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
  • C11D3/38609—Protease or amylase in solid compositions only

Definitions

• ABSTRACT Detergent compositions which contain compounds bearing one or more sulfhydryl radicals as activators for enzymes which themselves do not contain sulfhydryl groups or disulfide bonds.
• proteolytic enzymes which do contain sulfhydryl groups or disulfide bonds are reactivable by adding a suitable reducing agent. So, e.g., it is known from U.S. Pat. No. 3,019,171 that cysteine an sodium thiosulfate are satisfactory for the activation of proteolytic enzymes containing sulfhydryl groups or disulfide bonds.
• Proteolytic enzymes as meant in this patent are represented by vegetable enzymes such as pinguanain, papain, ficin, bromelin, bromelain, and asclepain. From French patent No.
• activated protease can be used in detergent compositions; the activation is attained through the addition of hydrogen sulfide, thisolulfate or cyanic acid.
• the proteases utilized are of vegetable origin and also contain sulfhydryl groups or disulfide bonds. Similar disclosures are found in British patent No. 475,880 which refers to detergent compositions containing vegetable enzymes which are reactivatable through the addition of sodium sulfides or polysulfides.
• enzymes which do not contain sulfhydryl groups or disulfide bonds are neither readily oxidizable nor reducable.
• Enzymes encompassed within the scope of this invention can contain sulfur in a form which does not respond readily to an oxidative or reductive treatment as taught in the prior art.
• An example of this is AL- CALASE bearing a methionine rest which is not likely to be reactivated when submitted to a prior art treatment.
• the enhancing agents suitable for being incorporated into enzyme containing detergent compositions in accordance with this invention have to hear one or more sulfhydryl groups. They can be substituted by inorganic or organic radicals or by a mixture of both, although, those derived from organic radicals are preferred for various reasons.
• the enhancing agents of this invention are their improved odor acceptance and/Or solubility relative to e.g., alkali-, earth-alkali or metal sulfides or polysulfides which are therefore less desirable in detergent compositions.
• the enzymatic activity enhancement can be obtained with all commonly known sulfliydryl bearing compounds.
• activators within the scope of this invention are: cysteine hydrochloride, thioglycollic acid esters derived from C fatty alcohols, calcium-thio-glycolate and their equivalents; the particularly preferred activators are: cysteine, thioglycollic acid, thioglycollic acid esters derived from mC, C,, alcohols, thioglycerol, and their equivalents.
• the activator should preferably be incorporated in an amount from about 0.0l to about 10 percent by weight, calculated on the total detergent composition.
• the preferred usage range is from about 0.05 weight percent to about 5 weight percent and most preferably from about 0.2 to about 2 weight percent.
• the enzymatic activity enhancement is not noticeable when less than 0.0] weight percent are incorporated into the detergent formulation while no additional activity synergism can be obtained by adding more than 10 weight percent of the activator compound.
• the enzymes suitable for use should not contain sulfhydryl groups or disulfide bonds. They can be of any origin although these enzymes are mostly of bacterial Origin. Most of the enzymes of vegetal origin do bear sulfhydryl groups and/or disulfide bonds, e.g., papain.
• Preferred for use in the detergent compositions of this invention are the enzyme preparations commercially available under the trade names of AL- CALASE," manufactured by Novo Industry A/S, Copenhagen, Denmark and DA-l0," manufactured by Monsanto Chemical Company. ALCALASE is described, in a trade bulletin bearing that name which was published by Novo Industry A/S, as a proteolytic enzyme preparation manufactured by submerged fermentation of a special strain of bacillus .rubtilis.
• the active enzyme is to be used in a quantity of from about 0.005 weight percent to about 4 percent by weight of the composition. Preferred is a quantity of enzymes of from about 0.01 to about 0.02 weight percent.
• the detergent compositions of this invention can contain the usual mixtures of other ingredients which are currently incorporated into detergent compositions. So, e.g., organic detergents, builders, suds depressors, antiflocculating agents, brighteners, dyes, perfumes and so on can be used.
• Suitable detergent compounds for being employed in accordance with the present invention include:
• water-soluble soaps such as the sodium, potassium, am-
• monium and alkanolammonium salts of higher fatty acids C -C and, particularly sodium and potassium tallow and coconut soaps.
• anionic synthetic non-soap detergents being represented by the water-soluble salts of organic, sulfuric acid reaction products having in their molecular structure an alkyl radical containing from about eight to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals.
