WO1999025802A1 - Method for cleaning using microwaves and a bleaching composition - Google Patents

Method for cleaning using microwaves and a bleaching composition Download PDF

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Publication number
WO1999025802A1
WO1999025802A1 PCT/US1998/024192 US9824192W WO9925802A1 WO 1999025802 A1 WO1999025802 A1 WO 1999025802A1 US 9824192 W US9824192 W US 9824192W WO 9925802 A1 WO9925802 A1 WO 9925802A1
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WO
WIPO (PCT)
Prior art keywords
peroxide
mixtures
bleach
composition
group
Prior art date
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PCT/US1998/024192
Other languages
French (fr)
Inventor
Howard David Hutton
Alan Scott Goldstein
Nancy Niehaus Casper
Original Assignee
The Procter & Gamble Company
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Publication date
Application filed by The Procter & Gamble Company filed Critical The Procter & Gamble Company
Priority to CA002309715A priority Critical patent/CA2309715A1/en
Priority to EP98958557A priority patent/EP1032636A1/en
Publication of WO1999025802A1 publication Critical patent/WO1999025802A1/en

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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/16Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using chemical substances
    • A61L2/18Liquid substances or solutions comprising solids or dissolved gases
    • A61L2/186Peroxide solutions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2/00Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor
    • A61L2/02Methods or apparatus for disinfecting or sterilising materials or objects other than foodstuffs or contact lenses; Accessories therefor using physical phenomena
    • A61L2/08Radiation
    • A61L2/12Microwaves
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/049Cleaning or scouring pads; Wipes
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • C11D3/3945Organic per-compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/395Bleaching agents
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2202/00Aspects relating to methods or apparatus for disinfecting or sterilising materials or objects
    • A61L2202/20Targets to be treated
    • A61L2202/23Containers, e.g. vials, bottles, syringes, mail
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2202/00Aspects relating to methods or apparatus for disinfecting or sterilising materials or objects
    • A61L2202/20Targets to be treated
    • A61L2202/24Medical instruments, e.g. endoscopes, catheters, sharps
    • C11D2111/46

Abstract

A method is disclosed for removing stains and/or odors and for disinfecting plastics, and other surfaces by contacting a substrate containing a liquid or gel treating composition with the surface and subjecting it to microwaves. The treating composition is a cleaning or detergent composition and includes a bleaching agent. The method is also very effective in disinfecting and deodorizing surfaces.

Description

METHOD FOR CLEAN ING USING MICROWAVES AND A BLEACHING COMPOSITION
TECHNICAL FIELD
The invention generally relates to the field of bleaching compositions. More specifically, the invention relates to a method for cleaning or otherwise removing stains, odors and microbes from surfaces by contacting a substrate having a bleaching composition impregnated or otherwise contained therein, and subjecting the surface and substrate to microwaves. The composition is a liquid or gel detergent composition. This method provides enhanced cleaning and improved stain removal on plastics, ceramics and other surfaces. The bleaching composition comprise a bleaching agent, preferably diacyl peroxide in a liquid or gel formulation.
BACKGROUND OF THE INVENTION
Detergents used for washing tableware (i.e., glassware, china, silverware, plastic, etc.) or kitchenware in the home or institution have long been .known. Dishwashing in the seventies is reviewed by Mizuno in Vol. 5, Part III of the Surfactant Science Series, Ed. W.G. Cutler and R.C. Davis, Marcel Dekker, N.Y., 1973, incorporated by reference. The particular requirements of cleansing tableware and leaving it in a sanitary, essentially stainless, residue-free state has indeed resulted in so many particular compositions that the body of art pertaining thereto is now recognized as quite distinct from other cleansing product art. Additionally, the body of art pertaining to fabric cleaning is immense and encompasses many foπnulations designed for stain removal, many including bleaches.
However, consumers continue to experience problems with stain removal on various surfaces, including typical kitchenware surfaces. In particular, formulators have experienced difficulties in foimulating detergents which remove both hydrophobic and hydrophilic stains. Typically for stain removal, formulators have turned to chlorine bleach or sources of hydrogen peroxide and bleach activators.
Numerous substances have been disclosed in the art as effective bleach activators. One widely-used bleach activator is tetraacetyl ethylene diamine (TAED). TAED provides effective hydrophilic cleaning especially on beverage stains, but has limited performance on hydrophobic stains, dingy stains and body soils. .Another type of activator, such as nonanoyloxybenzenesulfonate (NOBS) and other activators which generally comprise long chain alkyl moieties, is hydrophobic in nature and provides excellent performance on dingy stains and carotenoid stains.
It would seem that a combination of bleach activators, such as T.AED and NOBS, would provide an effective detergent composition which would perfoπn well on both hydrophilic and hydrophobic soils and stains. However, many of the hydrophilic activators developed thus far, including TAED, have been found to have limited efficacy, especially at wash water temperatures below 60 C. Another consideration in the development of consumer products effective on both types of soils is the additional costs associated with the inclusion of two or more bleach activators. Accordingly, it is of substantial interest to the manufacturers of bleaching systems to find a less expensive type of bleaching activator.
Chlorine bleaches are effective for stain and/or soil removal. While chlorine bleach is a very effective cleaning agent, it is not compatible with a variety of detergent ingredients and may require lengthy soaking time in which the bleach and the stained surface must remain in contact to ensure stain removal.
.Another known bleaching source is diacyl peroxides (DAPs). Although DAPs have been disclosed for use in the laundry and anti-acne area, they have had limited success in liquid or automatic dishwashing detergent area. In the laundry field, certain diacyl peroxides have been disclosed as beneficial in cleaning tea stains from fibrous material. Recently, DAPs have been used to improve stain removal performance on plastics. Another problem facing formulators is stability of the bleaching agents and other individual ingredients over time, especially in liquid products. This is particularly true for DAPs under alkaline conditions.
