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
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3907—Organic compounds
  • C11D3/3917—Nitrogen-containing compounds
  • C11D3/392—Heterocyclic compounds, e.g. cyclic imides or lactames
• • 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
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3905—Bleach activators or bleach catalysts
  • C11D3/3907—Organic compounds
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
  • D06L4/00—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
  • D06L4/10—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen
  • D06L4/12—Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which develop oxygen combined with specific additives

Definitions

• This invention relates to an improved process for activating peroxygen bleaching agents.
• it relates to bleaching compositions in concentrated form which alone or in combination with other ingredients can be added to water to effect the bleaching process of the instant invention.
• the invention employs as essential ingredients a combination of a peroxygen bleaching compound, an aldehyde or ketone compound as a bleach activator and a buffering agent.
• Bleaching processes and compositions can be used in several ways to solve cleaning and laundering problems encountered in the home.
• Bleaching systems are, of course, utilized in the home for direct bleaching of stains on fabrics and hard surfaces.
• Commonly encountered hypochlorite bleaches are effective at stain-removal when used in relatively high concentrations, but these hypochlorite, as well as other active chlorine bleaches, cause rather severe damage to fabric colors and can in addition damage textile fibers with repeated use.
• Liquid bleaches of this type also present handling and packaging problems. While color and fabric I damage may be minimized by employing milder oxygen bleaches such as potassium monopersulfate, stain removal characteristics of these peroxygen bleaches are much less desirable than those of the harsh halogen bleaching agents.
• activators i.e., compounds which enhance peroxygen bleaching performance.
• Prior art bleaching compositions have employed various types of such activator compounds including esters, carboxylic acid anhydrides, quaternary ammonium salts and carboxylic acid salts among others.
• Bleaching systems find utilization in the home in areas other than that of direct bleaching of stained material.
• a bleaching system can, for example, be employed to combat one of the most persistent and troublesome problems arising during modern fabric laundering operations the tendency of some colored fabrics to release into laundering solutions dye which is then transferred during laundering onto other fabrics being washed therewith.
• Suspended or solubilized dyes of all types can to some degree be oxidized in laundering solution by employing known chlorine, peroxygen, activated peroxygen or peroxygen-chlorine bleaching compositions in high concentrations. While such bleaches inhibit dye transfer, they also damage dyes on fabrics thereby making their use for laundering of colored fabrics undesirable. Some of the milder peroxygen and activated peroxygen bleaching formulations can be utilized during laundering of colored fabrics with minimal color damage. (Examples of such compositions include the above-described micelle-catalyzed peroxygen bleaching composition disclosed in the copending U.S. Patent Applications of John Paul Jones having Ser. Nos. 117,590 now U.S. Pat. No.
• compositions of this type are effective to some extent for the inhibition of transfer of certain solubilized or suspended dyes, overall dye transfer reduction is of minimal significance.
• This invention provides an improved peroxygen bleach activation process comprising conjoint dissolution in aque
• R is selected from the group consisting of alkylene groups containing from 1 to about 16 carbon atoms and arylene groups containing from 6 to about 8 carbon atoms and Y is hydrogen, halogen, alkyl, aryl or a group providing an anionic moiety in aqueous solution; or (4) a mixture of such bleaching compounds;
• B an aldehyde or ketone activator compound providing a Relative Oxidation Constant of 0.25 or greater; and
• C a buffering agent capable of maintaining the pH of said aqueous solution within the range of about 7 to 12.
• compositions comprising materials which yield these three components upon dissolution in water are also provided. Such compositions can be employed to carry out the instant bleach activation process for the purpose of bleaching stains on fabrics and hard surfaces and for reducing dye transfer in conventional laundering solutions.
• the instant invention relates to a process for activating peroxygen bleaching and to compositions useful for carrying out such a process.
• the bleach activation process is, of course, carried out by conjointly dissolving in aqueous solution, a peroxygen bleaching compound, an activator compound and a buffer.
• Compounds which provide these three types of materials in solution being the essential components of the bleaching compositions of the instant invention.
• the peroxygen bleach-activator-buifer combination finds utility in three major practical areas.
• Such a system can be used alone or in combination with other optional ingredients to effectuate (1) direct bleaching of stains on fabrics; (2) removal by bleaching of stains found on hard surfaces; and (3) inhibition of the transfer to fabric articles of solubilized or suspended dyes found in fabric laundering solutions.
• the essential peroxygen bleach, activator, and buffer components of the instant invention are discussed in detail followed by a discussion of the use of the instant peroxygen bleach-activator-bulfer combination in each of these three areas:
• the Peroxygen Compound The principal bleaching agents utilized in the instant process and composition are inorganic peroxygen salts and organic peroxy acids (and water-soluble salts thereof). Any such salt or acid which in aqueous solution yields a species containing a OO moiety is operable in the present process.
• inorganic peroxygen salts include the water-soluble monopersulfates and Water-soluble monoperoxyphosphates. Specific examples of such salts include sodium monopersulfate, potassium monopersulfate, disodium monoperphosphate and dipotassium monoperphosphate. Highly preferred peroxygen salts, i.e., those which are most highly activated by activators in the practice of the instant invention, are the sodium and potassium monopersulfates of the formulas NaHSO and KI-ISO respectively. Potassium monopersulfate is available commercially from E. I. du Pont de Nemours and Company, Inc. under the trade name Oxone. Oxone contains approximately 41.5% by weight KI-ISO the balance being KHSO and K 80 in about equal proportions.
• Operable peroxyacids of the present invention have the general formula wherein R is an alkylene group containing from 1 to about 16 carbon atoms or an arylene group containing from 6 to about 8 carbon atoms and Y is hydrogen, halogen, alkyl, aryl or any group which provides an anionic moiety in aqueous solution.
• Y groups can include, for example,
• the organic peroxyacids or salts thereof of the invention can contain either one or two peroxy groups and can be either aliphatic or aromatic.
