US3798181A - Enzymatic detergent bar - Google Patents

Enzymatic detergent bar Download PDF

Info

Publication number
US3798181A
US3798181A US00086594A US3798181DA US3798181A US 3798181 A US3798181 A US 3798181A US 00086594 A US00086594 A US 00086594A US 3798181D A US3798181D A US 3798181DA US 3798181 A US3798181 A US 3798181A
Authority
US
United States
Prior art keywords
detergent
bar
enzyme
sodium
employed
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US00086594A
Other languages
English (en)
Inventor
S Vazquez
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Colgate Palmolive Co
Original Assignee
Colgate Palmolive Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Colgate Palmolive Co filed Critical Colgate Palmolive Co
Application granted granted Critical
Publication of US3798181A publication Critical patent/US3798181A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C11D3/38636—Preparations containing enzymes, e.g. protease or amylase containing enzymes other than protease, amylase, lipase, cellulase, oxidase or reductase
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047—Detergents in the form of bars or tablets
    • C11D17/0065—Solid detergents containing builders
    • C11D17/0069—Laundry bars
    • 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
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • 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

  • An enzymatic detergent bar especially useful for washing laundry and removing stains therefrom, comprises: a synthetic organic detergent, e.g., linear higher alkyl aryl sulfonate; an enzyme, e.g., a protease; a builder or filter salt, e.g., alkali metal carbonate, alkali metal sulfate; a binder, e.g., corn starch; and water, in such proportions as result in production of a form-retaining, hard, nontacky, readily soluble and effectively cleaning bar.
  • a synthetic organic detergent e.g., linear higher alkyl aryl sulfonate
  • an enzyme e.g., a protease
  • a builder or filter salt e.g., alkali metal carbonate, alkali metal sulfate
  • a binder e.g., corn starch
  • water in such proportions as result in production of a form-retaining, hard, non
  • This invention relates to a detergent bar intended primarily for use in laundering applications. More particularly, the invention is of a detergent bar containing an enzyme or a mixture of enzymes useful to chemically convert hard-to-remove stains on natural or artificial fabric materials to a more readily removable form, so that they can be washed out in a laundering operation.
  • Also within the invention is a method of manufacturing such detergent bars in which the various components are mixed together at an elevated temperature, which may be obtained from a reaction of some of the ingredients, the enzyme is admixed with the rest of the composition at a lower temperature and the total mixture is milled, plodded and pressed into bars. Also claimed as part of this invention are novel processes for-use of enzymatic detergent bars wherein wet laundry is rubbed with the detergent bars at dirty or stained spots, soaked in wash water containing dissolved materials from the bar and subsequently agitated in such wash water or other detergent solution.
  • the invented detergent bars are sufficiently hard so as to be maintained in a solid form resembling soap, and yet, despite the inclusion of very soluble components, do not dissolve too readily and do not become soft or mushy after use, due to gelation with water.
  • the enzyme component although in the presence of a significant proportion of water in the bar, which helps to maintain the component in homogeneous form and prevents crystallizing out into hard kernels of the less soluble ingredients, does not decompose, and useful enzymatic action is obtained even after lengthy storage periods and after storage at high temperatures and high humidities.
  • the enzymes used do not discolor the bar objectionably on storage and do not become malodorous. In fact, they even seem to improve the bouquets of perfumes employed.
  • the invented detergent bars are easily manufactured with conventional equipment and may be made directly from detergent acid and soda ash (to form the active detergent ingredient), with addition of the various other constituents, followed by conventional milling, plodding and pressing operations.
  • the products are preferably employed in such a manner that advantage is taken of soaking the soiled and/or stained laundry in a solution of the detergent bar materials, so as to take advantage of then enzymatic action.
  • the sulfonic or sulfuric group of the anionic sulf(on)- ated detergents may be joined directly or indirectly to a hydrophobic organic group, which usually contains the mentioned higher alkyl.
  • a hydrophobic organic group which usually contains the mentioned higher alkyl.
  • the higher alkyl aryl sulfonates having about 8 to 18, preferably 10 to 16 carbon atoms in the alkyl group are particularly effective. It is preferred to use the higher alkyl benzene sulfonate detergents, although analogous materials containing mononuclear aryl groups such as xylene, toluene or phenol, may be employed instead of the benzene nucleus.
  • the useful sulfates include the alkyl oxyethylene sulfates, the monoglyceride sulfates, the sulfated higher alkyl phenyl oxyethylene ethanols or polyoxyethylene ethanols and the sulfated polyoxyethylene ethanols or sulfated poly-lower oxyalkylene lower alkanols.
  • anionic detergents known in the art to be useful solid or solidifiable cleaning agents and which can be incorporated as the principal synthetic organic detergents in the present compositions.
  • phosphorus analogues of the above compounds are useful in at least partial replacement of the sulf(on)ated materials.
  • nonionics as with the anionic compounds, it is preferred to employ those detergents which are normally solid and water soluble. Included within this group are higher alkyl aryl phenol polyoxy-lower alkylene lower alkanols, polyoxylower alkylene alkanols, higher fatty alcohol ethers of polyoxy-lower alkanols, block copolymers of different polyoxy-lower alkylene alkanols, and the heterocyclic mixed polyoxy-lower alkylene alkanols.
  • the lower alkylenes are usually of 2 to 4 carbon atoms.
  • the alkanol portion of the molecule in some cases, may be terminated with a lower alkoxy group, in-
  • amphoteric or ampholytic detergents although not preferred major constituents of the present synthetic detergent component, are useful mainly as partial replacements or supplements for anionic and nonionic detergents. These include the betaines, sulfobetaines, Miranols, amidobetaines, and amidosulfobetaines.
