types of enzymes.
• a preferred enzyme component is a proteolytic enzyme, a serine protease. It is commercially available under the tradename of ALCALASE' and manufactured by Novo lndustri A/S, Copenhagen, Denmark.
• Other enzyme preparations being almost identical to ALCALASE for use in the detergent compositions of this invention are:
• proteolytic enzyme derived from the genus Bacillus; this component is described in US. Pat. application Ser. No. 761,546, filed on Sept. 23, 1968, and has been deposited under the number 147 with The National Collection of Industrial Bacteria, Torry Research Station, Aberdeen Scotland.
• protease mixture derived from Bacillus subtilis as sold by KALl CHEMIE, Germany.
• the enzyme is to be used in a quantity of from about 0.005 percent to about 5 percent by weight of the composition.
• a preferred range includes a quantity of from about 0.1 percent to about l.5 percent by weight of the enzyme preparation.
• Several non-proteolytic enzyme components can be mixed in wide ranges with the proteases species for use in the preferred embodiments of this invention. So for example, amylolytic enzyme preparations can advantageously be added.
• inventive compositions can contain usual amounts of other ingredients and/or minor additives, all having well-defined functions in detergent technology and all being frequently present in the type of detergent compositions claimed. So, these compositions can contain solubilizing compounds which contribute in maintaining a uniform liquid detergent composition even during prolonged storage. From zero to percent of the solubilizing compounds are usually incorporated into liquid detergent compositions.
• Typical examples suitable for the compositions claimed are the sodium salts of benzene sulfonate, toluene sulfonate, and xylene sulfonate. Lower alcohols can also satisfactorily be used, preferably those having from one through five carbon atoms.
• Alkaline detergent builders can be employed in the compositions of this invention. In the event such builders are employed, their quantity does not normally exceed 20 percent because of the phase-stability problem which might flow from the use of higher quantities.
• Specific examples of inorganic builders suitable for use herein are alkali metal carbonates, phosphates, polyphosphates and silicates. The potassium and sodium salts of these builders are, for solubility reasons, the most suitable ones.
• Useful alkaline organic builders include the polyphosphonates, poly-acetates and polycarboxylates. Examples of polyphosphonates include the sodium and potassium salts of ethylene diphosphonic acid, ethane-l-hydroxy- 1,1-diphosphonic acid and ethane-l,l,2-triphosphonic acid.
• Polyacetate builders useful herein include the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diamine tetra-acetic acid; N-(2-hydroxyethyl)- ethylene diamine triacetic acid; N-(2-hydroxyethyl)-nitrilo diacetic acid; diethylenetriamine; and pentacetic acid.
• Watersoluble salts of polycarboxylate builders can also be used in these compositions. They are described in more detail in Us. Pat. No. 3,308,067.
• Enzyme-stabilizing agents in a quantity from 0 to 5 percent can also be used in the liquid detergent compositions of this invention. They have been found to be quite useful as they tend to improve the performance and particularly the storage stability advantages obtainable from the liquid detergent compositions claimed. Water-soluble calcium and magnesium chlorides, lactates and acetates represent the preferred stabilizing agents.
• liquid detergent compositions of the present invention can also contain other usual detergents additives not specifically referred to hereinbefore.
• perfumes, anti-tarnishing agents, anti-redisposition agents, bacteriostatic agents, dyes, optical brighteners, fiuorescers, suds depressors, suds boosters and the like can all be utilized herein without detracting from the advantageous stability and performance properties of the compositions of this invention.
• the enzymatic activity can advantageously be expressed as a cleaning index" (Cl) corresponding to the following definition:
• test conditions are as indicated in Example 1 except for what concerns the product concentration in solution which is 0.25 percent by weight.
• alkanesulfonate-Na C 20% by weight sulfated (ethoxyk-coconut alcohol-Na 20% by weight
• the test conditions and the reference sample composition are the same as for Example I.
• the CI values confirm that the active system is efiective with difierent types of enzymes.
• Liquid detergent samples are stored during one week at 35 C. The enzymatic activity is determined before and after storage.
• AU/g pH of composition is within the range from 7.0 to 9.0 water: balance to 100.
• EXAMPLE Vl Liquid detergent compositions identical to those described in Example V, except that 0.5 percent by ,weight of Ca acetate is added, were used for comparative testing as indicated in Example V.
• the active composition used corresponds to composition (b) of Example V containing ALCALASE as enzyme preparation.
• pH liquid composition 7.0
• Stabilizer salt used in detergent at a level of 1.0 percent by weight.
• AU/g pH of composition is within the range from 7.0 to 9.0 water: balance to 100 ofinitial by wt. enzymatic actives in activity Active System detergent retained (a) Linear C alkylbenzenesulfonate Na salt 20 Condensate of tallow alcohol with 25 moles of ethylene oxide I0 75 (b) Alkane sulfonate Na salt (C 20 Condensate of tallow alcohol with 25 moles ethylene oxide l0 (c) Linear C alkylbenzenesulfonate Na salt 20 Condensate of nonylphenol with 9 moles of ethylene oxide I0 75 (d) Alkane sulfonate Na salt (C 20 Condensate of nonylphenol with 9 moles of ethylene oxide I0 90 (c) Alkane sulfonate Na salt (C l9 Sulfatcd (ethoxy), coconut alcohol Na salt [9 Coconut monoethanolamide 2 9O at is claimed is:
• said Component B is a mixture of water soluble salts of bifunctionally-substituted sulfur-containing saturated aliphatic compounds, containing from about 10 to about 24 carbon atoms, the functional units being hydroxy and sulfonate radicals with the sulfonate radical always being on the terminal carbon and the hydroxyl radical being attached to a carbon atom at least two carbon atoms removed from the terminal carbon atom, at least 90 percent of the hydroxy radical substitutions being in the three, four, and five positions; and
• said Component C is a mixture comprising from about 30 percent water soluble salts of alkene disulfonates containing from about 10 to about 24 carbon atoms, and from about 5 percent to about 70 percent water soluble salts of hydroxy disulfonates containing from about 10 to about 24 carbon atoms, said alkene disulfonates containing a sulfonate group attached to a terminal carbon atom and a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, the alkene double bond being distributed between the terminal carbon atom and about the seventh carbon atom, said hydroxy disulfonates being saturated aliphatic compounds having a sulfonate radical attached to a terminal carbon, a second sulfonate group attached to an internal carbon atom not more than about six carbon atoms removed from said terminal carbon atom, and a hydroxy group attached to a carbon atom which is not more than about four carbon atoms removed from
• component (a) is present in an amount from about 10 percent to about 25 percent and component (b) is present in an amount from about 5% to about 20 percent and wherein X is sulfate.
• component (b) has from l0 to 16 carbon atoms in the alkyl chain.
• liquid detergent composition of claim 1 wherein the alkane sulfonate or alphaolefin sulfonate has from 12 20 carbon atoms in the hydrocarbon chain.
• liquid detergent composition of claim 1 wherein the amount of proteolytic enzyme employed is from about 0.1 percent to about 2.0 percent.
• liquid detergent composition of claim 5 wherein the proteolytic enzyme is from Bacillus subtilis.