As a consequence to the above-identified problems, there has been a substantial amount of research to develop bleaching systems which are stable and effective in liquid formulations and in which the amount of soaking time needed to remove stains is greatly reduced. Recently, certain bleaching agents have been applied directly to a surface and subjected to microwaves. Such a method of cleaning performs efficiently and effectively under mixed soil load conditions, especially mixtures of hydrophobic and hydrophilic soils. The bleaching agent is contained in a detergent composition which has the property of removing stains, especially tea, fruit juice and carotenoid stains objected to by the consumer from plastic dishware, glass, wood, and many other known surfaces when exposed to microwaving from any typical household or commercial microwave.
However, one problem associated with the aforementioned method involving microwaving a bleach-containing detergent composition is that the detergent composition is usually in liquid foim and sprayed onto the surface to be cleaned by the consumer. As a consequence of this, the dosing or amount of the detergent sprayed onto the surface is not uniform and is subject to misuse which can interfere with the overall cleaning performance. For example, excess amounts of the detergent composition can be unnecessarily applied to the surface, thereby adding to the costs associated with removing or otherwise cleaning the surfaces. On the other hand, insufficient amounts of the detergent composition may be sprayed on the surface resulting in poor or little performance. Additionally, the liquid spray on method only permits a relatively low amount of solvent such as water to be used, which in turn, reduces the duration of microwaving before the detergent dries up and is nonresponsive to microwaves.
Accordingly, there is a need for method by which plastic, ceramic and other surfaces can be efficiently and effectively cleaned without using excessive or insufficient amounts of a treating composition and subjecting the composition to misuse which inhibits the cleaning perfoimance.
SUMMARY OF THE INVENTION
The invention provides a method by which surfaces, such as tableware, can be cleaned using a substrate containing a detergent composition containing a bleaching agent. The method involves taking the substrate, such as a sponge, that has been impregnated with the bleach-containing detergent composition and contacting the substrate with the surface to be cleaned, sanitized or deodorized and subjecting both the substrate and surface to microwaves. The detergent composition foams during microwaving which delivers the detergent composition uniformly to the surface. Optionally, water can be added to prolong the response time to microwaves for enhanced cleaning.
By "effective amount" or "stain removal-improving amount", it is meant a bleaching agent is any amount capable of measurably improving stain removal (especially of tea stains and carotenoid stains) from the surface, i.e., soiled dishware, when it is washed by the consumer. In general, this amount may vary quite widely. By "tough food cleaning" herein is meant the ability to clean burned-on, dried-on, or baked- on foods. Examples include burned on lasagna, dried on egg, and burned on beef grease. All percentages and proportions herein are by weight, and all references cited are hereby incorporated by reference, unless otherwise specifically indicated.
In accordance with one aspect of the invention, a method of treating soiled, stained or otherwise infected surfaces is provided. The method comprises the steps of: (a) contacting the surface with a substrate containing an effective amount of a treating composition including a bleaching agent and a solvent which generates heat under microwave radiation; (b) subjecting the surface and the substrate to microwaves for an effective amount of time such that the treating composition foams onto the surface, thereby treating the surface.
In accordance with another aspect of the invention, a product for treating surfaces is provided. The product comprises a substrate containing a treating composition including a bleaching agent and a solvent which generates heat under microwave radiation, the product further including instructions for using of the treating composition comprising the steps of: (a) contacting a surface with the substrate; and (b) subjecting the surface to microwaves for an effective amount of time to treat the surface.
Accordingly, it is an object of the invention it is an object of the invention to provide a method by which plastic, ceramic and other surfaces can be efficiently and effectively cleaned without using excessive or insufficient amounts of a treating composition. These and other objects, features and attendant advantages of the present invention will become apparent to those skilled in the art from a reading of the following detailed description of the preferred embodiment and the appended claims.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The method of the invention essentially includes the steps of contacting the surface to be treated with a substrate containing a treating composition and subjecting both the substrate and surface to microwaves. Optionally, water can be added to the surface in order to prolong the response time to microwaves. This is a significant improvement over a typical liquid treating composition which has a limited amount of water or other solvent contained therein. Specifically, by using a spray-on liquid treating composition, the user would have to add water in addition to the sprayed on liquid composition which is counter-intuitive to conventional liquid spray-on treatment composition use, or the user would be required to spray on large mounts of the treatment composition which is difficult to persuade consumers to do as they feel they are wasting or incorrectly using excessive amounts of the composition. By contrast, the substrate in the present invention can be loaded with water or other solvent at higher amounts than that which would be present in the liquid spray on treatment composition usage, and optionally, additional water can be added as part of the method which is not counterintuitive to normal consumer usage of substrate-like products.
The treating composition is preferably a detergent composition which contains a bleaching agent. In preferred embodiments of the method invention, the treating composition further comprises an ingredient selected from the group consisting of surfactant, solvent, clay, water, polycarboxylate thickeners, baking soda, carbonates, phosphates, hydrobenzoic acid, dicarboxylic acid, siloxanes, perfumes, bleach catalysts, and mixtures thereof. The treating composition can be in a variety of foπns including a liquid, gel or granules.
