US3346502A - Bleaching composition - Google Patents

Bleaching composition Download PDF

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US3346502A
US3346502A US451348A US45134865A US3346502A US 3346502 A US3346502 A US 3346502A US 451348 A US451348 A US 451348A US 45134865 A US45134865 A US 45134865A US 3346502 A US3346502 A US 3346502A
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percent
sodium
weight
hypochlorite
composition
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US451348A
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Wixon Harold Eugene
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Colgate Palmolive Co
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Colgate Palmolive Co
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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C07D333/76—Dibenzothiophenes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0097—Dye preparations of special physical nature; Tablets, films, extrusion, microcapsules, sheets, pads, bags with dyes
    • 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
    • C11D3/395—Bleaching agents
    • C11D3/3953—Inorganic bleaching agents
    • 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
    • C11D3/40—Dyes ; Pigments
    • 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
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents
    • 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
    • D06L4/60—Optical bleaching or brightening
    • D06L4/657—Optical bleaching or brightening combined with other treatments, e.g. finishing, bleaching, softening, dyeing or pigment printing
    • 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
    • D06L4/60—Optical bleaching or brightening
    • D06L4/664—Preparations of optical brighteners; Optical brighteners in aerosol form; Physical treatment of optical brighteners

Definitions

  • the present invention relates to bleaching compositions. More particularly, it relates to bleaching compositions in the form of dry water soluble compositions, preferably in the form of powders, and to water soluble packets containing such powders.
  • a bleaching composition comprises a dry water soluble compound which, on contact with water, liberates hypochlorite chlorine, ultramarine blue, and a substantive fluorescent brightener stable in the presence of said hypochloritechlorine agent.
  • the instant dry compositions comprise from 1 to about 99 percent by Weight of the hypochlorite-liberating compound, about 0.05 to 5 percent by weight of ultramarine blue, and about 0.01 to 5 percent of fluorescent brightener.
  • the composition is packaged within a sealed envelope of water soluble polyvinyl alcohol film.
  • Also within the scope of the present invention is a process for improving the appearance of textiles which comprises bleaching a textile with an aqueous hypochlorite solution While simultaneously applying to said textile from said solution ultramarine blue and a fluorescent brightener stable in the presence of hypochlorite and substantive to said textile.
  • the instant dry compositions are highly advantageous in that the ultramarine blue pigment therein, which is employed in an amount suflicient visibly to whiten fabrics viewed under artificial illumination substantially devoid of ultraviolet radiation, deposits on fabrics bleached therewith and overcomes any yellowing which is not removed during the bleaching treatment or which may have been imparted to the fabric by repeated treatments or by the substantive fluorescent dye.
  • Use of the present bleaching compositions in household laundering compensates for the destructive action of hypochlorite bleaches on many fluorescent dyes used in conventional detergent compositions, and supplements the brightening action of a detergent composition which may contain a bleachstable fluorescent brightener.
  • textiles bleached with the instant compositions exhibit particularly improved appearance and whiteness when viewed by illumination having a low content of ultraviolet energy, thus effecting an improved, balanced whitening to fabrics irrespective of whether they are viewed under natural daylight, artificial illumination of low ultraviolet content or various mixtures thereof.
  • the preferred water soluble packet form of the instant product olfers the advantage of providing a highly effective chlorine-type bleaching agent in a dry form. These packets avoid the dustiness of powdered products, and the likelihood or dangers of spillage or splattering characteristic of liquid products. In use, the entire packet is dropped into a washing machine containing water and clothes to be bleached without any need for premeasuring by the housewife.
  • These packets also avoid the necessity for handling of bulky or heavy containers of glass or fiberboard cartons by the housewife and provide an effective means of masking the characteristic and sometimes irritating odor of chlorine-liberating bleaches. Moreover, use of these packets eliminates the possibility of contact of the hypochlorite-liberating bleach with the skin of the user, which is especially desirable in cases of those people who are allergic to hypochlorites.
  • the preferred packets offer the further outstanding advantage that the product container, i.e. the polyvinyl alcohol film in envelope form, contributes considerable soil antiredeposition properties to the system and thus the packets are specially suited for use in conjunction with soap and detergent products in connection with the washing and bleaching of soiled clothes.
  • the use of water soluble polyvinyl alcohol film is also advantageous in that it is thermoplastic and may readily be heat sealed, it offers high resistance to permeability by gases, it has excellent oil and grease resistance, long shelf life, and it can easily be printed with alcohol-type inks.
  • Hypochlorite-generating agents suitable for use in the compositions of the present invention are those water soluble dry solid materials which generate hypochlorite ion on contact with, or dissolution in Water.
  • dry, particulate heterocyclic N-chlor imides such as trichlorocyanuric acid, dichlorocyanuric acid and salts thereof such as sodium dichlorocyanurate and potassium dichlorocyanurate.
  • Other imides may also be used such as N-chlorosuccinimide, N-chloro malonimide, N-chloro phthalimide and N-chloro naphthalimide.
  • hydantoins such as 1,3 dilchloro 5,5 dimethyl hydantoin; N-monochloro- C,C dimethylhydantoin; methylene-bis(N chloro-C,C- dimethylhydantoin); 1,3 dichloro S-methyl-S-isobutylhydantoin; 1,3-dichloro-5 methyl-S-ethylhydantoin; 1,3- dichloro-S-methyl-Sn-amylhydantoin, and the like.
  • hypochlorite-liberating agents are trichloromelamine and dry, particulate, water soluble anhydrous inorganic salts such as lithium hypochlorite and calcium hypochlorite.
  • hypochlorite-generating agents are employed in the form of small particles substantially all of which are less than about 1 millimeter in diameter, and desirably less than about 0.5 millimeter in diameter, thus ensuring rapid solubility of the particles and mini mizing excessive localized hypochlorite concentrations and resulting pinholing on use of these compositions.
