CA1222923A - Method and article for toilet bowl cleaning - Google Patents

Abstract

ABSTRACT

A method of automatically maintaining a clean toilet bowl. The improvement comprises dispensing with the flush water during each flush of the toilet, a bleachable phthalocyanine dye, and an effective amount of an aqueous hypochlorite composition to said toilet bowl, whereby said bleaching and disinfecting composition, bleaches out the color in said phthalocyanine dye, without a change to an off color in an aminated water, as said hypochlorite composition cleans the toilet bowl, leaving the water, within the bowl, substantially clear. Also included are the dye and detergent cake and the dye and detergent cake within an appropriate dispenser.

Description

AlIP-8245 ~w METHOD AND ARTICLE POR TOILET BOWL CLEANn~G

The present invention relates to the automatic sanitizing of flush toilets by the dispensing of a bleachable dye and a hypochlorite sanitizing agent to the toilet bowl with each flush. The dye is bleached by the hypochlorite to a colorless state within a short time after flushing, thereby providing a visual signal of the activity of the hypochlorite, without changing to an off color in an aminated water.

BACKGRO~JND ART

This invention relates to a method of sanitizing a toilet bowl. More particularly, it relates to an improved method wherein a hypochlorite sanitizingagent and a water-soluble phthalocyanine dye, which is oxidizable by the hypochlorite from a colored to a colorless state, are automatically dispensed from separate dispensing means to the toilet bowl during flushing. The water in the bowl at the end of the flush is colored by the dye. However, the dye is oxidized to a colorless state within a short time thereby providing a visual signal that the hypochlorite sanitizing agent is present and "acting" in the bowl.

Kitkds US. patents 4,200,606 and 4,249,274 disclose respectively a method and article for sanitizing toilets using a dye selected from FD 5c C Blue No. 1,also known as Acid Blue 9, and FD 5c C Green No. 3 as being resistant to being attacked by hypochlorite. Kitkds US patents 4,248,827 and 4,308,625 disclose respectively a method and article for sanitizing toilets using certain oxidizable dyes and a hypochlorite sanitizing agent dispensed from separate dispesing means into the toilet flush water to provide a color to the bowl water.
According, to Kitko the dye color disappears within about 5 seconds to 10 minutes from the time the dye comes in contact with the oxidizing agent. These - dyes, however, turn an off color when in chlorinated waters which have been aminated to stabilize the chlorine such as occurs in Tampa, Florida; Phoenix, Arizona and Orange County, California. This amination occurs by the addition of ammonium salts, e.g. ammonium nitrate to the water supply. For instance FD 5c C Blue No. 1 turns an orange shade, C.I. 24401 turns a purple shade, C.I. 42040 turns a dark murky orange brown and Basic Blue 80 turns a light yellow.

'~
~ '' , : ' ' . '-.: ' 9~3 ~IIP-8245~

In addition to the objects of Kitko's patent No. 4,248,247, an object of the present invention is to provide a system which will not turn to an of ~ color even when used in a toilet having an aminated water supply.

SUMMARY OF THE INVENTION

An improved method is provided of automatically maintaining a clean and sani$ized toilet bowl, comprising dispensing with the flush water during each flush of the toilet, a detergent and an oxidizable colored dye solution, and separately dispensing an effective amount of an aqueous hypochlorite sanitizing solution to said toilet bowl, whereby said hypochlorite sanitizing solution, bleaches out the color in said colored dye as said hypochlorite sanitizing solution cleans the toilet bowl, leaving the water, within the bowl, clear. The improvement comprises using a phthalocyanine dye, having a C.I. number 74xxx, so that said dye solution does not change to an off color in an aminated water.
By "clear" we mean a solution when tested in a transmittance test instrument such as Bosch ~c Lomb's Spectronic 21 in its standard test tubes at an appropriate well length, has a value of at least 99% transmittance.

