US3108079A - Water soluble textile bleaching and detergent composition - Google Patents

Water soluble textile bleaching and detergent composition Download PDF

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US3108079A
US3108079A US15536A US1553660A US3108079A US 3108079 A US3108079 A US 3108079A US 15536 A US15536 A US 15536A US 1553660 A US1553660 A US 1553660A US 3108079 A US3108079 A US 3108079A
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water soluble
acid
dichlorocyanuric acid
olefin
dichlorocyanuric
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Wixon Harold Eugene
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Colgate Palmolive Co
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    • DTEXTILES; PAPER
    • D06TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06LDRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
    • D06L4/00Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs
    • D06L4/20Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen
    • D06L4/27Bleaching fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods; Bleaching leather or furs using agents which contain halogen using organic agents

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  • the present invention relates to an oxidizing process and to water soluble textile bleaching and detergent compositions containing dichlorocyanuric acid.
  • the invention relates to a process of oxidative treatment, such as bleaching or disinfecting, utilizing substantially dry solid particulate dichlorocyanuric acid which has been stabilized against decomposition, as well as to the process of preparing such stabilized dichlorocyanuric acid.
  • the invention further relates to particulate solid dichlorocyanuric acid so stabilized, and to compositions containing such stabilized dichlorocyanuric acid.
  • a process for oxidation of oxidiza'ole substances comprises admixing with water a water soluble composition containing solid particulate dichlorocyanuric acid stabilized against decomposition by an olefin having a double bond containing a tertiary carbon atom and a water soluble anionic detergent salt stable in the presence of dichlorocyanuric acid, and contacting said mixture with material to be oxidized.
  • Also part of the present invention is a water soluble textile bleaching and detergent composition
  • a water soluble textile bleaching and detergent composition comprising solid particulate dichlorocyanuric acid stabilized against decomposition by an olefin having a double bond containing a tertiary carbon atom and a water soluble anionic detergent salt stable in the presence of dichlorocyanuric acid.
  • a method for the preparation of such compositions in accordance with which solid particulate dichlorocyanuric acid is treated with an olefin having a double bond containing a tertiary carbon atom in the presence of an inert dispersion medium containing a water soluble anionic organic surface active agent stable towards dichlorocyanuric acid.
  • Dichlorocyanuric acid is a powerful oxidizing agent possessing two labile positive chlorine atoms, each held by only a nitrogen-chlorine or oxygen-chlorine bond, depending on the tautomeric configuration involved.
  • the stabilizing action of the instant olefins on dichiorocyanuric acid is especially surprising in view of the fact that these olefins, by virtue of their unsaturated character and reactivity with hypochlorous acid, normally tend to be quite unstable toward dichlorocyanuric acid, which of course,
  • the stabilized dichlorocyanuric acid of the present invention is in substantially dry, finely divided solid form, i.e. in a form suitable for dissolution in water so as to thereupon release its available chlorine.
  • the particle size of this material is such that substantially all of it passes through a 20 mesh screen.
  • a major portion (i.e. 90%) thereof passes through a 200 mesh screen (mesh being used herein to refer to the U.S.
  • the instant olefins have a carbonto-carbon double bond in which one of the carbon atoms is tertiary, i.e. is directly attached to a total of 3 carbon atoms, one sharing the double bond and two others in addition. These olefins readily undergo hypochlorous acid addition, their unsaturation being not exclusively of an aromatic or benzeno-id nature.
  • the instant olefins may be cyclic or acyclic, e.g. paraffinic or cycloparafiinic, and the tertiary carbon containing double bond may be terminal (in 1,2 position), or it may be non-terminal or part of a cyclic'structure.
  • the instant olefins are normally liquid or solid at roomtemperature and pressure, and it is preferred to employ those with a relatively low vapor pressure (eg. having a boiling point at one atmosphere above about C. and preferably in the range from ISO-250 0.), although relatively volatile olefins may be used where sealed containers and/ or volatility depressants such as mineral oil are employed.
  • a relatively low vapor pressure eg. having a boiling point at one atmosphere above about C. and preferably in the range from ISO-250 0.
  • relatively volatile olefins may be used where sealed containers and/ or volatility depressants such as mineral oil are employed.
  • Certain of the instant olefins such as the hypochlorous acid-reactive unsaturated terpenes, are odoriferous and have desirable (or undesirable as the case may be) perfume characteristics. These materials occur in nature as constituents, of, or indigenous to, essential oils (see Guenther, The Essential Oils, volume II (1949)).
  • Another group of suitable olefins which is non-terpenic, contains many olefins which are substantially odorless in nature, and may be preferred for this reason.
  • substantially odorless olefins may be mentioned polymerized isobutylene, e.g. diisobutylene, tetraisobutylene, polymerized propylene, e.g. propylene tetramer, and 5-butyl-4-nonene such as may conveniently
  • suitable odoriferous terpenes are those isoprenoid hydrocarbons containing two or more, usually from two to six, isoprene units in a cyclic or acyclic structure, i.e. the term terpene is employed as generic to terpenes, sesquiterpenes, diterpenes, triterpenes and the like.
  • terpenes are unsaturated and readily undergo hypochlorous acid addition, i.e. their unsaturation is not exclusively of an aromatic or benzenoid nature. They may have a monocycl-ic, dicyclic, tricyciic, tetracyclic or open chain structure, specific examples of suitable such unsaturated hypochlorous acid-reactive non-benzenoid terpenes being alpha-phellandrene, p-mothene-l, p-methene-3, alphaterpinene, terpinolene, terpinyl acetate, terpineol, alphapinene, beta-pinene, pulegone, allo-ocimene, linalyl acetate, neryl acetate, geranyl acetate, camphene, and mixtures thereof including naturally occurring materials suclr as geraniol, pine oil, pine-needle oil, orange terpenes, and oil of cedarwood.