  • the cationic compounds include principally the quarternary ammonium halides but analogous phosphorus compounds may also be employed. Substituents on the nitrogen will normally be lower alkyl, higher alkyl, benzyl or aryl, in various combinations.
  • the synthetic detergents of the anionic type will usually be employed as their water soluble salts, with the saltforming ion preferably being an alkali metal, e.g., sodium, potassium. However, other salt forming ions may also be employed, such as ammonium, lower alkanolamine and lower alkylamine.
  • the salt-forming ion will usually be halide, e.g., chloride, bromide 01' iodide.
  • Some specific examples of useful detergents which may be used as cleaning agents in the present bars are sodium n-dodecyl benzene sulfonate; sodium n-tridecyl benzene sulfonate; potassium n-hexadecyl benzene sulfonate; sodium n-dodecyl toluene sulfonate; sodium propylene tetramer benzene sulfonate; sodium propylene pentamer benzene sulfonate; sodium tridecyl benzene sulfonate, wherein the tridecyl is a mixture of propylene pentamer and propylene tetramer; sodium butylene trimer benzene sulfonate; potassium tridecyl benzene sulfonate; sodium lauryl sulfate; sodium lauryl sulfonate; ammonium coconut oil fatty acids mono
  • the builder salts which are useful in making the present bars include the conventional builders for synthetic organic detergents but of these, it is preferred to employ, at least in part, the alkali metal carbonates and/or bicarbonates.
  • the use of such builder(s) facilitates an economical manufacturing process wherein an anionic detergent acid is neutralized in situ.
  • various boron-containing builders e.g., borax
  • silicates such as those having an Na O:SiO ratio of from 1:1 to 1:3, preferably from 1:1.6 to 112.35
  • phosphates especially the polyphosphates e.g., pentasodium tripolyphosphate and tetrapotassium pyrophosphate.
  • organic builders which are usually employed to a lesser extent than the inorganic builders.
  • organic builders which are usually employed to a lesser extent than the inorganic builders.
  • exemplary of these are NTA (trisodium nitrilotriacetate monohydrate) and EDTA (ethylene diamine tetraacetic acid, usually used as the tetrasodium, tetrapotassium or trisodium salt).
  • Filler salts generally water soluble inorganic salts which add bulk to the detergent bar and sometimes desirably modify its solubility and physical characteristics, include the water soluble inorganic sulfates and bisulfates, plus other suitable water soluble salts which may be employed on occasion, e.g., sodium chloride.
  • the filler and builder salts may be anhydrous or hydrates. The fillers will often be present as byproducts from the manufacture of anionic detergents, etc.
  • Binding agents for holding the bar together in a cohesive, yet desirably soluble form include the natural and synthetic starches, gums and thickeners and derivatives thereof.
  • various starches such as corn starch, potato starch, yucca starch, tapioca starch and starches derived from cellulose are useful binders, as are the components and derivatives thereof, such as amylose, amylopectin and partially hydrolyzed starches.
  • the starch may be at least partially replaced by cereal flours which contain large proportions of it, such as wheat or potato flours.
  • Gums include alginates, agar agar, guar and mucilages.
  • Some binder compounds also possess soil-suspending properties and help to maintain the removed dirt in finely divided suspension in the wash water to prevent it from re-adhering to the laundered material.
  • Some binder compounds also possess soil-suspending properties and help to maintain the removed dirt in finely divided suspension in the wash water to prevent it from re-adhering to the laundered material.
  • polyvinyl alcohol and sodium carboxymethyl cellulose are polyvinyl alcohol and sodium carboxymethyl cellulose.
  • corn starch does not have as significant an effect as the PVA or CMC, as previously mentioned, it is the most preferred binder in the present bars, principally because it forms a bar with desired tactile properties, low density (compared to other detergent bars containing inorganic salts), desired solubility and smoothness, and, most important, it aids in stabilizing the enzymes, preventing their degradation and consequent inactivation and the development of malodorous byproducts.
  • Various corn starches appear to have this desired property, over a variety of amylopect
  • the enzyme constituent of the detergent bar is most preferably a proteolytic enzyme.
  • Such enzymes are active on proteinaceous materials and catalyze digestion or degradation of such matter when it is present in the form of a stain on a fabric.
  • the degradation by a hydrolysis mechanism for example, results in the production of a more soluble material which is removable by the built synthetic detergent solution.
  • the various enzymes employed are generally effective at pH ranges regulated by the content of builder salt in the detergent bar. Such a range may be from about 4 to 12 and is preferably about 8 to 11.
  • the proteolytic enzymes although subject to some degradation by heat, may be employed in washing solutions at temperatures up to about 80 C. and are also effective at low temperatures, down to about 10 C.
  • Proteolytic enzymes such as Alcalase, Maxatase, Protease AP, Protease ATP 40, Protease ATP 120, Protease L-252 and Protease L-423 are among those enzymes derived from strains of spore forming bacilli, such as Bacillus subtilis.
  • Different proteolytic enzymes have different degrees of effectiveness in aiding in the removal of stains from textiles and linen. Particularly preferred as stain removing enzymes are subtilisin enzymes.
  • Metalloproteases which contain divalent ions such as calcium, magnesium or zinc bound to their protein chains are of interest. The manufacture of proteolytic enzyme concentrates is described in German Offenlegenschrift 1,800,508 and Dutch patent application 6815944.
  • proteolytic enzymes The contents of particular enzymes are often measured by their activities in standard tests.
  • the activities of proteolytic enzymes may be measured by Anson units and that of amylase by Novo alpha-amylase units.
  • the number of Anson units of a highly preferable, commercially available subtilisin enzyme, such as Alcalase, produced by Novo Industri A/ S, Copenhagen, Denmark, is l-4/ g. and Anson ratings of starting materials up to about 8/g. are possible.
  • Such enzymes generally in the form of finely divided powders, beads or prills, may be distributed on a carrier or may be substantially salt-free.