The Saniti~ ing Agent The sanitizing agent of the present invention can be any compound which provides the hypohalite ion, i.e. hypochlorite ion (OCl-) or hypobromite ion (OBr-) in aqueous solution. Such compounds include alkali metal and alkaline earth metal hypochlorites, hypochlorite addition products, chloramines, chlorimines, chloramides, and chlorimides. Specific examples of compounds of this type include sodium hypochlorite, potassium hypochlorite, lithium hypochlorite, calcium hypochlorite, calcium hypochlorite dihydrate, monobasic calcium hypochlorite, dibasic magnesium hypochlorite, chlorinated trisodium phosphate dodecahydrate, potassium dichloroisocyanurate, sodium dichloroisocyanurate, sodium dichloroisocyanurate dihydrate, trichloroisocyanuric acid, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, Chloramine T, Dichloramine T, Chloramine B, Dichloramine B, and Di-Halo (bromochlorodimethyl hydantoin).
The last named compound also provides hypobromite ion. A particularly preferred sanitizing agent composition suitable for use in the practice of the present invention is trichloroisocysnuric ecid.

2~2g23 AHP-8245~ps By virtue of the strong oxidizing power of the hypochlorite ion, it is highly effective in bleaching stains, breaking down and removing soils and killing microorganisms, thereby providing effective sanitizing action to the toilet bowl.

The amount of hypochlorite-providing compound dispensed to the toilet in the process of the invention can vary over a wide range, but preferably should be sufficient to provide from about 2 to about 20 ppm (preferably from about 2 to about 8 ppm~ available chlorine in the bowl water at the end of the flush. Only a very small amount of the available chlorine, which is delivered to the bowl, will be utilized in oxidizing the dye. The sanitizing agent can be formulated as an aqueous liquid if it is to be dispensed from a dispensing means designed to receive liquids. The sanitizing agent can also be formulated into the form of a solid cake for use in dispensing means which are designed to receive a cake of solid material. The level of available chlorine in the bowl water can be measured by well-known methods such as the standard method of Sampling and Chemical Analysis of Chlorine containing Bleaches ASTM-D 2022-64 (Part 30/1979).

Dyes A water-soluble bleachable aminated water stable phthalocyanine dye is an essential feature of the present invention. The dye should be soluble in water to the extent of at least 0.01% by weight in water at 25C.

The amount of dye dispensed to the toilet in the process of the invention will depend on the color intensity desired, the amount of sanitizing agent dispensed into the toilet with the dye, and on the quickness with which it is desired to have the color disappear. Generally, the amount of dye dispensed willbe sufficient to produce a dye concentration of from about 2 to about 5 ppm, preferably from about 3 ppm to about 4 ppm in the toilet bowl. Dye concentrations herein are based upon the amount of the actual dye compound, unless specified otherwise. Dyes are normally sold in the form of mixtures of dye compound and inert diluent.

Dyes which are suitable for use in the method of the present invention are those which are oxidized by the sanitizing agent to a colorless state within a perioc of Irom about 2 to 30 minute~ from the time they come into contsct t~ith _4_ AilP-8245-p~

the sanitizing agent during the ~lushing of the toilet. Only phthalocyanine dyescan be utilized in the present process. These dyes have the Color Index No.
74xxx, wherein 74 represents the phthalocyanine dye class and xxx represents thespecies.

The following screening test can be used for determining the suitability of any particular dye for use in the method of the present invention. The test is conducted in tap water using Acid Blue 9, which has the same Color Index No. as FD ~ C Blue No. 1, namely C.I. 42090, as a control to discount any variations inthe test water supply. Enough of each dye is dissoived in water in separate containers so that a pleasant deep shade of blue, family color having about the same visual intensity, is obtained. Thereafter 10 ml of a saturated tricloroisocyanuric acid solution is added. If color remains for two (2) minutes, a few drops of dilute NH40H is addéd to ascertain (a) if an off color e.g. red, orange, purple, which may also be described as red or brown family colors, occurs and (b) if the blue family color is bleached out or oxidized by the trichloroisocyanuric acid within thirty (30) minutes from the start of the test.By blue family color, we mean a dye in the blue-green family of dyes, that is the dye is basically blue, but may have a greenish shade, e.g. turquoise.