  • the instant olefins are normally employed in a minor amount sufiicient to effect stabilization of the dichlorocyanuric acid but insufficient to substantially diminish the available chlorine thereof, i.e. in an amount which affords stabilization but which does not, on initial conavailable chlorine on mixing which is attributable to the presence of the olefin is less than about 40%, and preferably less than about 15%, i.e..about O-3%.
  • the exact proportion of olefin which is employed depends on the stabilizing activity of the olefin employed, which in turn is influenced by the degree of unsaturation and structure thereof.
  • the proportion of olefin employed may vary from about 1% to 40% and preferably from about 5% to 20% by Weight of the dichlorocyanuric acid present, higher relative amounts of olefin being used if the olefin is mono-unsaturated than if the olefin has multiple non-aromatic unsaturation.
  • the preparation of the present textile bleaching and detergent compositions maybe carried out by treating a solid particulate dichlorocyanuric acid under substantially dry conditions with the desired amount of olefin, theolefin being in a sufficiently diffuse form to prevent spontaneous thermal decomposition, e.g. fuming or smoking, of the dichlorocyanuric acid.
  • the olefin may be in liquid or gaseous form (most preferably liquid), and may, if desired, be carried by an inert liquid, gaseous or solid carrier.
  • camphene which is normally solid at room temperature may be dissolved in a liquid solvent carrier such as alcohol or perfume oils and atomized therein onto an inert' solid carrier such as a water soluble spray dried detergent composition containing a stable organic detergent and, optionally, Water soluble inorganic detergent builder salts.
  • a liquid solvent carrier such as alcohol or perfume oils
  • an inert' solid carrier such as a water soluble spray dried detergent composition containing a stable organic detergent and, optionally, Water soluble inorganic detergent builder salts.
  • suitable such dispersion media include substantially dry water soluble organic or inorganic solid diluents which are stable towards dichlorocyanuric acid, e.g. Water soluble anionic surface active agents and detergent salts, substantially dry Water soluble particulate detergent'compositions such as may be prepared by heat drying an aqueous slurry of a detergent composition as I by drum drying or spray drying. These substances are also suitable, of course, as olefin carriers as referred to hereinabove. Use of particulate solids as dispersion media is especially desirable in that they diminish effectively the extent of initial contact between the olefin and the dichlorocyanuric acid, they sorb the olefin at the time of addition and carry it throughout the compositionand later release.
  • substantially dry water soluble organic or inorganic solid diluents which are stable towards dichlorocyanuric acid e.g. Water soluble anionic surface active agents and detergent salts
  • substantially dry Water soluble particulate detergent'compositions such as may be
  • the dichlorocyanuric acid slowly and uniformly, and they inhibit uncontrolled overheating by absorbing any heat that is evolved during mixing.
  • the ratio of total inert solid diluent used as olefin carrier and/ or as dispersion medium to dichlorocyanuric acid be at least about 5:1 and preferably in the range of :1 to 100021.
  • compositions include contacting the dichlorocyanuric acid with the olefin by tumbling a particulate mixture of dichlorocyanuric acid and a suitable detergent salt while spraying the mixture with a liquid or liquefied olefin in finely divided form.
  • a suitable olefin in liquid form may be slurried with an inert solid diluent, the slurry may then be [thoroughly dispersed throughout a larger body of a suitably stable water soluble substantially dry wetting or detergent composition, and finally the dichlorocyanuric acid may be admixed therewith.
  • Another procedure consists of forming a pumpable aqueous slurry containing an appropriate organic detergent, adding dichlorocyanuric acid thereto and dispersing it uniformly throughout the slurry, and spray drying the mixture before substantial decomposition of the acid occurs, to form a substantially dry dichlorocyanuric acid-containing product.
  • the thus produced particulate product is then tumbled in a rotating drum and present invention may be employed in those Water soluble 1 substantially dry compositions in which dichlorocyanuric acid is otherwise suitable for use, such as Washing, bleaching, sterilizing and disinfecting compositions.
  • inert diluents including surface active agents and synthetic detergents stable in the presence of dichlorocyanuric acid.
  • Such detergents are known to the art, and include a Wide variety of anionic detergent salts such as the water soluble higher fatty acid alkali metal soaps, e.g. sodium myristate and sodium palmitate; water soluble sulfated and sulfonated anionic foaming 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 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 naphthalenesulfonate; and mixtures thereof.
  • these detergents are employed in the form of their alkali metal or alkaline earth metal salts as these salts possess the requisite stability towards dichlorocyanuric acid, solubility, and low cost essential to practical utility.
  • water soluble or dispersible materials such as inorganic builder salts e.g. sodium sulfate, sodium chloride, sodium silicate, alkali metal orthcphosphates and polyphosphate such as monosodium phosphate,
  • tripolyphosphate and tetrasodium pyrophosphate tripolyphosphate and tetrasodium pyrophosphate; acid salts such as sodium bisulfate or dry organic and inorganic acids such as tartaric, citric, and sulfamic acids; colloidally dispersible anti-caking agents such as bentonite and magnesium silicate; anti-redeposition agents such as sodium carbox-yrnethyl cellulose; optical or fluorescent brighteners; ethylene diamine tetra-acetic acid and itssalts; foam and detergency improving adjuvants such as higher fatty amides and higher fatty alkylolamides; dessicants such as calcium chloride and magnesium sulfate; and mixtures thereof, in addition to other materials inert to dichlorocyanuric acid.
  • the pH of dilute aqueous solutions of the present compositions is normally within the range of 3 to 12, and is preferably 7-10.
  • the present compositions normally contain a minor proportion (e.g. 0 .1 to 20%) of dichlorocyanuric acid stabilized by one or more of the instant olefins (in proportions in accordance with this disclosure), the balance of the composition being the instant water soluble organic deter-gent and optionally (and often a major proportion of the composition) a water soluble diluent or material inert to dichlorocyanuric acid, such as the foregoing dispersion media and adjuvants and mixtures thereof.
