CA1104451A - Detergent bleach composition and process - Google Patents

Detergent bleach composition and process

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Publication number
CA1104451A
CA1104451A CA297,842A CA297842A CA1104451A CA 1104451 A CA1104451 A CA 1104451A CA 297842 A CA297842 A CA 297842A CA 1104451 A CA1104451 A CA 1104451A
Authority
CA
Canada
Prior art keywords
composition
bleach
acid
porphine
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
Application number
CA297,842A
Other languages
French (fr)
Inventor
Manuel Juan De Luque
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to CA297,842A priority Critical patent/CA1104451A/en
Priority to PH22189A priority patent/PH15828A/en
Priority to EP79200082A priority patent/EP0003861A1/en
Priority to NLAANVRAGE7915006,A priority patent/NL187494C/en
Priority to DE19792948923 priority patent/DE2948923A1/en
Priority to BEBTR51A priority patent/BE51T1/en
Priority to GB8008028A priority patent/GB2042005B/en
Priority to BR7901212A priority patent/BR7901212A/en
Priority to US06/015,677 priority patent/US4240920A/en
Priority to AU44613/79A priority patent/AU524329B2/en
Priority to MX176757A priority patent/MX150169A/en
Priority to JP54023282A priority patent/JPS5858394B2/en
Priority to IE564/79A priority patent/IE48257B1/en
Priority to FR8000103A priority patent/FR2443500A1/en
Priority to SE8001309A priority patent/SE437533B/en
Priority to IT86212/80A priority patent/IT1148214B/en
Application granted granted Critical
Publication of CA1104451A publication Critical patent/CA1104451A/en
Priority to JP58017295A priority patent/JPS594479B2/en
Expired legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/39Organic or inorganic per-compounds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005Other compounding ingredients characterised by their effect
    • C11D3/0063Photo- activating compounds

Abstract

DETERGENT BLEACH COMPOSITION AND PROCESS

Manuel Juan de Luque ABSTRACT OF THE DISCLOSURE
Combined washing and bleaching of fabrics is accomplished by use of a composition comprising a mixture of surfactant, peroxy bleach, and porphine bleach. The surfactant is anionic, nonionic, semi-polar, ampholytic, zwitterionic, or cationic in nature. The peroxy bleach is inorganic or organic. The porphine bleach is a porphine or a mono-, di-, tri-, or tetra-aza porphine, solubilized with anionic, nonionic and/or cationic substituent groups, and metal free or metallated with Zn(II), Cd(II), Mg(II), Sc(III) or Sn(IV.)

Description

BACR~ROUND OF THE INVENTION
This invention relates to household laundry processes for combined washing and bleaching of fabrics, and to simultaneous removal of stains and fugitive dyes.

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11~44Sl British Patent 1,372,035 (Speakman~ published on December 23, 1975 related to a household washing and bleaching process for cotton fabrics utilizing photo-activating compounds, principally sulfonated zinc phthalo-cyanine, in a built detergent composition in the presence of visible light and atmospheric oxygen. In a patent of addition, British Patent 1,408,144 published January 28, i976, Speakman disclosed a surfactant/builder composi-tion which was dissolved in water to form a solution to , 10 which was addedj both separately and together, sodium , perborate and'sulfonated zinc phthalocyanine. Bleaching effects of the combination were said to be greater than would have been expected from the two components acting independently. It was postulated that the sulfonated zinc phthalocyanine enabled evolved oxygen from the sodium perborate, which would otherwise escape unused as mole-cular oxygen, to be converted into singlet oxygen which acted as the active chemical bleaching agent.
U.S. Patent 4,033,718 granted to Holcombe et al on July 5, 1977 teaches the use of specific mixtures of sulfonated zinc phthalocyanine species, principally tri-and tetra-sulfonates, as preferred bleach photoactivators.
Belgian Pa,tent No. 840,348 invented by Wiers, granted on October 4, 1976 discloses the use of zinc phthalocyanine tri- and tetra-sulfonates as bleach photoactivators in unbuilt liquid detergent compositions.
British Patent 1,372,036 invented by Speakman and published on October 30, 1974 describes a washing machine provided with a source of visible light which ~ - 2 -`Al' .

45~

irradiates wash liquor containing phthalocyanine photo-activator and fabrics. An example comparable to that described in British Patent l,408,144 described above showed results consistent therewith.
In Canadian patent application 274,869 filed March 28, 1977, Goodman eliminated the blue-green staining problem inherent in previous work by using much reduced concentrations of zinc phthalocyanine sulfonate in con-junction with a long pre-wash soaking time. As little as 0.003~ photoactivator was needed in conjunction with 18-hour soaking, which could optionally take place under illumination or in the dark. Light was, however, believed essential during the drying step which takes place after a washing.
In Canadian patent application 313,433 and 319,432 filed January lO, 1979, Sakkab disclosed the use of many porphine derivatives as alternatives to ; zinc phthalocyanine sulfonate; these derivatives were solubilized by anionic, nonionic or cationic moieties introduced into the porphine molecule. Not only stain removal but also removal of fugitive dyes and improvement in overall whiteness of the fabrics was obtained.
In Canadian patent application 319,431 filed January 10, 1979, Sakkab disclosed the use of porphine ~ derivatives in conjunction with cationic substances;
; previously thereto, usage of porphine derivatives as detergent bleaches had been limited to use with anionic, nonionic, semi-polar, ampholytic or zwitterionic surfactants. As in all previous disclosures, visible light was believed-essential to operability of the bleaching process.

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In all references identified above, zinc phthalo-cyanine sulfonate and other porphine bleaches have been referred to as "photosensitizers" or "photoactivators", and~the processes of use have invariably involved the presence of visible light (640-690 nm.) at one or more stages of soaking, washing or drying. It has now been unexpectedly found that porphine bleach, in combination with peroxy bleach, is effective when the entire washing and drying process takes place in darkness.
Furthermore, the effectiveness of the combination of peroxy bleach with porphine bleach is so great that levels of peroxy and/or porphine bleach hitherto '~ believed ineffective can be advantageously used. This represents an economic advantage, and one that might be particularly appreciated by those who are concerned about ecology and waste disposal.

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SU~LRY OF TEE INVENTION
This invention relates to a bleach composition comprising three components: (a1 a surfactant, (b) a peroxy bleach, and (c) a porphine bleach.
The surfactant can be anionic, nonionic, semi-polar, ampholytic, or cationic. The surfactant can be used at levels rom about ~% to about 50%, preferably from about 4~ to about 30%, by weight of the composition. ~ ;
The peroxy bleach can be an inorganic peroxide or peroxyhydrate; urea peroxide; or an organic peroxy acid or anhydride or salt thereof which has the general formula HO - O - C - R - Y
where R LS an-alkylene group containing from l to 20 carbon atoms or a phenylene group; and Y is hydrogen, halogen, alkyl, aryl or any group which provides an anionic moiety in aqueous solution.
Peroxy bleach, expressed in terms of available oxygen, is from 0.2% to 5.0%, preferably from 0.2% to 0~7~, more preferably from 0.2% to 0.5%, by weight of the composition. A conventional peroxy bleach activator, i.eO an organic peracid precursor, can be used option-ally.

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The porphine bleach has the general formula : ~ R ~ ~ R ~ (~M
~X

~ R, I
i ~, wherein each X is (-N-~ or (=CY-), and the total number of (=N-) groups is 0, 1, 2~ 3 or 4; wherein each Y, independently is hydrogen or meso substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or heteroaryl; wherein each R, independently, is hydrogen or pyrrole substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or heteroaryl, or wherein adjacent pairs of R's are joined together with ortho-arylene groups to form pyrrole substituted alicyclic or heterocyclic rings;
wherein A is 2(H) atoms bonded to diagonally opposite nitrogen atoms, or Zn(II), Cd(II), Mg(II), Sc(III), or Sn(IV); wherein B is an anionic, nonionic or cationic solubilizing group substituted into Y or R; wherein M is a counterion to the solublizing groups; and wherein s is the number of solubilizing groups.

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i ~ ` -~ . . , -For cationic solubili2ing group~ M, the counterion, is an anion such as halide and s is fro~ 1 to about 8. For polyethoxylaie nonionic solubili2ing groups -(CH2CH2O~n~, M is zero, s is from 1 to about 8, and N =~sn)- the number of (condensed ethylene oxide molecules per porphine molecule) is from about 8 to about 50. For anionic groups M, the -counterion, is ca~ionic. For anionic groups attached to - ~ .:.
atoms no more than S atoms displaced from the porphine core, --, .. . . . .
i.e. for "proximate" anionic groups as definea herein, s is from 3 to about 8. For anionic groups attached to atoms more than 5 atoms displaced from the porphine core, i.e. for "remote" anionic groups a~ defined herein, s is from 2 to about 8~ For sulfonate groups their number is no -greater than the number of aromatic and h~te~ocyclic 3ubsti-tuent groups.