Table I represents dyes tested, first by trade name and supplier, then sequentially by Color Index Name, Color Index No., where available, and Results.Under Results, item (1) is fading within the test time frame and (2) is production of an off color. "*"means no off color and is cumulative of suitability for tested purpose. Water Insoluble pigments are not suitable because of their water insolubility. "X" is also used to indicate unsuitability. For some dyes, e.g. 16-37, only the overall characteristics are set forth. Those dyes, to which NH40H was added, were stable to TCCA (trichloroisocynanuric acid).

_5_ l~lY-82~5-cw ? ? ? ¢
. . . ~
E E E
.E E~ X

~ O O X ~ X ~ X O X ~ ~C ~ O ~ X ~ ~

c:
m û~
Z O O ~ U~ 0 o~ a a a ~ ~ Y ~ ~ a ~ ~ a 2 31 ~ æ o O y 5 o ~ E :1 ~ o ~a ~a ~ = 3 g ~8 ~ ~E

~222923 AHP-8245-cw c ~ C ~ C X ~ c ~2 ~ c ~5 e ¢ 11 5 0 ¢ o y ~ 5 E E y>~Z ~ D C æ~ i E Z ~ 2 æ ¢
8 ~ E ~ ~ o ~ ¢ ~ 2 c o ~ ~ n 7 ~3 3 ~ O i~

_ O U~ }~ ~ ~

- ~
~ ¦ E 2' -- 3' : : ~ a 2 ~
t~ d m ~ a a ~ ¢ ¢ d m ~ o o o c~ ~ 3 c~ ~ 3 ! c cc ; c c ~ _ _ __ ._ ._ ._ E c~ c c g ~
a 5 S 5 5 5 5 m m.1l ô x c a aO~ ~ m d C
5~ ~ y 3~ 3 d ~ æ ~ c : ~ Z ,~ _ E ~ E c Y ~ ~v ~ E E

N N N N N N

', ' ~, .

7 12229:~3 A H P-8 2 4 S-c w b~ ~ Y = ~ u ~:
o ~l~ E o o ~ 2 ~ ¢ j 0~ 2 r E ~ o z ~ ~ c o ¦ ~, E ~ Z O ~ o C C
,C '~
OD Q9 :!~ a æ ~ ~ a a ~ ~ ~ ~
~I m m m m m m m m m m O m 201 s <1 ¢ ¢ ¢ ~ ¢ 3 3 3 ~¦ Y Y Y Y b Y Y Y Y~ Y Y ~c o ~ ~ o

3~ 3 ~ ,= =
z ~ m m ~ 3 8 o 8 0 m O m c~ o o o ~ 0 0 . . .

`

, . - ' - . - .
':''. ~

1222923 A H P-8245-cw From the above Table it can be seen that only those dyes, which are phthalocyanine dyes, that is those dyes with a color Index (C.I.) Number 74XXX
wherein XXX represents the particular dye within the phthalocyanine genus, namely dyes 1, 2, 3, 9,11,17,18, 23, 25, 35 and 37, are suitable.

Optionally, the dyes used in the method of the present invention can be formulated into compositions containing other ingredients, which it is desired to dispense into the toilet bowl, such as, for example, surfactants, sequestering agents, perfumes, and diluents such as water, organic solvents such as ethanol, and organic or inorganic salts such as sodium sulfate, sodium chloride, and sodium acetate, and inorganic acids such as boric acid.

Surfactants can provide enhanced sanitizing performance through breakup and emulsification of soils, and also provide some sudsing in the toilet bowl, which may be aesthetically desirable. Perfumes provide a pleasant odor to the area surrounding the toilet and also help to obscure the "bleach" odor of the sanitizing agent. Sequestrants aid soil removal by sequestration of multivalent metal ions.