Although this method can be employed to assist in bleaching the surface for any desired purpose, examples of likely uses include one or more of the following: stain removal, stain reducing, deodorizing, or disinfecting. Preferably, the surface is selected from the group consisting of ceramic, plastic, dishware, dentifrice/dentures, surgical/ medical equipment, baby bottles, wood, glass, and mixtures thereof. The surface after being treated with the bleach-containing detergent composition is then subjected to microwaves for an effective amount of time to "treat" the surface to the desired end result, i.e. stain reduction, deodorizing, disinfecting. Typically an "effective amount of time" is from about 30 seconds to about 5 minutes, preferably from about 30 seconds to about 3 minutes, and most preferably from about 1 minute to 2 minutes. During this effective amount of time, the treating composition on and/or in the substrate foams uniformly onto the surface and delivers the bleaching agent, which in turn, cleans the stains, deodorizes and or disinfects the surface. This provides a dramatically unexpectedly large increase in performance as compared to simply spraying or otherwise applying the treating composition to the surface.
Preferred aspects of the treating composition described herein include having the bleaching agent selected from the group consisting of diacyl peroxide, a source of hydrogen peroxide and bleach activator, a source of hydrogen peroxide, a chlorine bleach, and mixtures thereof. Another highly preferred treating composition is a gel or liquid detergent composition comprising by weight: (a) from about 0.1% to about 60% of said bleaching agent which is selected from the group consisting of: i) diacyl peroxide having the general formula:
RC(O)OO(O)CRl wherein R and Rl can be the same or different; ii) a source of hydrogen peroxide; iii) a source of hydrogen peroxide and a bleach activator; iv) a chlorine bleach; and v) mixtures thereof; (b) from 0% to about 95% of a solvent; (c) from 0% to about 50% of a surfactant; and (d) from 0% to about 7% of a thickener. Another highly preferred treating composition is a gel detergent composition comprising by weight: (a) from about 0.1% to about 10% of a diacyl peroxide having the general formula:
RC(O)OO(O)CRl
wherein R and Rl can be the same or different; (b) from 0% to about 50% of a surfactant; and (c) from 0% to about 7% of a thickener; the composition having a neat pH of from about 3 to about 10; and such that said diacyl peroxide remains undissolved in said composition.
Substrate - The substrate used in the method invention provided herein can be any material capable of carrying, holding, containing or otherwise delivering the bleach- containing detergent composition. In certain preferred embodiments, the treating composition is in gel form and impregnated in the substrate so that it can be conveniently packaged and stored on a commercially large scale. Preferably, the substrate is selected from the group consisting of comminuted wood pulp, creped cellulose wadding, hydrogel-forming polymer gelling agents, creped tissues, creped nonwovens containing fibers comprised of absorbent polymers, modified cross-linked cellulose fibers, capillary channel fibers, absorbent foams, thermally bonded airlaid materials, absorbent sponges, synthetic staple fibers, polymeric fibers, peat moss, and combinations thereof. The most preferred substrate is an absorbent sponge.
Microwaves - By microwaving herein is meant exposing said surface treated with said compositions to microwave electromagnetic radiation. This is by any conventional means such as by placing the surface in a typical microwave such as used in homes and microwaving the surface for a sufficient time. Microwaves have an electromagnetic radiation wavelength of from about 1cm to about lm, preferably from about 3 cm to about 30cm, more preferably from about 11cm to about 13cm. See Aust. J. Chem., 1995, 48 [10], 1665-1692, Developments in Microwave- Assisted Organic Chemistry, by Strauss and Trainor. Bleaching Agents
Suitable bleaching for use herein are listed below:
Diacyl Peroxide Bleaching Species - The composition of the present invention preferably contain diacyl peroxide of the general foimula:
RC(O)OO(O)CRl wherein R and Rl can be the same or different and are hydrocarbyls, preferably no more than one is a hydrocarbyl chain of longer than ten carbon atoms, more preferably at least one has an aromatic nucleus.
Examples of suitable diacyl peroxides are selected from the group consisting dibenzoyl peroxide, dianisoyl peroxide, benzoyl gluaryl peroxide, benzoyl succinyl peroxide, di-(2-methybenzoyl) peroxide, diphthaloyl peroxide, dinaphthoyl peroxide, substituted dinaphthoyl peroxide, and mixtures thereof, more preferably dibenzoyl peroxide, dicumyl peroxide, diphthaloyl peroxides and mixtures thereof. A particularly preferred diacyl peroxide is dibenzoyl peroxide.
Hydrogen Peroxide Source - The compositions of the present invention may comprise a source of oxygen bleach, preferably a source of hydrogen peroxide with or without a selected bleach activator. The source of hydrogen peroxide is typically any common hydrogen-peroxide releasing salt, such as sodium perborate or sodium percarbonate. Hydrogen peroxide sources are illustrated in detail in Kirk Othmer Review on Bleaching and include the various forms of sodium perborate and sodium percarbonate and modified forms. .An "effective amount" of a source of hydrogen peroxide is any amount capable of measurably improving stain removal (especially of tea and tomato stains) from the soiled surface compared to a hydrogen peroxide source-free composition when the soiled surface is washed by the consumer.
The preferred source of hydrogen peroxide used herein can be any convenient source, including hydrogen peroxide itself. For example, perborate, e.g., sodium perborate (any hydrate but preferably the mono- or tetra-hydrate), sodium carbonate peroxyhydrate or equivalent percarbonate salts, sodium pyrophosphate peroxy-hydrate, urea peroxyhydrate, or sodium peroxide can be used herein. Sodium perborate monohydrate and sodium percarbonate are particularly preferred. Mixtures of any convenient hydrogen peroxide sources can also be used.
Another source of hydrogen peroxide is enzymes. Examples include Lipoxidase, glucose oxidase, peroxidase, alcohol oxidases, and mixtures thereof.