• sodium or potassium alkyl sulfates of alcohols derived from tallow or coconut oil straight or branched chain sodium or potassium alkyl benzene sulfonates, sodium alkyl glyceryl ether sulfonates, sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid esters of the reaction product of 1 mole of a higher fatty alcohol and about 1 to 6 moles of ethylene oxide; sodium or potassium alkyl phenol ethylene oxide ether sulfates with l to 10 units of ehtylene oxide per molecule and wherein the alkyl radicals contain from eight to 12 carbon atoms;
• Nonionic synthetic detergents are marketed under the tradename of PLURONlC;" they are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol.
• Alkylphenol-polyethylene oxide condensates being condensation products of alkyl phenols with 5 to 25 moles of ethylene oxide per mole of alkyl phenol.
• Long chain tertiary amine oxides such as dimethyldodecylamine oxide and bis-( Z-hydroxyethyl) dodecylamine oxide.
• ampholytic synthetic detergents sodium-3- dodecylaminopropionate and sodium-3-dodecylaminopropane sulfonate.
• Zwitterionic synthetic detergents are for example 3- (N,N-dirnethyl-N-hexadecylammonio) propanel -sulfonate and 3-(N,N-dimethyl-N-hexadecylammonio)-2- hydroxy propanel -sulfonate.
• Suitable organic detergents include sodium alkyl benzene sulfonate, sodium alkyl sulfate, and mixtures thereof wherein the alkyl group is of branched or straight chain configuration and contains about l0 to about 18 carbon atoms.
• alkaline builder salts which can be employed in the detergent compositions of the present invention are employed in an amount to provide, for example, a weight ratio of alkaline builder salt to organic detergent of about 20zi to 1:5.
• These builders can be selected from a wide variety of known inorganic or organic builder salts.
• Suitable alkaline, inorganic builder salts include the alkali metal carbonates, phosphates, polyphosphates and silicates.
• Suitable organic builder salts include the alkali metal, ammonium, and substituted ammonium polyphosphonates, polyacetates, and polycarboxylates.
• the polyphosphonates can be represented by the sodium and potassium salts of methylene diphosphonic acid-, ethylene diphosphonic acid-, ethane-l-hydroxy-l,l-diphosphonic acid and of ethanel,l,2-triphosphonic acid.
• polyacetate builders suitable for use herein include the water-soluble salts of ethylenediaminetetraacetic acid, N-(2-hydroxyethyl)-ethylenediaminetriacetic acid, N( 2-hydroxyethyl )-nitrilodiacetic acid, diethylenetriaminepentaacetic acid, 1,2-diaminocyclohexanetetracetic acid and nitrilotriacetic acid.
• the trisodium salts of the above acids are preferably utilized.
• polycarboxylate builder salts suitable for use herein consist of water-soluble salts of polymeric aliphatic polycarboxylic acids as described in US. Pat. No. 3,308,067 which is incorporated herein by reference.
• Bleaching compounds should preferably not be used in compositions in accordance with this invention, as there would certainly be a direct interference between the sulfhydryl bearing compounds and the bleaching compounds resulting in a deterioration of the activators before they are able to enhance the enzymatic activity.
• Bleaching compounds can be added, however, provided they are physically protected from contact with the other ingredients of the detergent composition and particularly from being in contact with the activators. This is possible if they, as an example, are contained in hermetically sealed packages whose walls are made of a material which is only soluble in the laundering solution at a temperature exceeding about 65 C. as they will not interfere with the enzymatic activity enhancement which occurs in a temperature range from about ambient temperature to about 65 C. above which latter temperature the enzymes tend to be deteriorated by heat. Obviously, the same result can be attained when the bleach compounds are coated with a thin-coating of an inert water-soluble material which does not dissolve at a temperature of below 65 C.
• the sulfitydryl bearing activators can be incorporated into detergent compositions by any of the techniques known to be satisfactory for this purpose. Examples of the various possibilities which might be applied satisfactorily are enumerated in what follows:
• the activators can, as such, or being encapsulated, be drymixed with the finished detergent composition.
• the encapsulation seems to be in order in the event the sulfhydryl bearing compound is represented by a liquid material which is likely to cause lumping to a solid detergent composition and also when the activator (solid or liquid) tends to lose its activity, due to oxidation or for other reasons during a prolonged storage.
• the encapsulating material should be neutral versus the activator, provide an adequately closed coating and also dissolve in aqueous laundering solutions at ambient temperature.
• activators would be in preparing coagglomerates by spraying water onto mixtures of hydratable carrier with the activator alone or in mixture with the enzymes, Acceptable results are also obtained in spraying a solution of activators on a carrier, or a previously prepared agglomerate of the enzyme and the carrier as described in Belgian patent No. 697,481. It is quite obvious that this latter technique would work as well when a solution containing both the activator and the enzyme are sprayed on the hydratable carrier.
• the carriers suitable for being utilized should be compatible with the enhancing agents, particularly with respect to storage stability of the activator. Any of these techniques is suitable for preparing the detergent compositions referred to in the examples.