  • the carrier When employed, the carrier will often be calcium phosphate, sodium sulfate, sodium chloride or other suitable soluble or insoluble salt or other material, often depending on the product in which the enzyme is to be incorporated. Of course, as with other components of the present detergent bars, mixtures may be used to obtain most desired results.
  • the fluorescent brighteners which greatly improve the appearance of washed, previously stained laundry items may be any of the wide variety of such materials, also known as optical bleaches, optical brighteners and fluorescent whiteners. Include among these are brighteners specifically useful for whitening cotton, such as the CC/ DAS brighteners which are derived from the reaction be utilized as the corresponding acids, subsequently to be converted to salt form. They may be used essentially pure or on carriers.
  • Cotton brighteners will usually comprise a major proportion of the brightener system employed and such system will generally also include an amide-polyester brightener.
  • the brighteners usable in the present bars are Calcofluor White ALF (American Cyanamid); ALF-N (American Cyanamid); SO-F A- 2001 (Ciba); CWD (Hilton-Davis); Phorwite :RKH (Verona); CSL, powder, acid (American Cyanamid); CSL, liquid, monoethanolamine salt (American Cyanamid); PE 766 (Verona); Blancophor PD (GAF) UNPA (Geigy); Tinopal RBS (Geigy); and RES 200 (Geigy).
  • a good description of the optical brighteners is found in Optical Brighteners and Their Evaluation, by Per S. Stensby, a reprint of articles published in Soap and Chemical Specialties in April, May, July, August and September 1967, especially at pp. 3-5 thereof.
  • pH adjusting agents e.g., sodium hydroxide, triethanolamine, sulfuric acid
  • buffering agents e.g., sodium borate, sodium bisulfate
  • foam improvers e.g., lauric myristic diethanolamide, lauryl dimethylamine oxide
  • bactericides e.g., tetrachlorosalicylanilides, hexachlorophene
  • fungicides dyes; pigments (water dispersible); preservatives; ultraviolet absorbers; fabric softeners, and bleaches, e.g., sodium perborate.
  • the ad juvants to be employed, they will be chosen so as to be compatible with the main constituents of the bars.
  • alkyl benzene sulfonate may be completely replaced, in some instances, by other anionic or nonionic detergents and may be replaced in minor proportion by the ordinary higher fatty acid soaps which, strictly speaking, are not synthetic organic detergents within the usual meaning of that term.
  • the binder constituent will generally comprise from 5 to 40% of the detergent bar, preferably from 10 to 35% thereof. This will usually include a major proportion of starch, preferably from 70 to thereof and most preferably, it will be entirely corn starch. Other binders of the types previously mentioned may be employed to supplement the elfects of the starch in the product.
  • the enzyme as a concentrated commercial form thereof, may be from 0.05 to 5% of the bar. However, because of cost and functional considerations, this proportion will normally be 0.1 or 0.2 to -1% of the product, which proportion has been found to be commercially competitive and yet, sufiiciently active to improve the stain-removing properties of the bar significantly.
  • the entire proportion of the enzyme concentration will be protease or other useful proteolytic enzyme, because the proteinaceous stains appear to be those which are more common and most difficult to remove.
  • a major proportion preferably from 70 to 100%, will be proteolytic enzyme or protease. If the enzyme is present on a carrier, the percentage will be adjusted accordingly. In terms of Anson units, the proportion of enzyme in the detergent bar will be such as to result in from about 0.001 to 0.1 Anson unit per gram of bar.
  • the moisture content of the milled, plodded and pressed detergent bars will usually be within the range of from 5 to 25% thereof. Such a wide range of moisture contents is useful because some of the builder and filler salts are hydratable and moisture is taken up by the corn starch or other binder. Normally, the moisture content will be within the 8 to 22% range and preferably it is from 10 or 12 to 17%. Such a moisture content allows the bar to be processed easily, gives it desired solubility characteristics and promotes homogeneity in manufacture.
  • a sigma blade mixer is a suitable medium, especially where a subsequent drying operation is desirably avoided, as in the case of heat-sensitive enzymes.
  • a dry process of manufacture is found to be most efiicient, especially when anionic synthetic organic detergent salts are employed.
  • anionic synthetic organic detergent salts for example, in the case of alkyl benzene sulfonates, there may be used the corresponding detergent acid, usually in aqueous solution, and it may be dry neutralized with sodium carbonate or sodium bicarbonate powder or sodium hydroxide or other suitable agent.
  • proteolytic enzymes seem to be effective against a wide variety of staining materials, perhaps due to a proteinaceous link in the aflixation mechanism by which the stain is held to a substrate, whether that substrate be cotton or synthetic, such as polyester or nylon. In further discussion, for simplicity, reference will be made mostly to proteolytic enzymatic bars.
  • the laundry is initially moistened or wet, preferably by immersion in a tub of water, after which it is drained and the bar is rubbed by hand against the most badly soiled areas, e.g., shirt collars, cuffs, trouser knees, and on stained surfaces.
  • the stains to which the bar may be applied are, for example, food stains such as chocolate, cherry, blueberry, grape, blood, gravy, ketchup, mustard, wine and grease, but also removed are grass stains, inks, etc. Normally the stains will not have to be rubbed for more than seconds and rarely is this necessary for more than one minute.
  • the laundry may be placed in a tub with more water, allowing the dissolved detergent bar constituents to contact the entire area of the laundry, although in a more dilute state.
  • concentration of detergent bar materials in the soak water will be from 0.05 to about 1.0% and the soaking period will be from about /2 hour to 10 hours but it may be as long as 24 hours or even more.
  • the enzymes are effective for only about 2 to 10 hours, but even so, additional soaking allows the combination of detergent and builder better to loosen the partially broken down stain.
  • the temperature of the soak water will usually be about room temperature or slightly higher although temperatures within the range of 2060 C. are useful. Normally, however, the temperature will be from 20 C. to 40 C.