  • the instant chlorine liberating agents are employed in a proportion, within the range, indicated above, such as to yield a product which contains from about 1 to about 20% available chlorine on a total weight basis, although other proportions may be employed if desired.
  • the instant ultramarine blue pigment is stable in the presence of the hypochlorite-liberating agent during both storage and use of the instant compositions.
  • the pigment is in the form of particles substantially all of which ex hibit a diameter of less than about 0.05 millimeter, and is characterized by the ability to impart a faint blue visible shade to fabrics treated therewith Without staining such fabrics when used at recommended concentration and fashion, being generally considered to be non-substantive, or at least non-accumulative, on fabrics.
  • the instant ultramarine blue pigment is readily dispersible in water under conditions of use, and does not cause visible spotting of fabrics treated therewith.
  • the Ultramarine blue particles are employed in a proportion such that on use of the final product as directed in a home washing machine under normal conditions, a typical load of Wash is exposed to .05 to 0.5 gram thereof. Inasmuch as household washing machines generally are filled from 10 to 20 gallons of water during washing or a deep rinse, desirable proportions of bluing in the instant compositions has been found to be between .05 and 5 percent by weight thereof.
  • the fluorescent brighteners or optical dyes used in the instant compositions are substantive to textiles, e.g. cotton, and are resistant to attack by the hypochloriteliberating agent. Such brighteners are of particular assistance in connection with the bleaching of textiles or fabrics viewed under illumination wherein the visible bluing action supplied by the ultramarine is subject to being supplemented by a blue-fluorescent optical bleach.
  • Suitable such textile-substantive optical bleaches which may be present in amounts on the order of about 0.01 to 5 percent by Weight of the composition, are triazole compounds such as sulfonated 3,7-diaminodibenzothiophene dioxide such as I-ISOa SOaH and bisbenzimidazoles such as JHzCEhOH H Although for convenience the acid forms of certain of these compounds are depicted, it will be appreciated that these formulas as used herein are also indicative of suitable salts thereof compatible with the remaining constituents of the instant products, such as, e.g., the sodium salts.
  • hypochlorite-liberating agents co-act to produce on use of the product, bleached cotton fabrics having surprising and unexpectedly high visible whiteness characteristic under widely varying conditions of illumination.
  • compositions suitably may contain additional constituents such as water soluble organic surface active agents which are stable in the presence of the hypochlorite generating agent.
  • detergents may be anionic detergent salts having alkyl substituents of 8 to 22 carbon atoms such as the water soluble higher fatty acid alkali metal soaps, eg sodium myristate and sodium palmitate; water soluble sulfated and sulfonated anionic alkali metal and alkaline earth metal detergent salts containing a hydrophobic higher alkyl moiety (typically containing from about 8 to 22 carbon atoms) such as salts of higher alkyl monoor poly-nuclear aryl sulfonates having from about 10 to 16 carbon atoms in the alkyl group (e.g.
  • alkali metal salts of higher alkyl napthalene sulfonic acids alkali metal salts of higher alkyl napthalene sulfonic acids
  • sulfated higher fatty acid monoglycerides such as the sodium salt of the sulfated monoglycerides of coconut oil fatty acids and the potassium salt of the sulfated monoglyceride of tallow fatty acids
  • alkali metal salts of sulfated fatty alcohols containing from about 10 to 18 carbon atoms e.g.
  • alkali metal salts of higher fatty acid esters of low molecular weight alkylol sulfonic acids e.g. fatty acid esters of the sodium salt of isethionic acid; the fatty ethanolamide sulfates; the fatty acid amides of amino alkyl sulfonic acids, e.g. lauric acid amide of taurine; as well as numerous other ionic organic surface active agents such as sodium toluenesulfonate, sodium xylenesulfonate, sodium naphthalene sulfonate; and mixtures thereof.
  • these organic surface active agents are employed in the form of their alkali metal salts or alkaline earth metal salts as these salts possess the requisite stability, solubility, and low cost essential to practical utility.
  • Amphoteric or cationic detergents may also be employed in the instant products, examples thereof being sodium N-lauryl beta alanine and cetyl pyridinium chloride respectively.
  • the proportion of organic surface active agent which is used may vary widely, typically being from about 2 to 20% by weight of the composition.
  • inorganic salts in the instant bleach compositions are desirable in that the inorganic salt may serve to adjust pH and also to act as a carrier or dispersion medium for the bleaching agent and for any stabilizing olefin therefor which may be employed.
  • Water soluble inorganic salts suitable for use in the instant compositions include sodium sulphate, sodium chloride, a1- kaline detergent builder salts having a pH of from 8 to 11 or above such sodium carbonate, borax, and sodium silicate, alkali metal orthophosphates, and polyphosphates such as monosodium phosphate, trisodium phosphate, tetrasodium pyrophosphate, pentasodium tripolyphosphate, and acid salts such as sodium bisulphate.
  • sodium carbonate or sodium metasilicate in the instant packets has been found to aid in the retention of the Water soluble characteristics of these packets, sodium carbonate being especially benefiicial in that on dissolution in water, it reacts with any acidic components present (e.g. in the hypochloride generating agent) to produce bubbles of carbon dioxide gas which contribute a desirable mixing and agitating action.
  • compositions should be dry, i.e. desirably they contain less than 1 percent and preferably less than 0.5 percent moisture, in order to minimize decomposition of the hypochlorite-liberating agent prior to use of the composition, and desirably also should be soluble or dispersible in water under conditions of usage relatively quickly, e.g. Within about 30 seconds in the case of a normal charge thereof (ca. 40 grams) to a household washing machine.
  • One Way of achieving such rapid dispersion and solution rate is to incorporate one of the aforesaid surface active agents and to prepare the composition in particulate form of small particle size, such finely divided particulate product having a maximum particle diameter of about 0.5 millimeter.