• the organic peroxyacid is aliphatic
• the alkylene linkage and/or Y group (if alkyl) can contain halogen or other non-interfering substituents. Examples of preferred aliphatic peroxyacids include diperazelaic acid and diperadipic acid.
• the unsub stituted acid has the general formula HO-O( JCuH4-Y where Y is hydrogen, halogen, alkyl,
• Y groupings can be in any relative position around the aromatic ring.
• the ring and/or Y group (if alkyl) can contain any non-interfering substituent such as halogen groups.
• suitable aromatic peroxy acids or salts thereof include monoperoxyphthalic acid, diperoxyterephthalic acid, 4-chlorodiperoxyphthalic acid and the monosodium salt of diperoxyterephthalic acid.
• Preferred aromatic peroxyacids are m-chloroperoxybenzoic acid and p-nitroperoxybenzoic acid.
• a highly preferred aromatic peroxyacid is diperoxyisophthalic acid. Mixtures of the peroxygen salt compounds and the peroxyacids can be employed in the instant process.
• bleaching agents are, of course, dissolved conjointly with a bleach activator and a buffer in aqueous solutions to carry out the bleach activation process of the instant invention.
• the bleaching agent provides from about 2 p.p.m. to 2,000 p.p.m. available oxygen in soluiton.
• Preferred concentration in bleaching solution depends upon the intended use of the particular activated bleaching system employed. Preferred solution concentrations of the peroxygen compound for various uses of the instant process are provided hereinafter.
• peroxygen bleaching agent is present in concentration compositions of the instant invention to the extent of from about 1% to 75% by weight.
• concentration ranges for the peroxygen bleaching agent in concentrated compositions depend upon the particular utility for which a given composition is prepared. Such preferred embodiments are discussed more fully hereinafter.
• peroxygen compounds of the instant invention are limited to certain true persalts and peracids and do not include those common peroxygen bleaching agents which yield hydrogen peroxide in aqueous solution.
• Compounds of this type hydrogen and alkali metal peroxides, perborates, percarbonates and persilicates
• hydrochloride salts notably the peroxydisulfates are likewise not useful in the instant invention.
• the peroxygen bleaches of the instant invention are activated by certain aldehydes or ketones.
• An aldehyde is of course any compound which contains at least one carbonyl group and has two hydrogen atoms or a carbon atom and a hydrogen atom attached directly to at least one of the carbonyl carbon atoms.
• a ketone is any compound which contains at least one carbonyl group and has two carbon atoms attached directly to at least one of the carbonyl carbon atoms. These compounds may be aliphatic or aromatic, substituted or unsubstituted, saturated or unsaturated, or acyclic, carbocyclic or heterocyclic.
• aldehyde or ketone activation is believed to occur as follows:
• the peroxygen bleaches of the instant invention are believed to ionize in solution to form an anionic species having the general formula RO0 wherein R, for example, can be when a monopersulfate compound is used.
• This species will combine with the aldehyde or ketone activators of the present invention which can have, for example, the acyclic general formula 1 Rr--Rz to form an intermediate of the known Baeyer-Villiger reaction. It is believed that this intermediate species has the general formula It is this species which is thought to greatly enhance the bleaching in the instant invention over peroxygen bleaching alone.
• the activated bleaching s'pecies in addition to oxidizing stain or dye, can decompose. It is thus essential that activators employed in the instant invention have chemical properties which provide bleach activation, i.e., formation of the active bleaching species, and hence stain or dye oxidation at a rate which serves to overcome the eifect of bleaching species decomposition. Operable activators of the instant invention, thus, are those which provide an acceptably high rate of bleach activation. Identification of such activators can be made by a simple test measuring the rate at which the system being tested oxidizes a standard dye material (Polar Blue).
• r is the rate at which the test dye (Polar Blue) is oxidized;
• k is the rate constant for the oxidation reaction;
• K] is the concentration of aldehyde or ketone being tested,
• [B] is the concentration of peroxygen bleaching agent and
• [PB] is the concentration of Polar Blue dye being oxidized. If activator and bleach are present in amounts such that their concentrations remain essentially constant relative to that of the Polar Blue being oxidized throughout the reaction, k [K] and [B] can be combined into a single oxidation rate constant, k giving a Polar Blue oxidation rate equation of:
• k is determined experimentally by measuring with a spectrophotometer, light absorbence through a Polar Blue dye solution as the Polar Blue dye therein is being oxidized by the bleach-activator system being tested.
• a plot of the logarithm of light absorbence versus time theoretically yields a straight line, the slope of which is k
• a standard Dye Oxidation Rate Determination is utilized to determine which activators have the requisite bleach activation characteristics.
• the Dye Oxidation, Rate Determination employing the general principles outlined above, is established as follows:
• the oxidation rate constant (kox) determination is made with a water solution containing Oxone (41.5% KHSO 2.7 10- M KHSO in solution), the activator being tested; and Polar Blue dye (6.5 X 10 M Polar Blue in solution).
• the Polar Blue utilized is Polar Brilliant Blue GAW (marketed by the Geigy Chemical Corporation) recrystallized from acetone/methyl alcohol/benzene.
• Polar Brilliant Blue GAW marketed by the Geigy Chemical Corporation
• Some ketones which are better activators operate efiectively at much lower concentrations than the 6.8X10" M ketone solution concentration Specified above as an upper limit for use in the test.
• Such activators will, of course, oxidize dye at this higher specified concentration but so quickly that absorbence measurements are diflicult. Accordingly those activators having relatively high k s are tested at concentrations lower than 6.8 10 M with k at this standard concentration being determined by linear extrapolation.
• operable activators of the instant invention are defined in terms of a parameter K hereinafter referred to as the Relative Oxidation Constant.
• K is simply defined as ox-test ox-ac wherein komest is the numerical k obtained for the activator being tested in the above-described Dye Oxidation Rate Determination at an actual or extrapolated activator concentration of 6.8 M, and kmbac is the numerical k obtained in the same Determination for a standard activator, acetone, at the standard concentration of 6.8 1O' M.
