US3789000A

US3789000A - Formulating with a non-burning chlorinated dry bleach

Info

Publication number: US3789000A
Application number: US02778882*7A
Authority: US
Inventors: S Berkowitz
Original assignee: FMC Corp
Current assignee: FMC Corp; Olin Corp
Priority date: 1972-08-04
Filing date: 1972-08-04
Publication date: 1974-01-29
Anticipated expiration: 1991-01-29
Also published as: IL42678A0; CA1004946A; AU471641B2; DE2339117B2; IT992836B; NO144150C; FR2194773A1; CH581696A5; BR7305934D0; ZA734863B; HK17077A; JPS5318189B2; AR202632A1; AU5782573A; IL42678A; FR2194773B1; NO144150B; BE803084A; NL7310694A; DE2339117C3

Abstract

THIS INVENTION PROVIDES A PROCESS THAT SUBSTANTIALLY REDUCES THE PRECATUTIONS REQUIRED WHEN FORMULATING DRY BLEACHING, STERILIZING, DISINFECTING AND DETERGENT COMPOSITIONS PREPARED BY ADMIXING A DRY BLEACHING COMPOUND THAT YIELDS ACTIVE CHLORINE IN WATER WITH AN ADJUVANT FOR SUCH COMPOSITIONS. THIS INVENTION IS BASED UPON THE SURPRISING DISCOVERY THAT AN ORGANIC DRY BLEACHING COMPOUND, SODIUM DICHLOROISOCYANURATE DIHYDRATE IS NON-BURNING.

Description

United States Patent 3,789,000 FORMULATING WITH A NON-BURNING CHLORINATED DRY BLEACH Sidney Berkowitz, Highland Park, NJ assignor to FMC Corporation, New York, N.Y. No Drawing. Filed Aug. 4, 1972, Ser. No. 277,888 Int. Cl. C11d 7/54 U.S. Cl. 252-95 9 Claims ABSTRACT OF THE DISCLOSURE This invention provides a process that substantially reduces the precautions required when formulating dry bleaching, sterilizing, disinfecting and detergent compositions prepared by admixing a dry bleaching compound that yields active chlorine in water with an adjuvant for such compositions. This invention is based upon the surprising discovery that an organic dry bleaching compound, sodium dichloroisocyanurate dihydrate is; non-burning.

This invention concerns bleaching, sterilizing, disinfecting and detergent compositions containing a dry bleaching compound that yields active chlorine in water and a process that reduces the precautions associated with formulating such compositions in commercial quantities.

Bleaching, sterilizing and disinfecting compositions employing active chlorine have been produced in liquid form using aqueous solutions of sodium hypochlorite as the bleaching chemical that yields active chlorine in water. Dry bleaching compounds were substituted for aqueous solutions containing sodium hypochlorite in order to obtain increased stability (longer shelf life) and for convenience in handling, packaging, and shipping. Such compounds that yield active chlorine in Water include calcium hypochlorite, lithium hypochlorite and organic compositions such as l,3-dichloro-5,S-dimethylhydantoin, trichloroisocyanuric acid, chlorinated trisodium phosphate, and dihaloisocyanuric acids and their salts.

The use of dihaloisocyanuric acids and their salts is discussed in U.S. Pat. 2,913,460 issued to A. G. Brown et al. The use of sodium dichloroisocyanurate is also disclosed in U.S. Pat. 3,035,056 and its related British Pat. 923,147.

Although chlorinated dry bleach compounds are used commercially, the problems associated with formulating bleaching, sterilizing, disinfecting and detergent compositions containing such active chlorine yielding compounds are considerable and special precautions are used commercially to minimize the problems.

A major commercial problem encountered during handling, is due to the fact that such oxidizing chemicals can burn and evolve poisonous and noxious gases during burning. Specifically sodium, potassium and calcium dichloroisocyanurate salts and other chlorinated dry bleach compounds, when exposed to a flame, spark or other high temperature source, begin to burn and continue burning after the initial heat source has been removed until all of the material is consumed. This phenomenon is referred to as self-sustaining and self-propagating clecomposition.