When the dyes herein are formulated with surfactants, the resulting compositions will generally comprise from about 5% to about 90% surfactant and from about 2% to about 10% dye. Perfumes will normally be used at levels of up to about 10% and inert diluents at levels up to about 90%. Sequestering agents such as potassium wrophosphate, sodium tripolyphosphate and citric acid can be used at levels up to about 10%.

Compositions comprising the dye and a su~factant and/or other ingredients can be conveniently pressed into the form of a cake for use in dispensers which are designed to receive a cake of solid material. Such cakes can be made by extrusion or hydraulic stamping, or by pouring a melt of the compositions into amold and solidifying the composition by cooling. The latter method is presently preferred.

- If it is desired to use a dispensing means which is designed to receive liquids, the dye and any optional ingredients such as surfactants, etc., can be formulated into liquid compositions.

~' , - .
. , .
-- .

1222923 A~lP~ 4~-cw 9_ Anionic surf~ctants operable in compositions suitable for use In practicing the present invention can be broadly described as the water-soluble salts, particularly the alkali metal salts, of organic sulfuric acid reaction products having in their molecular structure an alkyl or alkaryl 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 the term alkyl is the alkyl portion of higher acyl radicals.) Important examples of the anionic surfactants which can be employed in the practicing of the present invention are the sodium or potassium alkyl sulfates, especially those obtained by sulfating the high alcohols (C8C18 carbon atoms~ produced by reducing the glycerides of tallow or coconut oil; sodium or potassium alkyl benzene sulfonates, in which the alkyl group contains from about 9 to 15 carbon atoms, (the alkyl group contains from about 9 to about 15 carbon atoms, (the alkyl radical can be a straight or branched aliphatic chain); paraffin sulfonate surfactants having thegeneral formula RS03M, wherein R is a primary or secondary alkyl group containing from about 8 to about 22 carbon atoms (preferably 10 to 18 carbon atoms) and M is an alkali metal, e.g., sodium or potassium; sodium alkyl glyceryl ether sulfonates, especially those ethers of the higher alcohols derived from tallow and coconut oil; fatty acid monoglyceride sulfates and sulfonates; sodiumor 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 10 moles of ethylene oxide; sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates with about 1 to about 10 units of ethylene oxide per molecule and in which the alkyl radicals contain from about 8 to 12 carbon atoms; the reaction products of fatty acids esterified with isothionic acid and neutralized with sodium hydroxide where, for example, the fatty acids are derived from coconut oil; sodium or potassium salts of fatty acid amides of a methyl tauride in whichthe fatty acids, for example are derived from coconut oil and sodium or potassium ,~-acetoxy- or B-acetamido-alkanesulfonates where the alkane has from 8 to 22 carbon atoms.

Nonionic surfactants which can be used in practicing the present invention can be of three basic types--the alkylene oxide condensates, the amides and the semipolar nonionics.