• operable activators for persalt systems of the instant invention include those aldehydes and ketones which produce a Relative Oxidation Constant (K of 0.25 or greater.
• persalt activators include aldehydes or ketones which produce a K of 5.0 or greater; highly preferred aldehyde and ketone persalt activators produce a K of 25.0 or greater.
• Operable activators for peracid systems of the instant invention include those aldehydes and ketones which produce a Relative Oxidation Constant (K of 25.0 or greater.
• Preferable peracid activators include aldehydes and ketones which produce a K of 200.0 or greater.
• Another operable class of activator compounds is that of aliphatic ketones.
• Table 2 provides representative examples of aliphatic ketones having the requisite dye oxidation characteristics.
• Another operable class of activator compounds is that of aromatic ketones.
• Table 3 provides representative examples of aromatic ketones which have the requisite dye oxidation characteristics.
• Another operable class of activator compounds is that of cyclic ketones.
• Table 4 provides representative examples of cyclic ketones which have the requisite dye oxidation characteristics.
• Another class of operable activator compounds is that of heterocyclic ketones.
• Representative examples of heterocyclic ketones having the requisite dye oxidation characteristics are shown in Table 5.
• Ketones operable in the process and compositions of the instant invention can be in either liquid or solid form.
• Liquid compositions are generally less physically and chemically stable and are hence not preferred.
• Preferred dry composition employ solid aldehydes or ketone-yielding compounds as the activator component.
• a solid activator is one which is solid at room temperature. Not all of the activators which operate in solution to enhance peroxygen bleaching according to the instant invention are available in solid form at room temperature. Those which are solid, however, include many of the preferred activators.
• aldehydes and ketones which are operable in the instant bleaching process are liquids at room temperature but can for use in dry compositions be put in solid form by reacting them with sodium bisulfite. Synthesis of these bisulfite addition products is a common reaction of aldehydes and some ketones and is described, for example, on page 298 of Cram and Hammond, Organic Chemistry, Second Edition, (McGraW-Hill, 1964). aldehydes and ketones which are not branched near the functional group add bisulfite ions in aqueous solution. The products are a-hydroxysulfonates which can be crystallized as sodium salts.
• these bisulfite compounds i.e., a-hydroxysulfonates, will dissolve to yield the ketone or aldehyde and bisulfite.
• the mole ratio of the bisulfite addition product to peroxygen bleach is preferably maintained at less than 1:1 in concentrated compositions.
• aldehydes and ketones which form such solid bisulfite addition products include acetaldehyde, butraldehyde, benzaldehyde, acetone, methyl ethyl ketone, methyl pyruvate, cyclohexanone and some substituted cyclohexanones.
• activator is generally present in aqueous solution to the extent of from about 0.1 p.p.m. to about 10,000 p.p.m. Preferred activator solution concentrations depend upon the desired end result for which the instant activation process is used.
• Activator is present in the instant bleaching composition to the extent of from about 0.01% to about 75% by Weight. Preferred activator concentrations depend upon the particular use to which the activated bleaching compositions of the instant invention are put, and are dis cussed more fully hereinafter.
• the bleach activator process of the instant invention is carried out in aqueous solution having a pH of from about 7 to about 12. Outside this pH range, bleaching performance falls off markedly. Since an aqueous solution of the persalts or peracids of the present invention is generally acidic, it is necessary to maintain the requisite pH conditions by utilization of standard buffering agents.
• a buffering agent is, of course, any non-interfering compound which can alter and/or maintain pH, such as any standard buffering agent or combination.
• phosphates, carbonates, or bicarbonates which butter within the 7-12 pH range are useful.
• suitable butfering agents include sodium bicarbonate, sodium carbonate, disodium hydrogen phosphate and sodium dihydrogen phosphate.
• Other buffering compositions for any desired pH can be obtained by the skilled artisan from any standard chemistry handbook or textbook. Buffering agents generally comprise from about 1% to about by weight of the instant concentrated bleaching compositions.
• the instant bleach activation process and compositions can be employed to carry out direct bleaching of stains on fabrics.
• Fabric bleaching is realized by contacting stained fabrics with an aqueous bleaching solution containing peroxygen compound dissolved in amounts sufficient to provide from about 10 p.p.m. to about p.p.m. available oxygen and activator compound dissolved in amounts suflicient to provide from about 250 p.p.m. to about 10,000 p.p.m. activator.
• Bleaching solution pH is generally maintained between 7 and 12.
• pH preferably varies between 8 and 10; for peracid systems pH preferably systems pH preferably varies between 7 and 10.
• Concentrated compositions especially suited for direct fabric bleaching generally contain from about 5% to about 75% by weight of the peroxygen compound and from about 5% to about 75 by weight of an aldehydeor ketone-producing activator. Concentrated fabric bleaching compositions also preferably contain from about 5% to about 60% by weight of a buffering agent suflicient to maintain a bleaching solution pH of from about 7 to 10.
• Preferred peroxygen bleaching agents for fabric stain removal include potassium monopersulfate, diperazelaic acid, and diperisophthalic acid.
• Preferred activators for fabric stain removal systems include methyl 4-oxo-cyclohexane carboxylate, acetol, 3-oxo-cyclohexyl acetic acid, cyclohexanone, sodium 4-oxo-cyclohexane carboxylate, acetone, 4-ethylcyclohexanone, cycloheptanone, S-diethylmethylammonio-Z-pentanone nitrate, N-methyl-p-morpholinioacetophenone nitrate, methyl ethyl ketone, 3- pentanone and 1,4-cyclohexanedione.
• a highly preferred embodiment of the instant fabric bleaching compositions comprises the optional addition of a water-soluble chloride salt.
• a water-soluble chloride salt In bleaching solutions such salts provide a source of chloride ions which then are oxidized in the presence of the activated peroxygen species to yield bleaching of a hypochlorite nature.
