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
  • 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

• pre-washes In order to effectively remove these difficult soils, various compositions are being marketed as “pre-washes” or “pre-spotters.” Such compositions are applied directly to the difficult stains before the washing process.
• the "pre-wash” compositions are formulated primarily to remove oily or greasy stains.
• Such compositions rely principally upon organic based solvents such as hydrocarbons, halogenated hydrocarbons etc. in combination with hydrocarbon compatible surfactants.
• Such compositions effectively dissolve and/or emulsify oily or greasy stains.
• These compositions are not nearly as effective in removing stains caused by protein sources such as blood, and grass; or from combined protein and fat sources such as sebum; or from fats and starches. These sources produce stains which are difficult to remove with solvent/surfactant combinations alone.
• the present invention solves the problems enumerated above.
• the present invention relates to laundry "pre-wash” compositions; and more particularly to pre-wash compositions that are single phase liquids effective against both oil and grease stains as well as protein, fat and/or starch stains.
• the invention compositions effectively combine the advantages of both hydrocarbon oil and grease solvents and enzymes in a single liquid composition.
• the normally incompatible hydrocarbon solvents and enzymes are combined without expressively limiting the products' "shelf-life", i.e., the enzyme component retains an effective activity against stains for extended periods; and the hydrocarbon solvents retain their effectiveness against oil and grease stains.
• the enzymes are water soluble and they must remain in aqueous solution to retain their activity against proteins, fats, and/or starches.
• the hydrocarbon solvents are quite hydrophobic and immiscible in aqueous solutions. The hydrocarbon solvents are effective against oil and grease in the absence of water. Any water present in the "pre-wash" composition tends to interfere with the solvents' ability to remove oil and grease.
• the present compositions reconcile these adverse properties by dispensing aqueous solutions of the enzymes as "reversed micelles" within the hydrocarbon solvent/surfactant medium.
• the "reversed micelles” are formed by providing suitable surfactants which facilitate encapsulation of an aqueous solution of the enzymes and subsequently dispersing the enzyme/surfactant mixture in the hydrocarbon solvent medium.
• the enzymes are dissolved in the aqueous solution; surfactants are added.
• the surfactants encapsulate the enzymes, and then permit the dispersion of the enzyme-aqueous portion in the hydrocarbon medium.
• aqueous enzyme-surfactant "reversed- micelles” are extremely small and are dissolved within the hydrocarbon medium to form a suspension or dispersion. Thus there is no problem with phase separation. Further, due to the unique fine structure, i.e., reversed micelles, the enzymes in the aqueous portion are protected from premature degradation by the surrounding hydrocarbon medium.
• compositions comprise a small percentage (by weight) of the enzymes; somewhat larger percentages of enzyme stabilizers, e.g., sodium chloride, calcium chloride, or triethanolamine, all of which are dissolved in aqueous solution with the total water content being less then 5% of the composition; substantial percentages of one or more surfactants, preferably nonionic; and a large percentage of hydrocarbon solvent.
• enzyme stabilizers e.g., sodium chloride, calcium chloride, or triethanolamine
• surfactants preferably nonionic
• hydrocarbon solvent substantial percentages of hydrotropes, such as glycols may also be present.
• small amounts of perfumes or dyes may be included for aesthetic purposes.
• the pre-wash compositions are prepared in a prescribed procedure so as to produce a solution of reversed micelles having the aqueous enzyme solution held within the interior thereof; and with the micelles dispersed throughout the hydrocarbon solvent-surfactant medium.
• compositions may comprise several tenths of a percent of solution (as a glycol/water solution) enzyme; about a tenth of a percent of NaCL (as enzyme stabilizer); less than five percent water; about twenty-five to thirty-five percent surfactant; about sixty to seventy percent hydrocarbon solvent; about two to three percent of a glycol as a hydrotrope; and if desired, several tenths of percent perfume and coloring material (dye).
• the water dissolved enzyme may comprise about 0.2 weight%; about 1.5 weight% of 1M NaCl aqueous solution; about 2.5 weight% of ethylene glycol; about 14.5 weight% of an ethoxy-propyloxy linear alcohol nonionic surfactant; about 14.5 weight% of an ethoxylated linear alcohol nonionic surfactant; with the remainder being hydrocarbon solvent, e.g., a nominal C-12 to C-16 mixture of isoparaffins. Very small percentages of perfumes or coloring agents may be added.
• the total amount of water in the compositions be maintained at levels no greater than 5 weight%. Quantities of water greater than 5 weight% may interfere'with the ability of the hydrocarbon solvent to effectively remove oil and grease stains.
• Pre-wash compositions that exhibit the ability to simultaneously remove oil/grease stains and protein, fat, and/or starch stains from fabrics are formulated from surfactants, enzymes, and hydrocarbon solvents. While enzymes and hydrocarbon solvents are normally incompatible, the invention compositions overcome this difficulty by enclosing the enzymes in nonionic surfactants, and then dispersing the mixture in hydrocarbon solvents. Reversed micelles are thus formed in the surfactant-hydrocarbon medium.
• the water content of the compositions is kept very low, i.e., no more than 5 weight%, so that the oil and grease stain removing ability of the hydrocarbon solvent substrate remains unimpaired. At the same time the encapsulated enzymes are released to attack protein stains when the pre-wash composition is applied to soiled fabrics.
• the pre-wash compositions comprise a hydrocarbon solvent medium in which surfactants are dispersed, as well as an aqueous enzyme solution in the form of reversed micelles.
• the dispersed surfactants form the "micelle" interface between the aqueous enzyme solution and the surrounding hydrocarbon solvent medium.
• the hydrocarbon solvent comprises the major component, ideally being present in amounts greater than 60% by weight.
• the surfactants comprise the next most abundant component, ideally being present in an aggregate amount in the neighborhood of 30%. It is desirable that the solvent-surfactant ratio be maintained at about 2:1, e.g., if the solvent is about 60%, then the surfactants should be present at about 30%.
• the total amount of solvent and surfactant is not critical; however, together they should comprise well over 90% of the composition.
• the water acts as a solvent for the enzyme component, which is necessary to remove protein, fat and/or starch based stains.
• the enzymes are dissolved in the water.
• the enzymes are stabilized in the aqueous solution by the addition of salt (NaCl). Only a small percentage, e.g., several (i.e. 1, 2, 3 , 4, 5 or 6) tenths of a percent of the enzyme solution is needed to be effective. Higher amounts of enzymes may also be utilized, but will add to the cost of materials.
• K.N.P.U. means Kilo Novo Protease Units. There is no industry-wide standard for measuring activity.), about 0.2% by weight is an effective amount.
• Such enzyme solutions may be further stabilized by the addition of 1-2% of a 1M NaCl solution.
• a hydrotrope such as ethylene glycol can be added in low percentages, e.g., 2-3%, to aid the solubility of the surfactants in the solvent.