1;:2;~9Z3 The alkylene oxide condensates are broadly defined as compounds produced by the condensation of alkylene oxide groups (hydrophilic in nature) with an organic hydrophobic compound, which can be aliphatic or alkyl aromatic in nature.
The length of the hydrophilic or polyoxyalkylene radical, which is condensed with any particular hydrophobic group, can be readily adjusted to yield a water-soluble-compound having the desired degree of balance between hydrophilic and hydrophobic elements.
Examples of such alkylene oxide condensates include:
1. The condensation products of aliphatic alcohols with ethylene oxide. The alkyl chain of the aliphatic alcohol can either be straight or branched and generally contains from about ~ to 22 carbon atoms. Examples of such ethoxylated alcohols include the condensation product of about 6 moles of ethylene oxlde with 1 mole of tridecanol, myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of myristyl alcohol, the condensation product of ethylene oxide with coconut fatty alcohols with alkyl chains varying is a mixture of fatty alcohols with alkyl chains varying form 10 to 14 carbon atoms and wherein the condensate contains about 6 moles of ethylene oxide per mole of alcohol, and the condensa-tion product of about 9 moles of ethylene oxide with the above described coconut alcohol. Examples of commercially available nonionic surfactants of this type include those supplied under the trademarks Tergitol 15-S-9 marketed by the Union Carbide Corporation, Neodol 23-6.5 marketed by the Shell Chemical Com-pany, Kyro EOB marketed by The Procter ~ Gamble Company and Emulphogene TB 970 marketed by GAF Corporation.
2. The polyetnylene oxide condensates of alkyl phe-nols. These compounds include the condensation products of alkyl phenols having an alkyl group containing from about 6 to lZ229Z3 about 12 carbon atoms ln either a straight chaln or branched chain configuration, with ethylene oxide, the said ethylene oxide being present in amounts equal to 5 to 25 moles of e-thy-lene oxide per mole of alky phenol. The alkyl substituent in such compounds can be derived, for example, from polymerized propylene, diisobutylene, octen, or nonene. Examples of com-pounds of this type include nonyl phenol condensed with about 9.5 moles of ethylene oxide per mole of nonyl phenol, dodecyl phenol condensed with about 12 moles of ethylene oxide per lo mole of phenol, dinonyl phenol condensed wlth about 15 moles of ethylene oxide per mole of phenol, diisooctylphenol con-densed with about 15 moles of ethylene oxide per mole of phe-nol. Commercially available nonionic surfactants of this type include those supplied under the trademarks Igepal CO-610 mar-keted by the GAF Corporation; Triton X-45, X-114, X-100 and X-102, all marketed by the Rohm and Haas Company; and Plurafac D-25 marketed by Wyandotte Chemicals Corporation.
3. The condensation products of ethylene oxide with , a hydrophobic base formed by the condensation of propylene oxide with propylene glycol. The hydrophobic portion of these compounds has a molecular weight of from about 1500 to 1800 and, of course, exhibits water insolubility. The addition of polyoxyethylene moieties of this hydrophobic portion tends to increase the water solubility of the molecule. Examples of compounds of this type include certain of the commercially available Pluronic (a trademark) surfactants marketed by the Wyandotte Chemicals Corporation. Polyethylene glycol conden-sates such as that supplled under the trademark Carbowax E-8000 marketed by Union Carbide are also included here.

4. The condens\ation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine. The hydrophobic base of these products con-, : - . -~2X2923 sists of the reaction product of ethylene dlamlne and excess propylene oxide, said base havin~ a molecular welght of from about 2,500 to about 3,000. Thls base ls condensed with ethy-lene oxide to the extent that the condensation product con-tains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000. Examples of this type of nonionic surfactant include certain of the commercially available Tetraonic (a trademark) compounds marketed by the Wyandotte Chemicals Corporation.
Examples of the amide type of nonionic surfactants include the ammonia, monoethanl and diethanol amides of fatty acids having an acyl moiety of from about 8 to about 18 carbon atoms. These acyl moieties are normally derived from natu-rally occurring glycerides, e.g., coconut oil, palm oil, soy-bean oil and tallow, but can be synthetically, e.g., by the oxidation of petroleum, or by hydrogenation of carbon monoxide by the Fishcher-Tropsch process.
-~ Ampholytic surfactants, which can be used in prac-ticing the present invention, can be broadly described as derivatives of aliphatic amines, which contain a long chain of about 8 to about 18 carbon atoms, and an anionic water-solubi-lizing group, e.g., carboxy, sulfo and sulfato. Examples of compounds ; 30 - lla -lZZ29;~3 A~IP-8245-cw falling within this definition are sodium-3-dodecylamino-propionate, sodium-3-dodecylamino propane sulfonate, and dodecyl deimethylammorium hexanoate.

Zwitterionic surfactants, which can be used in practicing the present invention, are broadly described as internally-neutralized derivatives of aliphatic quaternary ammonium and phosphonium and tertiary sufonium compounds, in which the aliphatic radical can be straight chain or branched, and wherein one of the aliphatic substituents contains from about 8 to 18 carbon atoms and one contains an anionic water-solubilizing group, e.g., carboxy, sulfo, sulfato, phosphato, or phosphono.