• the activator compound acts to promote generation of hypochlorite bleaching species as well as to activate peroxygen bleaching. Certain activator compounds are preferred for use in direct fabric bleaching processes and compositions because of their exceptional ability to promote hypochlorite generation.
• activators include those producing a Relative Oxidation Constant of 1.0 or greater such as acetone; tetrahydrothiopyran-4-one,S,S-dioxide; cyclohexanone sodium bisulfite adduct; di-Z-pyridyl ketone; methyl pyruvate; chloral hydrate; cyclohexanone, S-diethylbenzylammonio-Z-pentanone nitrate; 1-methyl-4-piperidone oxide and the ketones which form cations or zwitterions in solution.
• Relative Oxidation Constant such as acetone; tetrahydrothiopyran-4-one,S,S-dioxide; cyclohexanone sodium bisulfite adduct; di-Z-pyridyl ketone; methyl pyruvate; chloral hydrate; cyclohexanone, S-diethylbenzylammonio
• ketones examples include 3-(N methyl-4-oxopiperidinio)-propane sulfonate; tropinone methonitrate; tetrahydrothiopyron-4-one methonitrate; 1-benzyl-4-piperidone methonitrate; and 1,1- dimethyl-4-oxopiperidinium nitrate.
• activator concentrations for the chloride embodiment of the present invention can be lower than those employed when chloride is not utilized.
• a fabric bleaching process employing chloride ion preferably uses from about to 200 p.p.m. activator in bleaching solution.
• Concentrated fabric bleaching compositions utilizing the preferred chloride salt embodiment generally contain from about 0.2% to about 40% by weight of activator compound.
• the direct fabric bleaching compositions of the instant invention can, of course, be incorporated as one component into other laundry care formulations.
• Such formulations can contain in addition to the instant bleaching system such ingredients as non-interfering synthetic detergents, builders, perfumes, coloring agents, solubilizing agents, fillers, etc. These additional components, however, must not interfere with the essential chemical or physical functioning of the instant activated bleaching compositions.
• Hard Surface Bleaching The instant bleach activation process and compositions can also be employed to carry out stain removal on hard surfaces.
• Hard surface bleaching is realized by contacting stained hard surfaces with an aqueous bleaching solution containing peroxygen compound dissolved in amounts sufficient to provide from about 200 p.p.m. to about 2000 p.p.m. available oxygen and activator compound dissolved 12' in an amount sufiicient to provide from about 100 p.p.m. to about 2000 p.p.m. activator.
• Bleaching solution pH is again generally maintained between 7 and 12. For persalt systems pH preferably varies between 8 and 12; for peracid systems, pH preferably varies between 7 and 11.
• Concentrated compositions especially suited for hard surface bleaching preferably contain from about 1% to about 25% by weight of the peroxygen compound and from about 0.01% to about 5% by weight of an aldehydeor ketone-producing activator. Concentrated hard surface bleaching compositions also preferably contain from about 1% to about by weight of the abovedescribed buffering agent sufiicient to maintain a bleaching solution pH of from about 7 to 12.
• Preferred peroxygen bleaching agents for hard surface stain removal include potassium monopersulfate, diperazelaic acid and diperoxyisophthalic acid.
• Preferred activators for hard surface stain removal systems are those having a Relative Oxidation Constant (K of 25 or greater and include di-Z-pyridyl ketone; 1,1-dimethyl-4-oxopiperidinium nitrate; 1-benzyl-4-piperidone methonitrate; 8-hydroxyquinoline; tetrahydrothiopyran-4-one,S,S-dioxide; 1-benzyl-4-piperidone methochloride; 3-(N-methyl-4-oxopiperidinio)propane sulfonate; 2,2,6,6-tetramethyl-4-piperidone hydrate; N-carbethoxy-4-piperidone and tetrahydrothiopyran-4-one methonitrate.
• K Relative Oxidation Constant
• halide ions are oxidized to hypohalite during the instant hard surface bleaching process, it is still meaningful to specify a solution concentration of the halide (chloride or bromide) component in terms of parts per million (p.p.m.) of theoretical or initial halide ion. Accordingly, water-soluble chloride or bromide salts are preferably present in aqueous hard surface bleaching solution in an amount of from about 1000 p.p.m. to 50,000 of theoretical halide ion.
• chloride or bromide salt is added to compositions containing the peroxygen bleach activator with buffer compounds in an amount of from about 0.5% to 70% by weight of such compositions.
• a preferred halide salt range for such four component hard surface bleaching compositions is from about 1.0% to 50% by weight.
• Suitable water-soluble salts include the chloride and bromide salts of sodium, potassium, calcium and magnesium. Sodium chloride and sodium bromide are preferred.
• the peroxygen bleach-activator-buffer combination of the instant process and compositions involves elimination or reduction of the transfer from one fabric to another of dye released into laundering solution from colored fabrics during conventional laundering of such colored fabrics.
• the instant three component combination can be utilized either alone or in conjunction with other conventional laundering materials to bring about such a reduction of dye transfer.
• the instant peroxygen bleach activation process can be carried out by utilizing in such aqueous laundering solution sufficient peroxygen bleach to provide from about 2.5 p.p.m. to tabout 50 p.p.m. available oxygen and suflicient activator to provide from about 0.1 p.p.m. to about 500 p.p.m. aldehyde or ketone.
• Solution pH is, of course, maintained by a buffering agent between 7 and 12.
• pH preferably varies between 8 and 10; for peracid systems, pH preferably varies between 7 and 10.
• Concentrated compositions containing only the peroxyconventional fabric laundering compositions, the peroxygen bleach-activator-buffer component in such formulations has the preferred bleach, activator, and buffer concentrations specified above, and the combination is incorporated into the total composition to the extent necesgen compound, act1vator and buffer preferably contaln sary to provide the requ1s1te bleach and activator concenfrom about 1% to about 50% by Welght p r xygen COHI- tration in laundering solution when the conventional laun- Pf from about 0.04% to about 6 5% by welght twdering formulation is dissolved.