Furthermore, certain organic adjuvants for bleaching, sterilizing, disinfecting and detergent compositions are not readily compatible with chlorinated dry bleach compounds. An example of such adjuvants is cationic surfactants, especially quaternary ammonium compounds which can react with and thereby inititate the burning of certain chlorinated dry bleach compounds.

Another problem associated with formulating composi- "Ice tions containing chlorinated dry bleach compounds is known as the dust problem. Fine particles (dust) comprise a portion of chlorinated dry bleach compounds which particles tend to take on electrostatic charge. The charged dust particles tend to accumulate in corners and crevices of process equipment used to handle the chlorinated dry bleach. Accumulations of fine particles in and around bearings or other places where frictional heat develops is particularly undesirable because frictional heat can initiate decomposition. Precautions are taken to minimize such accumulations of dust in commercial operations.

Therefore, the use of such bleaching compounds commercially requires special precautions, especially if the compounds are stored in bulk and dispensed from a bulk container for admixing with adjuvants for bleaching, sterilizing, disinfecting or detergent compositions. Such precautions for handling commercial quantities include:

These precautions are intended to avoid accidental ignition of chlorinated dry bleach compounds with the resulting evolution of chlorine and other noxious gases.

The disclosure in U.S. Pat. 3,544,267 teaches the use;

of hydrated calcium hypochlorite as a solution to the substantial commercial need for a non-burning chlorinated inorganic dry bleach compound. However, using hydrated calcium hypochlorite (approximately the monohydrate) is not a satisfacory solution to the problem because it burns when mixed With certain organics as shown by its inferior performance in proposed U.S. Bureau of Mines procedure RI-7594 discussed hereafter. Furthermore, hydrated calcium hypochlorite introduces calcium ion into solution which is undesirable because it increases the hardness level of water.

This invention provides an improvement in the process of formulation bleaching, sterilizing, disinfecting and detergent compositions prepared by admixing a bleaching compound that yields active chlorine in water and a compound selected from the group consisting of a detergent builder, an anionic, nonionic or cationic surfactant and a detergent filler. The improvement comprises dispensing the bleaching compound from bulk storage in the form of nonburning dihydrate of sodium dichloroisocyanurate into a blending zone in which admixing of the components takes place whereby the fire hazards and dust problems during formulating are substantially diminished by employing a nonburning component having substantially reduced electrostatic charge.

The blending or admixing of components of bleaching, sterilizing, disinfecting, and detergent compositions can be accomplished in any of many known Ways and is typically performed in commercial blending equipment that mechanically mix components fed into the equipment. The blending and feeding of components can be either continuous or intermittent. Precautions to prevent dust accumulation are not necessary because dihydrate particles have substantially reduced electrostatic charge in comparison to other chlorinated dry bleaches.

Definitions Dispensing as used herein means the controlled removal of material from a first zone to a second zone and can be either a continuous removal or an intermittent removal in any convenient quantity (units of material).

Bulk storage zone is a space where a significant quantity of material is contained in an essentially pure state. About pounds or more is a significant quantity for bulk storage of a chlorinated dry bleach because burning about 10 pounds or more results in the release of unacceptably high quantities of noxious gas requiring evacuation of even a large building.

Blending zone is a space where admixing of material takes place.

Hazardous materials as used herein refers to those materials which when tested according to US. Bureau of Mines proposed procedure RI-7594, have a flame propagation rate greater than the pure sawdust standard used in the procedure. Therefore such material enhances rather than impedes the burning of sawdust.

Nonburning refers to a property of a material, namely, the inability of the material to separately support flames. Specifically, when an external flame is brought into contact with a nonburning material and then removed, the

material will not continue to burn as evidenced by a self-extinguishing of the flame with unburned material remaining.

Detergent BuilderA material that has the ability to improve the cleansing power and detergency levels of detergent formulations.