  • the binder or corn starch component of the enzymatic bar performs a useful function in tending to coat the item being soaked when the laundry is not placed into a dilute bath, preventing it from drying out excessively, which could inactivate the enzyme.
  • a dilute solution of the applied detergent bar materials may be formed and washing of the laundry may be conducted in this solution, generally at an elevated temperature of from 50 to 90 C. although preferably at a temperature of 50 to C. In some cases, colder water, at a temperature as low as 15 C., can be employed. If the enzyme has become inactivated, additional detergent bar or other enzymatic and detergent materials may be added to the wash water. The subsequent washing may be in an automatic washing machine for a period of from five minutes to one hour or may be by hand and may take a similar or shorter time. After completion of washing, the laundry is rinsed, wrung out and dried. If, after washing is finished, any stains are still noted on the laundry, they may be rubbed with the detergent bar and, if desirable, may be soaked again.
  • Titanium dioxide Anatase 0.3 Perfume, Rondelia detergent type 0.2
  • the detergent acid is admixed with soda ash in the presence of a suflicient small proportion of water to aid in the neutralization reaction.
  • a cooling jacket is employed, the heat of reaction raises the temperature to about 65 C.
  • the corn starch, titanium dioxide, sodium bisulfite, water and perfume are added with continued mixing. The neutralization occurs over a period of about ten minutes and the mixing with other materials lasts for an additional five minutes. At the end of the mixing, the temperature of the paste resulting is about 55 C.
  • the paste is removed from the sigma blade mixer and is cooled, utilizing a heat exchanger, to a temperature of about 40 C., after which it is returned to the sigma blade mixer and the Protease Alcalase enzyme is added. If desired, such addition may be in the presence of some of the water of the formula, to promote better dispersion.
  • Additional enzymatic detergent bars are made wherein minor proportions, 0.05 to 1.0% of optical brighteners of the cotton and amide-polyester brightener classes, previously described in the specification, are included in the formula in place of a similar proportion of corn starch.
  • Such products when used according to the washing techniques described previously, remove stains and dirt and also brighten the laundry so as to make any small signs of stains still present less apparent.
  • pentasodium tripolyphosphate granules, colored with blue and green dyes are mixed in with the milled enzymatic detergent composition before plodding and, using a total proportion of about 0.7% of such granules (which also contain minor proportions of dextrose).
  • a speckled and somewhat marbleized detergent bar appearance is obtained, which distinctively identifies the enzymatic product to a consumer.
  • the sulfonic acid is neutralized with the soda ash, in the presence of the sodium silicate and water, corn starch and perfume are added, after which the mix is cooled and the enzyme is added.
  • the product comprises about 27.5% of active detergent, 35.0% so dium bicarbonate, 6.6% of sodium carbonate, 11.1% of corn starch, 4.5% of sodium silicate and 14.7% water.
  • the enzyme When tested in the washing of laundry and in stain removal from cotton cloths, even after months of storage, the enzyme is noticeably active and the enzymatic detergent bar removes stains noticeably better than a control bar containing no enzyme.
  • brighteners such as Tinopal LCS, Uvitex 82R and Uvitex SEC are employed, to the extent of a total as small as 0.1% or 0.2%, the combined cleaning and brightening effects are significant improvements over similar bars not containing such ingredients.
  • the improved stability of the perfume of the bar apparently due to the presence of the enzyme and/or the combination of enzyme and corn starch in the formula.
  • the color of the bar is good and it is not darkened or otherwise degraded by the presence of enzymes, corn starch and water therein.
  • the bar density is about 1.3 g./cc., desirably light in weight, and it is non-tacky.
  • Example 1 Although the washing methods described in Example 1 are preferred means of effecting the best stain removal, since they utilize an extensive soaking period in contact with the enzymatic detergent bar, it is also found that ordinary rubbing and washing of stained and soiled laundry with the bar is effective, even when no extensive soaking period is employed intermediate the initial rubbing and the final washing steps.
  • Example 3 The procedure of Example 1 is repeated with the exception that the anionic detergent is charged to the mixer as a neutral salt, together with a proportion of water equivalent to that obtained in he neutralization reaction.
  • the neutralized detergent By utilizing the neutralized detergent, mixing can be effected at a lower temperature, even at room temperature, although it is preferred to mix at about 40 C. to improve the plasticity of the product during processing, so that it can be milled, plodded and pressed easily.
  • a detergent bar according to claim 3 in which the enzyme content is from 0.1 to 1% and from 70 to 100% thereof is proteolytic enzyme so that the detergent bar contains from 0.001 to 0.1 Anson unit per gram, the anionic synthetic organic detergent is selected from the group consisting of sulfated and sulfonated detergents having an alkyl group of 8 to 22 carbon atoms, the builder and filler salts are inorganic sodium salts and the binding agent is from 10 to 35% of the bar and 70 to 100% thereof is starch.
  • a detergent bar according to claim 6 which is milled and plodded and in which the moisture content is from 12 to 17%.
  • a detergent bar according to claim 7 which contains about 28% of sodium higher alkyl benzene sulfonate, 35% sodium bicarbonate, 7% sodium carbonate, 11% corn starch, 5% sodium silicate, 15% water and 0.6% proteolytic enzyme.
  • a detergent bar according to claim 7 which contains about 31% of sodium alkyl benzene sulfonate detergent, 18% sodium carbonate, 8% sodium bicarbonate, 26% of corn starch, 14% of moisture and at least 0.009 Anson unit/gram of protease.
  • a detergent bar according to claim 9 which contains from 0.5 to 1% of optical brightener and suflicient proportion of coloring material to give the bar a distinct speckled appearance to identify it to a consumer as an enzymatic detergent bar.