• a highly preferred dye tlvator P from 1% 75% y Welght transfer inhibition execution utilizing the instant peroxyof a buffer Sllfficlent t0 a l Solution P between gen bleach-activator-buffer system is realized by combin- 7 and 12 $1611 composltlons are to be used for the ing such a system with zwitterionic surfactants.
• This purpose of inhlbltmg ye transferhighly effective dye transfer inhibition system is the sub- Preferfed Q y COIPPOUHdS ⁇ ltlhzatlon dye ject of the copending US. patent application of J.
• Paul transfer inh1b1t1on systems include potassmm monopersul- J n h i 230 51 fil d 29 1972 fat? and dlperoxylsophthallc acld- Preferred afltlvators are 15 other highly preferred dye transfer inhibition execution of those havlng a ox greajlef Include
• Such the instant composition invention involves utilization of cofnpolmdsfis 'PY Y 'PY Y *1- the peroxygen bleach-activator-buifer combination with oxide; m-mtroacetophenone, p-nitroacetophenone; p-d1- certain l i l compounds h as l i l liacetyl'benzene; cyclohexanone; methyl pyruvate; 8-hydroxdone.
• Dye transfer inhibiting systems of this type are deyquinoline; 8-hydroxyquinoline, N-oxide; 2-acetylqu1noxoscribed in the copending US. patent application of J. Paul line; 2-acetyl-3-methylquinoxaline; Z-acetylpyridine; 3- Jones, having Ser. No. 230,491, filed Feb. 29, 1972.
• the bleach activation process and bleaching composimethylacetophenone nitrate; 4 trimethylammonioacetotions of the instant invention are illustrated by the followphenone nitrate; tetrahydrothiopyran 4 one-S,S-dioxide; ing examples. N-methyl-p-morpholinioacetophenone nitrate; 1-methyl-4
• Several bleaching compositions of the instant invention piperidone methonitrate; l-benzyl-4-piperidone methoniare set forth
• Preferred buffering agents for dye transfer inhibition systems include the standard phosphate and carbonate salts commonly found in commercial detergent formulations.
• Examples IX and X represent compositions of the instant invention especially suitable for incorporation into hard surface cleaning compositions.
• Examples XI-XIX represent compositions especially suitable for inhibiting dye transfer in commonly encountered fabric laundering solutions. Utilization of these compositions in carrying out the bleach activation process of the instant invention is illustrated as follows:
• Bleaching Performance Test Table H describes various bleaching solutions which at 120 for mmutes Swatches graded before were used to demonstrate the effectiveness of the instant and after bleaching on a Hunter Color Difference Meter. bleaching process in removing stains f the above- An initial and final whiteness grade is calculated from the described cloth swatch s,
• Grass Stain 200 g. of freshly cut untreated grass is mixed with 1000 cc. of 5 gr./gal. hardness water in a Waring Blender until a uniform slurry is produced. This slurry is strained through cotton, and the resulting extract is used in an Atlas Electric Padder by passing the cloth through three successive times. The cloth is aged three days and stored in the dark.
• Lipton tea 6 ounces of Lipton tea is added to 1 /2 gallons of 5 gr./ gal. hardness Water and simmer-boiled for 2 hours.
• Solution 7 simulates a bleaching solution obtained when a composition consisting of:
• Example VII Percent wt. Composition of Example VII (Table I) 89 NaCl 11 is dissolved in water to the extent of 0.250% by weight.
• Solution 8 simulates a bleaching solution obtained when a composition consisting of Percent wt.
• Composition of Example VIII (Table I) 88 NaCl 12 is dissolved in water to the extent of 0.228% by weight.
• Solutions 9 and 10 represent prior art nonactivated peroxygen bleaching solutions.
• Solution 11 represents a typical prior art halide-peroxygen bleaching solution.
• Solution 12 represents a typical prior art hypochlorite bleaching solution.
• the instant bleaching process provides superior stain removal performance under a variety of bleaching conditions. The particular efficacy of the preferred halide embodiment is also demonstrated.
• Hard Surface Cleaning Bleaching compositions of the instant invention were incorporated into typical hard surface cleanser formulations and such formulations tested for stain removal.
• Table III describes three hard surface cleaning formulations.
• Compositions a and b utilize compositions of Examples IX and X of Table I in conjunction with other conventional cleanser components.
• Composition c represents a commercially available sodium hypochloride-containing bleach, Comet.
• compositions are tested for their ability to quickly remove stains from a standard hard surface material.
• Etched porcelain plates were stained with a so lution of ferrous tannate and with a commercially available grape juice.
• the tannate stain was set by sprinkling sodium carbonate crystals onto the wet stain and the grape juice stain was set by sprinkling ferrous sulfate crystals onto the wet stain.
• 25% solutions of the composition samples in 10 grain/gallon city water were prepared and poured slowly and continuously over the stain spots until the stains were removed. The time needed to remove each spot was recorded.
• the Average Time to Bleach is an average of four runs on four different sets of spots. The lower the elapsed time, the faster is the bleaching. Results appear in Table III.
• the white tracer fabrics employed were 3 /2 x 3 /2 inch swatches obtained from Testfabrics, Inc., and are characterized as shown in Table V.
• L, a and b are the Gardner Meter lightness and chromaticity coordinates. Meter readings were made using a single layer thickness of fabric and white standardization and backup plates.
• Percent DTR Percent of Dye Transfer Reduction
• P t DTR ercen WFFD wherein percent DTR is Percent Dye Transfer Reduction; W is the Gardner Meter Whiteness of tracer cloths washed with the dyed fabrics in fluorescer-free Tide; W is the Gardner Meter Whiteness of tracer cloths washed with the dyed fabrics in the composition being tested; and W is the Gardner Meter Whiteness of tracer cloths washed by themselves in fluorescer-free Tide.
• Dye transfer performance of various solutions simulating aqueous solutions of Table I compositions is demonstrated by Table VI.
• the first column characterizes major components of the laundering solution being tested.