Chlorinated dry bleach is a bleaching compound that yields active chlorine in water. Active chlorine is chlorine of the type obtained by the hydrolysis of the chlorinecontaining composition to produce hypochlorous acid (HOCl) and/or 001- ion depending on the pH of the system. Such end products of hydrolysis are composed of oxygen having two negative charges in combination with a chlorine which must be positively charged. Such a positive chlorine is considered an active chlorine. Active chlorine is not only obtained by the hydrolysis of inorganic hypochlorite but is also obtained from N-chloro compounds such as chlorinated cyanuric acid, and other chloro compounds containing an N-Cl bond at which site hydrolysis takes place cleaving the N-Cl bond and yielding HOCl and/ or 001* ion.

Whenever a chlorinated dry bleach is stored as an essentially pure material in bulk amounts in excess of about 10 pounds the burning of such material is dangerous and can seriously disrupt a commercial operation. The danger is not only due to the heat or flames evolved during the burning of the material, but a serious hazard is caused by chlorine gas and other noxious gases being evolved during the rapid thermally-induced decomposition of such material.

There are many types of suitable bulk storage zones from which material can be dispensed. The choice of a specific type depends upon the convenience of the user taking into account such factors as type of dispensing means used, quantities to be dispensed, and type of shipping container in which the chlorinated dry bleach is received. Often an integrated system is used employing a single container designed for the convenience of the manufacturer, shipper and user of the chlorinated dry bleach. Examples of such containers in which the chlorinated dry bleach is shipped and stored and from which the chlorinated dry bleach can be dispensed include tote bins, drums and the like. The dispensing of chlorinated dry bleach directly from such a container transforms the container into a bulk torage zone during the period of dispensing. The dispens g of material from such containers can be accomplished by any suitable means such as conveyor belts, screw conveyors and manual or automated scoop systems.

The best mode contemplated for dispensing the material from a bulk storage zone and then blending the components into a formulation consists of (1) storing components in individual hoppers (bulk storage zone) which can be readily filled; (2) dispensing each component from its hopper by standard means such as a conveyor belt,

screw conveyor, gravity dispensing means or other similar apparatus which also transfers the material from the storage zone to a blending zone, usually a commercial mixer, in which the materials are added in their desired proportions and blended into a homogeneous mixture. The mixture is then taken from the blending zone and packaged in any convenient unit depending upon the contemplated end use.

Typical adjuvants for bleaching, sterilizing, disinfecting and detergent formulations used in combination with a chlorinated dry bleach compound include a detergent builder, an anionic, nonionic or cationic surfactant and a detergent filler. Selections of specific adjuvants and their concentrations in a particular formulation depends upon the specific use for the formulation. Examples of formulations employing a chlorinated dry bleach are household automatic dishwash compositions, commercial dishwasher compositions, scouring powders, household bleach, commercial laundry bleaches, sanitizers, broad spectrum biocides and general detergency sanitizing compositions. Typical formulations of detergent compositions containing a chlorinated dry bleach and typical adjuvants are as follows:

Concentration range, percent 1. Household automatic dishwashing composition:

Chlorinated dry bleach 0.5-10.0

Sodium tripolyphosphate (or other builder) 0-60 Soda ash (or other alkaline carbonates) 10-40 Sodium silicate (ratio 1.0:1 to 33:1) 10-40 Nonionic surfactant 1-10 Balance sodium sulfate (or other filler) 0-60 2. Commercial dishwashing machine composition:

Chlorinated dry bleach (LS-10.0

S o d i u m tripolyphosphate (or other builder) 0-60 Caustic soda 1 5-20 Silicate (1:1 anhydrous) 1 10-40 Balance soda ash (or other filler) 0-40 1 0r orthosilicate equivalent of these two components.