Landscapes

  • 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)
  • Molecular Biology (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
US00086594A 1970-11-03 1970-11-03 Enzymatic detergent bar Expired - Lifetime US3798181A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US8659470A 1970-11-03 1970-11-03

Publications (1)

Publication Number Publication Date
US3798181A true US3798181A (en) 1974-03-19

Family

ID=22199607

Family Applications (1)

Application Number Title Priority Date Filing Date
US00086594A Expired - Lifetime US3798181A (en) 1970-11-03 1970-11-03 Enzymatic detergent bar

Country Status (5)

Country Link
US (1) US3798181A (it)
AR (1) AR198483A1 (it)
CA (1) CA982506A (it)
IT (1) IT942263B (it)
PH (1) PH9809A (it)

Cited By (39)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3953353A (en) * 1974-11-08 1976-04-27 Purex Corporation Laundering pre-spotter and method of production
US4006056A (en) * 1975-09-19 1977-02-01 Midwest Biochemical Corporation Controlled release composition containing stabilized urease
US4012341A (en) * 1975-06-24 1977-03-15 American Cyanamid Company Unique all synthetic detergent shampoo bar
US4077890A (en) * 1973-02-23 1978-03-07 Graham Barker Composition for treating fabrics, method for making and using the same
US4096870A (en) * 1977-06-09 1978-06-27 Burton, Parsons And Company, Inc. Method for cleaning soft hydrophilic gel contact lenses
US4100097A (en) * 1977-02-02 1978-07-11 The Hewitt Soap Company, Inc. Low pH detergent bar
US4390441A (en) * 1980-04-11 1983-06-28 Lever Brothers Company Machine dishwashing composition
JPS60168798A (ja) * 1983-11-14 1985-09-02 ザ、プロクタ−、ギヤンブル、カンパニ− 臭気精製タンパク分解酵素および香料を含有する組成物
US4543204A (en) * 1983-08-17 1985-09-24 Colgate-Palmolive Company Sodium higher fatty alkyl sulfate detergent laundry bars and process for manufacture thereof
EP0142886A3 (en) * 1983-11-14 1986-03-12 The Procter & Gamble Company Compositions containing odor purified proteolytic enzymes and perfumes
US4606839A (en) * 1984-02-06 1986-08-19 Harding John A S Solid soap and a process for the production thereof
EP0205999A3 (en) * 1985-06-07 1988-07-06 Dow Consumer Products Inc. Laundry soil and stain remover
US4842762A (en) * 1985-06-07 1989-06-27 The Dow Chemical Company Laundry soil and stain remover in applicator stick form
US4874537A (en) * 1988-09-28 1989-10-17 The Clorox Company Stable liquid nonaqueous detergent compositions
US4919834A (en) * 1988-09-28 1990-04-24 The Clorox Company Package for controlling the stability of a liquid nonaqueous detergent
US5336424A (en) * 1992-12-23 1994-08-09 Eftichios Van Vlahakis Improved urinal block composition
GB2274849A (en) * 1993-02-05 1994-08-10 Unilever Plc Detergent bars containing enzymes.
WO1994023006A1 (en) * 1993-04-06 1994-10-13 The Procter & Gamble Company Lavatory blocks containing enzymes
GB2277325A (en) * 1993-04-23 1994-10-26 Unilever Plc Detergent bar
WO1995027036A1 (en) * 1994-03-30 1995-10-12 The Procter & Gamble Company Laundry detergent bars containing fabric softening clay and cellulase enzyme
US5571287A (en) * 1993-01-11 1996-11-05 Colgate-Palmolive Company Soap composition containing sodium pyrophosphate
WO1997008283A1 (en) * 1995-08-25 1997-03-06 The Procter & Gamble Company Detergent composition with bleach system stabilized by enzymes
WO1997036985A1 (en) * 1996-03-29 1997-10-09 The Procter & Gamble Company Low moisture laundry detergent bar with improved enzyme stability
WO1998018897A1 (en) * 1996-10-31 1998-05-07 The Procter & Gamble Company Process for incorporating enzymes into laundry bars
WO1998018896A1 (en) * 1996-10-31 1998-05-07 The Procter & Gamble Company High moisture laundry bar compositions with improved physical properties
US5759982A (en) * 1994-06-17 1998-06-02 The Procter & Gamble Company Laundry bars with polyethylene glycol as a processing aid
WO1998054285A1 (en) * 1997-05-30 1998-12-03 The Procter & Gamble Company Laundry bar with improved protease stability
WO1998055406A1 (fr) * 1997-06-05 1998-12-10 Bevil Sprl Produit biologique pour l'entretien des canalisations et pour l'epuration des eaux usees
US5858117A (en) * 1994-08-31 1999-01-12 Ecolab Inc. Proteolytic enzyme cleaner
WO1999010466A1 (en) * 1997-08-22 1999-03-04 The Procter & Gamble Company Cleaning compositions comprising a phosphatase
WO2000005332A1 (en) * 1998-07-22 2000-02-03 The Procter & Gamble Company Process for manufacturing a laundry detergent bar
WO2001007556A1 (en) * 1999-07-27 2001-02-01 The Procter & Gamble Company Compositions comprising xet and a polysaccharide and/or oligosaccharide
WO2001040427A1 (en) * 1999-11-30 2001-06-07 Unilever Plc High moisture soap bars comprising borax
WO2002046341A3 (en) * 2000-12-05 2002-08-29 Unilever Nv Process for manufacture of non-granular solid detergent composition
WO2003083034A1 (en) * 2002-04-02 2003-10-09 Unilever N.V. Detergent bar compositions
WO2015070119A1 (en) 2013-11-11 2015-05-14 Ecolab Usa Inc. Multiuse, enzymatic detergent and methods of stabilizing a use solution
US9353335B2 (en) 2013-11-11 2016-05-31 Ecolab Usa Inc. High alkaline warewash detergent with enhanced scale control and soil dispersion
US11898125B2 (en) 2020-07-28 2024-02-13 Nicole Smith Composition for an organic cleaning product
WO2025008400A1 (en) * 2023-07-03 2025-01-09 Novozymes A/S Enzymatic detergent bars having improved enzyme stability