• the solutions A-I simulate solutions obtained by dissolving respectively compositions of Examples XI-XIX (Table 19 I) along with 505 p.p.m. of fluorescer-free Tide from which the sodium tripolyphosphate builder had been removed.
• the sodium tripolyphosphate butler from the Examples XI-XlX compositions in combination with the builderless Tide simulates a 1000 p.p.m. solution concentration of fully-built Tide.
• the second column provides the sum of the Percent Dye Transfer Reduction (percent DTR) as defined above obtained for the cotton terrycloth tracer material and for the double knit Nylon tracer cloth.
• Table VI data demonstrate the dye transfer inhibition efficacy of compositions of the instant invention in a standard anionic detergent formulation, for both cotton and Nylon fabric types, with a variety of peroxygen bleach and ketone activator compounds.
• Substantially similar dye transfer inhibition is obtained when the activators of Solutions A-I are replaced with di 2 pyridyl ketone, N-oxide; p-diacetylbenzene; mnitroacetophenone; cyclohexanone; methyl pyruvate; 8- hydroxyquinoline; 8-hydroxyquinoline, N-oxide; 2-acetylquinoxaline; Z-acetylpyridine; 3-acetylpyridine N oxide; 4 acetylpyridine N oxide; 3 trimethylacetophenone nitrate; N methyl p morpholinioacetophenone nitrate; 1 methyl 4 piperidone methonitrate; 1 benzyl 4- piperidone methonitrate; 5 diethylmethylammonio 2- pentanone nitrate; or 5 benzyldiethylammonio-2-pentanone nitrate.
• a peroxygen bleaching agent selected from the group consisting of water-soluble monopersulfates and water-soluble monoperphosphates
• a buffering agent to maintain the pH of said aqueous solution within the range of from about 7 to 12.
• activator produces a Relative Oxidation Constant of 5.0 or greater; and is present in an amount sufiicient to provide from about 0.1 p.p.m. to about 10,000 p.p.m. of activator in aqueous solution.
• a concentrated peroxygen bleach-containing composition consisting essentially of:
• composition in accordance with Claim 3 especially adapted for bleaching stains on fabrics wherein:
• the peroxygen bleaching agent is potassium monopersulfate and is present to the extent of from about 5% to about 75 by weight;
• the activator is present to the extent of from about 5% to 75% by weight;
• the buffering agent is capable of maintaining aqueous bleaching solution pH within the range of from about 7 to 10.
• the activator is selected from the group consisting of methyl 4 oxo cyclohexane carboxylate; acetol; 3 oxo cyclohexylacetic acid; cyclohexanone; sodium 4-oxo-cyclohexane carb
• a concentrated composition especially adapted for bleaching stains on fabrics consisting essentially of:
• activator selected from the group consisting of aldehydes, ketones, 1:1 aldehyde bisulfite adducts, 1:1 ketone bisulfite adducts, and hydroxyquinoline compounds, said activator producing a Relative Oxidation Constant of 1.0 or greater;
• a Watersoluble chloride selected from the group consisting of sodium chloride, potassium chloride, calcium chloride and magnesium chloride.
• the activator is selected from the group consisting of actone; tetrahydrothiopyran 4 0ne,S,S-di0Xide; 1:1 cyclohexanone sodium bisulfite adduct; di-2- pyridyl ketone; methyl pyruvate; chloral hydrate; cyclohexanone; 5 diethylbenzylammonio 2 pentanone nitrate; 1 methyl 4 piperidone, N-oxide;
• the water-soluble chloride is selected from the group consisting of sodium chloride, potassium chloride, calcium chloride and magnesium chloride, and is present to the extent of from about 4% to about 40% by weight.
• a method for bleaching fabrics consisting essentially of contacting said fabrics with an aqueous solution consisting essentially of:
• a potassium monopersulfate peroxygen bleaching agent present in an amount suflicient to provide from about 10 p.p.m. to about 100 p.p.m. available oxygen in solution;
• an activator selected from the group consisting of acetone; tetrahydrothiopyran 4 one,S,S dioxide; 1:1 cyclohexanone sodium bisulfite adduct; di 2- pyridyl ketone, methyl pyruvate; chloral hydrate; cyclohexanone; 1 methyl 4 piperidone oxide, 3(N- methyl 4 oxopiperidinio) propane sulfonate; tropinone methonitrate; tetrahydrothiopyranl-one methonitrate; 1 benzyl 4 piperidone methonitrate; and 1,1-dimethyl 4 oxopiperidinium nitrate, present in an amount sulficient to provide from about 10 p.p.m. to about 200 p.p.m. activator in solution;
• a water-soluble chloride selected from the group consisting of sodium chloride, potassium chloride, calcium chloride and magnesium chloride present in an amount suflicient to provide from about 50 p.p.m. to 1000 p.p.m. theoretical chloride ion in solution;
• a buffering agent capable of maintaining the pH of said aqueous solution within the range of from about 8 to 10.
• composition in accordance with Claim 3 especially adapted for bleaching stains on hard surfaces wherein:
• the peroxygen bleaching agent is potassium monopersulfate and is present to the extent of from about 1% to about 25% by weight;
• the activator is present to the extent of from about 0.01% to about by weight.
• the activator is selected from the group consisting of 1,1 dimethyl 4 oxopiperidinium nitrate; 1 benzyl 4 piperidone methonitrate; di-2- pyridyl ketone; 1 benzyl 4 piperidone methochloride; 3 (
• a concentrated composition especially adapted for bleaching stains on hard surfaces consisting essentially of:
• activator selected from the group consisting of aldehydes, ketones, 1:1 aldehyde bisulfite adducts, 1:1 ketonc bisulfite adducts and hydroxyquinoline compounds, said activator producing a Relative Oxidation Constant of 25 or greater;
• the activator is selected from the group consisting of di-2-pyridyl ketone; 1,1-dimethyl-4-oxopiperidinium nitrate; 8-hydroxyquinoline; 1-benzyl-4-piperidone methonitrate; 1-benzyl-4-piperidone methochloride; 3 (N methyl-4-oxopiperidinio) propane sulfonate; 2,2,6,6 tetramethyl-4-piperidonehydrate; N carbethoxy-4-piperidone; tetrahydrothiopyran-4- one,SS-dioxide; and tetrahydrothiopyran-4one methonitrate, and
• the water-soluble halide is selected from the group consisting of sodium chloride and sodium bromide, and is present to the extent of from about 1.0% to about 50% by weight.