Bleach Activators - Numerous conventional bleach activators are known. See for example activators referenced hereinabove in the background as well as U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al, and U.S. Patent 4,412,934. Nonanoyloxybenzenesulfonate (NOBS) or acyl lactam activators may be used, and mixtures thereof with TAED can also be used. See also U.S. 4,634,551 for other typical conventional bleach activators. Also known are amido-derived bleach activators of the formulae: R1N(R5)C(O)R2C(O)L or R1C(O)N(R5)R2C(O)L wherein R1 is an alkyl group containing from about 6 to about 12 carbon atoms, R2 is an alkylene containing from 1 to about 6 carbon atoms, R-> is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group. Further illustration of bleach activators of the above formulae include (6- octanamidocaproyl)oxybenzenesulfonate, (6-nonanamidocaproyl)-oxybenzenesulfonate, (6-decanamidocaproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551. .Another class of bleach activators comprises the benzoxazin-type activators disclosed by Hodge et al in U.S. Patent 4,966,723, issued October 30, 1990. Still another class of bleach activators includes acyl lactam activators such as octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethyl-hexanoyl valerolactam, t-butylbenzoylcaprolactam, t-butylbenzoylvalerolactam and mixtures thereof. The present compositions can optionally comprise aryl benzoates, such as phenyl benzoate, and acety triethyl citrate. Quaternary Substituted Bleach Activators - The present compositions can also comprise quaternary substituted bleach activators (QSBA). QSBA's herein typically have the formula E-[Z]n-C(O)-L, wherein group E is referred to as the "head", group Z is referred to as the "spacer" (n is 0 or 1, i.e., this group may be present or absent, though its presence is generally preferred) and L is referred to as the "leaving group". These compounds generally contain at least one quaternary substituted nitrogen moiety, which can be contained in E, Z or L. More preferably, a single quaternary nitrogen is present and it is located in group E or group Z. In general, L is a leaving group, the pKa of the corresponding carbon acid (HL) of which can lie in the general range from about 5 to about 30, more preferably, from about 10 to about 20, depending upon the hydrophilicity of the QSBA. pKa's of leaving groups are further defined in U.S. Pat. No. 4,283,301.
Preferred QSBA's herein are water-soluble but have a tendency to partition to a definite extent into surfactant micelles, especially into micelles of nonionic surfactants.
Leaving groups and solubilizing tendencies of quaternary moieties which can be present in the QSBA's are further illustrated in U.S. 4,539,130, Spt. 3, 1985 incorporated by reference. This patent also illustrates QSBA's in which the quaternary moiety is present in the leaving group L.
British Pat. 1,382,594, published Feb. 5, 1975, discloses a class of QSBA's found suitable for use herein. In these compounds, Z is a poly(methylene) or oligo(methylene) moiety, i.e., the spacer is aliphatic, and the quaternary moiety is E. U.S. 4,818,426 issued Apr. 4., 1989 discloses another class of QSBA's suitable for use herein. These compounds are quaternary ammonium carbonate esters wherein, with reference to the above formula, the moiety Z is attached to E via a carbon atom but is attached to the carbonyl moiety through a linking oxygen atom. These compounds are thus quaternary ammonium carbonate esters. The homologous compounds wherein the linking oxygen atom is absent from Z are likewise known and are useful herein. See, for example, U.S. 5,093,022 issued March 3, 1992 and U.S. 4,904,406, issued Feb. 27, 1990. Additionally, QSBA's are described in EP 552,812 Al published July 28, 1993, and in EP 540,090 A2, published May 5, 1993.
Chlorine Bleach - Any chlorine bleach typically known in the art is suitable for use herein. Preferred chlorine bleaches for use herein include sodium hypochlorite, lithium hypochlorite, calcium hyposhlorite, chlorinated trisodium phosphates, and mixtures thereof. For more about chlorine bleaches see Surfactant Science Series, Vol. 5, Part II, pages 520-26.
Other Ingredients - Detersive ingredients or adjuncts optionally included in the instant compositions can include one or more materials for assisting or enhancing cleaning performance, treatment of the surface to be cleaned, or designed to improve the aesthetics or ease of manufacture of the compositions. Other adjuncts which can also be included in compositions of the invention at their conventional art-established levels, generally from 0% to about 20% of the composition, preferably at from about 0.1% to about 10%, include one or more processing aids, color speckles, dyes, fillers, bleach- compatible enzymes, germicides, alkalinity sources, hydrotropes, stabilizers, perfumes, solubilizing agents, carriers. In general, materials used for the production of detergent compositions herein are preferably checked for compatibility with the essential ingredients used herein.
In the preferred embodiments, additional ingredients such as water-soluble silicates (useful to provide alkalinity and assist in controlling corrosion), dispersant polymers (which modify and inhibit crystal growth of calcium and/or magnesium salts), chelants (which control transition metals), builders such as citrate (which help control calcium and/or magnesium and may assist buffering action), and alkalis (to adjust pH) are present. Additional bleach-improving materials such as bleach catalysts may be added.
Solvent - The solvent of the present invention is of the type which the diacyl peroxide will dissolve in. The preferred solvents are selected based upon the solubility parameter value of the diacyl peroxide employed. The solubility parameter value of a compound is available from literature sources such as Polymer Handbook. Values obtained by experiments are preferred. If the solubility parameter value is not available in the literature, the value can be calculated by using any of the methods described by Robert F. Fedor's article "A Method of Estimating Both the Solubility Parameters & Molar Volumes of Liquids", Polymer Engineering & Science, February, 1974, Vol 14, No. 2. Once the solubility parameter value is obtained of the diacyl peroxide, solvents are selected having a solubility parameter which fall within the diacyl peroxide solubility parameter.