• the compositions are a clear solution with the enzymes encapsulated in reversed micelles within the surfactant-hydrocarbon solvent medium.
• the compositions exhibit excellent activity against both oil and grease stains as well as protein, and/or starch and/or fat-based stains.
• the compositions also retain an appreciable portion of the enzyme activity when stored for extended periods.
• the selection of the enzymes for use in the compositions may be made from any number of commercially available liquid enzyme solutions that are useful against proteins, lipids, and starchy substances. Such enzyme solutions are available from several commercial sources.
• proteases are supplied as aqueous stabilized solutions of the enzyme.
• the enzymes are generally stabilized by the addition of glycols such as propylene glycol.
• glycols such as propylene glycol.
• These solutions are also supplied in various strengths wherein the strengths are defined by the activity exhibited by the enzyme.
• the enzyme solution has an activity of 8 K.N.P.U.
• enzyme solutions of lesser or greater activity can be utilized in the invention compositions.
• lipases effective against fats; or amylases, effective against starches can also be used in the formulations. Both types of enzymes are commercially available, e.g. lipases - (see U.S. Patent 3,950,277 column 3, lines 15-55 for a description of lipase enzymes, their origins, and sources - incorporated herein by reference) amylases; - Rapidase from Societa Rapidase, France; and Milezyme e from Miles Labs., Elkhurst, Ind.
• compositions also include aqueous salt solution as stabilizing agent. While the exact amounts of the stabilizer is not critical, the inclusion of roughly 1.5 weight% of 1M NaCl to the aqueous enzyme solution has been found to aid in maintaining enzyme activity when the product is stored.
• Surfactants comprise a major component of the pre-wash compositions. Surfactants that are compatible with the hydrocarbon solvent medium are most necessary; and in addition such surfactants must not degrade, or interfere with the enzymes in the reversed micelles. The surfactants are also responsible for the micelle formation within the hydrocarbon medium. Nonionic surfactants are ideal for the above stated purposes.
• the long chain alcohols such as linear ethoxylated and linear propoxylated alcohols and mixtures thereof are particularly useful in the invention compositions.
• Such surfactants are completely compatible with the hydrocarbon solvents; they efficiently form reversed micelles to encapsulate the aqueous enzyme solutions; they do not degrade the enzymes; and they contribute significantly to the removal of soil from fabrics to which the compositions are applied.
• Alkyl ethoxylated and propoxylated alcohols in the nominal C-12 to C-16 range are most preferred.
• Such surfactants are available as standard articles of commerce under the name "Biosoft” from the Stepan Chemical Co.; or under the name “Neodol” from the Shell Chemical Co.
• the "Biosoft” series of nonionic surfactants are ethoxylated and propoxylated fatty alcohols sold in liquid form.
• the "Neodol” series of surfactants comprise a large group of nonionic surfactants including ethoxylated long chain alcohols with ethoxy groups ranging from 3 to 12 and the carbon chains from 12 to 15.
• Neodol 25-3 is composed of carbon chains nominally in the C-12 to C-15 range with an average of three ethoxy moieties per mole of alcohol.
• Biosoft EA-10 is a mixture of ethoxylated and propoxylated long chain fatty alcohols wherein the carbon chains are nominally in the C-10 to C-12 range with an average of 7.1 ethoxy and 2 propoxy moieties per mole of alcohol.
• nonionic surfactants can be substituted for the aforementioned surfactants in the compositions so long as they met the criteria set forth above.
• the surfactants are included in the compositions in substantial quantities making up somewhat less than one-third of the weight. While the total surfactant percentage is not critical, they should be present in roughly one-half the amount of hydrocarbon solvent. It has been found that this ratio of surfactant to solvent is necessary to achieve good removal of oil and grease based soil wherein both the hydrocarbon solvent and surfactants play key roles.
• the hydrocarbon solvent is the major component in the compositions and, in conjunction with the surfactants, is the primary agent for treating oil and grease based stains.
• the hydrocarbon solvent comprises well over half the compositions by weight; generally the percentages are in the 60-70% range.
• the solvent component be compatible with the formation of micelles, in this instance reversed micelles, i.e., micelles having an encapsulated aqueous component dispersed within an organic solvent medium. Because of this requirement it is desirable to employ solvents that are low in sulfur, acids, and oxygenated compounds. Pure hydrocarbon solvents, especially paraffinic hydrocarbons having fairly long carbon chains, e.g., C-10 to C-14 are highly preferred for use in the compositions. Such solvents are available from the Exxon Corporation of Houston, Texas under the trademark "Isopar” and "Norpar". Both of these groups of hydrocarbon solvents have a very high ( 98%) normal or isoparaffin content and very low concentrations of sulfur, acids, carbonyls, chlorides, etc. These solvents, or their equivalents from other manufacturers, are the preferred organic solvents for use in the compositions.
• compositions wherein the aqueous enzyme component is protected from degradation by the organic solvents, i.e., encapsulation within reversed micelles, it is necessary to proceed according to the following method:
• the clear liquid product may be packaged in any suitable container and stored for periods of several months and yet retain a good percentage of the enzyme activity. When used it is preferred to spray the product on the soiled fabrics a few minutes before placing them into a washing machine. Normal laundering procedures may be utilized. Of course, an effort should be made to spray the product directly on the visibly soiled portions of the fabric as direct contact will ensure full opportunity for attacking the oil/grease, and/or protein, fat or starch stains prior to the laundering process. I
• compositions were prepared wherein the enzyme content was varied from 0 up to 1.0%. These compositions were then tested for effectiveness against various types of stains, i.e., grass, ballpoint pen ink, dirty motor oil, and azocasein. Laundry detergent and a commercial pre-wash formulation, i.e., Clorox pre-wash, were, in each instance, used for comparison purposes. Table II below sets forth the compositions. Tables III, IV and VII set forth the results of % stain removal as measured by instrument. Tables V, VI, and VIII set forth the results measured by visual grading (on a scale of 1-5, with 5 highest, 1 lowest).
• compositions set forth in Table IX above were stored for periods of time up to 2 months at storage temperatures varying between 35° and 100°F.
• the samples of the compositions were tested against both grass and azocasein stains at intervals up to the 2 months stated above.
• Table XIII below sets forth the results, thus indicating the enzyme stability in the compositions as a function of time and storage temperature.
• TABLE XV below presents some prewash formulations wherein several different enzymes were utilized. These formulations were also tested for performance on various stains. These samples were evaluated for performance on grass, blood and gravy. All three formulas provided a benefit on grass and gravy. The blood stain was totally removed by detergent alone. No enzyme stability test was conducted.