In the foregoing description, the term "alkyl" is defined to be not only a simple carbon chain but also a - carbon chain interrupted by other chain-forming atoms, such as O, N or S.
Porphine bleach is used in amounts from 0.001 to 0.5~, more preferably from 0.003 to 0.022%, especially preferably from 0.005 to 0.017%, by weight of the composi-tion.
Other components are optional, for instance conventional alkaline detergent builders, exotherm control agents, soil suspending agents, fluorescers, colorants, perfumes and the like. The composition of this invention may take the form of granules, liquids or bars.
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Detailed Description of the Invention The essential components of the instant invention are three in number. One is a surfactant which can be _._ anionic, nonionic, semi-polar, ampholytic, zwitterionic, or cationic in nature. Surfactants can be used at levels from about 1~ to about 50% of the composition by weight, preferably at levels from about 4% to about 30% by weight.
Preferred anionic non-soap surfactants are ~ater soluble salts of alkyl benzene sulfonate, alkyl sulfate, alkyl polyethoxy ether sulfate, paraffin sulfonate, alpha-olefin sulfonate, alpha-sulfoearboxylates and their esters, alkyl glyceryl ether sulfonate, fatty acid monoglyceride sulfates and sulfonates, alkyl phenol polyethoxy ether sulfate, 2-acy1oxy-alkane-1-sulfonate, and beta-aIkyloxy alkane sulfonate. Soaps are also preferred anionic surfaetants.
Espeeially preferred alkyl benzene sulfonates have about 9 to about 15 earbon atoms in a linear or branched alkyl ehain, more espeeially about 11 to about 13 carbon atoms. Espeeially preferred alkyl sulfate has about 8 to about 22 earbon atoms in the alkyl ehain, more especially from about 12 to about 18 carbon atoms. Especially preferred alkyl polyethoxy ether sulfate has about 10 to about 18 carbon atoms in the alkyl chain and has an average of about 1 to about 12 -CH2CH2O- groups per moleeule, espeeially about 10 to about 16 carbon atoms in the alkyl ehain and an average of about 1 to about 6 -CH2CH2O- groups per moleeule.

j , Especially preferred paraffin sulfonates are essentially linear and contain from about 8 to about 24 i carbon atoms, more especially from about 14 to a~out 18 carbon atoms. Especially preferred alpha-olefin sulfonate has about 10 to about 24 carbon atoms, more especially about 14 to about 16 carbon atoms; alpha-olefin sulfonates can be made by reaction with sulfur trioxide followed by- - `~
¦ neutralizatio~ under conditons such that any sultones -present are hydrolyzea to the corresponding hydroxy alk~ne sulfonate~. Especially prefer-ed alpha-sulfocarboxylates ! contain from about 6 to about 20 carbon atoms; included herein are not only the salts of alpha-sulfonated fatty acids but also their esters made from alcoholæ containing about 1 to about 14 carbon atoms.

E~pecially preferred alkyl glycëryl ether sulfates are ethers of alcohols having about 10 to about 18 carbon atoms, more especially those derived from coconut oil and tallow. Especially preferred alkyl phenol polyethoxy ~ ether sulfate has about 8 to about 12 carbon atoms in the -~
20 ~ ~ alkyl chain and an average of about 1 to about 10 -CH2CH2O-groups per molecule. Especially preferred 2-acylox~-alkane-l-sulfonates contain from about 2 to about 9 carbon atoms . . . .
in the aryl group and about 9 to about 23 carbon atoms in the alkane moiety. Especially preferred beta-alkyloxy alkane sulfonate contains about 1 to about 3 carbon atoms in the alkyl group and about 8 to about 20 carbon atoms in the alkyl moiety.
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The alkyl chains of the foregoing non-soap anionic surfactants can he derived from na~ural sources such as coconut oil or tallow, or can be made synthetically as for example using the Ziegler or Oxo processes. Water solubility can be achieved by using alkali metal, ammonium, or alkanol~

.....
ammonium cations; sodium is preferred. Magnesium and calcium -~ ~
- . . ~ . . ~
are preferred cations under circumstances described by Belgia~
patent 843,636 invented by Jones et al, issued December 30, 1976. Mixtures of anionic surfactants are contemplated by this invention; a preferred mixture contains aIXyl ~enz~ne sulfonate ~aving 11 to 13 carbon atoms in the alkyl group and alkyl polyethoxy alcohol sulfate having 10 to 16 carbon atoms in the alkyl group and an average degree of ethoxylation of 1 to 6.

.
Especially preferred soaps contain about 8 to about 24 carbon atoms, more especially about 12 to about 18 carbon atoms. Soaps can be made by direct saponification ; of natural fats and oils such as coconut oil, tallow and ~ ~ ~fish oil, or by the nèutralization of free fatty-acids~
---- 20 obtained from either natural or synthetic sources. The---~
I soap cation can be alkali metal, ammonium or alkanolammonium; ~ -~ sodium is preferred~ ~ ~-- --~- ~ -- - --~------Preferred nonionic surfactants are water soluble - - -~polyethoxyla~es of alcohols, alkyl phenols, polypropoxy -glycols, and polypropoxy ethylene diamine.
Especially preferred polyethoxy alcohols are the condensation product of 1 to 30 mols of ethylene oxide with 1 mol of branched or straight chain, primary or secondary aliphatic alcohol having from about 8 to about 22 carbon atoms; more especially 1 to 6 mols of ethylene oxi,de ~- , i .

~a44sl condensed with 1 mol of straight or branched chain, prim-arily or secondary aliphatic alcohol having from about 10 to about 16 carbon atoms; certain species of polyethoxy alcohols are commercially available from the Shell Chemical Company under the trade mark 'Neodol'. Especially pre- :-ferred polyethoxy alkyl phenols are the condensation product of about 1 to about 30 mols of ethylene oxide with 1 mol of alkyl phenol having a branched or straight chain alkyl group containing about 6 to about 12 carbon atoms;
certain species of polyethoxy alkyl phenols are commer-cially available from the GAF Corporation under the trade mark 'Igepal'.
Especially preferred polyethoxy polypropoxy glycols . are commercially available from BASF-Wyandotte under the trade mark 'Pluronic'. Especially preferred condensates of ethylene oxide with the reaction product of propylene oxide and ethylene diamine are commercially available from BASF-Wyandotte under the trade mark 'Tetronic'.
: Preferred semi-polar surfactants are water soluble amine oxides containing one alkyl moiety of from about 10 to 28 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxyalkyl groups con-taining from 1 to about 3 carbon atoms, and especially alkyl dimethyl amine oxides wherein the alkyl group contains from about 11 to 16 carbon atoms; water soluble phosphine oxide detergents containing one alkyl moiety :
of about 10 to 28 carbon atoms and 2 moieties selected from the group consisting of alkyl groups and hydroxy-alkyl groups containing from about 1 to 3 carbon atomsj and water soluble.sulfoxide detergents containing C
.~ .

Sl one alkyl moiety of from about 10 to 28 carbon atoms and a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of from 1 to 3 carbon atoms.
Preferred ampholytic surfactants are water soluble derivatives of aliphatic secondary and tertiary amines in which the aliphatic moiety 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, sulfonate, sulfate, phosphate, or phosphonate.
Prefered zwitterionic surfactants are water soluble derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium cationic compound in which the aliphatic moieties 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, espécially alkyl-dimethyl-ammonio-propane-sulfonates and alkyl-dimethyl-ammonio-hydroxy-propane-sulfonates wherein the alkyl group in both types contains from about 14 to 18 carbon atoms.
A typical listing of the classes and species of non-cationic surfactants useful in this invention appear in U.S. Patent 3,664,961 issued to Norris on May 23, 1972.
This listing, and the foregoing recitation of specific surfactant compounds and mixtures which can be used in the instant compositions, are representative of such materials but are not intended to be limitlng.

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As disclosed in Canadian Patent Application Serial No. 306,456, and 306,474, both filed June 29, 1978, under appropriate circumstances cationic surfactants are highly effective soil removal agents. The cationic surfactants of Cockrell and Murphy applicable to the instant invention have the formula R R Y Z
m x L

whereln each Rl is an organic group containing a straight or branched alkyl or alkenyl group optionally substituted with up to 3 phenyl groups and optionally interrupted by up to 4 structures selected from the group consisting of Il 11 11 I 11 , -C-O-, -O-C-, -C-N-, -N-C-, -O-, ~ ' , .

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( l ) --N ~

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(2~ N -- C--- --- C - . - .
N C-- . .

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, ,- ~ "~-~-,.,.-,:-.. , ~ 3 ~-- P~

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(4) -- S~ , -I , ... . , .- ,.
... : I~ . -. . (5) -- N ~ . , wnerein p ls from 1 ~o 20, (C2H4) pH
-l O ( 6 ) C N ~ - -~C~ /C~
C - : ~ :~

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~ C\ ~C ~ , and N

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( 8 ) mixtures thereof, ~ .
L is a number frc)m 1 to lO, Z is an anion in a number to give electrical neutrality. : ~.

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.

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In cationic surfactants preferred in the practice of the instant invention, Z is a halide, methylsulfate, tolune sulfonate, hydroxide or nitrate ion, particularly preferred being chloride, bromide or iodide anions. In certain preferred cationic surfactants, L is equal to l and Y is as defined in paragraph (l), (2) or (5) supra; in other preferred cationic surfactants more than one cationic charge center is present and L is greater than l, as in the substance Z C1~13 1 3 18H35 ~ CH2-CH2-CH2-N -CH3 In preferred cationic materials, described above, where m is equal to l, it is preferred that x is equal to 3, and R2 is a methyl group. Preferred compositions of this monolong chain type include those in which Rl is a ClO to C20 alkyl group. Particularly preferred components of this class include Cl6 (palmityl) trimethyl ammonium halide and Cl2 (coconut alkyl) trimethyl ammonium halide.
Where m is equal to 2 it is preferred that x is equal to 2, and that R is a methyl group. In this instance it is also preferred that R is a ClO to C20 alkyl group. I
Particularly preferred cationic materials of this class include distearyl (Cl8) dimethyl ammonium halide and ditallow alkyl (Cl8) dimethyl ammonium halide materials.
Where m is equal to 3, only one of the Rl chains can be greater than 12 carbon atoms in length. The reason for this chain length restriction is the relative insolubility in water of these tri-long chain materials. Where tri-long chain materials are used, it is preferred that x is equal to 1 and that R is a methyl group. In these compositions it is preferred that Rl is a C8 to Cll alkyl group. Particularly preferred tri-long chain cationic materials include trioctyl (C8) methyl ammonium halide and tridecyl (C10) methyl ammonium halide.
Another particularly preferred type of cationic surfactant useful in the compositions of the present invention is of the imidazolinium variety. A particularly preferred surfactant of this type is one having the structural formula N - CH