• a method for bleaching hard surfaces consisting essentially of contacting said hard surfaces with an aqueous solution consisting essentially of:
• a potassium monopersulfate bleaching agent present in an amount sufiicient to provide from about 200 p.p.m. to about 2000 p.p.m. available oxygen in solution;
• an activator selected from the group consisting of di-2-pyridyl ketone; l,1-dimethyl-4-oxopiperidinium nitrate; 1-benzyl-4-piperidone methonitrate; l-benzyl- 4-piperidone methochloride; 8-hydroxyquinoline; 3- (N-methyl 4 oxopiperidinio)-propane sulfonate; 2,2,6,6 tetramethyl-4-piperidonehydrate; N-carbet-hoxy 4-piperidone; tetrahydrothiopyran-4-one,'S,S-dioxide; and tetrahydrothiopyran-4-one methonitrate, present in an amount sufficient to provide from about p.p.m. to about 2000 p.p.m. activator in solution;
• a water-soluble halide selected from the group consisting of chloride and bromide salts of sodium, potassium, calcium and magnesium present in an amount suflicient to provide from about 1000 p.p.m. to about 50,0000 p.p.m. theoretical halide ion in solution;
• a buflering agent capable of maintaining the pH of said aqueous solution within the range of from about 8 to 12.
• composition in accordance with Claim 3 especially adapted for inhibiting laundering solution dye transfer wherein:
• the peroxygen bleaching agent is potassium monopersulfate and is present to the extent of from about 1% to about 50% by weight;
• the activator is present to the extent of from about 0.04% to about 65% by weight.
• a method for inhibiting dye transfer within a laundering solution consisting essentially of adding to said solution:
• a potassium monopersulfate peroxygen bleaching agent in an amount suflicient to provide from about 2.5 p.p.m. to about 50 p.p.m. available oxygen in laundering solution;
• an activator selected from the group consisting of di-Z-pyridyl ketone; di-2-pyridyl ketone, N-oxide; pnitroacetophenone; m-nitroacetophenone; p-diacetyl- 'benzene; cyclohexanone; methyl pyruvate; 8-hydroxyquinoline; 8 hydroxyquinoline, N-oxide; 2-acetylquinoxaline; 2-acetyl-3-methylquinoxaline; 2-acetylpyridine; 3-acetylpyridine-N-oxide; 4-acetylpyridine- N-oxide; 3-trimethylacetophenone nitrate; 4-trimethylammonioacetophenone nitrate; tetrahydrothio-pyran-4-one-S,S-dioxide; N-methyl-p-morpholinioacetophenone nitrate; 1-methy1-4-piperidone methonitrate; 1 benz
• a buffering agent capable of maintaining the pH of said laundering solution within the range of from about 8 to 10.
• a peroxygen bleaching agent selected from the group consisting of (i) organic peroxyacids having the general formula wherein R is selected from the group consisting of alkylene groups containing from about one to about 16 carbon atoms and arylene groups containing from 6 to about 8 carbon atoms and Y is selected from the group consisting of hydrogen, halogen, alkyl, aryl II I and (ii) water-soluble salts of said peroxy acids;
• an activator selected from the group consisting of aldehydes and ketones, said activator producing a Relative Oxidation Constant of 25.0 or greater;
• a buffering agent to maintain the pH of said aqueous solution within the range of from about 7 to 12.
• bleaching agent is selected from the group consisting of diperadipic acid, diperazelaic acid, diperoxyisophthalic acid, sodium diperoxyisophthalate and potassium diperazelate and is present in an amount sufl'icient to provide from about 2 p.p.m. to 2000 p.p.m. available oxygen in aqueous solution;
• activator is present in an amount sufficient to provide from about 0.1 p.p.m. to about 10,000 p.p.m. of activator in aqueous solution;
• the buffering agent maintains the pH of said aqueous solution within the range of from about 8 to 10.
• a concentrated peroxygen bleach-containing composition consisting essentially of:
• a peroxygen bleaching agent selected from the group consisting of (i) organic peroxyacids having the general formula wherein R is selected from the group consisting of alkylene groups containing from about one to about 16 carbon atoms and arylene groups containing from 6 to about 8 carbon atoms and Y is selected from the group consisting of hydrogen, halogen, alkyl, aryl,
• composition in accordance with claim 21 especially adapted for bleaching stains on fabrics wherein:
• the peroxygen bleaching agent is selected from the group consisting of diperazelaic acid and diperoxyisophthalic acid and is present to the extent of from about 5% to about 75 by weight;
• the activator is present to the extent of from about 5% to 75% by weight;
• the buffering agent is capable of maintaining aqueous bleaching solution pH Within the range of from about 7 to 10.
• a concentrated composition especially adapted for bleaching stains on fabrics consisting essentially of:
• activator selected from the group consisting of aldehydes, ketones, 1:1 aldehyde bisulfite adducts, 1:1 ketone bisulfite adducts and hydroxyquinoline compounds, said activator having a Relative Oxidation Constant of 25.0 or greater;
• the activator is selected from the group consisting of di-Z-pyridyl ketone; tetrahydrothiopyran-4-one,S, S-dioxide; chloral hydrate; 1-methyl-4-piperidone oxide, 3 (N-methyl 4-oxopiperidino)propane sulfonate; tropinone methonitrate; tetrahydrothiopyran-4- one methonitrate; 1 benzyl-4-piperidone methonitrate; and 1,1 dimethyl-4-oxopiperidinium nitrate; and
• the water-soluble chloride is selected from the group consisting of sodium chloride, potassium chloride, calcium chloride and magnesium chloride, and is present to the extent of from about 4% to about 40% by weight.