  • compositions may contain further optional ingredients such as, inter alia, organic sequestrants such as ethylene diamine tetraacetic acid and its salts, sodium carboxymethyl cellulose, citric acid, resins and polymers such as polyvinyl pyrrolidone, polyacrylates and the like, starch, urea, perfumes, corrosion inhibitors, coloring matter, and the like.
  • organic sequestrants such as ethylene diamine tetraacetic acid and its salts, sodium carboxymethyl cellulose, citric acid, resins and polymers such as polyvinyl pyrrolidone, polyacrylates and the like, starch, urea, perfumes, corrosion inhibitors, coloring matter, and the like.
  • the composition is a mechanically dry-mixed finely divided powder having a maximum particle size of less than 0.5 millimeter.
  • the ultramarine blue pigment has an extremely small particle size, at least 99.5 percent by weight thereof having a particle diameter of less than 0.05 millimeter.
  • the entire packet is dropped into a household washing machine (containing white household linens including bed sheets, pillow cases, and towels) at the start of a ten-minute washing period.
  • the water used has a hardness of 150 ppm. and a temperature of about 120 F.
  • a commercial heavy duty detergent composition is present in a concentration of 0.15 percent, and the concentration of the instant composition is 0.05%.
  • the packet promptly dissolves, forming a hypochlorite solution containing the bleach-stable fluorescent dye and the ultramarine blue, which cooperate to produce cotton textiles of substantially improved appearance, i.e., a highly whitened or brightened appearance to the eye.
  • Example 11 The powder composition of Example I may be replaced by the following, which exhibits the same particle size characteristics:
  • Example III Packets may be prepared and used as in Example I utilizing the following dry powder composition:
  • the composition is a mechanically dry-mixed finely divided powder having a maximum particle size of less than 0.5 millimeter.
  • the ultramarine blue pigment has an extremely small particle size, at least 99.5 percent by Weight thereof having a particle diameter of less than 0.05 millimeter.
  • Example IV The powder composition of Example III may be modified by direct substitution of particulate trichlorocyanuric acid having a particle diameter of less than 0.5 millimeter for the potassium dichlorocyanurate of that example.
  • Example V The following composition is prepared in the form of an eifervescing tablet by admixing 65 parts thereof with 35 parts of conventional effervescing agents such as citric acid and soda ash and compressing the dry mixture in tablet form.
  • conventional effervescing agents such as citric acid and soda ash
  • a nine-pound load of soiled household linens are simultaneously washed, bleached, and blued in a conventional household automatic washing machine in which the wash water contains approximately 0.15% by weight of the following:
  • Nonyl phenol ethylene oxide condensation product containing an average of 9.5 moles of ethylene oxide per mole of condensation product 4.47 Pentasodium tripolyphosphate 37.38 Sodium metasilicate, anhydrous 37.38 Sodium carboxy methyl cellulose 2.39 Chlorine-bleach stable fluorescent 'brightener of Example I 0.30 Potassium dichlorocyanurate 14.92 Limonene 0.24 Ultramarine blue pigment 0.24
  • Examples VII-X I V The following table sets forth dry compositions which exemplify additional specific embodiments of the instant invention, being prepared in the form of uniform mixtures of the components indicated in a particulate form having a particle diameter of less than about 0.5 millimeter.
  • the ultramarine blue pigment employed is characterized by a particle diameter of less than 0.05 mil-limeter such that the pigment does not cause visible spotting of fabrics treated therewith. All proportions and parts are by weight.
  • Triazole type 0. 0. 10 0 Bisbenzimidazole type Ultramarine blue pigment..- 0.30 0. 10 0.15 0.20 0.10 0.90 0. 1. 6 Sodium sulfate 79. 50 94. 83 89. 75 49. 68 4. 85 23. 50 79. 95
  • a bleaching composition consisting essentially of from about 1 to 99 percent by weight of a heterocyclic N-chloroimide selected from the group consisting of trichlorocyanuric acid, dichlorocyanuric acid and salts thereof, about 0.01 to 5 percent by Weight of a fluorescent brightener substantive to cotton and stable in the presence of said N-chloroimide selected from the group consisting of l CHaOHaOH H and ultramarine blue pigment of a particle diameter less than 0.05 millimeter in an amount from about 0.05 to 5 percent by weight sufficient to impart a faint blue shade to fabrics treated with an aqueous solution of said composition, said composition being in the form of a finely divided particulate product having a maximum particle diameter of about 0.5 millimeter so as to be readily dispersible in water when used in a household Washing machine.
  • a heterocyclic N-chloroimide selected from the group consisting of trichlorocyanuric acid, dichlorocyanuric acid and salts thereof, about 0.01 to
  • a bleaching composition consisting essentially of about 1 to 99 percent by weight of potassium dichlorocyanurate, about 0.01 to 5 percent of a fluorescent brightener having the structure and ultramarine blue pigment of a particle diameter less than 0.05 millimeter in an amount from about 0.5 to 5 percent by weight sufficient to impart a faint blue shade to fabrics treated with an aqueous solution of said c0mposition, said composition being in the form of a finely divided particulate product having a maximum particle diameter of about 0.5 millimeter so as to be readily dispersible in water when used in a household washing machine.
  • a bleaching composition consisting essentially of from about 1 to 99 percent by weight of a dry watersoluble compound which, on contact with water, liberates hypochlorite-chlorine, about 0.01 to 5 percent by weight of a fluorescent brightener substantive to cotton and stable in the presence of said hypochlorite-chlorine liberating agent selected from nsoa- SO3H onao-Ocorrn- ⁇ S/ NHCO-O-OCI-I O:
  • ultramarine blue pigment of a particle diameter less than 0.05 millimeter in an amount from about 0.05 to 5 percent by weight sufiicient to impart a faint blue shade to fabrics treated with an aqueous solution of said composition, and about 2 to 30 percent of a Water-soluble organic anionic surface-active agent stable in the presence of the hypochlorite-chlorine liberating agent, said composition being in the form of a finely divided particulate product having a maximum particle diameter of about 0.5 mil-limeter so as to be readily dispersible in water when used in a household washing machine.