Bleach-stable (i.e., hypohalit~stable) surfactants, which are especially resistant to oxidation, are the aryl sulfonates, e.g. sodium xylene sulfonates.

DISPENSING MEANS

In order to provide automatic sanitizing of the toilet bowl in accordance with the present invention, it is essential that the hypochlorite sanitizing agent and the dye, in the form of relatively concentrated solutions, be dispensed intothe flush water each time the toilet is flushed.

It is within the contemplation of the present invention that the concentrated solution of one of the components (i.e., either the dye or the sanitizing agent) be dispensed into the flush tank during the refill after a flush (therby forming a dilute solution of one component in the flush water which is stored in the tank between flushes) and that the concentrated solution of the other component be dispensed into this treated flush water during the time it isflowing from the tank to the bowl during the next succeeding flush Dispensing means which operate to dispense solutions into a toilet tank during the time it is refilling are described, for example, in U.S. Pat. Nos. 1,798,090, Lebegue, issued March 24, 1931; 3,339,801. Hronas, issued Sept. 5, 1967; 3,121,236, Yodro et al., issued February 18,1964.

It is preferred that both of the concentrated solutions be dispensed into the flush water on the downflush, i.e., that they be dispensed into the flush water during the time the flush water is flowing from the tank into the bowL In this preferred mode of operation, it is additionally preferred that the dispensing of .

~2Z2923 the hypochlorite and dye should occur near the end of the flush in order to avold wastage of dye and hypochlor~te and to keep to a minimum the time of contact between dye and hypochlorite before they enter the bowl. The respective dis-pensing means for the hypochlorite and dye solutions should preferably be positioned relative to each other in the toilet tank so that these concentrated solutions will be diluted by flush water during the flush before they come into contact with each other, i.e., intimate mixture of streams of the two concentrated solutions in the flush tank should preferably be avoided. Dispensing means for automatically dispensing solu-tions of chemicals into the flush water during the down-flush are well known to the art. U.S. Patent No. 3,504,384, Radley et al., issued April 7, 1970, discloses a dual dispenser for separately dispensing a detergent/dye solution and a hypochlo-rite solution into the flush water during the flush. Water from the flush tank flows into the respective dispenser cham-bers as the tank fills after a flush, where it comes into con-tact with a solid detergent/dye composition and a solid hypochlorite-producing composition in the respective chambers.
During the interval between flushes, relatively concentrated solutions of the hypochlorite and detergent/dye compositions form in the respective chambers, and these solutions are dis-charged into the flush water on the next flush. Also and par-- ticularly suitable ~s the device described and claimed in Ronayne "Toilet Bowl Cleaning and Disinfecting Device" in Canadian patent application Serial No. 444,575 filed January 3, 1984.

Z;22923 All P-8245-cw EXAMPLE I

A solid, compacted composition cake was prepared using trichloroisocyanuric acid (TCCA) presently available, inter ali&, from Monsanto Corporation, St. Louis, Missouri under the trademark ACL-90 and sodium stearate, available, inter alia, from Witco New York, N.Y. in the proporions setforth;

Ingredient Weight %
TCCA 99.5 Na stearate 0.5 100.00 by compacting on a commercially available tablet press, e.g. Stokes or Carver.

A solid cake containing detergent and dye was prepared by mixing in the proportions set forth the following:

Material Function Wt. %
I) Emulphogene TB 970 non ionic surfactant 35.0 2) Carbowax E-8000 non ionic surfactant 8.0 3) Plurafac ~25 non ionic surfactant 4.78 4) Pyrazol Fast Turguoise dye 3.0 GLL (Conc 150%) (Sandoz, Hanover, N.J.)