  • the detergent normally constitutes at least about 2 to 50% and the additive the balance of the final stabilized dichlorocyanuric acid-containing composition.
  • the instant compositions are substantially dry, i.e.
  • the present wetting and detergent compositions contain a substantial proportion of hydratable inorganic salt such as incompletely hydrated, i.e. anhydrous or partially hydrated, inorganic alkaline salt such as, for example, pentasodium tripolyphosphate, tetrasodiumpyrophosphate, trisoduim orthophosphate, sodium sulfate, and the like, pentasodium tripolyphosphate being preferred because of its considerable capacity and affinity for moisture, i.e. its low vapor pressure.
  • hydratable inorganic salt such as incompletely hydrated, i.e. anhydrous or partially hydrated, inorganic alkaline salt such as, for example, pentasodium tripolyphosphate, tetrasodiumpyrophosphate, trisoduim orthophosphate, sodium sulfate, and the like
  • pentasodium tripolyphosphate being preferred because of its considerable capacity and affinity for moisture, i.e. its low vapor pressure.
  • ta typical preferred formulation will contain hydratable inorganic salt and any moisture therein (as determined by azeotropic distillation with xylol using the Dean and Stark apparatus, ASTM method D-460-54, or by the Karl Fischer titration method) will be less than that moisture which can be strongly retained in an inactive form as the hydrate of the hydratable inorganic salt.
  • the hydratable salt may be employed in any desired amount, and typically may constitute from about 1% to 90% or more of the present compositions.
  • the instant compositions are prepared in particulate form having an average particle size of less than about mesh, e.g. from about 10-100 mesh (2 mm. to 0.15 mm. diameter) in the case of spray dried detergent compositions.
  • the instant compositions be packaged in moisture impermeable containers, e.g. containers fabricated from glass, metal or metal foil, metal foil covered paperboard being preferred in view of its light weight and resilient character.
  • a preferred substantially dry water soluble bleaching detergent composition in accordance with the present invention comprises at least about 5% and desirably 40% organic foaming detergent, 0.1-10% of dichlorocyanuric acid, the instant olefin in an amount sufiicient to stabilize the dichlorocyanuric acid up to 40% thereof, 02% of a fluorescent brightener (preferably one resistant to decomposition by dichlorocyanuric acid or aqueous solutions thereof), and hydratable inorganic builder salt as the balance, e.g. about 45-95%.
  • the present water soluble compositions preferably are dissolved in water prior to contact with the textile to be bleached in order to avoid spotting or uneven or localized bleaching which may result if the substantially dry composition is first placed in contact with the textile and then contacted with and dissolved in water.
  • Suitable concentrations of the present compositions range from about 0.05% to about 15% in water, 0.1% to 1% being preferred.
  • the preferred bleaching and washing process comprises dissolving the composition in water at an effective bleaching concentration, and contacting the aqueous solution with textile to be bleached.
  • Contact of the textile with the solution should occur immediately following dissolution of the water soluble composition, i.e. within about three minutes, and may be accomplished by immersion of the textile in the aqueous medium prior to dissolution of the instant substantially dry composition there in. Alternatively, a solution of the composition may be prepared in the absence of the textile, and then be contacted therewith.
  • Example I Sodium tridecyl benzene sulfonate 27.00 Pentasodium tripolyphosphate 38.50 Sodium carboxymethylce llulose 0.4-0 Bleach resistant optical brightener 0.09 Antitarnishing agent for German silver 0.10 Moisture 3.00
  • the moisture present in the foregoing formulation is in the form of hydrates of the inorganic salts, the pentasodium tripolyphosphate alone being capable of combining with water of crystallization in an amount equal to about 12% by weight of the product.
  • the spray dried granules are tumbled in a rotating drum and sprayed with 0.16 part by weight of d-limonene. Thereafter 1.96 parts by weight of dichlorocyanuric acid are added slowly and are thoroughly admixed therewith.
  • the dichlorocyanuric acid employed has a particle size such that at least thereof has a minimum diameter of about 53 microns or less.
  • a sample of the product which by analysis is found to contain 1.15% available chlorine, is then packaged in aluminum foil-covered paperboard containers which are substantially impermeable to moisture vapor. After standing under room conditions for 62 days, there is only a 3% diminution in its content of available chlorine.
  • a second sample is packaged in a sealed glass jar and is subjected to accelerated aging at F. After 68 hours it loses 10% of its available chlorine whereas under the same conditions a limonene-free control (which does not form part of this invention) loses approximately twothirds of its initial available chlorine content.
  • a composition having greater bleaching power than that of the foregoing example may be prepared by increasing the proportions of limonene and dichlorocyanuric acid therein to 1.0% and 19.6% respectively by weight of the final product (replacing appropriate amounts of sodium sulfate).
  • camphene may be employed in place of limonene, in which case the camphene may be dissolved in ethanol to obtain a liquid form suitable for spraying on the spray dried granules.
  • ter-traisobutylene may be employed in place of limonene with similar results.
  • Example 11 7.5 parts of the dichlorocyanuric acid 7 of Example I are mixed with 91.75 parts of the following detergent composition:
  • Example III A dichlorocyanuric acid-containing aqueous detergent slurry is prepared at about 100 F. Immediately upon incorporation of the dichlorocyanuric acid and adequate caustic soda to adjust the pH to about 6.2, the slurry, which contains 55% solids and 45% moisture, is spray dried. The resulting substantially dry particulate product is uniform in composition and contains:
  • Example IV 22 parts by weight of the unstabilized spray dried particles of Example III are tumbled in a rotary drum and are commingled with 77.84 parts of a spray dried detergent composition having the following analysis:
  • the mixture is then further tumbled and sprayed with 0.16 part of d-limonene.
  • 0.16 part of d-limonene On accelerated aging in a closed glass jar at 140 F. for 65 hours, the available chlorine content of the composition diminishes by only about 9%.