  • a bleaching composition consisting essentially of from 1 to 99 percent by weight of a dry water-soluble compound which, on contact with water, liberates hypochlorite-chlorine, about 0.01 to 5 percent by Weight of a fluorescent brightener substantive to cotton and stable in the presence of said hypochlorite-chlorine liberating agent selected from the group consisting of N SOaH Hso3 SOaH cnaoO-oomp NHO o-Ooom s and ultramarine blue pigment of a particle diameter less than 0.05 millimeter in an amount from about 0.05 to 5 percent by weight suflicient to impart a faint blue shade to fabrics treated with an aqueous solution of said composition, and about 2 to 30 percent of sodium tridecyl benzene sulfonate, said composition being in the form of a finely divided particulate product having a maximum particle diameter of about 0.5 millimeter so as to be readily dispersible in water when used in a household washing machine.
  • a bleaching composition consisting essentially of about 1 to 99 percent by weight of a dry water-soluble compound which, on contact with water, liberates hypochlorite-chlorine, about 0.01 to 5 percent by weight of a fluorescent brightener substantive to cotton and stable in the presence of said hypochlorite liberating agent, and ultramarine blue pigment of a particle diameter less than 0.05 millimeter in an amount from about 0.05 to 5 percent by weight suflicient to impart a faint blue shade to fabrics treated with an aqueous solution of said composition, said composition being in the form of a finely divided particulate product having a maximum particle diameter of about 0.5 millimeter so as to be readily dispersible in water when used in a household washing machine.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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Description

United States Patent 3,346,502 BLEACHING COMPOSITION Harold Eugene Wixou, New Brunswick, N.J., assignor to Colgate-Palmolive Company, New York, N.Y., a corporation of Delaware No Drawing. Filed Apr. 27, 1965, Ser. No. 451,348 5 Claims. (Cl. 252-102) This application is a continuation-in-part of application Ser. No. 172,121, filed Feb. 9, 1962, now abandoned.
The present invention relates to bleaching compositions. More particularly, it relates to bleaching compositions in the form of dry water soluble compositions, preferably in the form of powders, and to water soluble packets containing such powders.
In accordance with the present invention, a bleaching composition comprises a dry water soluble compound which, on contact with water, liberates hypochlorite chlorine, ultramarine blue, and a substantive fluorescent brightener stable in the presence of said hypochloritechlorine agent. Typically, the instant dry compositions comprise from 1 to about 99 percent by Weight of the hypochlorite-liberating compound, about 0.05 to 5 percent by weight of ultramarine blue, and about 0.01 to 5 percent of fluorescent brightener. Preferably the composition is packaged within a sealed envelope of water soluble polyvinyl alcohol film.
Also within the scope of the present invention is a process for improving the appearance of textiles which comprises bleaching a textile with an aqueous hypochlorite solution While simultaneously applying to said textile from said solution ultramarine blue and a fluorescent brightener stable in the presence of hypochlorite and substantive to said textile.
The instant dry compositions are highly advantageous in that the ultramarine blue pigment therein, which is employed in an amount suflicient visibly to whiten fabrics viewed under artificial illumination substantially devoid of ultraviolet radiation, deposits on fabrics bleached therewith and overcomes any yellowing which is not removed during the bleaching treatment or which may have been imparted to the fabric by repeated treatments or by the substantive fluorescent dye. Use of the present bleaching compositions in household laundering compensates for the destructive action of hypochlorite bleaches on many fluorescent dyes used in conventional detergent compositions, and supplements the brightening action of a detergent composition which may contain a bleachstable fluorescent brightener. In addition, textiles bleached with the instant compositions exhibit particularly improved appearance and whiteness when viewed by illumination having a low content of ultraviolet energy, thus effecting an improved, balanced whitening to fabrics irrespective of whether they are viewed under natural daylight, artificial illumination of low ultraviolet content or various mixtures thereof.
The preferred water soluble packet form of the instant product olfers the advantage of providing a highly effective chlorine-type bleaching agent in a dry form. These packets avoid the dustiness of powdered products, and the likelihood or dangers of spillage or splattering characteristic of liquid products. In use, the entire packet is dropped into a washing machine containing water and clothes to be bleached without any need for premeasuring by the housewife.
These packets also avoid the necessity for handling of bulky or heavy containers of glass or fiberboard cartons by the housewife and provide an effective means of masking the characteristic and sometimes irritating odor of chlorine-liberating bleaches. Moreover, use of these packets eliminates the possibility of contact of the hypochlorite-liberating bleach with the skin of the user, which is especially desirable in cases of those people who are allergic to hypochlorites.
The preferred packets offer the further outstanding advantage that the product container, i.e. the polyvinyl alcohol film in envelope form, contributes considerable soil antiredeposition properties to the system and thus the packets are specially suited for use in conjunction with soap and detergent products in connection with the washing and bleaching of soiled clothes. The use of water soluble polyvinyl alcohol film is also advantageous in that it is thermoplastic and may readily be heat sealed, it offers high resistance to permeability by gases, it has excellent oil and grease resistance, long shelf life, and it can easily be printed with alcohol-type inks.