R - C~ ¦ Z

N ~ CH2 .
wherein R is C10 to C20 alkyl, particularly C14 to C20 alkyl.
Another type of preferred cationic surfactant for ; use in the compositions of the present invention are the alkoxylated alkyl quaternaries. Examples of such compounds are given below:

Z R-l-(C2H4)pH H(OC2H4) +(C H O) H Z~
R R
wherein p is from 1 to 20 and each R is a C10 to C20 alkyl group. -- 16 - ~-X

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A particularly preferred type of cationic component, which is described in Canadian Patent Application 306,513, Letton, filed June 29, 1978, has the formula:

R2-(zl)a-(R3)n-z2-(cH2)m-N -R X ~ :
Rl wherein Rl is Cl to C4 alkyl or hydroxyalkyl; R2 is C5 to 30 straight or branched chain alkyl or alkenyl, alkyl phenyl, or Rl X R - ~-(CH2)S; wherein s is from 0 to 5;

R3 is Cl to C20 alkyl or alkenyl; a is 0 or 1; n is 0 or 1;
m is from 1 to 5; zl and z2 are each selected from the group consisting of O O O O H H O O H H O
-C-O-, -O-C-, -O-, -O-C-O-, -C-N-, -N-C-, -O-C-N, -N-C-O-, and wherein at least one of said groups is an ester, reverse ester, amide or reverse amide; and X is an anion which makes the compound at least water-dispersible, preferably selected from the group consisting of halide, : methyl sulfate, and nitrate, preferably chloride, bromide or iodide.

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9cSl Other preferred cationic surfactants of this type are the choline ester derivati~es having the following formula:

O C~3 5R2-C-O-~H2C~2-N -C~3 X
- .
' C~3 ~ ~ ~

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as well as those compounds ~herein the ester linkage in the -above formula is replacea wi.h a reverse ester, amide or reverse amide linkage.

Particularly preferred examples o~ this type of cationic surfactant incluae stearoyl choline ester qua~ernary ammonium haiides (R2 = C17 alkyl), palmitoyl choline ester ~uaternary : ammonium halides (R2 = C15 alkyl), myristo~l choline es~er quaternary ammonium halides (~2 = C13 alkyl3, iauroyl choline ester ammonium halides (R2 = Cll alXyl), and tallo~yl .choline ester ~uaternary ammonium halides ~R2 = C15-C17 alkyl).
Additional pre~erred cationic component.~ of the choline ester varie~y are given by the structural formulas below, wherein p may be from 0 to 20.
, . , . '''.
O O C~l
2 ~ 3 R -o~c-(c~2~p-c-o-cEl2cH?-N -CEI3 X

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-: . . ,. ., . , ~ ' : , _ +l I CjH3 X CH3- N-CH2-CH2--C-(CH2) -C-0-cH2-cH2-N -CH3 X~

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Another type of novel, particularly preferred cationic material, described in Canadian Patent Application Serial No. 306,513, Letton, filed June 29, 1978, has the formula:

R2 IRl 5R3-o~(CH)n]y~(Z )a~(R )t-Z -(CH2~m-N -R X
R

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In the above formula, each R is a Cl to C4 alkyl or hydroxy-alkyl group, preferably a methyl group. Each R~ is either hydrogen or Cl to C3 alkyl, preferably hydro~en. R3 is a C4 to C30 straight or branched chain alkyl, alkenylene, or alkyl benzyl group, preferably a C8 to C18 alkyl group, most preferably a C12 alkyl group. R is a Cl to C10 alkylene or alkeylene group. n is from 2 to 4, preferably 2; y is from 1 to 20, preferably from about 1 to 10, most preferably about 7; a may be 0 or 1; t ma~ be 0 or 1; and m is from 1 to 5, preferably 2. Z and Z are each selected from the group consisting of O O O O H H O O H H O
-C-O-, -C-, -O-, -O-C-O-,-C-N-, -N-C-, -O-C-N-, -N-C-O- , and wherein at least one of said groups is selected from the group consisting of ester, reverse ester, amide and reverse amide. X is an anion which will make the compound at least water-dispersible, and is selected from the group-consisting of halides, methyl sulfate, and nitrate, particularly chloride, bromide and iodide. Mixtures of the a~ove structures can also be used.
Preferred embodiments of this type of cationic component are the choline esters (Rl is a methyl group and Z is an ester or reverse ester group), particular examples of which are given below, in which t is 0 or 1 and y is from 1 to 20.

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- .
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~ - 20 -.. .. . , - - - : . . : , 5 ~

O CH
3 ( 2C 120) y~ ~CH2) t--C--O--CE~2~CH2--N ~--CH3 X--O CH
CH3--R --O (CH2CH20) --C--CEI2--N -CE~3 X

3 i . Il ~C~3 C~3-R --O ~CHCH20) y~C~CH2~N~CH3 X ~ - -- ' ' ' ' ,' ' ' .
CE3 o CH3 3 ( 2) y (CH2) t-C--O-CH2-CH2--N~-C~3 X--' 3 ( 2 H20) y C (CE2) t-C-O-CH2CH2-N+-CH X--CH3-R3-o ~CH2CH2CH2CH20) y C CE~2 ~ 3 CH
: ~ 3 CH3-R --o~cH2cE2cH2cH2o)y-(cH2)t-c--l)-c~ cE~2-N~-cH3 X--~ ' . ', ' ~: - 21 -. ~ -iit~445~

O H H O CH
3 ~ 3 CH3-R -O(CH2cH2O)y-c-c=c-c-o-cH2cH2-7 - CH3 X

The second essential element of the instant invention is a peroxy bleach. The peroxy bleach can be inorganic or organic, and if the former can optionally contain a peroxy bleach activator.
By inorganic peroxy bleaches are meant inorganic peroxyhydrates; examples are alkali metal salts of perborates, percarbonates, persulfates, pe~silicates, perphosphates, and perpolyphosphates.
Preferred inorganic peroxy bleaches are the sodium and potassium salts of perborate monohydrate and perborate tetrahydrate. Sodium perborate tetrahydrate is especially preferred.
By organic peroxy bleach is meant urea peroxide CO(NH2)2-H202 or an organic peroxy acid or anhydride or salt thereof which has the general formula -Il .
. HO-O-C-R-Y
wherein R is an alkylene group containing from 1 to about 20 carbon atoms, preferably 7 to 16 carbon atoms, or a phenylene group and Y is hydrogen, halogen, alkyl, aryl or any group which provides an anionic moiety in aqueous solution. Such Y groups can include, for example, '.
' '' .
- 22 - ~

:
,, .

S~

o o . o Il 11 11 -C-OM , -C-O-OM or -S-O~I

wherein M is H or a water-soluble, salt-forming cation.
: The organic peroxyacids and salts thereo~ operable ~ .~~
"
in the instant invention can contain either one or two peroxy ~ ~ 5 groups and can be either aliphatic or aromatic~ When the ---",- organic peroxyacid is aliphatic, the unsubstituted acid has - the general formula ~ .
, ' O
11 . .
' HO-O-C-(CH2)n-Y
, , , I .
where Y, for example, can be CH3, CH2Cl, : :: : : , `~ n o o ': 11 11 1~
C-OM , -S-OM or -C-O-OM
: i1 ., O

~; ~ and n can ~e an integer rom 1 to 20. Diperazelaic acid ~ (n = 7) and diperdodecanedioic acid (n = 10) are the preferred -~ compounds of this type. The alkylene linkage and~or Y tif alkyl~ can contain halogen or other noninterfering substituents.
:: 15 When the organic peroxyacid is aromatic, the unsubstituted aci~ has the general formula ,: ~ . ..
~ 23 -!y S~

- - H-O-O-C-C H -Y

wherein Y is hydrogen, halogen, alkyl, O o o Il 11 11 ':
-C-OM , -S-OM or -C-O-O~ , ~-~', -,':
O . . . ~

for example. The percarboxy and Y groupings can be in any relative position around the aromatic ring. The ring and/or Y group ~if alkyl) can contain any noninterering substituents such as halogen groups. Examples of suitable aromatic peroxy-acids and salts thereof include monoperoxyphthalic acid, diperoxyterephthalic acid, 4-chlorodiperoxyphthalic acid, the monosodium salt of diperoxyterephthalic acid, m-chloroperoxy-benzoic acid, p-nitroperoxybenzoic acid, and diperoxyisophthalic acid.
Of all the above described organic peroxyacid compounds, the most preferred for use in the instant compositions are diperdodecanedioic acid and diperazelaic acid.
. .~
By peroxy bleach activator is meant an organic peracid precursor containing one or more acyl groups which is susceptible to perhydrolysis. The preerred activators are those of the N-acyl or O-acyl-compound type containing an acyl radical R-CO- wherein R is a hydrocarbon group having from 1 to 8 carbon atoms. If the radicals R are aliphatic, they preferably contain 1 to 3 carbon atoms while, if they are aromatic, they pre~erably contain up to 8 carbon atoms. R may ~ - 24 -` : :

11~4~S~

be unsubstitut~d or substitut~a with~Cl 3 alkoxy groups, halogen atoms, nitro- or nitrilo groups. Aromatic radicals, in particular, may be chloro- and/or nit~o-substituted.
Examples of activators coming wi~hin this definition follow:

RlCO
(a~ N-diacetylated amines of formula N - X wherein X is RlCo CORl CORl/ CORl :
C~2 N \ ~ -CH - CH - N or -N \
CORl CORlCOR

and Rl is as defined above for R and may be the same or different. N,N,N', N'-tetraacetyl-methylenediamine, ; N,N,N',N'-tetraacetyl-ethylene-diamine, and N,N-diacetyl-p-- toluidine are examples of N-diacylated amines.
, ~ (b) N-alkyl-N-sulphonyl carbonamides of formula R2 ~ N

, .
; wherein R2 is as defined above for R, preferably Cl 3 alkyl. Examples of suitable carbonamides are N-methyl-N-meSylacetylamide, N-methyl-N-mesyl-p-nitro benzoylamide and N-methyl N-mesyl-p-methoxybenzoylamide.