  • a water soluble textile bleaching and detergent composition consisting essentially of from 0.1 to of solid particulate dichlorocyanuric acid stabilized against decomposition by an olefin having a double bond containing a teritary carbon atom, said olefin being present in a small but sufficient amount to stabilize said dichlorocyanuric acid up to about by weight thereof, about 2 to of a Water soluble anionic organic detergent salt stable in the presence of said dichlorocyanuric acid, and a balance substantially of a water soluble inorganic salt. 7
  • a water soluble textile bleaching and detergent composition consisting essentically of about 0.1 to 10% of dichlorocyanuric acid stabilized against decomposition by about 1 to 40% by weight thereof of an olefin having a double bond containing a tertiary carbon atom, about 5 to 40% of a water soluble anionic organic detergent salt stable towards said dichlorocyanuric acid, and about 45 to 95% of water soluble inorganic builder salts.
  • a water soluble textile bleaching and detergent coma position consisting essentially of about 0.1 to 10% of d cblorocyanuric acid stabilized against decomposition by about 1 to 40% by weight thereof of limonene, about 5 to 40% of a water soluble anionic; organic detergent salt stable towards said dichlorocyanuric acid, and about 45 to 95% of water soluble hydratable inorganic builder salts.
  • a process for the preparation of a stable water solubie textile bleaching and detergent composition consisting essentially of stabilized dichlorocyanuric acid and a balance substantially of water soluble material, which comprises contacting, on the basis of a total of 100 parts, about 0.1 to 20 arts of solid particulate dichlorocyanuric acid With from about 1 to 40% by Weight thereof of an olefin having a double bond containing a tertiary carbon atom in the presence of about 45 to parts by weight of a water soluble inorganic builder salt stable in the presence of said dichlorocyanuric acid, whereby said olefin is rendered sufliciently diffuse to prevent localized overheating and spontaneous thermal decomposition of said dichlorocyanuric acid, and cornmingling therewith about 2 to 50 parts of a water soluble anionic organic detergent salt stable towards said dichlorocyanuric acid.

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Description

3,3634%79 WATER GLUBLE TEXTILE BLEACHENG AND DETERGENT tlflMPOSITION Harold Eugene Wixon, Jersey City, NJZ, assignor to Colgate-ialmoiiye (Iompany, New York, N.Y., a corporation of Delaware No Drawing. Filed Mar. 17, E60, Scr. No. 15,536 9 Clm'ms. (Cl. 252F-99) The present invention relates to an oxidizing process and to water soluble textile bleaching and detergent compositions containing dichlorocyanuric acid. More particularly it relates to a process of oxidative treatment, such as bleaching or disinfecting, utilizing substantially dry solid particulate dichlorocyanuric acid which has been stabilized against decomposition, as well as to the process of preparing such stabilized dichlorocyanuric acid. The invention further relates to particulate solid dichlorocyanuric acid so stabilized, and to compositions containing such stabilized dichlorocyanuric acid.
In accordance with the present invention a process for oxidation of oxidiza'ole substances comprises admixing with water a water soluble composition containing solid particulate dichlorocyanuric acid stabilized against decomposition by an olefin having a double bond containing a tertiary carbon atom and a water soluble anionic detergent salt stable in the presence of dichlorocyanuric acid, and contacting said mixture with material to be oxidized. Also part of the present invention is a water soluble textile bleaching and detergent composition comprising solid particulate dichlorocyanuric acid stabilized against decomposition by an olefin having a double bond containing a tertiary carbon atom and a water soluble anionic detergent salt stable in the presence of dichlorocyanuric acid. Further within the ambit of the instant invention is a method for the preparation of such compositions in accordance with which solid particulate dichlorocyanuric acid is treated with an olefin having a double bond containing a tertiary carbon atom in the presence of an inert dispersion medium containing a water soluble anionic organic surface active agent stable towards dichlorocyanuric acid.
Dichlorocyanuric acid is a powerful oxidizing agent possessing two labile positive chlorine atoms, each held by only a nitrogen-chlorine or oxygen-chlorine bond, depending on the tautomeric configuration involved. The stabilizing action of the instant olefins on dichiorocyanuric acid is especially surprising in view of the fact that these olefins, by virtue of their unsaturated character and reactivity with hypochlorous acid, normally tend to be quite unstable toward dichlorocyanuric acid, which of course,
readily liberates hypo-chlorous acid in aqueous media. The highly etlicacious nature of the instant olefin in on the one hand rendering dichlorocyanuric acid stable against decomposition on storage and aging and on the other hand permitting such stabilized dichlorocyanuric acid to liberate readily hyposchlorite chlorine contacted with an aqueous medium is indeed surprising and highly beneficial and permits the aforesaid process to be employed with advantage under circumstances where it is desired to have available a bleaching or similar oxidation process involving a water soluble dry solid oxidizing product. Thus the process of the present invention is especially adapted to household bleaching and disinfecting of textiles.
The stabilized dichlorocyanuric acid of the present invention is in substantially dry, finely divided solid form, i.e. in a form suitable for dissolution in water so as to thereupon release its available chlorine. Typically the particle size of this material is such that substantially all of it passes through a 20 mesh screen. Preferably a major portion (i.e. 90%) thereof passes through a 200 mesh screen (mesh being used herein to refer to the U.S.
be prepared by dehydration of tributyl carbinol.
3,18,0 79 Patented Get. 22, 1963 sieve series). By means of the present invention, it is possible to maintain a high level of available chlorine in water soluble textile bleaching and detergent composirtion-s containing solid, particulate dichlo-rocyanuric acid over a relatively long period of time and under conditions which would otherwise cause the dichlorocyanuric acid to decompose and sufiier extensive loss of available chlorine. Stabilization of the dichlorocyanuric acid employed in textile bleaching and detergent compositions in accordance with the present invention is also beneficial in that it diminishes corrosion of metallic containers or packages in which the present compositions are stored.