Hypochlorite-generating agents suitable for use in the compositions of the present invention are those water soluble dry solid materials which generate hypochlorite ion on contact with, or dissolution in Water. Examples thereof are the dry, particulate heterocyclic N-chlor imides such as trichlorocyanuric acid, dichlorocyanuric acid and salts thereof such as sodium dichlorocyanurate and potassium dichlorocyanurate. Other imides may also be used such as N-chlorosuccinimide, N-chloro malonimide, N-chloro phthalimide and N-chloro naphthalimide. Additional suitable imides are the hydantoins such as 1,3 dilchloro 5,5 dimethyl hydantoin; N-monochloro- C,C dimethylhydantoin; methylene-bis(N chloro-C,C- dimethylhydantoin); 1,3 dichloro S-methyl-S-isobutylhydantoin; 1,3-dichloro-5 methyl-S-ethylhydantoin; 1,3- dichloro-S-methyl-Sn-amylhydantoin, and the like. Other useful hypochlorite-liberating agents are trichloromelamine and dry, particulate, water soluble anhydrous inorganic salts such as lithium hypochlorite and calcium hypochlorite. These hypochlorite-generating agents are employed in the form of small particles substantially all of which are less than about 1 millimeter in diameter, and desirably less than about 0.5 millimeter in diameter, thus ensuring rapid solubility of the particles and mini mizing excessive localized hypochlorite concentrations and resulting pinholing on use of these compositions. The instant chlorine liberating agents are employed in a proportion, within the range, indicated above, such as to yield a product which contains from about 1 to about 20% available chlorine on a total weight basis, although other proportions may be employed if desired.
The instant ultramarine blue pigment is stable in the presence of the hypochlorite-liberating agent during both storage and use of the instant compositions. The pigment is in the form of particles substantially all of which ex hibit a diameter of less than about 0.05 millimeter, and is characterized by the ability to impart a faint blue visible shade to fabrics treated therewith Without staining such fabrics when used at recommended concentration and fashion, being generally considered to be non-substantive, or at least non-accumulative, on fabrics. The instant ultramarine blue pigment is readily dispersible in water under conditions of use, and does not cause visible spotting of fabrics treated therewith.
The Ultramarine blue particles are employed in a proportion such that on use of the final product as directed in a home washing machine under normal conditions, a typical load of Wash is exposed to .05 to 0.5 gram thereof. Inasmuch as household washing machines generally are filled from 10 to 20 gallons of water during washing or a deep rinse, desirable proportions of bluing in the instant compositions has been found to be between .05 and 5 percent by weight thereof.
The fluorescent brighteners or optical dyes used in the instant compositions are substantive to textiles, e.g. cotton, and are resistant to attack by the hypochloriteliberating agent. Such brighteners are of particular assistance in connection with the bleaching of textiles or fabrics viewed under illumination wherein the visible bluing action supplied by the ultramarine is subject to being supplemented by a blue-fluorescent optical bleach. Examples of suitable such textile-substantive optical bleaches, which may be present in amounts on the order of about 0.01 to 5 percent by Weight of the composition, are triazole compounds such as sulfonated 3,7-diaminodibenzothiophene dioxide such as I-ISOa SOaH and bisbenzimidazoles such as JHzCEhOH H Although for convenience the acid forms of certain of these compounds are depicted, it will be appreciated that these formulas as used herein are also indicative of suitable salts thereof compatible with the remaining constituents of the instant products, such as, e.g., the sodium salts.
In the instant compositions, the hypochlorite-liberating agents, fluorescent dye, and ultramarine blue particles co-act to produce on use of the product, bleached cotton fabrics having surprising and unexpectedly high visible whiteness characteristic under widely varying conditions of illumination.
The instant compositions suitably may contain additional constituents such as water soluble organic surface active agents which are stable in the presence of the hypochlorite generating agent. Such detergents may be anionic detergent salts having alkyl substituents of 8 to 22 carbon atoms such as the water soluble higher fatty acid alkali metal soaps, eg sodium myristate and sodium palmitate; water soluble sulfated and sulfonated anionic alkali metal and alkaline earth metal detergent salts containing a hydrophobic higher alkyl moiety (typically containing from about 8 to 22 carbon atoms) such as salts of higher alkyl monoor poly-nuclear aryl sulfonates having from about 10 to 16 carbon atoms in the alkyl group (e.g. sodium dodecylbenzene sulfonate, magnesium tridecylbenzene sulfonate, lithium or potassium pentapropylene benezene sulfonate); alkali metal salts of higher alkyl napthalene sulfonic acids; sulfated higher fatty acid monoglycerides such as the sodium salt of the sulfated monoglycerides of coconut oil fatty acids and the potassium salt of the sulfated monoglyceride of tallow fatty acids; alkali metal salts of sulfated fatty alcohols containing from about 10 to 18 carbon atoms (e.g. sodium lauryl sulfate and sodium stearyl sulfate); alkali metal salts of higher fatty acid esters of low molecular weight alkylol sulfonic acids, e.g. fatty acid esters of the sodium salt of isethionic acid; the fatty ethanolamide sulfates; the fatty acid amides of amino alkyl sulfonic acids, e.g. lauric acid amide of taurine; as well as numerous other ionic organic surface active agents such as sodium toluenesulfonate, sodium xylenesulfonate, sodium naphthalene sulfonate; and mixtures thereof. In general these organic surface active agents are employed in the form of their alkali metal salts or alkaline earth metal salts as these salts possess the requisite stability, solubility, and low cost essential to practical utility.
Amphoteric or cationic detergents may also be employed in the instant products, examples thereof being sodium N-lauryl beta alanine and cetyl pyridinium chloride respectively.
The proportion of organic surface active agent which is used may vary widely, typically being from about 2 to 20% by weight of the composition.
The presence of inorganic salts in the instant bleach compositions is desirable in that the inorganic salt may serve to adjust pH and also to act as a carrier or dispersion medium for the bleaching agent and for any stabilizing olefin therefor which may be employed. Water soluble inorganic salts suitable for use in the instant compositions include sodium sulphate, sodium chloride, a1- kaline detergent builder salts having a pH of from 8 to 11 or above such sodium carbonate, borax, and sodium silicate, alkali metal orthophosphates, and polyphosphates such as monosodium phosphate, trisodium phosphate, tetrasodium pyrophosphate, pentasodium tripolyphosphate, and acid salts such as sodium bisulphate. The presence of sodium carbonate or sodium metasilicate in the instant packets has been found to aid in the retention of the Water soluble characteristics of these packets, sodium carbonate being especially benefiicial in that on dissolution in water, it reacts with any acidic components present (e.g. in the hypochloride generating agent) to produce bubbles of carbon dioxide gas which contribute a desirable mixing and agitating action.