Said solvent is preferably selected from the group consisting of N-alkyl pyrrolidones, such as N-ethyl pyrrolidone, diacetone alcohol, long chain (greater than Cg) alkyl ethers, cyclic alkyl ketones, and mixtures thereof. .amines, ethers and short chain (less than Cg) primary and secondary alcohols are preferably not present. Without being limited by theory, it is believed that the presence of these compounds may introduce stability problems. Thus, when diacyl peroxide and solvent are present in the compositions of this invention, it is further preferable that the amount of amine, ether, or primary or secondary alcohol be limited to no more than about 5%, preferably no more than about 3%, by weight of the composition. Surfactants - Nonlimiting examples of surfactants useful herein include the conventional C\ j-Cj alkyl benzene sulfonates ("LAS") and primary, branched-chain and random C10-C20 alkyl sulfates ("AS"), the Cjo-Cig secondary (2,3) alkyl sulfates of the formula CH3(CH2)χ(CHOSO3-M+) CH3 and CH3 (CH2)y(CHOSO3-M+) CH CH3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, the C10-C1 g alkyl alkoxy sulfates ("AEXS"; especially EO 1-7 ethoxy sulfates), Cjo-Ci alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the CjQ-Ci glycerol ethers, the CjQ-Cig alkyl polyglycosides and their corresponding sulfated polyglycosides, and C^-Cig alpha-sulfonated fatty acid esters.
If desired, the conventional nonionic and amphoteric surfactants such as the Cj2" Cj alkyl ethoxylates ("AE") including the so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxylates (especially ethoxylates and mixed ethoxy/propoxy), Cl2"Cl betaines and sulfobetaines ("sultaines"), and the like, can also be included in the overall compositions. The Cjo-Cig N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the Ci2-Cιg N-methylglucamides. See WO 9,206,154. Other sugar-derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C1 Q-Cj N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl Cj2- Cig glucamides can be used for low sudsing. C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain C10-C16 soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in standard texts.
Preferably, anionic surfactants are used herein. Without being limited by theory, it is believed that the use of anionic surfactants maximizes both cleaning performance and removal of residual bleach from the surface being treated.
One example of a group of surfactants suitable for use herein are those selected from the group consisting of alkyl ether sulfate, long chain (greater than about C7) alkyl ethoxylate, linear alkyl benzene sulfonate (LAS), alkyl (ether) carboxylates, alkyl polyglucaside (APG), and mixtures thereof.
Thickeners - Thickeners for use herein can be selected from clay, polycarboxylates, such as Polygel®, gums, carboxymethyl cellulose, polyacrylates, and mixtures thereof. The preferred clay type herein has a double-layer structure. The clay may be naturally occurring, e.g., Bentonites, or artificially made, e.g., Laponite®. Laponite® is supplied by Southern Clay Products, Inc. See The Chemistry and Physics of Clays, Grimshaw, 4th ed., 1971, pages 138-155, Wiley-Interscience. Bleach catalysts - If desired, detergent compositions herein may additionally incorporate a catalyst or accelerator to further improve bleaching or starchy soil removal. Any suitable bleach catalyst can be used. The compositions will comprise from about 0.0001% to about 0.1% by weight of bleach catalyst.
Typical bleach catalysts comprise a transition-metal complex, for example one wherein the metal coordinating ligands are quite resistant to labilization and which does not deposit metal oxides or hydroxides to any appreciable extent under the conditions of cleaning herein. Such catalyst compounds often have features of naturally occurring compounds such as enzymes but are principally provided synthetically. Highly preferred accelerators include, for example, the cobalt 3+ catalysts, especially {Co(NH3)5Cl}2+or equivalents thereof with various alternate donor ligands. Such complexes include those formerly disclosed for use in laundry compositions in U.S. Pat. 4,810,410 to Diakun et al, issued March 7, 1989. The active species thereof is believed to be {Co(NH3)5(OOH)}2+ and is disclosed in J. Chem. Soc. Faraday Trans., 1994, Vol. 90, 1105-1114. Alternate catalysts or accelerators are the noncobalt transition metal complexes disclosed in this reference, especially those based on Mo(VI), Ti(IV), W(VI), V(V) and Cr(VI) although alternate oxidation states and metals may also be used. Such catalysts include manganese-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. 5,244,594; U.S. 5,194,416; U.S. 5,114,606; and EP Nos. 549,271 Al, 549,272 Al, 544,440 A2, and 544,490 Al; preferred examples of these catalysts include Mn^2(lΛ" ,)3(TACN)2- (PF6)2, Mnπi2(μ.O)1(μ-OAc)2(TACN)2(Clθ4)2, MnIV4(μ.θ)6(TACN)4(ClO4)4, MnIIlMnIV4.(μ-θ)1(μ-OAc)2-(TACN)2-(ClO4)3, MnIV-(TACN)-(OCH3)3(PF6), and mixtures thereof wherein TACN is trimethyl-l,4,7-triazacyclononane or an equivalent macrocycle; though alternate metal-coordinating ligands as well as mononuclear complexes are also possible and monometallic as well as di- and polymetallic complexes and complexes of alternate metals such as iron or ruthenium are all within the present scope. Other metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611. The use of manganese with various complex ligands to enhance bleaching is also reported in the following United States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5J53J61; and 5,227,084.
Transition metals may be precomplexed or complexed in-situ with suitable donor ligands selected in function of the choice of metal, its oxidation state and the denticity of the ligands. Other complexes which may be included herein are those of U.S. Application Ser. No. 08/210,186, filed March 17, 1994. Other suitable transition metals in said transition-metal-containing bleach catalysts include iron, cobalt, ruthenium, rhodium, iridium, and copper. Builders - Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of particulate soils.
The level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least about 1% builder. Liquid formulations typically comprise from about 5% to about 50%, more typically about 5% to about 30%, by weight, of detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.
Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates.