As referred to above, the instant olefins have a carbonto-carbon double bond in which one of the carbon atoms is tertiary, i.e. is directly attached to a total of 3 carbon atoms, one sharing the double bond and two others in addition. These olefins readily undergo hypochlorous acid addition, their unsaturation being not exclusively of an aromatic or benzeno-id nature. The instant olefins may be cyclic or acyclic, e.g. paraffinic or cycloparafiinic, and the tertiary carbon containing double bond may be terminal (in 1,2 position), or it may be non-terminal or part of a cyclic'structure. The instant olefins are normally liquid or solid at roomtemperature and pressure, and it is preferred to employ those with a relatively low vapor pressure (eg. having a boiling point at one atmosphere above about C. and preferably in the range from ISO-250 0.), although relatively volatile olefins may be used where sealed containers and/ or volatility depressants such as mineral oil are employed.
Certain of the instant olefins, such as the hypochlorous acid-reactive unsaturated terpenes, are odoriferous and have desirable (or undesirable as the case may be) perfume characteristics. These materials occur in nature as constituents, of, or indigenous to, essential oils (see Guenther, The Essential Oils, volume II (1949)). Another group of suitable olefins, which is non-terpenic, contains many olefins which are substantially odorless in nature, and may be preferred for this reason.
Among the instant substantially odorless olefins may be mentioned polymerized isobutylene, e.g. diisobutylene, tetraisobutylene, polymerized propylene, e.g. propylene tetramer, and 5-butyl-4-nonene such as may conveniently Among the suitable odoriferous terpenes are those isoprenoid hydrocarbons containing two or more, usually from two to six, isoprene units in a cyclic or acyclic structure, i.e. the term terpene is employed as generic to terpenes, sesquiterpenes, diterpenes, triterpenes and the like. These terpenes are unsaturated and readily undergo hypochlorous acid addition, i.e. their unsaturation is not exclusively of an aromatic or benzenoid nature. They may have a monocycl-ic, dicyclic, tricyciic, tetracyclic or open chain structure, specific examples of suitable such unsaturated hypochlorous acid-reactive non-benzenoid terpenes being alpha-phellandrene, p-mothene-l, p-methene-3, alphaterpinene, terpinolene, terpinyl acetate, terpineol, alphapinene, beta-pinene, pulegone, allo-ocimene, linalyl acetate, neryl acetate, geranyl acetate, camphene, and mixtures thereof including naturally occurring materials suclr as geraniol, pine oil, pine-needle oil, orange terpenes, and oil of cedarwood. It is preferred to employ the normally liquid polyunsaturated terpenes containing at least two isoprenoid units, such as limonene and myrcene, as these materials have been found to be effective as stabilizers in somewhat lower proportions than the monounsaturated terpenes.
The instant olefins are normally employed in a minor amount sufiicient to effect stabilization of the dichlorocyanuric acid but insufficient to substantially diminish the available chlorine thereof, i.e. in an amount which affords stabilization but which does not, on initial conavailable chlorine on mixing which is attributable to the presence of the olefin is less than about 40%, and preferably less than about 15%, i.e..about O-3%. The exact proportion of olefin which is employed depends on the stabilizing activity of the olefin employed, which in turn is influenced by the degree of unsaturation and structure thereof. Typically the proportion of olefin employed may vary from about 1% to 40% and preferably from about 5% to 20% by Weight of the dichlorocyanuric acid present, higher relative amounts of olefin being used if the olefin is mono-unsaturated than if the olefin has multiple non-aromatic unsaturation.
The preparation of the present textile bleaching and detergent compositions maybe carried out by treating a solid particulate dichlorocyanuric acid under substantially dry conditions with the desired amount of olefin, theolefin being in a sufficiently diffuse form to prevent spontaneous thermal decomposition, e.g. fuming or smoking, of the dichlorocyanuric acid. The olefin may be in liquid or gaseous form (most preferably liquid), and may, if desired, be carried by an inert liquid, gaseous or solid carrier. For example, camphene, which is normally solid at room temperature may be dissolved in a liquid solvent carrier such as alcohol or perfume oils and atomized therein onto an inert' solid carrier such as a water soluble spray dried detergent composition containing a stable organic detergent and, optionally, Water soluble inorganic detergent builder salts.
, Contact of dichlorocyanuric acid with the stabilizing olefin (either per se or on a carrier) is carried out in the presence of a dispersion medium, the expression dispersion medium referring to the means of dispersing the olefin throughout the particulate dichlorocyanuric acid so as to obtain a substantial homogeneous contact of the olefin with the particles comprising the body of dichlorocyanuric acid being stabilized. Uniform, even contact of the olefin with the particulate dichlorocyanuric acid prevents undesirable extensive localized reaction between these two materials, which reaction may lead to overheating and spontaneous decomposition of the dichlorocyanuric acid. 'Suitable such dispersion media include substantially dry water soluble organic or inorganic solid diluents which are stable towards dichlorocyanuric acid, e.g. Water soluble anionic surface active agents and detergent salts, substantially dry Water soluble particulate detergent'compositions such as may be prepared by heat drying an aqueous slurry of a detergent composition as I by drum drying or spray drying. These substances are also suitable, of course, as olefin carriers as referred to hereinabove. Use of particulate solids as dispersion media is especially desirable in that they diminish effectively the extent of initial contact between the olefin and the dichlorocyanuric acid, they sorb the olefin at the time of addition and carry it throughout the compositionand later release. it to the dichlorocyanuric acid slowly and uniformly, and they inhibit uncontrolled overheating by absorbing any heat that is evolved during mixing. In general it is preferred that the ratio of total inert solid diluent used as olefin carrier and/ or as dispersion medium to dichlorocyanuric acid be at least about 5:1 and preferably in the range of :1 to 100021.