(c) N-acylhydantoins of formula Y
CO -- C -- Y
X - N N - X
C
o l ~ "
~ - 2~

wherein a-t.least one of X represents R3 - CO - while the other X represents. R3 - CO - or an esterified carboxymeth~l radical (R3 as defined above for R~, Y
represents. hydrogen or Cl 2 alkyl radicals.: 1,3-diacetyl-5,5-dimethylhydantoin and 3-benzoyl-hydantoin-l-acetic acid ethyl ester are representative of the hydantoin activators.

N
(d) Cyclic N-acylhydrazide of formula ¦- COR4 wherein the N
nitrogen atoms are part of a 5- or 6-numbered hetero-cyclic ring from the group maleic acid hydrazide, phthalic acid hydrazide, triazole or urazole and R4 is as above for R. Monoacetyl-maleic acid hydrazide is one example of a satisfactory activator from this-class.
.~
(e) Triacyl-cyanurates of formula D \
~ N N
.,, 1 11 ~N /

wherein R5 is defined as above for R. Triacetyl- or tribenzoyl-cyanurates are examples of this activator class.

(f) Benzoic acid or phthalic acid anhydrides, substituted or unsubstituted. Examples are benzoic anhydride or m-chlorobenzoic anhydride.

.

.~
... ; .
4~5i (g) O,N,N-trisubstituted hydroxyl amines of formula ~6 \

N - o - CO - ~C~ ) - R
/

Xl wherein R7 is as de~ined aboYe for R, preferably Cl 2' ;:
aryl radical or OCR
. - CO - N
X2 ',
- 5 and .Xl and X2 are R9CO-, R9-S02 - whi~h can be linked with R6 or R8 to give a succinyl- or phthalyl residue, . R6 9 ~eing defined as above for R, and n is from O - 2.
Examples of this type of activator include O-benzoyl-N,N-succinyl-hydroxyl~mine, O-acetyl-N,N-succinyl-hydroxyl-.: . 10 amine, O-p-nitrobenzoyl-N,N-succinyl-hydroxylamine, and O,N,N-triacet~lhydroxylamine.

~ . (h) N,N'-diacyl-sulphurylamide of formula `: ' Rl o 10 ,~ ~ /
~ . N - S02 - N

~ wherein R10 represents preferably Cl 4 alkyl radicals, , ~
. 15 or aryl radicals and Rll represents preferably Cl 5 alkyl radicals. N,N'dimethyl-N,N-diacetyl-sulphuryl-amide is one example of a satisfactory activator of this class.

. ~ :
~ 27 ~

~:,: - :

(i) 1,3-diacyl-4,5-dialyloxy-imid~zolidine of formula N

~ \ CH - O - CO ~ R
X - CH
\ CH - O - CO - R
N :
C~12 wherein R12 is as defined above for R and X i~ hydrogen or R. 1,3-diformyl-4,5-diacetoxy-imidazolidine ana 1,3-diacetyl-4,5-diacetoxy-imidazolidine are represen-tative examples of this activator class.

(j) Acylated glycolurils of formula / N - CH - N
O = C C - O
N - CH - N
13 o OCR13 ; wherein R13 is as defined above for R and X represents . 10 R or R-CO. Tetraacetylglycoluril, di-(chloracetyl)-diacetyl~glycoluril, tetrapropionylglycoluril, l-methyl-3,4,6-triacetyl-glycoluril, and diacetyldibenzoylglycol-uril are suitable examples of the glycolurils of this invention.

. 15. ~k) Carboxylic esters as disclosed in British Patent 836,988, for instance sodium p-acetoxybenzene sulphonate, ,~

sodium p-benzyloxy benzene sulphbnate, ace~yl salicylic acid and chloracetoxysalicylic acid.

Of all the above acti~ators, particularly preferred are:

N,N,N',N'-tetraacetyl ethylene diamine, N-acetyl imidazole, N-benzoyl imidazole, N,N'-dimethyl barbitone, N~N'-diacetyl-5,5'-dimethylhydantoin, N,N,N',N'-tetracetyl glycoluril, sodium p-acetoxybenzene sulphonate, sodium p-benzyloxy - - benze~le sulphonate, acetyl salicylic acid, chloracetoxy salicylic acid, trimethylcyanurate and mixtures thereof.

The amount of peroxy bleach in the compositions of this invention expressed in terms of active or "available"
oxygen is from 0.2% to 5.0%, preferably from 0.2% to p.7~, more preferably from 0.2% to 0.5%, by weight of the composi-tion. For sodium perborate tetrahydrate which contains 10.4% available oxygen, this is equivalent to from 1.92 to 48.1 wt.%, preferably from 1.92 to 6.73 wt.%, more prefer-ably from 1.92 to 4.81 wt.%, based on the weight of the composition. For diperoxyazeleic acid which contains 14.5% available oxygen, the equivalent figures are 1.38 to 34.5 wt.%, preferably from 1.38 to 4.83 wt.%, more preferably from 1.38 to 3.45 wt.%, based on the weight of the composition.
The amount of peroxy bleach activator; when used, i~ at a ratio to inorganic peroxy bleach of 1:1 to about 1:20, preferably from 1:2 t~ 1:8.
When an inorganic peroxy bleach is used, the hydrogen peroxide which is a constituent part of the ~ ' --, -11C~4~53 compound is believed to react according to the two - equations which follow:

H-O-O-H + -O- ~ heat, H-O- ~ + H-O-H (1) o O H meta1_ions- ~ o = O + 2 H-o-H (2) In conventional bleaching technology, reaction (1) produces the HO ~ ion which reacts chemically with stains to oxidize and decolorize them. In contrast thereto, reaction (2) is wasteful, because it converts peroxide to molecular oxygen and water.
Reaction (1) above is known to take place to an effective extent only at relatively high temperature, above about 70C. Where normal washing conditions take , ~
place in water cooler than about 70C., it has been common to use a peroxy bleach activator which reacts with the HOO~
ion to form a peracetate, perbenzoate or perphthalic moiety which bleaches effectively at low temperatures.
This type of reaction can be exemplified as follows:
' , O O
H3C - C ~ C - CH3 N - CH2 - CH2 - N ~ H-O-O-H -H3C - C ~ ~ C - CH3 O O

O HO OH
11 \ / ' 4 CH3 - C-O-OH ~ / N ~ ~H2 ~ CH2 ~ N (3) HO OH

When an organic peroxy ~leach is used, its anion - is itself the bleach-effective moiety. It can also, however, , decompose wastefully in the presence of metal ions in a~
manner analagous to that of hydrogen peroxide. For example, O
HO-O-C-(CH2)7 - C-O-OH metal ions O O
il 11 o = O + HO - C - (CH2)7 - C - OH (4) In granular or solid compositions of this invention containing an organic peroxy bleach it is desirable to include therein an exotherm control agent. Organic peroxy bleach compounds are known to decompose at elevated tem-~ 10 peratures thereby generating heat which can result in 8 sufficiently high temperatures to ignite the organic peroxy bleach. As taught in Hutchins et al U.S. Patent 4,100,095, issued July 11, 1978, the stabilization of organic peroxy bleach compounds against excessive heat generation is accomplished with an exotherm control agent.
As described therein an exotherm control agent is a non-hydrated material which will release from about 200% to - about 500% of water based on the amount of available oxygen i~
supplied by the organic peroxy bleach. The formation of water is the result of chemical decomposition. The exo-therm control agent should start to decompose at a temper-ature below the decomposition temperature of the peroxy bleach compound.
- The preferred exotherm control agents are those which release the requisite amount of water when present in an amount equal to about 50% or more of the amount of organic peroxy bleach compound present. A preferred amount is 50~ -to about 400%. - 31 -.
' .

r~ -., ~,~
. .

11~445~

The type of material which best meets the a~ove mentioned requirements are acids. Such acids include but are not limited to borlc acid, malic acid, maleic acid, succinic acid, phthalic acid, gl~taric acld, adipic acld, s azelaic acid, dodecanedioic acid and the like. Preferred acids are boric acid, malic acid and maleic acid.

The third essential component of the instant inven-tion is a porphine bleach as described hereinbelow. The .
structure or the compound porphine is: - -.

H
~"C ~

: 10 HC C~ -'; ' ' ~C ~
H

., Porphine has a large closed ring designated as a macrocyclic structure,~and more~specifically as a quadri-dentate macrocyclic molecule.. Porphine can be described as ~
tetramethine tetrapyrrole, and.has.also been designated-as~- ~
: 15 porphin or porphyrin. This. structure~is someti:mes referred to herein as the porphine 'core', because the porphine bleaches..
of this invention are species of substituted porphines.
One form of substitution involves substituting 1, 2, 3, or 4 aza groups (=N-) for the methine groups (-C~-) in porphine. As an example of conventional nomenclature, a compound having 3 aza groups and one methine group is referred to as triaza porphine.

- 31a -A-~1 . . ' Another form of substitution involves substituting for one or more of the hydrogen atoms attached to the carbon atoms in the pyrrole rings of porphine. This can be substi-tution by an aliphatic or aromatic group, ~r can be orthofused polycyclic substitution as for example to form benzene or naphthalene ring structures. The compound having the common name 'phthalocyanine' contains 4 ortho-fused benzene rings, each substituted on a pyrrole ring of the porphine core; and also contains 4 aza groups substituted for the methine groups of the porphine core; it can therefore be designated tetrabenzo tetraaza porphine, and has the structure which follows. The numbers designate the positions of pyrrole substitution according to conventional nomenclature.