3. Scouting powder:

Chlorinated dry bleach 0.4-4.0 Anionic surfactant 1-6 Soda ash (or other alkaline carbonates) 5-20 S o d i u m tripolyphosphate (or other builder) 0-5 Balance silica flour 55-93 4. Household bleach:

Chlorinated dry bleach 5-80 S o d i u m tripolyphosphate (or other builder) 0-40 Anionic surfactant 2-10 Soda ash (or other alkaline carbonates) 0-10 Balance sodium sulfate (or other filler) 10-78 5. Commercial laundry bleach:

Chlorinated dry bleach 10-90 S o d i u m tripolyphosphate (or other builder) 0-4 Balance sodium sulfate (or other filler) 10-80 6. Detergent-sanitizer:

Chlorinated dry bleach 5-50 S o d i u m tripolyphosphate (or other builder) 0-40 Silicate (1:1 ratio, or 1.0-3.2 ratio) 10-40 Anionic surfactant 2-10 Balance sodium sulfate (or other filler such as sodium chloride or soda ash if more alkalinity desired) 0-68 TABLE-Continued Concentration 7. Sanitizer: range, percent Chlorinated dry bleach 5-80 Balance sodium sulfate (or other filler such as sodium chloride or soda ash if more alkalinity desired) 50-90 8. Broad spectrum biocide:

Chlorinated dry bleach 1 0-90 Cationic surfactant 0.4--- Balance sodium sulfate (or other filler such as sodium chloride or soda ash if more alkalinity desired) 6-90 Weight ratio of cationic surfactant to bleach must not exceed 1:24.

Typical detergent builders include alkali salts of nitrilotriacetic acid, ethylenediaminetetraacetic acid, gluconic acid, and citric acid. Other suitable adjuvants include polycarboxylates, organic phosphonates, alkali metal carbonates, bicarbonates, borates, silicates and cyanuric acid.

Suitable fillers used in such compositions are well known and can be passive or actively aid the detergency function or storage by such means as pH adjustment or the like. Examples of suitable detergent fillers include sodium sulfate, sodium chloride, borax, soda ash or other carbonates.

Suitable surfactants for use in this invention are listed in Table VI.

0f the active chlorine sources only sodium dichloroisocyanurate dihydrate has been discovered to have fire resistant properties that would place it in the proposed Bureau of Mines Class 1, the least hazardous class whereas most of the other chlorinated dry bleach compounds would be in proposed Class 3, which is more hazardous.

The combination of dihydrate with sodium dichloroisocyanurate having less water than the dihydrate, such as the monohydrate and/or anhydrous forms, results in a mixture having the beneficial properties described herein if there is sufficient dihydrate in the mixture so that the average combined water content of the mixture is greater than 11% Such mixtures having greater than 11% water are referred to herein as hydrated sodium dichloroisocyanurate. Since the dihydrate contains 14.1% combined water, hydrated sodium dichloroisocyanurate having greater than 11% up to and including 14.1% average combined H O are suitable for use in this invention. Additional uncombined water up to 2% may be present (in addition to the 14.1% combined water) without altering the properties of the dihydrate.

In addition to their nonburning property, sodium dichloroisocyanurate dihydrate particles possess substantially less electrostatic charge than anhydrous particles which reduces the tendency of fine particles to accumulate thereby eliminating one of the hazards of handling chlorinated dry bleach compounds.

The following examples substantiate the surprising difference in fire resistant properties between the dihy drate of sodium dichloroisocyanurate and other chlorinated dry bleach chemicals. All proportions used herein are based upon weight unless indicated otherwise.

EXAMPLE 1 An 18 gauge Nichrome wire was embedded in a g. sample of chlorinated dry bleach. The wire was heated by passing a current through it for several seconds until the material in contact with the wire began to decompose. The current was then shut off and the sample observed to determine the tendency for self propagated decomposition after the initial cause of decomposition was removed. This procedure was followed with samples of anhydrous and hydrated forms of both sodium dichloroisocyanurate and potassium dichloroisocyanurate. The results are listed in Table I.

6 TABLE I Sample Decomposition rate Sodium dichloroisocyanurate Anhydrous Complete and rapid. Monohydrate Complete and rapid. 11.0% average H O Complete but very slow. 12% average H O 1 incomplete. Dihydrate incomplete.