• a method for bleaching fabrics consisting essentially of contacting said fabrics with an aqueous solution consisting essentially of:
• an activator selected from the group consisting of di-Z-pyridyl ketone; tetrahydrothiopyran 4-one,S,S- dioxide; chloral hydrate; 1-rnethyl-4-piperidone oxide, 3-(N-methyl-4-oxopiperidino)-propane sulfonate; tropinone methonitrate; tetrahydrothiopyran 4 one methonitrate; l-benzyl 4 piperidone methonitrate; and 1,1-dimethyl-4-oxopiperidinium nitrate, present in an amount sufiicient to provide from about 10 p.p.m. to about 200 p.p.m. activator in solution;
• a water-soluble chloride selected from the group consisting of sodium chloride, potassium chloride, calcium chloride and magnesium chloride present in an amount suificient to provide from about 50 p.p.m. to 1000 p.p.m. theoretical chloride ion in solution;
• a buffering agent capable of maintaining the pH of said aqueous solution within the range of from about 7 to 10.
• composition in accordance with Claim 21 especially adapted for bleaching stains on hard surfaces wherein:
• the peroxygen bleaching agent is selected from the group consisting of diperazelaic acid and diperoxyisophthalic acid and is present to the extent of from about 1% to about 25% by weight; and (b) the activator is present to the extent of from about 0.01% to about 5% by weight.
• the activator is selected from the group consisting of 1,1-dimethyl-4-oxopiperidinium nitrate; 1-benzyl-4-piperidone methonitrate; di-Z-pyridyl ketone; 1-benzy1-4-piperidone methochloride
• a concentrated composition especially adapted for bleaching stains on hard surfaces consisting essentially of:
• activator selected from the group consisting of aldehydes, ketones, 1:1 aldehyde bisulfite adducts, 1:1 ketone bisulfite adducts and hydroxyquinoline compounds, said activator producing a Relative Oxidation Constant of 25.0 or greater;
• the water-soluble halide is selected from the group consisting of sodium chloride and sodium bromide.
• a method for bleaching hard surfaces consisting essentially of contacting said hard surfaces with an aqueous solution consisting essentially of:
• a peroxygen bleaching agent selected from the group consisting of diperazelaic acid and diperoxyisophthalic acid present in an amount sufficient to provide from about 200 p.p.m. to about 2000 p.p.m. available oxygen in solution;
• an activator selected from the group consisting of di-2-pyridyl ketone; 1,1-dimethyl-4-oxopiperidinium nitrate; 1-benzyl-4-piperidone methonitrate; lbenzyl-4-piperidone methochloride; 8-hydroxyquinoline; 3-(N-methyl 4 oxopiperidino)-propane sulfonate; 2,2,6,6 tetramethyl-4-piperidonehydrate; N-carbethoxy-4-piperidone; tetrahydrothiopyran-4-one,S,S-dioxide; and tetrahydrothiopyran 4 one methonitrate, present in an amount sufiicient to provide from about p.p.m. to about 2000 p.p.m. activator in solution;
• a water-soluble halide selected from the group consisting of chloride and bromide salts of sodium, p0- tassium, calcium and magnesium present in an amount sufiicient to provide from about 1000 p.p.m. to about 50,000 p.p.m. theoretical halide ion in solution;
• a buiiering agent capable of maintaining the pH of said aqueous solution within the range of from about 7 to 11.
• composition in accordance with Claim 21 especially adapted for inhibiting laundering solution dye transfer wherein:
• the peroxygen bleaching agent is diperoxyisophthalic acid and is present to the extent of from about 1% to about 50% by weight;
• the activator is present to the extent of from about 0.04% to about 65% by weight.
• the activator is selected from the group consisting of di-2-pyridyl ketone; di-2-pyridyl ketone, N-oxide, S-hydroxyquinoline; Z-acetylquinoxaline; tetrahydrothiopyran-4-one-S,S-dioxide; l-methyl-4-piperidone methonitrate; l-benzyl-4-piperidone methonit
• a method for inhibiting dye transfer within a laundering solution consisting essentially of adding to said solution:
• an activator selected from the group consisting of di-Z-pyridyl ketone; di-Z-pyridyl ketone, N-oxide; 8 hydroxyquinoline; Z-acetylquinoxaline; tetrahydrothiopyran-4-one-S,S-dioxide; 1 methyl-4-piperidone methonitrate; l-benzyl 4 piperidone methonitrate; and 1-benzyl-4-piperidone methochloride, present in an amount sufficient to provide from about 0.1 p.p.m. to about 500 p.p.m. activator in said laundering solutions; and
• a buffering agent capable of maintaining the pH of said laundering solution within the range of from about 7 to 10.

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• 1972
  • 1972-08-01 GB GB3587872A patent/GB1368400A/en not_active Expired
  • 1972-08-03 DE DE2238207A patent/DE2238207A1/de active Pending
  • 1972-08-04 CH CH1157872A patent/CH574497A5/xx not_active IP Right Cessation
  • 1972-08-04 CA CA148,764A patent/CA991364A/en not_active Expired
  • 1972-08-04 NL NL7210754A patent/NL7210754A/xx not_active Application Discontinuation
  • 1972-08-04 FR FR7228368A patent/FR2148302B1/fr not_active Expired
  • 1972-08-07 SE SE7210264A patent/SE385718B/xx unknown
  • 1972-08-07 AU AU45357/72A patent/AU4535772A/en not_active Expired
  • 1972-09-28 US US00293262A patent/US3822114A/en not_active Expired - Lifetime
• 1973
  • 1973-02-27 CA CA164,704A patent/CA993754A/en not_active Expired
  • 1973-02-27 CA CA164,705A patent/CA993755A/en not_active Expired

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