NH N

==N HN -~ N

Another form of substitution involves substituting for the hydrogen of the methine groups; this is conventionally referred to as meso substitution, and the positions of substitution are conventionally designated by Greek letters as illustrated on the phthalocyanine structure above.
Still another form of substitution is metallation by a heavy metal atom in a chelation structure:

. ~, replac~ment of the two hydrogen atoms attached to two diagonally opposite inner nitrogen atoms of the four pyrrole groups by a heavy metal atom bonded to all four - inner nitrogen atoms.

StLll another form of substitution is substitu-tion of a solubilizing group into the porphine molecule.

Referring to the structure shown hereinbefore in the SUMMARY OF THE INVENTION, porphine bleaches which are effective and within the scope of this invention contain 0, 1, 2, 3 or 4 aza groups land, according to the nomenclature defined above, contain 4, 3, 2, l or 0 methine groups, respectively].

The groups designated as R's in the structural formu~a above càn, independently, be hydrogen or pyrrole substitute~ alkyl, cycloalkyl, aralkyl, aryl, alkaryl, or - .
heteroaryl. Adjacent pairs of Rls can also ~e joined together with ortho-arylene groups to form alicyclic or hete~o- -cyclic rings~ Benzo substitution is especially pre~erred; i.e_ R} and Rz~ R3 and R6, and/or R7 and R8~are connected togëth2r pairwiss by methylene groups to ~orm fused benzene rinss,~
Other preferred`forms of pyrrole substitution are naphtho, ;
- pyrido, phenyi ~nd naph~nYl.

Substitutions can also be made or the hydrogen atoms of the methine groups o~ the photoactivators of this inYention; thus each Y in ~he above structural formula can independently be hydro~on or meso substi~ut2d alkyl, cyclo-5~

alk~l, aralXyl, aryl, alXaryl, or heteroa~l. It is pre~2rred that Y is H, phenyl, naphthyl, thienyl, ~uryl, ~hioazyl, oxa-zyalyl, indolyl, benzothienyl, or pyridyl. No meso su~sti-tution at all or tetra phenyl meso su~s~itution are especially preferred.

,'7, In the foregoing descriptio~, the term "alkyl" is -~
:.~ defined to be not-only a simple carbon chain but also a ~ - ~
:~;........ carbon chain interrupted ~y other chain-forming atoms, such :
-.~ as O, W or S. Non-limiting examples of such interruptions . -. 10 are those of the following groups: - -. O O O
ether - O -, ester - CO -, reverse ester - CO -, carbonyl - C -, O . O ,' amide - C - NH -, reverse amide - NH - C -, amino sul~nyl O ' O
u - NH - S -, and sulfonamido - S - NH -.
O O . ~: - -.. -The porphine bleaches of~the instant invention can-~
be unmetallated, A in the foregoing structural formula being~
comprised of two hydrogen atoms bonded.to diagonally-oppo~
- site inner nitrogen:atoms of the pyrrole groups in~.the -~
molecule. Alternatively, the porphine bleaches of this-invention can be metallated with zinc~ , cadmium(Ilj, -~
magnesium(II), scandium(III), or tin(IV). Thus, altogether, A can be 2(H) atoms bonded to diagonally opposite N atoms, or Zn(II), Cd(II~, Mg(II), Sc(III~ or Sn~IV~. It is preferred that A be 2(H) or Zn(II).
. Solubilizing groups can be located anywhere on ~ ~t .

4~

the porphine molecule other than the porphine core as hereinbefore defined. Accordin~ly the solu~ilizing groups can be described as substitu~ed into Y or R as hereinbefore defined Solubilizing groups can be a~ionic, nonionic, or cationic in nature. Preferred anionic solubilizing groups are carboxylate - C~; sulfate - O - S - ~ ; -c~ . ... - -, :: .~ ~- ,.-, -- - - - - . ::
O O
phosphate - O - P - ~; and sulfonate - S - 0~.

OH O

- -Other preferred anionic solubilizing agents are ethoxylated derivatives of the foregoing, especially the polyethoxysulfate group - ~C~2C~20)nS03~ and the polyethoxy carboxylate group -(C~2CH20)nCO ~ where n is an integer from l to about 20.
, For anionic solubilizing groups, M the counterion is any cation that confers water solubilit~ to the porphina ; molecuIe. A monovalent cation is preferred, especially ~ . ~ . , .... ~
ammonium, ethanola~monium, or alkali metal. Sodium is most -preferred. The number of anionic solubilizing groups - ~
.. .. , ~ ~
opera~le in the compositions of this invention is a function of the location of such groups or the porphine molecule. A solubilizing group attached to a carbon atom of the porphine bleach molecule displaced moXe than 5 atoms away from the porphine core is sometimes herein referred to as "remote", and is to be distinguished from an attachment to a carbon atom displaced no more than `: ~

:
~i s~

5 atoms from the porphine core, which is sometimes referred to herein as "proximate". For proximate solubilizing groups, the number of such groups per molecule, s, is from 3 to about 8, preferably from 3 to about
6, most pre~erably 3 or 4. For remote solubilizing groups, ; s is from 2 to about 8, preferably from 2 to about 6, most preferably 2 to 4. . .-~
Preferred nonionic solubilizing groups are poly- :
ethoxylates -(CH2CH20)nH. Defining s as the number of solubilizing groups per molecule, the number of condense~
ethylene oxi~e molecules per porphine molec~le is N = sn.
- The wat~r solub~e nonionic.photoact~vators o~ this invention have a value of N betw.een abou~:8 and ab~ut.50,. pxeferably - from about l2 to. a~out.4~,: most pre~erably from about .16 to about 30. Within that limitation the separate. values of s and n are not:critical.-. For nonio~ic solu~ilizing groups,.there is no counterion and accordingly M is numerically equal to zero.
Preferred cationic solubilizin~ groups are quaternary compounds such as ~uaternary ammonium salts .--~

R3 . .
~ ~ .
Rl ~-R2, and quaternary pyridium salts ~ - R, where all R's are alkyl or substituted alkyl groups.
. For cationic solubilizing groups, M the counterion is any anion that confers water solubility to the porphine molecule. A monovalent anion is preferred, especially iodide, bromide, chloride or toluene sulfonate ~' .

' ~
: ~ `''''' CH3 ~ SO3 The number of cationic solubilizing groups can be from 1 to about 8, preferably from about 2 to about 6, most -- preferably from 2 to 4.
Usage of porphine bleach in the compositions of this invention can be from about 0.001% to about Q.5~ by weight of the composition. Preferable usage is from about 0.003 to about 0.022~ by weight of the composition, and especially preferred is from about 0.005 to about 0.017 by weight of the composition.
The mechanism postulated for porphine bleaches by the prior art, especially Speakman, British Patent 1,372,035 and Sakkab Canadian applications 319,431, 319,432 and 319,433, all cited hereinbefore, can be briefly described as the following sequence of events:
by the photoactivator ---Adsorption on the fabric.
Excitation by visible light to the singlet state.
Intersystem crossing to the triplet excited state.
Reaction with ground state (triplet) atmospheric oxygen to produce excited state (singlet) oxygen.
by singlet oxygen ---Chemical bleaching of the stain.
The mechanism postulated by the prior art, especially Speakman, British Patent 1,408,144, for the combination o peroxy and porphine bleaches is that the porphine bleach activates, in the presence of light, not only .~ , ,, 11~4~5:1 atmospheric oxygen, but also oxygen liberated by decomposi-tion of the hydrogen peroxide upon reaction with metal ions present in the washing solution, according to reactio~s (2) and (4) hereinbefore.
Howsoever, the bleaching results in darkness, which are described hereinbefore, cannot be explained on the basis of these mechanisms. According to the prior art, bleaching should not occur under these conditions.
That it does in fact ta~e place is unexpected.
By darkness is meant herein a substanti~lly complete absence o light. A process is considered to take place in darkness even if, in automatic laundry devices, tiny gaps may be present between adjoining metal suxfaces, gaskets are ill-fitted or missing, or the like; or if the laundr~ is moved manually in a lighted room from one substantially totally enclosed device to another.
The compositions of this invention are unexpect-edly use~ul to persons whose normal washing process takes place in darkness, for example those using window-less automatic washers and dryers. Persons habitually doing their laundry under low-light conditions are also bene-~ited, for example those using an automatic washer or -~
dryer having a glass window in the door or those drying on indoor clotheslines.
Furthermore, the effectivenes= of these two drasses I

'~ ' ~ ~ ~ 38 -., ~., ~, , . . . , - - : ~

Sl of bleaches, operating in concert, is so yreat that unexpectedly low amounts of peroxy b~each and/or porphine bleach are needed to achieve important, noticeable results.
This achieves both economic and ecological advantages. In commercial experience, sodium perborate tetrahydrate is most comm~nly us~d at levels of about 16 to 25% by weight of the composition, and occasionally as low as 5 to 7%. Prior art suggestions for peroxy bleach/porphine bleach combina-tions are also in the 16-25% range. These usages corres-pond to available oxygen contents of most commonly 1.66 to2.60%, occasionally 0.52 to 0.73%. They contrast with the pre~erred usages in the compositions of this invention as defined hereinbefore which approach as little as 0.2 available oxygen.
Similarly, remarkably lo~ levels of porphine bleach are required. The prior art suggests, for peroxy bleach~
porphine bleach combinations, zinc phthalocyanine sulfonate usages at 0.025 to 1.25 wt.% based on the composition.
Levels as low as 0.001% have been suggested by the prior art for use under circumstances of a laundry soak which gives a long exposure time for adsorption o~ bleach upon the textiles, plus drying in sunlight. It is hence unexpected that levels in the 0.001 to 0.022~ range are effective in the absence of both the long soaking time and the strong light.
The foregoing description concerns compositions containing only sur~actant, peroxygen bleach, and porphine bleach, which the essential elements of this invention.
They are unbuilt compositions. - Other components are optional, as the elements of this invention are useful ~ - 39 -in a great variety of otherwise conventional compositions.