1 Incomplete since the decomposition stopped after the current was shut 01f with undecomposed material remaining.

Potassium dichloroisocyanurate 2 Anhydrous Complete and rapid. Monohydrate Complete and rapid.

2 No dihydrate exists.

EXAMPLE .2

The procedure of Example 1 Was repeated with samples of chlorinated dry bleach mixed with 2% by weight of the cationic surfactant [dimethyl benzyl di-(isobutyl phenoxy ethoxy) ethyl ammonium chloride] to demonstrate the hazard of mixing a cationic surfactant with conventional chlorinated dry bleaches. The dihydrate was tested with both 2% and 4% surfactant mixtures. The results are listed in Table II.

TABLE II Sample Decomposition rate Sodium dichloroisocyanurate Anhydrous+2% Complete and rapid. Dihydrate+2% Incomplete. Dihydrate +4% Incomplete. Potassium dichloroisocyanurate Anhydrous+2% Complete and rapid. Anhydrous+2% trichloroisocyanuric acid+2% Complete and rapid.

EXAMPLE 3 A quantity of each of the chlorinated dry bleaches listed in Table III was placed in a bed 1" x 2 x 7 long and ignited at one end with a flame according to proposed Bureau of Mines procedures RI-7593. The horizontal rate of spread of the flame in the material was timed with the results listed in Table III.

TABLE III Sample Flame propagation Sodium dichloroisocyanurate Anhydrous 1.61 inches/min. Monohydrate 0.65 inch/min. Dihydrate No value; material would not burn.

EXAMPLE 4 Samples were prepared containing an :20 mixture of a chlorinated dry bleach listed in Table IV and red oak sawdust following proposed Bureau of Mines procedure RI-7594. In addition, a control sample was also prepared with pure sawdust. Each sample was placed in a bed 1" x 2" X 7 long and ignited with a flame as in Example 3, and the rate of spread of the flame was timed. The

7 As can be readily determined from Examples 14, sodium dichloroisocyanurate dihydrate is not only nonburning but actually impedes the flame propagation rate of flammable material (dihydrate-sawdust combination burns significantly slower than sawdust alone.)

EXAMPLE TABLE V Component Composition, percent Sodium silicate (2:1 ratio SiO /Na O, 18%

water) 27 Sodium carbonate, anhydrous 15 Nonionic surfactant 1 5 Sodium tripolyphosphate, anhydrous 35 Sodium sulfate anhydrous 15.2 Sodium dichloroisocyanurate dihydrate 2.8

Oxyethylated straight chain alcohol (Plurafac RA 43- Wyandotte Chemical Corp.)

TABLE VI 1. Anionic surfactants suitable for use in this invention include both soap and nonsoap detergent compounds. Examples of suitable soaps are the sodium, potassium, ammonium and alkylolammonium salts of higher fatty acids (C -C Particularly useful are the sodium or potassium salts of the mixture of fatty acids derived from coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap. Examples of anionic organic non-soap detergent compounds are the water-soluble salts, alkali metal salts, of organic sulfuric reaction'products having in their molecular structure an alkyl radical containing from about 8 to about 22 carbon atoms and a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. (Included in this term alkyl is the alkyl portion of higher acyl radicals.) Important examples of the synthetic detergents which form a part of the compositions of the present invention are the sodium or potassium alkyl sulfates especially those obtained by sulfating the higher alcohols (C -C carbon atoms) produced by reducing the glycerides of tallow or coconut oil; sodium or potassium alkyl benzenesulfonates, such as are described in United States Letters Pats. No. 2,220,009 and No. 2,477,383 in which the alkyl group contains from about 9 to about 15 carbon atoms; other examples of alkali metal alkylbenzene sulfonates are those in which the alkyl radical is a straight chain aliphatic radical containing from about 10 to about 20 carbon atoms for instance, 2-phenyl-dodecanesulfonate and 3-pheny1-dodeoanesulfonate; sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher alcohols derived from tallow and coconut oil; sodium coconut oil fatty acid monoglyceride sulfates and sulfonates; sodium or potassium salts of sulfuric acid esters of the reaction product of one mole of a higher fatty alcohol (e.g., tallow or coconut oil alcohols) and about 1 to 6 moles of ethylene oxide; sodium or potassium salts of alkylphenol ethylene oxide ether sulfate with about 1 to about 10 units of ethylene oxide per molecule and in which the alkyl radicals contain about 9 to about 12 carbon atoms; the reaction product or fatty acids esterified with isethionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amide of a methyl tauride in which the fatty acids, for example, are derived from coconut oil; and others known in the art, a number being specifically set forth in United States Letters Patents NOS. 2,486,921; 2,486,922; and 2,396,278.