Cited By (67)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4077890A (en) * 1973-02-23 1978-03-07 Graham Barker Composition for treating fabrics, method for making and using the same
US3953353A (en) * 1974-11-08 1976-04-27 Purex Corporation Laundering pre-spotter and method of production
US4012341A (en) * 1975-06-24 1977-03-15 American Cyanamid Company Unique all synthetic detergent shampoo bar
US4006056A (en) * 1975-09-19 1977-02-01 Midwest Biochemical Corporation Controlled release composition containing stabilized urease
US4100097A (en) * 1977-02-02 1978-07-11 The Hewitt Soap Company, Inc. Low pH detergent bar
US4151105A (en) * 1977-02-02 1979-04-24 The Hewitt Soap Company Inc. Low pH detergent bar
US4096870A (en) * 1977-06-09 1978-06-27 Burton, Parsons And Company, Inc. Method for cleaning soft hydrophilic gel contact lenses
US4390441A (en) * 1980-04-11 1983-06-28 Lever Brothers Company Machine dishwashing composition
US4543204A (en) * 1983-08-17 1985-09-24 Colgate-Palmolive Company Sodium higher fatty alkyl sulfate detergent laundry bars and process for manufacture thereof
JPS60168798A (ja) * 1983-11-14 1985-09-02 ザ、プロクタ−、ギヤンブル、カンパニ− 臭気精製タンパク分解酵素および香料を含有する組成物
EP0142886A3 (en) * 1983-11-14 1986-03-12 The Procter & Gamble Company Compositions containing odor purified proteolytic enzymes and perfumes
US4606839A (en) * 1984-02-06 1986-08-19 Harding John A S Solid soap and a process for the production thereof
EP0205999A3 (en) * 1985-06-07 1988-07-06 Dow Consumer Products Inc. Laundry soil and stain remover
US4842762A (en) * 1985-06-07 1989-06-27 The Dow Chemical Company Laundry soil and stain remover in applicator stick form
JPH0788519B2 (ja) 1985-06-07 1995-09-27 ダウブランズ・インコーポレーテッド 洗濯用汚れおよびしみ除去剤
US4919834A (en) * 1988-09-28 1990-04-24 The Clorox Company Package for controlling the stability of a liquid nonaqueous detergent
US4874537A (en) * 1988-09-28 1989-10-17 The Clorox Company Stable liquid nonaqueous detergent compositions
US5336424A (en) * 1992-12-23 1994-08-09 Eftichios Van Vlahakis Improved urinal block composition
US5489415A (en) * 1992-12-23 1996-02-06 Eftichios Van Vlahakis Urinal block dispenser assembly and composition
US5571287A (en) * 1993-01-11 1996-11-05 Colgate-Palmolive Company Soap composition containing sodium pyrophosphate
GB2274849A (en) * 1993-02-05 1994-08-10 Unilever Plc Detergent bars containing enzymes.
WO1994023006A1 (en) * 1993-04-06 1994-10-13 The Procter & Gamble Company Lavatory blocks containing enzymes
GB2277325A (en) * 1993-04-23 1994-10-26 Unilever Plc Detergent bar
WO1995027036A1 (en) * 1994-03-30 1995-10-12 The Procter & Gamble Company Laundry detergent bars containing fabric softening clay and cellulase enzyme
US5759982A (en) * 1994-06-17 1998-06-02 The Procter & Gamble Company Laundry bars with polyethylene glycol as a processing aid
US6197739B1 (en) 1994-08-31 2001-03-06 Ecolab Inc. Proteolytic enzyme cleaner
US5858117A (en) * 1994-08-31 1999-01-12 Ecolab Inc. Proteolytic enzyme cleaner
WO1997008283A1 (en) * 1995-08-25 1997-03-06 The Procter & Gamble Company Detergent composition with bleach system stabilized by enzymes
WO1997036985A1 (en) * 1996-03-29 1997-10-09 The Procter & Gamble Company Low moisture laundry detergent bar with improved enzyme stability
WO1998018897A1 (en) * 1996-10-31 1998-05-07 The Procter & Gamble Company Process for incorporating enzymes into laundry bars
WO1998018896A1 (en) * 1996-10-31 1998-05-07 The Procter & Gamble Company High moisture laundry bar compositions with improved physical properties
WO1998054285A1 (en) * 1997-05-30 1998-12-03 The Procter & Gamble Company Laundry bar with improved protease stability
WO1998055406A1 (fr) * 1997-06-05 1998-12-10 Bevil Sprl Produit biologique pour l'entretien des canalisations et pour l'epuration des eaux usees
WO1999010466A1 (en) * 1997-08-22 1999-03-04 The Procter & Gamble Company Cleaning compositions comprising a phosphatase