5) Na2SO4 filler 49.22 100.00 ~ X2923 A~lP-824$-~w After mixing, the mixture was melted and poured into a mold having 2-1/2 inch square cavities to a depth of about 5/8". When solidified, cakes particularly suitable for use in the Ronayne device were obtained. Any of the phthalcyanine dyes in Table 1, a solution of which is bleachable by a hypochlorite solution and which does not change to a off color in the presence of NH40H can be substituted for the particular Sandoz dye used in Example I above. The dyes are used in a concentration of from about 2 to about 10% by weight with the Na2S04 adjusted accordingly. The surfactants, of course can be raised. Direct Blue 199 in presently preferred.

Dispensers of the type described in the above mentioned Ronayne application using a trichloroisocyanuric acid cake and a detergent-dye cake (Direct Blue 189) according to the present invention was inserted into the flush tanks of toilets thoughout the country. During the flushing of these toilets, a detergent-dye solution, and a hypohalite sanitizing solution were co-dispensed into the toilet bowl. The hypochlorite solution Meached out or oxidized the color of the detergent-phthalocyanine dye in a period of from 2 to 30 minutes without the color changing to an off color in an aminated water such as present in Tampa, Florida. Devices containing detergent-Direct Blue 199 cakes have been tested in certain aminated waters are as, e.g. Tampa, Florida, and are preferredover those containing Direct Blue 189, which is also suitable.

Claims (20)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. In a method of automatically maintaining a clean and sanitized toilet bowl, comprising dispensing with the flush water during each flush of the toilet, a detergent and an oxidizable colored dye solution, and separately dispensing aneffective amount of an aqueous hypochlorite sanitizing solution to said toilet bowl, whereby said hypochlorite sanitizing solution bleaches out the color in said colored dye as said hypochlorite sanitizing solution cleans the toilet bowl, leaving the water, within the bowl, substantially colorless, the improvement, which comprises using a phthalocyanine dye having a Color Index number 74xxx so that said dye solution does not change to an off color in an aminated water.

2. The method of claim 1, wherein sufficient dye is dispensed so that at the end of the flush there is from about 2 to about 5 ppm. in said toilet bowl and sufficient sanitizing solution is dispensed so that at the end of the flush there is from about 2 to 20 ppm. of available halogen in the bowl.

3. The method of claim 2, wherein at the end of the flush there is from about 2 to 5 ppm available chlorine present in the toilet bowl.

4. The method of claim 1, wherein said dye has the Color Index number 74180.

5. The method of claim 1, wherein said dye is Direct Blue 189.

6. The method of claim 1, wherein said dye is Direct Blue 199.

7. The method of claim 1, wherein said dye is Direct Blue 283.

8. The method of claim 1, wherein the said dye is Acid Blue 185.

9. A water-stable detergent and dye cake for dispensing a compatable combination of detergent and dye with the flush water into a toilet bowl, said dye comprising a phthalocyanine dye, a solution of which is bleachable by a hypohalite solution and which does change to an off color in the presence of an aminated hypohalite solution.

10. The detergent and dye cake of claim 9, wherein said dye is Direct Blue 189.

11. The detergent and dye cake of claim 9, wherein said dye is Direct Blue 199.

12. The detergent and dye cake of claim 9, wherein said dye is Direct Blue 283.

13. The detergent and dye cake of claim 9, wherein said dye has the Color Index number 74180.

14. The detergent and dye cake of claim 9, wherein said dye is Acid Blue 185.

15. In an article of manufacture designed for placement in the water of the flush tank of a toilet, said article comprising two dispensing means, the first dispensing means containing a solid composition, which is soluble in water and comprises a compound which provides hypochlorite ions in aqueous solution, and a second dispensing means containing a solid composition, which is soluble in water and which contains a dye, the improvement wherein said dye is a blue family phthalocyanine dye.

16. The article of claim 15, wherein said dye is Direct Blue 189.

17. The article of claim 15, wherein said dye is Direct Blue 199.

18. The article of claim 15, wherein said dye is Direct Blue 283.

19. The article of claim 15, wherein said dye is Acid Blue 185.

20. The article of claim 15, wherein said dye has the Color Index number 74180.