2. Nonionic surfactants suitable for use in this invention may be broadly defined as compounds aliphatic or alkylaromatic in nature which do not ionize in water solution. For example, a well known class of nonionic synthetic detergents is made available on the market under the trade name of Pluronic. These compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of the molecule which, of course, exhibits water insolubility has a molecular weight of from about 1,500 to 1,800. The addition of polyoxyethylene radicals to this hydrophobic portion tends to increase the water solubility of the molecules as a whole and the liquid character of the product is retained up to the point where polyoxyethylene content is about 50% of the total weight of the condensation product.

Other suitable nonionic synthetic detergents include: (a) The polyethylene oxide condensates of alkyl phenols, e.g., the condensation products of alkyl phenols having an alkyl group containing from about 6 to 12 carbon atoms in either a straight chain or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 10 to 25 moles of ethylene oxide per mole of alkyl phenol. The alkyl substitute in such compounds may be derived from polymerized propylene, diisobutylene, octene, or nonene, for example.

(b) Those derived from the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. For example, compounds containing from about 40% to about polyoxyethylene by weight and having a molecular weight of from about 5,000 to about 11,000 resulting from the reaction of ethylene oxide groups with a hydrophobic base constituted of the reaction product of ethylenediamine and excess propylene oxide, said hydrophobic base having a molecular weight of the order of 2,500 to 3,000, are satisfactory.

(c) The condensation product of aliphatic alcohols having from 8 to 18 carbon atoms, in either straight chain or branched chain configuration, with ethylene oxide, e.g., a coconut alcohol-ethylene oxide condensate having from 10 to 30 moles of ethylene oxide per mole of coconut alcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms.

(d) Long chain tertiary amine oxides corresponding to the following general formula, R R R N O, wherein R is an alkyl radical of from about 8 to 18 carbon atoms, and R and R are each methyl or ethyl radicals. The arrow in the formula is a conventional representation of a semipolar bond. Examples of amine oxides suitable for use in this invention include dimethyldodecylamine oxide, dimethyloctylamine oxide, dimethyldecylamine oxide, dimethyltetradecylamine oxide, dimethylhexadecylamine oxide.

(e) Long chain tertiary phosphine oxides corresponding to the following formula RR'R 0, wherein R is an alkyl, alkenyl or monohydroxyalkyl radical ranging from 10 to 18 carbon atoms in chain length and R and R" are each alkyl or monohydroxyalkyl groups containing from 1 to 3 carbon atoms. The arrow in the formula is a con- Ventional representation of a semipolar bond. Examples of suitable phosphine oxides are:

Dimethyldodecylphosphine oxide, Dimethyltetradecylphosphine oxide, Ethylmethyltetradecylphosphine oxide, Cetyldimethylphosphine oxide, Dimethylstearylphosphine oxide, Cetylethylpropylphosphine oxide, Diethyldodecylphosphine oxide,