For instance, conventional alkaline detergent builders, inorganic or organic, can be used at levels up to about 80% by weight of the composition, i.e. from 0 to about 80~. For built compositions, levels from about 10% to about 60% are preferred, and levels from about 20% to about 40%
are especially preferred. The weight ratio of surfactant ~ ~¦
to total builder in built compositions can be from about ~ !

- 5:1 to about 1:5, preferably from about 2:1 to about 1:2. ~
Examples of suitable inorganic alkaline detergency builder salts useful in this invention are water soluble -¦
alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates. Specific examples of such j salts are sodium and potassium tetraborates, bicarbonates, carbonates, tripolyphosphates, pyrophosphates, orthophos-phates, and hexametaphosphates.
Examples of suitable organic alkaline detergency builder salts are: (1) Water-soluble aminopolycarboxylates, e.g. sodium and potassium ethylenediaminetetraacetates, nitrilotriacetates and N-(2-hydroxyethyl)-nitrilodiacetates;
(2) Water-soluble salts of phytic acid, e.g., sodium and potassium phytates -- See U.S. Pat. No. 2,739,942; (3) Water-soluble polyphosphonates, including specifically, soaium~
potassium and lithium salts of ethane-l-hydroxy-l,l-diphos-phonic acid; sodium, potassium and lithium salts of methylenediphosphonic acid; sodium, potassium and lithium salts of ethylene diphosphonic acid; and sodium, potassium and lithium 6alts of ethane-1,1,2-triphosphonic acid. Other examples -- ~ O
A...l `

. .~.~

4~

include the alkali metal salts. or ethane-2-carboxy-L,l-diphos-- phonic acid, hydroxymet~anediphosphonic acid, carbonyldiphos-phonic acid, ethane-l-hydroxy-1,1,2-triphosphonic acid, ethane-2-hydroxy-1,1,2-triphosphonic acid, propane-l,1,3,3-tetra-phosphonic acid, propane-1,1,2,3-tetraphosphonic acid, and . . propane-1,2,2,3-tetraphosphonic acid; (4) Water-soluble salts of polycarboxylate polymers and copolymers as described in U.S. Pat. No. 3,308,067.
. _ A useful detergent builder which may bé employed : 10 in the present invention comprises a water-soluble salt of a polymeric aliphatic polycarboxylic acid having the following structural relationships as to the position of the carboxylate groups and possessing the following prescribed physical characteristics: (a) a minimum molecular weight of about 350 calculated as to the acid form; (b) an equivalent weight of about 50 to about 80 calculated as to acid form; (c) at ~ least 45 mole percent of the monomeric species having at.~ least two carboxyl radicals separated from each other by ~ not more than two carbon atoms; ~d) the site of attachment : 20 of the polymer chain of any carboxyl-containing radical being separated by not more than three carbon atoms along ~ the polymer chain from the site of attachment of the next carboxyl-containing radical. Specific examples of the abo~e-: described builders include polymers of itaconic acid, aconitic acid, maleic acid, mesaconic.acid, fumaric acid, methylene malonic acid and citraconic acid and copolymers with them-selves.
~ In addition, other polycarboxylate bui.lders which .~ . can be used satisfactorily include water-solubl:e salts of , ~
':
: - 41 -. ~ . ...

1.~0~

mellitic acid, citric acid, pyromellitic acid, benzene pentacarboxylic acid, oxydiacetic acid, carboxymethyloxy-succinic acid and oxydisuccinic acid.
Certain zeolites or aluminosilicates enchance the function of the alkaline metal pyrophosphate and add building capacity in that the aluminosilicates sequester calcium hardness. One such aluminosilicate which is useful in the compositions of the invention is an amor-phous water-insoluble hydrated compound of the formula Nax(xAl02.Si02), wherein x is a number from 1.0 to 1.2 and y is 1, said amorphous material being further characterized by a Mg++ exchange capacity of from about 50 mg eq. CaCO3/g.
to about 150 mg eq. CaCO3/g. and a particle diameter of from about 0.01 microns to about 5 microns. This ion exchange builder is more fully described in British patent No. 1,470,250 invented by B. H. Gedge et al, published April 14, 1977.
A second water-insoluble synthetic aluminosilicate ion ~, exchange material useful herein is crystalline in nature and has the formula Naz[Al02)z.(Si02)]xH20, wherein z and y are integers of at least 6; the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer ~ from about 15 to about 264; said aluminosilicate ion ex-; change material having a particle size diameter from about .. .
0.1 micron to about 100 microns; a calcium ion exchange capacity on an anhydrous basis of at least about 200 milli- -grams equivalent of CaCO3 hardness per gram; and a calcium ion exchange rate on an anhydrous basis of at least about 2 grains/gallon/minute!gram. These synthetic aluminosili-cates are more ;
" rC

~ .

S~
fully described in British Patent No. 1,429,143 invented by Corkill et al, published March 24, 1976.
For nominally unbuilt compositions, it is contem-plated that compositions can contain minor amounts, i.e.
up to about 10~, of compounds that, while commonly classified as detergent builders, are used primarily for purposes other than reducing free hardness ions; for example electrolytes used to buffer pH, add ionie strength, control viscosity, prevent gelling, etc.
It is understood that the compositions of the present invention ean contain other components commonly used in detergent compositions. Soil suspending agents sueh as water-soluble salts of earboxy methylcellulose, earboxy-methylhydroxyethyleellulose, eopolymers of maleic anhydride and vinyl ethers, and polyethylene glycols having a molecular weight of about ~00 to 10,000 are common components of the detergent compositions of the present invention and ean be used at levels of about 0.5% to about 10~ by weight. Other soil suspending agents that ean be used are glassy phosphates - 20 as diselosed in Belgian patent 838,751 and aluminosilieates and precipitated silieas as diselosed in Jones, Canadian patent applieation no. 293,605 filed on December 21, 1977.
Other materials sueh as fluoreseers, colorants, perfumes, antiseptics, germieides, enzymes in minor amounts, and anti-eaking agents sueh as sodium sulfosueeinate and sodium benzoate may be also be added. Other materials useful in detergent compositions are clay, espeeially the smeetite elays diselosed in U.S. Patent No. 3,915,882, suds 4~51 depressants, ~illers such as sodium sNlfate, pH buffers, ~ and hydrotropes such as sodium toluene sulfonate and urea.
Granular formulations embodying the compositions of the present invention may be formed by any of the conven-tional techniques i.e., by slurrying the individual compo-nents in water and ,hen atomizing and spray-drying the resultant mixture, or ~y pan or drum granulation of the components. A preferred method of spray drying compositions in granule form is disclosed in U.S. Patents 3,629,951 and 3,629,955, issued to Davis et al on December 28, 1971.
Liquid detergents embodying the compositions of the present in~ention can be unbuilt or can contain builders.
They ordlnarily contain organic rather than inorganic peroxy bleaches. If unbuilt, they can contain about lO
to about 50% surfactant, up to ab~ut 15% of an organic base such a~ mono-, di-, or tri-alkanolamine, and a solubilization system containing various mixtures of water, lower alcohols and glycols, and hydrotropes.
Built liquid single-phase compositions can contain about 2~ l~ to about 25~ surfactant, from about lO to about 20~
builder which can be inorganic or organic, about 3 to about lO~ hydrotrope, and water. Built li~uid compositi~ns in multi-phase heterogeneous form can contain comparable amounts of surfactant and builder together with viscosity modifiers and st~bilizers to maintain stable emulsions or suspensions~
Compositions in the form of detergent laundry bars can be prepared as described in U.S. Patent 3,178,370 issu~d April 13, 1965 and British Patent 1,064,414 issued April 5, :

~ ..

~1~4~
1967, both to Okenfuss. A preferred process, called "dry neutralization", involved spraying the surfactant in li~uid, acid forin upon an agitated mixture of alkaline components such as phosphates and carbonates, followed by mechanically working as by milling, extruding as in -~
a plodder, and forming into bars.
The compositions of this invention can also be incorporated if desired into substrate articles. These articles consist of a water-insoluble substrate which releasably incorporates an effective amount, preferably from about ~ to about 120 gramsl of the compositions described herein.
Formulations embodying the compositions of the present invention are commonly used in laundry practice at product concentrations from about 0.1 to about 0.6 wt.% in water.
Within these approximate ranges are variations in typical usage from household to household and from country to country, depending on washing conditions such as the ratio of fabric to water, degree of soiling of the fabrics, temperature and hardness of the water, method of washing whether by hand or by machine, specific formulation ^.~
employed, etc.
It has been stated hereinbefore that peroxy bleach usage is from 0.2% to 5.0%, preferably from 0.2% to 0.7~, on an available oxygen basis; also that porphine bleach usage is from 0.001% to 0.5%, preferably from 0.003% to about 0.022~; where all figures are by weight of the composition. Combining those figures with the foregoing product concentrations yield the result that peroxy bleach concentrations in water, expressed in terms of available .
. ,, f'~

- , : , ,: ~, , , oxygen, range from about 2 to. about 300 parts per million (ppm). ~ithin this range, from about.10 to about 40 ppm are preferred. Porphine bleach concentrations in water range from about 0.01 to about 30 ppm, while from about 0~05 to. about 1.5 ppm are preferred.