The instant compositions should be dry, i.e. desirably they contain less than 1 percent and preferably less than 0.5 percent moisture, in order to minimize decomposition of the hypochlorite-liberating agent prior to use of the composition, and desirably also should be soluble or dispersible in water under conditions of usage relatively quickly, e.g. Within about 30 seconds in the case of a normal charge thereof (ca. 40 grams) to a household washing machine. One Way of achieving such rapid dispersion and solution rate is to incorporate one of the aforesaid surface active agents and to prepare the composition in particulate form of small particle size, such finely divided particulate product having a maximum particle diameter of about 0.5 millimeter.
The instant compositions may contain further optional ingredients such as, inter alia, organic sequestrants such as ethylene diamine tetraacetic acid and its salts, sodium carboxymethyl cellulose, citric acid, resins and polymers such as polyvinyl pyrrolidone, polyacrylates and the like, starch, urea, perfumes, corrosion inhibitors, coloring matter, and the like.
Example I The following product is highly effective in improving the appearance of both whiteand bleach-fast colored cottons:
Parts by Weight Pentasodium tripolyphosphate 30.00 Alkylaryl sulfonate (containing 76 percent sodium tridecyl benzene sulfonate, 9.9 percent sodium silicate, 10.8 percent sodium sulfate, and 3.3 percent moisture) 2.62 Fluorescent dye 0.16
The composition is a mechanically dry-mixed finely divided powder having a maximum particle size of less than 0.5 millimeter. The ultramarine blue pigment has an extremely small particle size, at least 99.5 percent by weight thereof having a particle diameter of less than 0.05 millimeter.
Forty grams of this formulation are heat sealed within an envelope of commercial polyvinyl alcohol film which has been prepared by a hydrolysis of polyvinyl acetate. This polyvinyl alcohol contains about 15 percent of unhydrolyzed vinyl acetate, and is devoid of ethoxylation.
In use, the entire packet is dropped into a household washing machine (containing white household linens including bed sheets, pillow cases, and towels) at the start of a ten-minute washing period. The water used has a hardness of 150 ppm. and a temperature of about 120 F. A commercial heavy duty detergent composition is present in a concentration of 0.15 percent, and the concentration of the instant composition is 0.05%. The packet promptly dissolves, forming a hypochlorite solution containing the bleach-stable fluorescent dye and the ultramarine blue, which cooperate to produce cotton textiles of substantially improved appearance, i.e., a highly whitened or brightened appearance to the eye.
Example 11 The powder composition of Example I may be replaced by the following, which exhibits the same particle size characteristics:
Percent Pentasodium tripolyphosphate 30.00 Sodium carbonate 5.00 Sodium sulfate, anhydrous 40.6 15 Fluorescent brightener of Example I 0.16 Ultramarine blue pigment 0.375 Alkylarylsulfonate of Example I 2.62 Perfume 0.25 Limonene 0.25 Potassium dichlorocyanurate 20.60 Mineral oil 0.13
Example III Packets may be prepared and used as in Example I utilizing the following dry powder composition:
omo-O-oonn s/ 6 The composition is a mechanically dry-mixed finely divided powder having a maximum particle size of less than 0.5 millimeter. The ultramarine blue pigment has an extremely small particle size, at least 99.5 percent by Weight thereof having a particle diameter of less than 0.05 millimeter.
Example IV The powder composition of Example III may be modified by direct substitution of particulate trichlorocyanuric acid having a particle diameter of less than 0.5 millimeter for the potassium dichlorocyanurate of that example.
Example V The following composition is prepared in the form of an eifervescing tablet by admixing 65 parts thereof with 35 parts of conventional effervescing agents such as citric acid and soda ash and compressing the dry mixture in tablet form.
A nine-pound load of soiled household linens are simultaneously washed, bleached, and blued in a conventional household automatic washing machine in which the wash water contains approximately 0.15% by weight of the following:
Parts by weight Nonyl phenol ethylene oxide condensation product containing an average of 9.5 moles of ethylene oxide per mole of condensation product 4.47 Pentasodium tripolyphosphate 37.38 Sodium metasilicate, anhydrous 37.38 Sodium carboxy methyl cellulose 2.39 Chlorine-bleach stable fluorescent 'brightener of Example I 0.30 Potassium dichlorocyanurate 14.92 Limonene 0.24 Ultramarine blue pigment 0.24
Examples VII-X I V The following table sets forth dry compositions which exemplify additional specific embodiments of the instant invention, being prepared in the form of uniform mixtures of the components indicated in a particulate form having a particle diameter of less than about 0.5 millimeter. The ultramarine blue pigment employed is characterized by a particle diameter of less than 0.05 mil-limeter such that the pigment does not cause visible spotting of fabrics treated therewith. All proportions and parts are by weight.
TABLE.-EXAMPLES VIIXIV VII VIII IX X XI XII XIII XIV Potassium dlchloroeyanurate 20. 20.00 97 7 'Irichlorocyanuric acid 5.00 1,3 diohloro 5,5 dimethyl hy 'm 10.00 Lithium hypochlorite. 50. 00 Chlorinated trisodium ph nsnbate N,N dichloro p-toluene sulfonamido. Hypochlorite-stable fluorescent brighteuer:
Triazole type 0. 0. 10 0 Bisbenzimidazole type Ultramarine blue pigment..- 0.30 0. 10 0.15 0.20 0.10 0.90 0. 1. 6 Sodium sulfate 79. 50 94. 83 89. 75 49. 68 4. 85 23. 50 79. 95
N S03 Na CHzCHzOH H While there has been disclosed that which at present is considered to be the preferred embodiment of the invention, it will be understood, of course, that changes, modifications, or substitutions may be made therein without departing from the true scope of the invention as defined in the appended claims.