Diethyltetradecylphosphine oxide, Bis(hydroxymethyl)dodecylphosphine oxide, Bis(2-hydroxyethyl)dodecylphosphine oxide, 2-hydroxypropylmethyltetradecylphosphine oxide, Dimethyloleylphosphine oxide, and Dimethyl-2hydroxydodecylphosphine oxide (f) Dialkyl sulfoxides corresponding to the following formula, RR'S 0, wherein R is an alkyl, alkenyl, betaor gamma-monohydroxyalkyl radical or an alkyl or betaor gamma-monohydroxyalkyl radical containing one or two other oxygen atoms in the chain, the R groups ranging from to 18 carbon atoms in chain length, and wherein R is methyl or ethyl. Examples of suitable sulfoxide compounds are:

Dodecyl methyl sulfoxide,

Tetradecyl methyl sulfoxide, 3-hydroxytridecyl methyl sulfoxide, 2-hydroxydodecyl methyl sulfoxide, 3-hydroxy-4-decoxybutyl methyl sulfoxide, 3-hydroxy-4-dodecoxybutyl methyl sulfoxide, 2-hydroxy-3-decoxypropyl methyl sulfoxide, 2-hydroxy-3-dodecoxypropyl methyl sulfoxide, Dodecyl ethyl sulfoxide, and 2-hydroxydodecyl ethyl sulfoxide.

3. Cationic surfactants suitable for use in this invention are compounds having one of the following generic formulas where R and R are hydrophobic alkyl or alkylaryl groups containing 10 or more carbon atoms, a, b, and c are methyl, ethyl, or benzyl groups, AI is a nitrogen-containing aromatic group, and X is halide, sulfate, methosulfate or ethosulfate. Examples of R and R are saturated unsaturated alkyl groups having 10 to 18 carbon atoms (cetyl, lauryl, myristyl, stearyl, oleyl) and mixtures of these such as those derived from natural products such as tallow and monoand dialkylbenzyl groups; examples of Ar are pyridine and isoquinoline and the like. Typical examples of cationic surfactants are the following quaternary ammonium compounds:

Trimethyl methyldodecylbenzyl ammonium chloride Trimethyl cetyl ammonium chloride Trimethyl stearyl ammonium chloride Trimethyl tallow ammonium chloride Dimethyl dioctyl ammonium chloride Dimethyl octyl decyl ammonium chloride Dimethyl didecyl ammonium chloride Dimethyl octyl dodecyl ammonium chloride Dimethyl distearyl ammonium chloride Dimethyl ethyl cetyl ammonium chloride Dimethyl dodecyl 2-phenoxyethyl ammonium chloride Dimethyl di(tallow) ammonium chloride Dimethyl benzyl tallow ammonium chloride Dimethyl benzyl cetyl ammonium chloride Dimethyl benzyl lauryl ammonium chloride Dimethyl benzyl myristyl ammonium chloride Dimethyl benzyl stearyl ammonium chloride Dimethyl benzyl di-(isobutyl cresoxy ethoxy) ethyl ammonium chloride Dimethyl benzyl di-(isobutyl phenoxy ethoxy) ethyl ammonium chloride Lauryl pyridinium chloride Cetyl pyridinium chloride Lauryl isoquinolinium chloride Dioctyldimethylarmnonium chloride Didecyldimethylammonium chloride Didodecyldimethylammonium chloride Ditetradecyldimethylammonium chloride Dihexadecyldimethylammonium chloride Dioctadecyldimethylammonium chloride Dioleyldimethylammonium chloride Di(hydrogenated tallow) dimethylammonium chloride Di(tall oil) dimethylammonium chloride Di-coco dimethylammonium chloride Benzyldidodecylmethylammonium chloride Benzyldicocomethylammonium chloride Benzyldi(hydrogenated tallow) methylammonium chloride Trioctylmethylammonium chloride Tridodecylmethylammonium chloride Tricocomethylammonium chloride Dodecyltrimethylammonium chloride Tetradecyltrimethylammonium chloride Hexadecyltrimethylammoniurn chloride 9-octadecenyltrimethylammonium chloride Octadecyltrimethylammonium chloride Tallow trimethylammonium chloride Soya trimethylammonium chloride Cotton trimethylammonium chloride Tall oil trimethylammonium chloride Coco trimethylammonium chloride Dodecylbenzyldimethylammonium chloride Coco benzyl dimethylammonium chloride Hydrogenated tallow benzyldimethylammonium chloride Dodecylbenzyl hydrogenated tallow dimethylammonium chloride Dodecylbenzyltri (octyldecyl) ammonium chloride What is claimed is:

1. In the process of formulating bleaching, sterilizing, disinfecting and detergent compositions prepared by admixing a bleaching compound that yields active chlorine in water and a component selected from the group consisting of a detergent builder, an anionic, nonionic or cationic surfactant and a detergent filler wherein the improvement comprises,

dispensing the bleaching compound from a bulk storage zone in the form of a non-burning dihydrate of sodium dichloroisocyanurate into a blending zone in which admixing of the components takes place whereby the fire hazards during formulating are diminished by employing a non-burning component having substantially reduced electrostatic charge.

2. The process of claim 1 in which the sodium dichloroisocyanurate dihydrate is contained in a mixture with sodium dichloroisocyanurate having less combined water than the dihydrate so that the average combined water content of the mixture is greater than 11%.

3. The process of claim 1 in which the bleaching, sterilizing, disinfecting and detergent composition is a household automatic dishwashing composition containing from 0.5 to 10% sodium dichloroisocyanurate dihydrate.

4. The process of claim 1 in which the bleaching, sterilizing, disinfecting and detergent composition is a commercial dishwashing machine composition containing from 0.5 to 10% sodium dichloroisocyanurate dihydrate.

5. The process of claim 1 in which the bleaching, sterilizing, disinfecting and detergent composition is a scouring powder containing from 0.4 to 4% sodium dichloroisocyanurate dihydrate.

6. The process of claim 1 in which the bleaching, disinfecting, sterilizing and detergent composition is a dry household bleach containing from 5% to sodium dichloroisocyanurate dihydrate.

7. The process of claim 1 in which the bleaching, sterilizing, disinfecting and detergent composition is a com- 11 mercial laundry bleach containing from 10% to 90% sodium dichloroisocyanurate dihydrate.

8. The process of claim 1 in which the bleaching, sterilizing, disinfecting and detergent composition is a detergent-sanitizer containing from 5% to 50% sodium dichloroisocyanurate dihydrate.

9. The process of claim 1 in which the bleaching, sterilizing, disinfecting and detergent composition is a sanitizer containing from 5% to 80% sodium dichloroisocyanurate dihydrate.

12 References Cited UNITED STATES PATENTS UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,789,000 Dated January 29, 197 4 Inventorfii) Sidney BePkOWit Z It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 2, line 50, "nonburning" should read -nonburning-.

Column 2, line 5 "nonburning" should read non-burning-.

Column 3, line 16, "nonburning" should read -nonburning--. Column 3, line 19, "nonburning" should read nonburning-.

Column line 17, "dishwash" should read -dishwasher. Column 1, line 65, "O-Q" should read 0 l0 Continued...

Patent No, Dated January 29,

Inventoflx) Sidney Berkowitz PAGE 2 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 6, line 1'4, Table I should read as follows:

TABLE I Sample Decomposition Rate Sodium Dichloroisocyanurate anhydrous complete 8: rapid monohydrate complete & rapid 11.0% average H2O complete but very slow 12% average H O incomplete* dihydrate I incomplete* Potassium Dichloroisocyanurate** anhydrous complete & rapid monohydrate I complete & rapid Trichloroisocyanuric acid incomplete* incomplete since the decomposition stopped after the current was shut off with undecomposed material remaining.

** no dihydrate exists. C ntinued..

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,7 9, Dated January 9, 97

Inventor) Sidney Berkowitz PAGE 3 It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 8, line 61, "RR'R"+O" should read -RR'R"P+O-- Signed and sealed this 10th day of Junel975.

(SEAL) At test C MARSHALL DANN RUTH C. MASON Commissioner of Patents Attesting Officer and Trademarks