Examples of silicate builders are the alkali metal silicates, particularly those having a SiO2:Na2O ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). NaSKS-6 can be prepared by methods such as those described in German DE-A-3,417,649 and DE-A-3, 742,043. Other layered silicates, such as those having the general formula NaMSixθ2x+ι -y^O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20 can be used herein. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms.
Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.
Aluminosilicate builders may be useful in the present invention. Aluminosilicate builders include those having the empirical formula:
Mz(zAlθ2)y]-xH2O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.
Useful aluminosilicate ion exchange materials are commercially available. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:
Naι2[(AlO2)i2(Siθ2)i2]- H2θ wherein x is from about 20 to about 30, especially about 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein. Preferably, the aluminosilicate has a particle size of about OJ-10 microns in diameter.
Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.
Included among the polycarboxylate builders are a variety of categories of useful materials. One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.
Other useful detergency builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5- tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.
Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of importance for liquid detergent formulations due to their availability from renewable resources and their biodegradability. Oxydisuccinates are also especially useful in such compositions and combinations.
Also suitable in the compositions of the present invention are the 3,3-dicarboxy-4- oxa-l,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.
Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226, Crutchfield et al, issued March 13, 1979 and in U.S. Patent 3,308,067, Diehl, issued March 7, 1967. See also Diehl U.S. Patent 3,723,322.
Fatty acids, e.g., Ci2"Cl8 monocarboxylic acids, can also be incorporated into the compositions alone, or in combination with the aforesaid builders, especially citrate and/or the succinate builders, to provide additional builder activity.
Various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate builders such as ethane- 1-hydroxy-lJ-diphosphonate and other known phosphonates (see, for example, U.S. Patents 3,159,581 ; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.
Enzymes - Suitable enzymes include proteases, amylases, Upases, cellulases, peroxidases, and mixtures thereof of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin. Preferred selections are influenced by factors such as pH-activity and/or stability optima, thermostability, and stability to active bleach, detergents, builders and the like. In this respect bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.
Enzymes are normally incorporated into detergent or detergent additive compositions at levels sufficient to provide a "cleaning-effective amount". The term "cleaning effective amount" refers to any amount capable of producing a cleaning, stain removal, soil removal, whitening, deodorizing, or freshness improving effect on surfaces such as dishware and the like. In practical terms for current commercial preparations, the compositions herein may comprise from 0.001% to 5%, preferably 0.01%-1% by weight of a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide from 0.005 to 0J Anson units (AU) of activity per gram of composition.
The preparation of protease enzyme and analogous enzymes is described in GB 1,243,784 to Novo. Other suitable proteases include ALCALASE® and SAVINASE® from Novo and M.AXATASE® from International Bio-Synthetics, Inc., The Netherlands; as well as Protease A as disclosed in EP 130,756 A, January 9, 1985 and Protease B as disclosed in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985. See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 9203529 A to Novo. Other preferred proteases include those of WO 9510591 A to Procter & Gamble . When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 9507791 to Procter & Gamble. A recombinant trypsin-like protease for detergents suitable herein is described in WO 9425583 to Novo.
Amylases suitable herein, especially for, but not limited to automatic dishwashing purposes, include, for example, α-amylases described in GB 1,296,839 to Novo; RAPID ASE®, International Bio-Synthetics, Inc. and TERMAMYL®, Novo. FUNGAMYL® from Novo is especially useful. Engineering of enzymes for improved stability, e.g., oxidative stability, is known. See, for example J. Biological Chem., Vol. 260, No. 11, June 1985, pp 6518-6521 Preferred amylases include (a) an amylase according to the hereinbefore incorporated WO 9402597, Novo, Feb. 3, 1994. Other amylases include variants having additional modification in the immediate parent as described in WO 9510603 A and are available from the assignee, Novo, as DURAMYL® . Other particularly preferred oxidative stability enhanced amylase include those described in WO 9418314 to Genencor International and WO 9402597 to Novo.
Cellulases usable herein include those disclosed in U.S. 4,435,307, Barbesgoard et al, March 6, 1984. Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A- 2.095.275 and DE-OS-2.247.832. CAREZYME® (Novo) is especially useful. See also WO 9117243 to Novo.
Suitable lipase er zymes for detergent usage include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB 1,372,034. See also lipases in Japanese Patent Application 53,20487, laid open Feb. 24, 1978. Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. LIPOLASE® enzyme derived from Humicola lanuginosa and commercially available from Novo, see also EP 341,947, is a preferred lipase for use herein. Lipase and amylase variants stabilized against peroxidase enzymes are described in WO 9414951 A to Novo. See also WO 9205249 and RD 94359044.
Cutinase enzymes suitable for use herein are described in WO 8809367 A to Genencor.
Peroxidase en^mes may be used in combination with oxygen sources, e.g., percarbonate, perborate, hydrogen peroxide, etc., for "solution bleaching" or prevention of transfer of dyes or pigments removed from surfaces during the wash to other surfaces present in the wash solution. Known peroxidases include horseradish peroxidase, ligninase, and haloperoxidases such as chloro- or bromo-peroxidase. Peroxidase- containing detergent compositions are disclosed in WO 89099813 A, October 19, 1989 to Novo and WO 8909813 A to Novo.
A range of enzyme materials and means for their incorporation into synthetic detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A to Genencor International, WO 8908694 A to Novo, and U.S. 3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed in U.S. 4,101,457, Place et al, July 18, 1978, and in U.S. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations, and their incorporation into such formulations, are disclosed in U.S. 4,261,868, Hora et al, April 14, 1981. Enzymes for use in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S. 3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. 3,519,570. A useful Bacillus, sp. AC 13 giving proteases, xylanases and cellulases, is described in WO 9401532 A to Novo.