,.~

- 4~ - .

llQ44Sl - EXAMPLE I
Composit;ons were prep'ared as ~ollo~s: .
' Co~o~ition No. ~ '''1'3'] '''15']_ ' [9]
.. . . .
Com~on~t (~t.%~
Cll 8 linear alkyl ~enzene ,,, sulfonate--~ 24'.0 8.5 8.5 5.8 tallow,alkyl sulfate' - - - 2.5 nonionic surfactanta ~ 3 0 3-0 3.. '1 , hydrogenated fish oil fatty acid~. - 3.0 3.0 3.7 coconut monoethanol amide . l.54 sodium t~ipolyphosphate 36.2 44.0 38.0 27.0 sodium silicate solids 8.0c 6.0c 6.0c 8.2d sodium perborate tetra-hydrate 7.l, 12.0 . 18.0 32.5 sodium sulfate 13.9 lO.0 lO.8 8.3 optical brightener 0.24 0.30 0.30 0.23 proteolytic enzyme 0.32 0.60 0.60 0.22 ethylene diamine tetra-acetic acid - - - 0.21 carboxymethyl cellulose 0.36 0.76 0.76 0.89 polyethylene glycol 0.25e 0.25e 0.25e 0.25f color 0.03 0.02 O.Ol perfume 0.15 0.15 0.18 0.17 ,25 water 7.4 9.l 9.7 5.7 miscellaneous , bal.ance,,'bal. .,.'bal,. .. '.bal., .
. 10~ 100 100 100 a tallow fatty alcohol ethoxylated with'an average of ll mols ethylene oxide per mol of alcohol over 70~ Cl6 ~ Cl8 c 3.'2'ratio SiO2/Na2O
d 2.0'ratio SiO2/Na2O
e' molecular weight 600 .
f molecular weight 400 . . .

, ..._...

Composition ~2~ was prepared like composition-Il~
except that O.Oa7% zinc pht~alocyanine tetlasulfonate, tetrasodium salt was added. This ~as prepared ~y condensing pht~alonitrile'and zinc dus. in t~e presence of molybdic acid, followed by sulfonation wlth oleum according to the met~o'd of U.S'. Patent 4,033,718.
Composit~ons ~1] and r2] were used to wash soiled - family laundry in a commercial ~ATA upright-style automatic washer having a metal lid w~ich was closed during the washing cycle. Water temperature was 35C~; water hardness 15 grains per U.S. gallon; and washing time 10 minutes~
For certain tests identified below a 3-hour soaking period using the same kind of water preceded washing. The ratio of soiled fabrics to water was 1/27 ~y weight. Product concentration was 0.37% in the soak, if present, and 0.32 in the wash.
Clean white cotton's~atches and cotton and polycotton stained swatches were added to the soiled clothes in each washer load. Stained swatches were of two kinds:
(a) tea, which were prepared by boiling swatches in a 1.1%
tea solution for 30 minutes, followed by rinsing and drying, and (b) mixed foods, which were prepared by similarly boiling swatches in an aqueous solution containi ng: ~ ~
2.7~ instant coffee, 5.8% strawberry jam, 10.2~ milk, 13.6% sugar, and 13.6~ red wine. Swatches were replicated 4 times and judged by a panel of graders on a visual Scheffé scale.
After washing, the'artificial illumination of the laundry room was extinguished and the clothes and - 48 - `

~ ~a ~4~51 swatches were transferred manuall~ from the washer to an automatic electric dr~er. The glass window in the door was covered by black paper to substantially preclude the admission of light.

Wh~teness and stain removal performance of Composition ~2], an example of this invention, as compared with that of control Composition :Il] was as shown below.
All units are panel score units and th.e 90% statistical yardstick.is given in parentheaes for each test,. with statistically significant comparisons identified with. an asterisk.

_ stain remo~a-l - - ~
fa~ric :stain (wash) (soak and wash) cotton none . +1.3~J*(1.02) +1.64*(1.28) cotton tea -0.15(.71) +0.92*(.78) cotton mixed foods +1.07*(.84~ +1.27*(.98) polycotton tea ~0.30(.81) ~0.92*(.7B~
polycotton mixed foQds +0.55(.78) +0.17(.68~

: In most instances Composition ~2] of this invention was superior to that of control Composition [1]. Superiority I was greater for cotton abric as compared with polycotton ¦ and ~ox the soak and wash treatment as compared with washing only.
Compositions-~l] and [2] were also tested using a procedure like that described hereinbefore except that drying took place in the sunlight out of doors; product concentrations wPre 0.26% in both the soak and wash; water hardness was 4 ~rains per U.S. gallon; soaking timej if : , ., ~ - 49 -.,.. ~ ...... .... , .. ., .. ., ... , ,,,.. , _ _ 11~4~5~

used, was 2 hours, and the washing machines were commercial BRU top loading machines identified as model numbers B-32 anq Super A-51. There are no windows in either model.
In the following tests, Composition [2~ was statistic-ally superior: soak and wash using cotton swatches:
unstained, grease stain, cocoa/milk stain, and tea/mixed foods stain; using polycotton swatches: tea/mixed foods stain; wash only using cotton swatches unstained and grease stain. Composition [2] was directionally but not statistically superior in the following tests: using cotton swatches: cocoa/milk stain and tea/mixed foods stain; using polycotton swatches: tea/mixed foods stain.
In none of this series of tests was composition [1]
superior to composition [2], even directionally.
Composition [4] was prepared like composition [3~
except that 0.007% zinc phthalocyanine sulfonate, tetra-sodium salt was added. Tests were run as described hereînbefore, except that the machines used were a Kelvinator~ K-2806 having a 20-minute soak cycle and a BALA~ T-548 having a 30-minute soak cycle. Half the swatches were washed in each machine, and the results combined. Both machines are front loading machines with windows in the doors; ~or the test described hereinbelow the windows were left uncovered. Stain removal perform-ance of Composition [4], an example of this invention, in comparison with that o~ control Composition [3] was as ~ollows:
.~ ' ' ~ .
.
~ - 50 -~ ~.

~C ' ' ,~ .
.

5~
stain removal fabric stain (wash) cotton tea +2.16*(1.64) cotton mixed foods +0.41t2.21 polycotton tea ~1.08*(0.93~
polycotton mixed foods ~1.29*~0.58) As before, the composition containing both perborate and porphine bleach exhibited superior properties of stain removal.
Aqueous solutions were prepared of composition ~5] and also composition [5] to which zinc phthalocyanine sulfon-ate, tetrasodium salt was added in an amount equivalent to 0.007~ on a composition basis. Tests were run as described hereinbefore, except that water temperature was 40C.;
water hardness 15 grains per U.S. gallon; washing time 90 minutes; product concentrations 0.5% for the soak, 0.8%
for the wash. Machines used were the KELVINATO ~ K-2806 and BALA~ T-548 described hereinbefore; for the tests described below the windows were covered with black paper, as was the window of the PETITE~ automatic electric dryer, and the laundry transfer from washer to dryer took place with the lights extinguished.
~3 Stain removal performance of the solution containing zinc phthalocyanine sulfonate, tetrasodium salt, as compared to that of the control solution, was as follows:

' `:

,r ~

~1~4~5~

stain removal fabric stain _ (wash) cotton tea +1.62*(.76) cotton mixed foods ~1.56*(.88) polycotton tea +2.71*(.45) polycotton mixed foods +0.99*(.36) The solution containing porphine-bleach was ``
signiicantly better than the control solution in every instance. ~
Composition I6] is prepared like composition I5]
except that 0.007% of zinc phthalocyanine sulfonate, tetra~
sodium salt, is added. Tests as described supra s~ow Composition l6] of this in~ention to be superior to Composi-tion ~5] to a degree compara~le to that shown in the preceding table.
Aqueous solutions were prepared that correspond to composition [53 except that they contained sodium perborate tetrahydrate in amounts corresponding to 15~
and 13.5%, respectively, on a composition basis. Both solutions also contained 0.007% zinc phthalocyanine sulfonate, tetrasodium salt, on a composition basis. The solution containing lS% perborate and porphine bleach was statistically superior in stain removal to the solution of composition 15] under all conditions described in the foregoing test. While the stain removal performance of the solution containing 13.5~ perborate could not be distinguished from that of the solution of Composition [5]

.. . .

under those test conditions, it ~as directionally superior thereto under all conditions except tea stains on cotton.
' ' .

.

.
.

11&4q~5~ ~
Compositions [7] and [8] are prepared like Composition ~6] except that their levels of sodium perborate tetra-hydrate were 15~ and 13.5%, respectively. The stain removal performance of each of the compositions is compared to that of the corresponding solutions described supra.
The above tests on solutions of Composition [5] and Composition [5] containing 0.007% zinc phthalocyanine sulfonate, tetrasodium salt, were repeated under different washing conditions: temperatures ranging from 40 to 90C., water hardness from 7 to 24 grains per U.S. gallon; washing times from 50 to 90 minutes; product concentrations from 0.5 to 1.3~; drying with and without a black paper cover on the window of the electric dryer. Results were compar-able to those deseribed hereinbefore, with the solutions containing porphine bleach consistently outperforming the eontrol. When fabrics were dried outdoors in the sunlight, this superiority inereased about 0.5 panel score units or the average.
Aqueous solutions were prepared of Composition [9] and also Composition [9] to whieh 0.007% zinc phthalocyanine sulfonate, tetrasodium salt, was added by admixing a blue sodium tripolyphosphate speekle eontaining the photo-aetivator. The two solutions were tested at 60C and at 90C. at usages eorresponding to produet coneentrations of 0.8% in water having 11 grains hardness per U.S. gallon, using Zanussi RE ~ SL-50 commercial front loading wash-ing machine. The window on the washer door was not covered. The fabrics were dried in an electric dryer having no window. Washing soiled fabrics obtained from eonsumer ~:

F~

5~

households, a signi~icant advantage ~as observed for the~
~olution contalnin~ porphine bleach as compared wlth the solution of Composition l~ on pillo~ cases~ terr~-cloth towels, and undershirts at ~o~h temperatures, and on - 5 kitchen to~els at 60C. The solution of compositionr9] ~a5 not-~u~er.ior. on an~ ~abr'ic~ of t~s t~.pe.''Washing stained.swatches prepared in the'la~orator~, the's-olution cont~ining porphine bleach ~as significantly superior to the solution of Compo5ition I93 for grass stain at 90C., lipstick at 90C., dirty motor oil at-90 and'60C., tea at 60C., wine at 60~C., and coffee at'60C. No statis-tically significant differences were`observed for shoe polish, makeup, blood, tomato or cocoa stains, though they : collectively showed directional advantages for the solu-tion containing porphine bleach in 8 out:of the 10 compari-sons.
: Composition Ilo3 is prepared like Composition t9]
except that 0.007~ zinc phthalocyanine sulfonate, tetra-sodium salt, is added. Stain removal tests. as described supra show Composition-tlO~ to be superior to Composition ~9] to a degree comparable to that described above for the corresponding solutions.