Other more specific procedures for preparing the instant compositions include contacting the dichlorocyanuric acid with the olefin by tumbling a particulate mixture of dichlorocyanuric acid and a suitable detergent salt while spraying the mixture with a liquid or liquefied olefin in finely divided form. Alternatively, a suitable olefin in liquid form may be slurried with an inert solid diluent, the slurry may then be [thoroughly dispersed throughout a larger body of a suitably stable water soluble substantially dry wetting or detergent composition, and finally the dichlorocyanuric acid may be admixed therewith. Another procedure consists of forming a pumpable aqueous slurry containing an appropriate organic detergent, adding dichlorocyanuric acid thereto and dispersing it uniformly throughout the slurry, and spray drying the mixture before substantial decomposition of the acid occurs, to form a substantially dry dichlorocyanuric acid-containing product. The thus produced particulate product is then tumbled in a rotating drum and present invention may be employed in those Water soluble 1 substantially dry compositions in which dichlorocyanuric acid is otherwise suitable for use, such as Washing, bleaching, sterilizing and disinfecting compositions. Thus it may be used in admixture With inert diluents including surface active agents and synthetic detergents stable in the presence of dichlorocyanuric acid. Such detergents are known to the art, and include a Wide variety of anionic detergent salts such as the water soluble higher fatty acid alkali metal soaps, e.g. sodium myristate and sodium palmitate; water soluble sulfated and sulfonated anionic foaming 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, lithium, or magnesium dodecyl benzene or toluene sulfonate, potassium pentapropylene benzent sulfonate), alkali metal salts of higher alkyl naphthalene sulfonic acids, sulfated higher fatty acid monoglycerides such as the potassium salt of the sulfated monoglycerides of coconut oil and/ or 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 naphthalenesulfonate; and mixtures thereof. In general these detergents are employed in the form of their alkali metal or alkaline earth metal salts as these salts possess the requisite stability towards dichlorocyanuric acid, solubility, and low cost essential to practical utility.
In addition to the foregoing organic detergents, various adjuvants suitable for use in Water soluble textile Washing, bleaching, sterilizing and disinfecting compositions may also be present, including water soluble or dispersible materials such as inorganic builder salts e.g. sodium sulfate, sodium chloride, sodium silicate, alkali metal orthcphosphates and polyphosphate such as monosodium phosphate,
tripolyphosphate and tetrasodium pyrophosphate; acid salts such as sodium bisulfate or dry organic and inorganic acids such as tartaric, citric, and sulfamic acids; colloidally dispersible anti-caking agents such as bentonite and magnesium silicate; anti-redeposition agents such as sodium carbox-yrnethyl cellulose; optical or fluorescent brighteners; ethylene diamine tetra-acetic acid and itssalts; foam and detergency improving adjuvants such as higher fatty amides and higher fatty alkylolamides; dessicants such as calcium chloride and magnesium sulfate; and mixtures thereof, in addition to other materials inert to dichlorocyanuric acid. The pH of dilute aqueous solutions of the present compositions is normally within the range of 3 to 12, and is preferably 7-10.
The present compositions normally contain a minor proportion (e.g. 0 .1 to 20%) of dichlorocyanuric acid stabilized by one or more of the instant olefins (in proportions in accordance with this disclosure), the balance of the composition being the instant water soluble organic deter-gent and optionally (and often a major proportion of the composition) a water soluble diluent or material inert to dichlorocyanuric acid, such as the foregoing dispersion media and adjuvants and mixtures thereof. In those cases wherein an optional additive is present, the detergent normally constitutes at least about 2 to 50% and the additive the balance of the final stabilized dichlorocyanuric acid-containing composition. The instant compositions are substantially dry, i.e. are solid compositions which are dry to the touch and which are substantially completely devoid of free or uncombined moisture. In this connection, it is preferred that the present wetting and detergent compositions contain a substantial proportion of hydratable inorganic salt such as incompletely hydrated, i.e. anhydrous or partially hydrated, inorganic alkaline salt such as, for example, pentasodium tripolyphosphate, tetrasodiumpyrophosphate, trisoduim orthophosphate, sodium sulfate, and the like, pentasodium tripolyphosphate being preferred because of its considerable capacity and affinity for moisture, i.e. its low vapor pressure. Thus ta typical preferred formulation will contain hydratable inorganic salt and any moisture therein (as determined by azeotropic distillation with xylol using the Dean and Stark apparatus, ASTM method D-460-54, or by the Karl Fischer titration method) will be less than that moisture which can be strongly retained in an inactive form as the hydrate of the hydratable inorganic salt. The hydratable salt may be employed in any desired amount, and typically may constitute from about 1% to 90% or more of the present compositions.
Desirably, the instant compositions are prepared in particulate form having an average particle size of less than about mesh, e.g. from about 10-100 mesh (2 mm. to 0.15 mm. diameter) in the case of spray dried detergent compositions. In order to maintain their substantially dry condition it is desirable that the instant compositions be packaged in moisture impermeable containers, e.g. containers fabricated from glass, metal or metal foil, metal foil covered paperboard being preferred in view of its light weight and resilient character.
A preferred substantially dry water soluble bleaching detergent composition in accordance with the present invention comprises at least about 5% and desirably 40% organic foaming detergent, 0.1-10% of dichlorocyanuric acid, the instant olefin in an amount sufiicient to stabilize the dichlorocyanuric acid up to 40% thereof, 02% of a fluorescent brightener (preferably one resistant to decomposition by dichlorocyanuric acid or aqueous solutions thereof), and hydratable inorganic builder salt as the balance, e.g. about 45-95%.