WO2000005332A1 (en) * 1998-07-22 2000-02-03 The Procter & Gamble Company Process for manufacturing a laundry detergent bar
WO2001007556A1 (en) * 1999-07-27 2001-02-01 The Procter & Gamble Company Compositions comprising xet and a polysaccharide and/or oligosaccharide
WO2001040427A1 (en) * 1999-11-30 2001-06-07 Unilever Plc High moisture soap bars comprising borax
US6440908B2 (en) 1999-11-30 2002-08-27 Unilever Home & Personal Care Usa, Division Of Conopco, Inc. High moisture retaining bars compositions comprising borax as water structurant
WO2002046341A3 (en) * 2000-12-05 2002-08-29 Unilever Nv Process for manufacture of non-granular solid detergent composition
WO2003083034A1 (en) * 2002-04-02 2003-10-09 Unilever N.V. Detergent bar compositions
CN1298831C (zh) * 2002-04-02 2007-02-07 荷兰联合利华有限公司 洗涤剂条组合物
KR20180061413A (ko) * 2013-11-11 2018-06-07 에코랍 유에스에이 인코퍼레이티드 다용도의 효소 세정제 및 사용 용액을 안정화시키는 방법
US10316272B2 (en) 2013-11-11 2019-06-11 Ecolab Usa Inc. High alkaline warewash detergent with enhanced scale control and soil dispersion
CN105705625A (zh) * 2013-11-11 2016-06-22 艺康美国股份有限公司 多用途的酶洗涤剂和稳定使用溶液的方法
KR20160085322A (ko) * 2013-11-11 2016-07-15 에코랍 유에스에이 인코퍼레이티드 다용도의 효소 세정제 및 사용 용액을 안정화시키는 방법
JP2017503061A (ja) * 2013-11-11 2017-01-26 エコラボ ユーエスエー インコーポレイティド 多目的酵素洗剤及び使用溶液を安定化する方法
US9683203B2 (en) 2013-11-11 2017-06-20 Ecolab Usa Inc. High alkaline warewash detergent with enhanced scale control and soil dispersion
EP3068861A4 (en) * 2013-11-11 2017-06-28 Ecolab USA Inc. Multiuse, enzymatic detergent and methods of stabilizing a use solution
RU2642077C2 (ru) * 2013-11-11 2018-01-24 ЭКОЛАБ ЮЭсЭй ИНК. Многоцелевой ферментный детергент и способы стабилизации применяемого раствора
KR101863562B1 (ko) 2013-11-11 2018-06-01 에코랍 유에스에이 인코퍼레이티드 다용도의 효소 세정제 및 사용 용액을 안정화시키는 방법
WO2015070119A1 (en) 2013-11-11 2015-05-14 Ecolab Usa Inc. Multiuse, enzymatic detergent and methods of stabilizing a use solution
US10011808B2 (en) 2013-11-11 2018-07-03 Ecolab Usa Inc. Multiuse, enzymatic detergent and methods of stabilizing a use solution
US20180282668A1 (en) * 2013-11-11 2018-10-04 Ecolab Usa Inc. Multiuse, enzymatic detergent and methods of stabilizing a use solution
US10179892B2 (en) 2013-11-11 2019-01-15 Ecolab Usa Inc. Multiuse, enzymatic detergent and methods of stabilizing a use solution
US9353335B2 (en) 2013-11-11 2016-05-31 Ecolab Usa Inc. High alkaline warewash detergent with enhanced scale control and soil dispersion
EP3068861B1 (en) 2013-11-11 2020-03-18 Ecolab USA Inc. Multiuse, enzymatic detergent and methods of stabilizing a use solution
US10597613B2 (en) 2013-11-11 2020-03-24 Ecolab Usa Inc. Multiuse, enzymatic detergent and methods of stabilizing a use solution
US10745651B2 (en) 2013-11-11 2020-08-18 Ecolab Usa Inc. High alkaline warewash detergent with enhanced scale control and soil dispersion
US10995303B2 (en) 2013-11-11 2021-05-04 Ecolab Usa Inc. Multiuse, enzymatic detergent and methods of stabilizing a use solution
CN113637535A (zh) * 2013-11-11 2021-11-12 艺康美国股份有限公司 多用途的酶洗涤剂和稳定使用溶液的方法
US11339354B2 (en) 2013-11-11 2022-05-24 Ecolab Usa Inc. High alkaline warewash detergent with enhanced scale control and soil dispersion
US12371640B2 (en) 2013-11-11 2025-07-29 Ecolab Usa Inc. High alkaline warewash detergent with enhanced scale control and soil dispersion
US11905497B2 (en) 2013-11-11 2024-02-20 Ecolab Usa Inc. Multiuse, enzymatic detergent and methods of stabilizing a use solution
US11920109B2 (en) 2013-11-11 2024-03-05 Ecolab Usa Inc. High alkaline warewash detergent with enhanced scale control and soil dispersion
US12264298B2 (en) 2013-11-11 2025-04-01 Ecolab Usa Inc. Multiuse, enzymatic detergent and methods of stabilizing a use solution
US11898125B2 (en) 2020-07-28 2024-02-13 Nicole Smith Composition for an organic cleaning product
WO2025008400A1 (en) * 2023-07-03 2025-01-09 Novozymes A/S Enzymatic detergent bars having improved enzyme stability