What is claimed is:
1. A bleaching composition consisting essentially of from about 1 to 99 percent by weight of a heterocyclic N-chloroimide selected from the group consisting of trichlorocyanuric acid, dichlorocyanuric acid and salts thereof, about 0.01 to 5 percent by Weight of a fluorescent brightener substantive to cotton and stable in the presence of said N-chloroimide selected from the group consisting of l CHaOHaOH H and ultramarine blue pigment of a particle diameter less than 0.05 millimeter in an amount from about 0.05 to 5 percent by weight sufficient to impart a faint blue shade to fabrics treated with an aqueous solution of said composition, said composition being in the form of a finely divided particulate product having a maximum particle diameter of about 0.5 millimeter so as to be readily dispersible in water when used in a household Washing machine.
2. A bleaching composition consisting essentially of about 1 to 99 percent by weight of potassium dichlorocyanurate, about 0.01 to 5 percent of a fluorescent brightener having the structure and ultramarine blue pigment of a particle diameter less than 0.05 millimeter in an amount from about 0.5 to 5 percent by weight sufficient to impart a faint blue shade to fabrics treated with an aqueous solution of said c0mposition, said composition being in the form of a finely divided particulate product having a maximum particle diameter of about 0.5 millimeter so as to be readily dispersible in water when used in a household washing machine.
3. A bleaching composition consisting essentially of from about 1 to 99 percent by weight of a dry watersoluble compound which, on contact with water, liberates hypochlorite-chlorine, about 0.01 to 5 percent by weight of a fluorescent brightener substantive to cotton and stable in the presence of said hypochlorite-chlorine liberating agent selected from nsoa- SO3H onao-Ocorrn- \S/ NHCO-O-OCI-I O:
and
l l CHaCHzOH H and ultramarine blue pigment of a particle diameter less than 0.05 millimeter in an amount from about 0.05 to 5 percent by weight sufiicient to impart a faint blue shade to fabrics treated with an aqueous solution of said composition, and about 2 to 30 percent of a Water-soluble organic anionic surface-active agent stable in the presence of the hypochlorite-chlorine liberating agent, said composition being in the form of a finely divided particulate product having a maximum particle diameter of about 0.5 mil-limeter so as to be readily dispersible in water when used in a household washing machine.
4. A bleaching composition consisting essentially of from 1 to 99 percent by weight of a dry water-soluble compound which, on contact with water, liberates hypochlorite-chlorine, about 0.01 to 5 percent by Weight of a fluorescent brightener substantive to cotton and stable in the presence of said hypochlorite-chlorine liberating agent selected from the group consisting of N SOaH Hso3 SOaH cnaoO-oomp NHO o-Ooom s and ultramarine blue pigment of a particle diameter less than 0.05 millimeter in an amount from about 0.05 to 5 percent by weight suflicient to impart a faint blue shade to fabrics treated with an aqueous solution of said composition, and about 2 to 30 percent of sodium tridecyl benzene sulfonate, said composition being in the form of a finely divided particulate product having a maximum particle diameter of about 0.5 millimeter so as to be readily dispersible in water when used in a household washing machine.
5. A bleaching composition consisting essentially of about 1 to 99 percent by weight of a dry water-soluble compound which, on contact with water, liberates hypochlorite-chlorine, about 0.01 to 5 percent by weight of a fluorescent brightener substantive to cotton and stable in the presence of said hypochlorite liberating agent, and ultramarine blue pigment of a particle diameter less than 0.05 millimeter in an amount from about 0.05 to 5 percent by weight suflicient to impart a faint blue shade to fabrics treated with an aqueous solution of said composition, said composition being in the form of a finely divided particulate product having a maximum particle diameter of about 0.5 millimeter so as to be readily dispersible in water when used in a household washing machine.
References Cited UNITED STATES PATENTS 2,635,400 4/1953 Abbott et a1 25293 XR 2,636,008 4/1953 Jurgenson et al. 25293 XR 2,702,759 3/1957 Scalera et al. 252-3013 XR 2,784,183 3/1957 Keller et ,al. 252301.3 XR 2,930,760 3/1960 Gebhardt 252-117 XR 3,112,274 11/1963 Morganthaler et a1. 25299 FOREIGN PATENTS 3/1955 Canada.
JULIUS GREENWALD, M. WEINTBLATT,
Examiners.