In use in bleaching and washing stained and/or soiled textiles, e.g. fabrics, garments, household laundry and the like, the present water soluble compositions preferably are dissolved in water prior to contact with the textile to be bleached in order to avoid spotting or uneven or localized bleaching which may result if the substantially dry composition is first placed in contact with the textile and then contacted with and dissolved in water. (Suitable concentrations of the present compositions range from about 0.05% to about 15% in water, 0.1% to 1% being preferred.) The preferred bleaching and washing process comprises dissolving the composition in water at an effective bleaching concentration, and contacting the aqueous solution with textile to be bleached. Contact of the textile with the solution should occur immediately following dissolution of the water soluble composition, i.e. within about three minutes, and may be accomplished by immersion of the textile in the aqueous medium prior to dissolution of the instant substantially dry composition there in. Alternatively, a solution of the composition may be prepared in the absence of the textile, and then be contacted therewith.
The following examples are given to additionally illustrate the nature of the invention and it will be understood that the invention is not limited thereto. All parts or percentages are by weight unless otherwise indicated, and references to moisture content denote total moisture as 6 determined by the Karl Fischer titration method or by xylol distillation in accordance with ASTM method D46054. The components used are substantially and completely dry or anhydrous unless otherwise indicated.
Example I Sodium tridecyl benzene sulfonate 27.00 Pentasodium tripolyphosphate 38.50 Sodium carboxymethylce llulose 0.4-0 Bleach resistant optical brightener 0.09 Antitarnishing agent for German silver 0.10 Moisture 3.00
Sodium sulfate, balance to 97.88 parts.
The moisture present in the foregoing formulation is in the form of hydrates of the inorganic salts, the pentasodium tripolyphosphate alone being capable of combining with water of crystallization in an amount equal to about 12% by weight of the product.
The spray dried granules are tumbled in a rotating drum and sprayed with 0.16 part by weight of d-limonene. Thereafter 1.96 parts by weight of dichlorocyanuric acid are added slowly and are thoroughly admixed therewith. The dichlorocyanuric acid employed has a particle size such that at least thereof has a minimum diameter of about 53 microns or less.
A sample of the product, which by analysis is found to contain 1.15% available chlorine, is then packaged in aluminum foil-covered paperboard containers which are substantially impermeable to moisture vapor. After standing under room conditions for 62 days, there is only a 3% diminution in its content of available chlorine. A second sample is packaged in a sealed glass jar and is subjected to accelerated aging at F. After 68 hours it loses 10% of its available chlorine whereas under the same conditions a limonene-free control (which does not form part of this invention) loses approximately twothirds of its initial available chlorine content.
In use, approximately nine pounds of soiled and stained color-fast household laundry is placed in a conventional household automatic washing machine, the machine is filled with water to its customary working level, and the water soluble composition of this example is then added to the water in an amount such as to form a 0.2% solution having a pH of 9.0. The composition dissolves readily, and the clothes are then washed and rinsed by the machine in the conventional manner. 0n inspection at the end of the normal laundering cycle, it is found that the fabrics are evenly and effectively bleached and washed.
A composition having greater bleaching power than that of the foregoing example may be prepared by increasing the proportions of limonene and dichlorocyanuric acid therein to 1.0% and 19.6% respectively by weight of the final product (replacing appropriate amounts of sodium sulfate). If desired, camphene may be employed in place of limonene, in which case the camphene may be dissolved in ethanol to obtain a liquid form suitable for spraying on the spray dried granules. Alternatively, if it is desired to employ a non-terpenic, substantially odorless olefin, ter-traisobutylene may be employed in place of limonene with similar results.
Example 11 7.5 parts of the dichlorocyanuric acid 7 of Example I are mixed with 91.75 parts of the following detergent composition:
Percent Tetrasodium pyrophosphate 32.8 Sodium 'dodecyl benzene sulfonate 2.48 Sodium toluene sulfonate 5.0 Hypochlorite stable fluorescent dye 0.12 Sodium sulfate 58.6 Moisture 1.0
Example III A dichlorocyanuric acid-containing aqueous detergent slurry is prepared at about 100 F. Immediately upon incorporation of the dichlorocyanuric acid and adequate caustic soda to adjust the pH to about 6.2, the slurry, which contains 55% solids and 45% moisture, is spray dried. The resulting substantially dry particulate product is uniform in composition and contains:
Percent by weight Sodium tridecyl benzene sulfonate 2.2 Pentasodium tripolyphosphate 10.9
Caustic soda 1.4 Dichlorocyanuric acid 9.0 Moisture 2.0
Sodium sulfate, balance to 100%.
These unstalized particles, substantially all of which pass through a 10 mesh screen and are retained on a 100 mesh screen, are tumbled in a rotating mixing drum and is sprayedwith atomized d-limonene in an amount equal to about 0.7% by weight of the finished product.
Example IV 22 parts by weight of the unstabilized spray dried particles of Example III are tumbled in a rotary drum and are commingled with 77.84 parts of a spray dried detergent composition having the following analysis:
7 Percent by weight Sodium tridecyl benzene sulfonate 34.00
Pentasodium tripolyphosphate 46.30 Sodium carboxymethyl cellulose 0.51 Bleach resistant fluorescent dye 0.12 Moisture 3.3
Sodium sulfate, balance to 100%.
The mixture is then further tumbled and sprayed with 0.16 part of d-limonene. On accelerated aging in a closed glass jar at 140 F. for 65 hours, the available chlorine content of the composition diminishes by only about 9%.
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 and substitutions may be made therein without departing from the true scope of the invention as defined in the appended claims.
What is claimed is: e
1. A water soluble textile bleaching and detergent composition consisting essentially of from 0.1 to of solid particulate dichlorocyanuric acid stabilized against decomposition by an olefin having a double bond containing a teritary carbon atom, said olefin being present in a small but sufficient amount to stabilize said dichlorocyanuric acid up to about by weight thereof, about 2 to of a Water soluble anionic organic detergent salt stable in the presence of said dichlorocyanuric acid, and a balance substantially of a water soluble inorganic salt. 7
2. A water soluble textile bleaching and detergent composition as set forth in claim 1 wherein said olefin is a hypochlorous acid-reactive unsaturated terpene.