Also Published As

Publication number Publication date
IT942263B (it) 1973-03-20
CA982506A (en) 1976-01-27
AR198483A1 (es) 1974-06-28
PH9809A (en) 1976-03-26

Similar Documents

Publication Publication Date Title
US3798181A (en) Enzymatic detergent bar
US3790482A (en) Enzyme-containing detergent compositions
US3553139A (en) Enzyme containing detergent composition and a process for conglutination of enzymes and detergent composition
US3741911A (en) Phosphate-free detergent composition
US3726797A (en) Detergent compositions and processes incorporating n-(2-hydroxy hydrocarbyl)iminodicarboxylates
US3634266A (en) Liquid detergent compositions containing amylolytic enzymes
US4842758A (en) Stabilized enzyme system for use in aqueous liquid built detergent compositions
US3893954A (en) Detergent compositions containing enzyme and chlorine scavenger
USH1776H (en) Enzyme-containing heavy duty liquid detergent
US5500151A (en) Heavy duty fabric softening laundry detergent composition
JPS6123218B2 (it)
JP7000554B2 (ja) 官能化シロキサンポリマー及びそれを含む組成物
JPH02504649A (ja) 皿を洗いすすぐための酵素組成物
US3600318A (en) Enzyme-containing detergent compositions for neutral washing
US3753915A (en) Biological cleaning preparation
US3876563A (en) Liquid detergent compositions
JP2757967B2 (ja) 重質粒状合成有機ノニオン洗剤組成物
US3661786A (en) Detergent compositions containing stabilized alpha-amylase
US3732170A (en) Bio-soaking performances
JPH11504977A (ja) エンドデキストラナーゼを含有したクリーニング組成物
US3781228A (en) Laundry product containing enzyme
EP0781836A1 (en) Detergent composition having improved cleaning power in neutral or acidic medium
JP2001514304A (ja) ホスファターゼを含む洗浄用組成物
US3627683A (en) Detergent composition
US4715990A (en) Stable soil release promoting liquid detergent containing stabilized enzymes