Claims (1)

1. A BLEACHING COMPOSITION CONSISTING ESSENTIALLY OF FROM ABOUT 1 TO 99 PERCETN BY WEIGHT OF A HETEROCYCLIC N-CHLOROIMIDE SELECTED FROM THE GROUP CONSISTING OF TRICHOROCYANURIC ACID, DICHLOROCYANURIC ACID AND SALTS THEREOF, ABOUT 0.01 TO 5 PERCENT BY WEIGHT OF A FLUORESCENT BRIGHTENER SUBSTANTIVE TO COTTON AND STABLE IN THE PRESENCE OF SAID N-CHLOROIMIDE SELECTED FROM THE GROUP CONSISTING OF
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Cited By (20)

* Cited by examiner, † Cited by third party
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US3491028A (en) * 1969-06-03 1970-01-20 Grace W R & Co Chlorine stable machine dishwashing composition
US4094808A (en) * 1975-11-18 1978-06-13 Ppg Industries, Inc. Solubility stable encapsulated diperisophthalic acid compositions
US5078301A (en) * 1987-10-02 1992-01-07 Ecolab Inc. Article comprising a water soluble bag containing a multiple use amount of a pelletized functional material and methods of its use
US5234615A (en) * 1987-10-02 1993-08-10 Ecolab Inc. Article comprising a water soluble bag containing a multiple use amount of a pelletized functional material and methods of its use
US6022307A (en) * 1998-07-14 2000-02-08 American Cyanamid Company Substituted dibenzothiophenes having antiangiogenic activity
US6566320B1 (en) 1999-10-19 2003-05-20 The Procter & Gamble Company Bleaching composition containing chromotropic compound
US6569826B1 (en) 1999-10-19 2003-05-27 The Procter & Gamble Company Radical scavenger
US20060105992A1 (en) * 2004-11-08 2006-05-18 Buchanan Charles M Pharmaceutical formulations of cyclodextrins and selective estrogen receptor modulator compounds
US20060105045A1 (en) * 2004-11-08 2006-05-18 Buchanan Charles M Cyclodextrin solubilizers for liquid and semi-solid formulations
WO2007073702A2 (en) 2005-12-29 2007-07-05 Osmotica Corp. Multi-layered tablet with triple release combination
WO2007104916A1 (en) * 2006-03-15 2007-09-20 Dylon International Limited Whitener for polyester fabrics
US20070287651A1 (en) * 2006-06-08 2007-12-13 The Procter & Gamble Company Bleaching compositions
US20130216947A1 (en) * 2012-01-18 2013-08-22 Tatsuya Susuki Chemical coating composition for forming a laser-markable material and a laser-markable material
US9029441B2 (en) 2011-12-15 2015-05-12 Fujifilm Hunt Chemicals Us, Inc. Low toxicity solvent system for polyamideimide and polyamide amic acid resins and coating solutions thereof
FR3045662A1 (en) * 2015-12-21 2017-06-23 Eurotab FIBER PROTECTIVE WHITE CHLORINATED SOLID COMPOSITION
US9725617B2 (en) 2014-04-17 2017-08-08 Fujifilm Hunt Chemicals U.S.A., Inc. Low toxicity solvent system for polyamideimide and polyamide amic acid resin coating
US9751986B2 (en) 2011-12-15 2017-09-05 Fujifilm Hunt Chemicals Us, Inc. Low toxicity solvent system for polyamideimide resins and solvent system manufacture
US9815941B2 (en) 2014-04-17 2017-11-14 Cymer-Dayton, Llc Low toxicity solvent system for polyamdieimide and polyamide amic acid resin manufacture
WO2019115830A1 (en) * 2017-12-15 2019-06-20 Eurotab Chlorine tablet packaging
FR3075183A1 (en) * 2017-12-15 2019-06-21 Eurotab PACKAGING FOR CHLORINATED TABLET

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Cited By (25)

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US3491028A (en) * 1969-06-03 1970-01-20 Grace W R & Co Chlorine stable machine dishwashing composition
US4094808A (en) * 1975-11-18 1978-06-13 Ppg Industries, Inc. Solubility stable encapsulated diperisophthalic acid compositions
US5078301A (en) * 1987-10-02 1992-01-07 Ecolab Inc. Article comprising a water soluble bag containing a multiple use amount of a pelletized functional material and methods of its use
US5234615A (en) * 1987-10-02 1993-08-10 Ecolab Inc. Article comprising a water soluble bag containing a multiple use amount of a pelletized functional material and methods of its use
US6022307A (en) * 1998-07-14 2000-02-08 American Cyanamid Company Substituted dibenzothiophenes having antiangiogenic activity
US6566320B1 (en) 1999-10-19 2003-05-20 The Procter & Gamble Company Bleaching composition containing chromotropic compound
US6569826B1 (en) 1999-10-19 2003-05-27 The Procter & Gamble Company Radical scavenger
US20040097391A1 (en) * 1999-10-19 2004-05-20 The Procter & Gamble Company Radical scavenger
US6991747B2 (en) 1999-10-19 2006-01-31 Procter & Gamble Company Radical scavenger
US20060105992A1 (en) * 2004-11-08 2006-05-18 Buchanan Charles M Pharmaceutical formulations of cyclodextrins and selective estrogen receptor modulator compounds
US20060105045A1 (en) * 2004-11-08 2006-05-18 Buchanan Charles M Cyclodextrin solubilizers for liquid and semi-solid formulations
WO2007073702A2 (en) 2005-12-29 2007-07-05 Osmotica Corp. Multi-layered tablet with triple release combination
WO2007104916A1 (en) * 2006-03-15 2007-09-20 Dylon International Limited Whitener for polyester fabrics
US20070287651A1 (en) * 2006-06-08 2007-12-13 The Procter & Gamble Company Bleaching compositions
US9029441B2 (en) 2011-12-15 2015-05-12 Fujifilm Hunt Chemicals Us, Inc. Low toxicity solvent system for polyamideimide and polyamide amic acid resins and coating solutions thereof
US9751986B2 (en) 2011-12-15 2017-09-05 Fujifilm Hunt Chemicals Us, Inc. Low toxicity solvent system for polyamideimide resins and solvent system manufacture
US20130216947A1 (en) * 2012-01-18 2013-08-22 Tatsuya Susuki Chemical coating composition for forming a laser-markable material and a laser-markable material
US9725617B2 (en) 2014-04-17 2017-08-08 Fujifilm Hunt Chemicals U.S.A., Inc. Low toxicity solvent system for polyamideimide and polyamide amic acid resin coating
US9815941B2 (en) 2014-04-17 2017-11-14 Cymer-Dayton, Llc Low toxicity solvent system for polyamdieimide and polyamide amic acid resin manufacture
FR3045662A1 (en) * 2015-12-21 2017-06-23 Eurotab FIBER PROTECTIVE WHITE CHLORINATED SOLID COMPOSITION
WO2017109399A1 (en) * 2015-12-21 2017-06-29 Eurotab Chlorinated solid bleaching composition which protects the fibre
US10894933B2 (en) 2015-12-21 2021-01-19 Eurotab Chlorinated solid bleaching composition which protects the fibre
WO2019115830A1 (en) * 2017-12-15 2019-06-20 Eurotab Chlorine tablet packaging
FR3075183A1 (en) * 2017-12-15 2019-06-21 Eurotab PACKAGING FOR CHLORINATED TABLET
FR3075184A1 (en) * 2017-12-15 2019-06-21 Eurotab PACKAGING FOR CHLORINATED TABLET

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