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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)
• Detergent Compositions (AREA)
• Enzymes And Modification Thereof (AREA)

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Cited By (31)

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Citations (3)

• 0
  • BE BE759360D patent/BE759360A/xx not_active IP Right Cessation
• 1969
  • 1969-11-25 LU LU59883D patent/LU59883A1/xx unknown
• 1970
  • 1970-11-20 US US91596A patent/US3676374A/en not_active Expired - Lifetime
  • 1970-11-24 FR FR7042173A patent/FR2072316A5/fr not_active Expired
  • 1970-11-24 AT AT1058670A patent/AT317395B/de not_active IP Right Cessation
  • 1970-11-24 SE SE7015905A patent/SE370721B/xx unknown
  • 1970-11-24 NL NL7017143.A patent/NL165784C/xx not_active IP Right Cessation
  • 1970-11-24 GB GB55828/70A patent/GB1291163A/en not_active Expired
  • 1970-11-24 DE DE19702057754 patent/DE2057754A1/de not_active Ceased
  • 1970-11-24 CA CA098,969A patent/CA941767A/en not_active Expired
  • 1970-11-25 CH CH1742470A patent/CH548446A/de not_active IP Right Cessation
  • 1970-11-25 JP JP45103986A patent/JPS4830646B1/ja active Pending

Patent Citations (3)

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