Enzyme Stabilizing System - Enzyme-containing, including but not limited to, liquid compositions, herein may comprise from about 0.001% to about 10%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to about 6%, by weight of an enzyme stabilizing system. Such stabilizing systems can, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids, and mixtures thereof, and are designed to address different stabilization problems depending on the type and physical form of the detergent composition. See Severson, U.S. 4,537,706 for a review of Borate stabilizers.
Stabilizing systems may further comprise from 0 to about 10%, preferably from about 0.01% to about 6% by weight, of chlorine bleach scavengers, added to prevent chlorine bleach species present in many water supplies from attacking and inactivating the enzymes, especially under alkaline conditions. Suitable chlorine scavenger anions are widely known and readily available, and, if used, can be salts containing ammonium cations with sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc. .Antioxidants such as carbamate, ascorbate, etc., organic amines such as ethylenediaminetetracetic acid (EDTA) or alkali metal salt thereof, monoethanolamine (MEA), and mixtures thereof can likewise be used. Other conventional scavengers such as bisulfate, nitrate, chloride, sources of hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate, tartrate, salicylate, etc., and mixtures thereof can be used if desired. Material Care Agents - The present compositions may optionally contain as corrosion inhibitors and/or anti-tarnish aids one or more material care agents such as silicates. Material Care Agents are preferred especially in countries where electroplated nickel silver and sterling silver are common in domestic flatware, or when aluminium protection is a concern and the composition is low in silicate. Material care agents include bismuth salts, transition metal salts such as those of manganese, certain types of paraffin, triazoles, pyrazoles, thiols, mercaptans, aluminium fatty acid salts, and mixtures thereof and are preferably incorporated at low levels, e.g., from about 0.01% to about 5% of the composition. A preferred paraffin oil is a predominantly branched aliphatic hydrocarbon comprising from about 20 to about 50, more preferably from about 25 to about 45, carbon atoms with a ratio of cyclic to noncyclic hydrocarbons of about 32 to 68 sold by Wintershall, Salzbergen, Germany as WINOG 70®. Bi(NO3)3 may be added. Other corrosion inhibitors are illustrated by benzotriazole, thiols including thionaphtol and thioanthranol, and finely divided aluminium fatty acid salts. All such materials will generally be used judiciously so as to avoid producing spots or films on glassware or compromising the bleaching action of the compositions. For this reason, it may be preferred to formulate without mercaptan anti-tamishes which are quite strongly bleach- reactive or common fatty carboxylic acids which precipitate with calcium.
Chelating Agents - The detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents. Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined.
Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilo- triacetates, ethylenediamine tetraproprionates, triethylenetetra-amine-hexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.
Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2- dihydroxy-3,5-disulfobenzene. A preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.
If utilized, these chelating agents will generally comprise from about 0.1% to about 10% by weight of the detergent compositions herein. More preferably, if utilized, the chelating agents will comprise from about 0.1% to about 3.0% by weight of such compositions.
Polymeric Dispersing Agents - Polymeric dispersing agents can advantageously be utilized at levels from about 0.1% to about 7%, by weight, in the compositions herein, especially in the presence of zeolite and/or layered silicate builders. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art can also be used. It is believed, though it is not intended to be limited by theory, that polymeric dispersing agents enhance overall detergent builder performance, when used in combination with other builders (including lower molecular weight polycarboxylates) by crystal growth inhibition, particulate soil release peptization, and anti-redeposition.
Brightener - Any optical brighteners or other brightening or whitening agents known in the art can be incorporated at levels typically from about 0.05% to about 1.2%, by weight, into the detergent compositions herein. Commercial optical brighteners which may be useful in the present invention can be classified into subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acid, methinecyanines, dibenzothiphene-5,5-dioxide, azoles, 5- and 6- membered-ring heterocycles, and other miscellaneous agents. Examples of such brighteners are disclosed in "The Production and Application of Fluorescent Brightening Agents", M. Zahradnik, Published by John Wiley & Sons, New York (1982).
Product/Instructions - This invention also encompasses the inclusion of instructions on the use of a product including a substrate containing the treating composition with the package or with other forms of advertising associated with the sale or use of the substrate. The instructions may be included in any manner typically used by consumer product manufacturing or supply companies. Examples include providing instructions on a label attached to the container holding the substrate; on a sheet either attached to the container or accompanying it when purchased; or in advertisements, demonstrations, and/or other written or oral instructions which may by connected to the purchase or use of a product containing a substrate and the treating composition.
Specifically the instructions will include a description of the use of the substrate in connection with microwaving. The instructions, for instance, may additionally include information relating to the length of microwaving time; the recommended settings on the microwave; the recommended positioning of the substrate relative to the surface to be cleaned, or whether soaking or rubbing is appropriate; the recommended amount of water, if any, to apply to the surface before and after treatment; other recommended treatment to accompany the microwave application. Process - Methods for producing diacyl peroxide particles for use in the compositions herein wherein an abrasive particle is desired may include any particle making process commonly known in the art, including shear mixing. The diacyl particles for use herein can range in size from sub-micron (0J) to about 100 microns. A preferred range is from about 1 to about 20 microns. Another process for making particles follows:
Process Description - The diacyl peroxide raw material particles are dissolved in an appropriate solvent (n-ethylpyrrolidone) and added to the rest of the formulation (primarily water, surfactant and thickener) with stirring. This procedure results in the in situ precipitation of the diacyl peroxide particles, resulting in a dispersion of small homogeneous particles ranging in size of from about 1 to about 20 microns. Optionally, commercially available diacyl peroxide raw material particles can be used which have particle sizes on the order of 800 microns or more, although these are not preferred.