3. A water soluble textile bleaching and detergent composition as set forth in claim 1 wherein said olefin is substantially odorless.
4. A'water soluble textile bleaching and detergent composition in accordance with claim 1 wherein said water soluble anionic organic detergent salt is an alkali metal salt of an alkyl aryl sulfonic acid.
5. A water soluble textile bleaching and detergent composition consisting essentically of about 0.1 to 10% of dichlorocyanuric acid stabilized against decomposition by about 1 to 40% by weight thereof of an olefin having a double bond containing a tertiary carbon atom, about 5 to 40% of a water soluble anionic organic detergent salt stable towards said dichlorocyanuric acid, and about 45 to 95% of water soluble inorganic builder salts.
6. A water soluble textile bleaching and detergent composition as set forth in claim 5 wherein said inorganic builder salt is hydratable.
7. A water soluble textile bleaching and detergent composition as set forth in claim 6 wherein said hydratable inorganic builder salt is pentasodium tripolyphosphate.
8. A water soluble textile bleaching and detergent coma position consisting essentially of about 0.1 to 10% of d cblorocyanuric acid stabilized against decomposition by about 1 to 40% by weight thereof of limonene, about 5 to 40% of a water soluble anionic; organic detergent salt stable towards said dichlorocyanuric acid, and about 45 to 95% of water soluble hydratable inorganic builder salts.
9. A process for the preparation of a stable water solubie textile bleaching and detergent composition consisting essentially of stabilized dichlorocyanuric acid and a balance substantially of water soluble material, which comprises contacting, on the basis of a total of 100 parts, about 0.1 to 20 arts of solid particulate dichlorocyanuric acid With from about 1 to 40% by Weight thereof of an olefin having a double bond containing a tertiary carbon atom in the presence of about 45 to parts by weight of a water soluble inorganic builder salt stable in the presence of said dichlorocyanuric acid, whereby said olefin is rendered sufliciently diffuse to prevent localized overheating and spontaneous thermal decomposition of said dichlorocyanuric acid, and cornmingling therewith about 2 to 50 parts of a water soluble anionic organic detergent salt stable towards said dichlorocyanuric acid.
References Cited in the file of this patent UNITED STATES PATENTS 818,695 Von Konigswarter 'Apr. 2 4, 1906 2,105,407 Clark Jan. 11, 1938 FOREIGN PATENTS 208,587 .Australia June 3, 19 57 OTHER REFERENCES Lesser: Household Scouring Cleansers, Soap and Sanitary Chemicals, May, 1950, pages 40-43 and 98.

Claims (1)

1. A WATER SOLUBLE TEXTILE BLEACHING AND DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF FROM 0.1 TO 20% OF SOLID PARTICULATE DICHLOROCYANURIC ACID STABILIZED AGAINST DECOMPOSITION BY AN OLEFIN HAVING A DOUBLE BOND CONTAINING A TERITARY CARBON ATOM, SAID OLEFIN BEING PRESENT IN A SMALL BUT SUFFICIENT AMOUNT TO STABILIZE SAID DICHLOROCYANURIC ACID UP TO ABOUT 40% BY WEIGHT THEREOF, ABOUT 2 TO 50% OF A WATER SOLUBLE ANIONIC ORGANIC DETERGENT SALT STABLE IN THE PRESENCE OF SAID DICHLOROCYANURIC CID, AND A BALANCE SUBSTANTIALLY OF A WATER SOLUBLE INORGANIC SALT.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3250720A (en) * 1963-11-18 1966-05-10 Allied Chem Stabilizing and deodorizing chlorinated cyanurates
US3278443A (en) * 1961-07-24 1966-10-11 Lever Brothers Ltd Stabilized chlorinated cyanuric acid bleaching compositions
US3281370A (en) * 1963-02-22 1966-10-25 Lever Brothers Ltd Stabilized trichlorocyanuric acid
US3422029A (en) * 1966-11-18 1969-01-14 Hercules Inc Conversion of 3-carene to a composition comprised of meta-menthadienes and para-menthadienes in substantial amounts
US4334610A (en) * 1979-01-23 1982-06-15 Nissan Chemical Industries, Ltd. Method of storing a solid chlorinating agent and an article for storing same
US20040164029A1 (en) * 2003-02-21 2004-08-26 The Procter & Gamble Company Water treatment compositions with masking agent

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US818695A (en) * 1905-10-16 1906-04-24 Julius Von Koenigswarter Vessel for packing and storing washing-powders containing alkaline peroxids.
US2105407A (en) * 1935-05-25 1938-01-11 Gen Electric Liquid insulating composition

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US818695A (en) * 1905-10-16 1906-04-24 Julius Von Koenigswarter Vessel for packing and storing washing-powders containing alkaline peroxids.
US2105407A (en) * 1935-05-25 1938-01-11 Gen Electric Liquid insulating composition

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3278443A (en) * 1961-07-24 1966-10-11 Lever Brothers Ltd Stabilized chlorinated cyanuric acid bleaching compositions
US3281370A (en) * 1963-02-22 1966-10-25 Lever Brothers Ltd Stabilized trichlorocyanuric acid
US3250720A (en) * 1963-11-18 1966-05-10 Allied Chem Stabilizing and deodorizing chlorinated cyanurates
US3422029A (en) * 1966-11-18 1969-01-14 Hercules Inc Conversion of 3-carene to a composition comprised of meta-menthadienes and para-menthadienes in substantial amounts
US4334610A (en) * 1979-01-23 1982-06-15 Nissan Chemical Industries, Ltd. Method of storing a solid chlorinating agent and an article for storing same
US20040164029A1 (en) * 2003-02-21 2004-08-26 The Procter & Gamble Company Water treatment compositions with masking agent
US7153438B2 (en) * 2003-02-21 2006-12-26 Pur Water Purification Products, Inc. Water treatment compositions with masking agent

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