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)
• Detergent Compositions (AREA)
• Immobilizing And Processing Of Enzymes And Microorganisms (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Enzymes And Modification Thereof (AREA)

Priority Applications (1)

Applications Claiming Priority (2)

Publications (2)

Family

ID=24609613

Family Applications (1)

Country Status (9)

Cited By (12)

Families Citing this family (1)

Citations (2)

Family Cites Families (3)

• 1985
  • 1985-08-23 CA CA000489369A patent/CA1263944A/fr not_active Expired
  • 1985-09-02 EP EP85306215A patent/EP0177183B1/fr not_active Expired
  • 1985-09-02 DE DE8585306215T patent/DE3574483D1/de not_active Expired - Lifetime
  • 1985-09-02 AT AT85306215T patent/ATE48285T1/de active
  • 1985-09-05 AU AU47103/85A patent/AU577148B2/en not_active Ceased
  • 1985-09-12 TR TR85/37851A patent/TR24582A/xx unknown
  • 1985-09-12 MX MX206600A patent/MX162714A/es unknown
  • 1985-09-12 ES ES547587A patent/ES8700312A1/es not_active Expired
  • 1985-09-12 JP JP60200717A patent/JPS6172100A/ja active Pending

Patent Citations (2)

Also Published As

Similar Documents

Legal Events