Procedure for preparation of in situ particles: Laponite (33g, 6% active) is dispersed in tap water (lOOg) with stirring. Sodium Alkylethoxy sulfate (14g, 70% active) is stirred into the Laponite dispersion and Sodium bicarbonate (lg, 100% active) is added. In a separate container, Benzoyl peroxide (2g, 75% active) is dissolved in N- ethylpyrrolidone (lOg, 100% active) with stirring. This benzoyl peroxide solution is then poured into the Laponite and surfactant solution with stirring. The mixture immediately turns cloudy and results in a homogeneous dispersion of 10-50 micron benzoyl peroxide particles.
In order to make the present invention more readily understood, reference is made to the following examples, which are intended to be illustrative only and not intended to be limiting in scope.
EXAMPLE
Figure imgf000021_0001
Figure imgf000022_0001
1 Commercially available as Laponite RD®
2Acyl Peroxides selected from dibenzoyl peroxide, dianisoyl peroxide, benzoyl gluaryl peroxide, benzoyl succinyl peroxide, di-(2-methybenzoyl) peroxide, diphthaloyl peroxide, dinaphthoyl peroxide, substituted dinaphthoyl peroxide, and mixtures thereof.
Treating compositions A and B above are identical except that treating composition A (liquid) is impregnated into and on an absorbent sponge material in the form of a 1 cm thick circular spong having a 5 cm diameter, while treating composition B is a sparyable liquid. Treating composition C is a conventional chlorine bleach composition. Ceramic and plastic cups, bowls etc. are stained by heating tomato sauce and/or tea under consumer relevant conditions in the microwave. The stained items are washed with a conventional light duty liquid dishwashing detergent that is commercially available under typical home wash conditions. The objects remain stained by the tomato and tea. An absorbent sponge impregnated with treating composition A (8-10 grams) is contacted with the stained item. An amount of treating composition B (8-10 grams) is sprayed onto the stained item until the stained item is evenly coated with the composition. The items treated with composition B are individually placed in a typical household microwave and microwaved on high setting for 30 seconds, while items treated with the absorbent sponge are microwaved on high setting for 60 seconds. All the items are then rinsed out. The treating composition C is applied to the items and soaked for 20 minutes, after which it was rinsed. The percent removal is estimated visually based on comparison with a stained control and a clean control. As can be seen in this Example, composition A as impregnated in the absorbent sponge in accordance with the invention unexpectedly allowsfor proper dosage while also exhibiting superior stain removal ability compared to compositions B and C which outside the invention.
Having thus described the invention in detail, it will be clear to those skilled in the art that various changes may be made without departing from the scope of the invention and the invention is not to be considered limited to what is described in the specification.

Claims

What is claimed is:
1. A method for treating surfaces characterized by the steps of:
(a) contacting said surface with a substrate containing an effective amount of a treating composition including a bleaching agent and a solvent which generates heat under microwave radiation;
(b) subjecting said surface and said substrate to microwaves for an effective amount of time such that said treating composition foams onto said surface, thereby treating said surface.
2. A method according to Claim 1 wherein said substrate is selected from the group consisting of comminuted wood pulp, creped cellulose wadding, hydrogel-forming polymer gelling agents, creped tissues, creped nonwovens containing fibers characterized by absorbent polymers, modified cross-linked cellulose fibers, capillary channel fibers, absorbent foams, thermally bonded airlaid materials, absorbent sponges, synthetic staple fibers, polymeric fibers, peat moss, and combinations thereof.
3. A method according to Claims 1-2 further characterized by the step of adding water to said surface or substrate prior to said step (b).
4. A method according to Claims 1-3 wherein said surface is selected from the group consisting of ceramic, plastic, dishware, dentifrice/dentures, surgical/ medical equipment, baby bottles, wood, glass, and mixtures thereof.
5. A method according to Claims 1-4 wherein said bleaching agent is selected from the group consisting of: a) diacyl peroxide; b) a source of hydrogen peroxide and bleach activator; c) a source of hydrogen peroxide; c) a chlorine bleach; and d) mixtures thereof.
6. A method according to Claim 5 wherein said treating composition is further characterized by an ingredient selected from the group consisting of surfactant, solvent, clay, water, polycarboxylate thickeners, baking soda, carbonates, phosphates, hydrobenzoic acid, dicarboxylic acid, siloxanes, perfumes, bleach catalysts, and mixtures thereof.
7. A method according to Claims 1-6 wherein said effective amount of time is from 30 seconds to 5 minutes, preferably from 30 seconds to 3 minutes.
8. A method according to Claims 1-7 wherein said microwaves have an electromagnetic radiation wavelength of from 1cm to lm.
9. A method according to Claims 1-8 wherein said bleaching agent is a diacyl peroxide selected from the group consisting dibenzoyl peroxide, dianisoyl peroxide, benzoyl gluaryl peroxide, benzoyl succinyl pero)dde, di-(2-methybenzoyl) peroxide, diphthaloyl peroxide, dinaphthoyl peroxide, substituted dinaphthoyl peroxide, and mixtures thereof.
10. A method according to Claims 1-9 wherein said treating composition is a gel or liquid detergent composition characterized by weight:
(a) from 0.1% to 60% of said bleaching agent which is selected from the group consisting of: i) diacyl peroxide having the general formula:
RC(O)OO(O)CRl wherein R and Rl can be the same or different; ii) a source of hydrogen pero.xide; iii) a source of hydrogen peroxide and a bleach activator; iv) a chlorine bleach; and v) mixtures thereof;
(b) from 0% to 95% of a solvent;
(c) from 0% to 50% of a surfactant; and
(d) from 0% to 7% of a thickener.
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