• Detergent compositions (a) and (b) having the compositions as indicated hereafter are prepared by conventional spray-drying of all ingredients but the enzyme carrier agglomerate.
• the latter is prepared separately by spraying a suspension or a solution of the enzyme preparation onto sodium tripolyphosphate, thereby using the technique described in French Pat. No. 1,520,262, and admixed afterwards.
• the sulfhydryl containing activators are dry mixed with the finished detergent composition.
• the stain removal resulting from the soaking and washing tests, as described hereabove, are each time compared to the stain removal resulting from identical tests carried out in the absence of an activator for the enzymatic activity.
• the blood-ink-milk (Art. 1 l6) and cocoa (Art 1 l2) swatches are supplied by EMPA, St. Gallen. Switzerland.
• the milk-ink and egg-white-ink staining solutions are prepared by Stained swatches were washed in a T adding a 15 percent aqueous solution of egg-white or milk according to procedure A using detergent composition (powdered or crystalline to a 15 percent aqueous solution of (a) containing cysteine as activator. black drawing ink. "pvhw 5
• the swatches are immersed in the solution and passed 40 through a handwringer whereafter they are heated for 20 B E H minutes in 70C. water.
• test swatches are then soaked and/or washed thereby ai removal proceeding as follows: without 3% A.
• the stained swatches are washed for 30 minutes at 45 staining 5011mm used cysteine C. in a washing solution containing the enzymatic deter- Egg-white-ink 25 32 gent composition and the activator.
• the operation is carg ggg g 2% ried out in a Launder-ometer supplied by Atlas Electric W vow-.. Devices Co., Chicago. Illinois, U.S.A.; or in a Terg-O- tometer" supplied by U.S. Testing company, Hoboken, N.J.,U.S.A. Any of the following examples has been carried out by B.
• the stained swatches are soaked at ambient temperature washing with egg-white-ink swatches according to procedure for 2 hours in a soaking solution, containing the enzy- A. matic detergent composition and the activator,
• the detergent formulation used corresponds to (a) of examwhereafter the swatches to be soaked are agitated for 10 pic i wherein the quantities of enzyme preparation have been m nutesvaried esinsi sated- TABLE III Wt. percent of Stain removal (R%) Wt. per- ALCALASE cent of (same as in Without With Example Activator activator Example I activator activator 0.5 0.4 27.5 33.5 1.5 0.4 27.5 42 II Cysteine 3 0.4 27.
• a detergent composition prepared as described in example I Table -Ebnlinued having the following formula (in weight percent) sulfide 0.6 0.6 25 495 1.2 0.6 1s 5s 'l'etrapropylene benzene sulfonate sodium salt 10 2.4 b 25 56.5 Sodium tripolyphosphate 30 mdium- 3 19 5 26 Condensation product oftallow alcohol with l 1 moles of OJ I95 4 ethylene oxide 4 L2 0.3 1945 36.5 Hydrogenated fatty acids (CM-C”) 4 0.6 043 30,5 43 Sodium sulfate l2 Sodium silicate (ratio SiO,/Na,O 2/l 6.0.
• Enzyme (ALCALASE containing 1.5 Anson: haemoglobin we claim t method units/8,) (M I.
• An enzyme-containing detergent composition consisting Sodium sulfide Q6 essentially of an organic detergent and an alkaline builder salt Mi cel n l nc to 100 in a ratio of builder salt to detergent of about 20: l to 1:5; was used for the washing of Stained switches accordmg IQ from about 0.01 to about 10 weight percent of the composi- Procedure tion of an enzyme activity-enhancing agent containing one or more sulfhydryl groups and selected from the 'ANSONJoum. Gen. Physiol.
• compositions listed hereafter have been tested as The detergem composition 0f claim 2 wherein the described for examples ll through IX except that the detergent Zyme used obtained from 3 of fformulation used in the first composition corresponds to for- The detergent Composmo" of claim 1 wherein the mulation (b) of example I and the composition used in the zyme 15 present in an amount of from about 0.01 to about 0.2 second composition corresponds to the last composition weight Percent ifi ll i l d 5.
• the detergent composition of claim I wherein the sulfhydryl beating compound is presen! in 3: amount ofwfrom oto TABLE V m 6: ;E:;gent composition of claim 5 wherzinn'2 g hydryl bearing compound IS P amo eight percent.

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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)

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Publications (1)

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Family Applications (1)

Country Status (7)

Cited By (7)

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Citations (5)

• 1968
  • 1968-11-19 NL NL6816505A patent/NL6816505A/xx unknown
• 1969
  • 1969-11-07 US US874945A patent/US3627683A/en not_active Expired - Lifetime
  • 1969-11-18 FR FR6939671A patent/FR2023628A1/fr not_active Withdrawn
  • 1969-11-18 BE BE741841D patent/BE741841A/xx unknown
  • 1969-11-18 DE DE19691957816 patent/DE1957816A1/de active Pending
  • 1969-11-19 AT AT1082769A patent/AT308269B/de not_active IP Right Cessation
  • 1969-11-19 CH CH1722169A patent/CH522032A/de not_active IP Right Cessation

Patent Citations (5)

Non-Patent Citations (1)

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