: ~ .

5~
Other porphine bleaches have been prepared according to the methods of Sakkab, cited hereinbefore:
pa) ~, ~, y~ ~ - tetrakis (4-carboxyphenyl) porphine, tetrasodium salt pb) ~ tetrakis (4-carboxyphenyl) porphine zinc, tetrasodium salt _ _ ~ - tetrakis (4-carboxyphenyl) porphine was prepared by refluxing a propionic acid solution, 0.24 molar in both 4-carboxybenzaldehyde and pyrrole, for 2 hours.
IJpon cooling the reaction mixture, purple crystals of Y, ~- tetrakis (4-carboxyphenyl) porphine precipitated.
Yield was 32%. The product was purified by recrystalliza-tion from methanol/chloroform solutions.
Metallation was accomplished as by reacting tetrakis (4-carboxyphenyl) porphine with an excess of zinc acetate in refluxing dimethyl formamide, removing the solvent on a rotavaporator to obtain a residue dissolving the residue in water, acidifying to pH 3, and passing through the form of the cation exchange resin Dowe ~ 5DW-X8(50-100 mesh) to remove the excess ionic zinc. The residue after evaporation yielded a red crystalline product with about 98% yield.
The acid form of photoactivator, prepared as described above, was converted to the tetra sodium salt upon addition to alkaline (pH ~ 10) detergent solution, the cations of which were predominantly sodium.
pc) ~ tetrakis (4-N-methyl pyridyl) porphine, tetra (4-toluene sulfonate) salt pd) ~ -tetrakis (4-N-methyl pyridyl) porphine zinc, tetra (4-toluene sulfonate) salt .

S~

~ , ~, y, ~ - tetrakis (4-N-methyl pyridyl) porphine., tetra (4-to.luene sulfonate~ salt was prepared by refluxing a propionic acid solution which was equimolar in pyridine 4-carboxaldehyde and pyrrole.- The solvent was flashed off and the residue was washed with dimethyl-formamide to dissolve the tarry by-products leaving purple crystals of tetra (4-pyridyl) porphine. Yield was 22.5~.
The tetra (4-pyridyl) porphine was then refluxed with sodium 4-toluene sulfonate overnight in dimethyl formamide.. The reaction was then cooled in an ice bath and the product was removed by filtrati.on. The c~llected violet crystals of a, ~ tetra (N-methyl pyridyl) porphine, tetra 4-toluene sulfonate salt were washed with acetone and dried under vacuum. Yield was 92%.
Metallation was accomplished in a manner similar to that described above for the tetracarboxy phenyl porphine described supra, with purification accomplished by chromato-graphic chloroform solutions on alumina. The metallation was done prior to quaternization with 4-toluene sulfonate.
pe) Tetra ~2-sulfatoethyl ~ulfonamido benzo) tetraaza porphine zinc, tetrasodium salt .

. . . _ Tetra (2-sulfatoethyl sulfonamido benzo) tetra-aza porphine zinc, tetrasodium salt was prepared by heating tetrasulfo tetrabenzo tetraaza porphine zinc, tetrasodium ~5 salt to 60C. with chlorosulfonic acid and agitation. At this temperature, thionyl chloride was added dropwise and the mixture was then heated for 4 hours at .80C. The reaction mixture was then cooled and added with agitation ~: to cold water from which the tetrachloro sulfo tetrabenzo .

, ,~.~,''~ .
- , S~

I tetraaza porphine zinc was separated by filtration and subse-i - ~ quently washed with cold water. The tetrachlorosulfo tetrabenzo tetraaza porphine paste was then suspended in cold water and mixed with 2-aminoethanol for 20 hours at 20C. The suspension was then acidified with hydrochloric acid to obtain a precipitate which was separated by filtra-tio~, washed with water and dried. Twenty parts of the already obtained ethanolsulfonamide deri~ative of tetra-benzo tetraaza porphine zinc were then mixed at 20C with ; ~ 10 10% oleum. The solution was then poured in a solution of sodium chloride into water, and ice was added. A
blue/green precipitate wa ZZ formed and was separated by filtration and was washed with a solution of sodium chloride in water and ethyl alcohol until it was neutral to Congo red. The blue/green powder obt~ined was then dried at 105C.
for 2 hours. The product was purified by six successive precipitations from aqueous solution by the addition of four volumes of acetone. Yield was 28~.
... _ pf) Tetras~ obenzo triaza porphine, tetrasodium salt , . _ .. ~
Tetrabenzo triaza porphine was prepared as follows: A solution of methyl magnesium iodide was prepared from magnesium and methyl iodide in ether; this was decanted from the residual metal and added to a mixture of finely powdered phthalonitrile and ether. Upon addition, the liquid at once turned reddish-brown, the nitrile dissolving, the ether gently boiling, and a tarry mass forming. After three hours at room temperature, the , remainder of the ether was remo~ed on a steam bath and the `i tarry residue was rapidly heated to 200C. Three ml. of H2O were added dropwise, liberating first white fumes and ,: - ' :, - 57 _ ~A-I -, ~, ~1 .. -s , . . .. . - ..

5~

th~n iodine v~por. After a further 1/2 hour at 200qC, the powdery residue was cooled, crushed and repeatedly extracted with a mIxture of alcohol and 10~ concentrated hydrochlor~c acid until the extract was no longer brown in color. The residue was then washed with absolute ethanol and dried in an oven at 105C for one hour. The product was freed from magnesium by dissolving it in concentrated sulfuric acid, followed by filtration and precipitation of the pigment with ice. The green precipitate was then :
collected on a filter and was washed wi~h hot water containing 5% ammonium hydroxide. It was then dried at 105C and crystallized from chloronaphthalene. Yield was 4.2 gm. of tetrabenzo triaza porphine in the form of purple ; needle-like crystals.
lS Tetrabenzo triaza porphine was metallated to tetrabenzo triaza porphine zinc by the following process:
reagent grade N,N' dimethylformamide was brought to reflux on a stirring hot plate. Tetrabenzo triaza porphine was then added, 1 minute allowed for complete solution to occur, and then a 10% excess of the stoichiometric amount of zinc acetate was added and reaction was allowed to proceed under reflux for one hour. The reaction vessel was then removed from the hot plate and cooled in an ice-water bath for 15 minutes. Chilled distilled water was then added, and the ; 25 resulting partially crystalline precipitate was filterad, washed with water, and air-dried. The product was then ~ecrystallized from chloronaphthalene. Yield was 1.9 gm.
in the form of purplish cr~stals.
Sulfonation of tetrabenzo triaza porphine zinc led` to the compound tetrasulfobenzo triaza porphine, t~trasodiu~ sa1t, ~Yith demetallation occuring sLmultaneously:
Tetrabenzo triaza porphine zinc and concentrated X2S04 were ground together into a homogeneous paste with a mortar and pe~tl.e.''Additional concentrated H2S04 was admixed, and the mixture'was heated on a steam ~ath ror 4 hours, removed and allow~d to stand at room temperature for 48 hours, and filtered to remove unreacted pigment. The filtr.ate was '--then dilutea with two ~olumes of ~2 to precipitate the ~
br1ght green ~S04 salt of the sulfonated matexial, which ~' 10' was ~iltered and washed with acetone and then dissolved in .alkaline met~anol. The sulfonated porphine was then preci-pitated as the sodium salt by addition of 3 volumes of acetone. After the product was then dried, it was extracted with hot methanol to remove Na2S04 residues. After extrac-. 15 tion, the porphine was dissolved in H~0, acidified to pH 3,and passed'~through the H+ form of the cation exchange resin Dowex 50W-X8 ~5Q-100 mesh) to remove ionic zinc. Pure tetrasulfobenzo triaza porphine in the form of a fine green powder was then isolated from a pH 5 solution by the addition o four volumes of acetone.

_ pg) Tetra (4-sulfophenyl) porphiner tetraammonium salt : ph) Tetra (4-sulfophenyl) porphine zinc, tetrasodium salt . _ Tetra(4-sulfophenyl) porphine, tetraamonium salt ` was prepared as follows: Tetraphenyl porphine, obtained '~ 25 from the Aldrich Chemical Company, Milwaukee, Wisconsin, U.S.A., was sulfonated in the manner described supra for tetrabenzo triaza porphine with the exception that neutralization was done with methanolic ammonia (5%1.
'' Yield was 2.5 gm~ of tetra~4~sulfophenyll porphine tetra-ammonium salt.

: - 59 -~-~``t ~.~, . 1 Si Metallation was accomplished in a manner similar to that described under item (pf) supra. One gram of tetra (4-sulfophenyl) porphine, tetraammonium salt was reacted with a 10~ excess of zinc acetate in refluxing dimethyl formamide for one hour. However isolation of the product was accomplished by a different procedure. After com-pletion of the reaction, the solvent was removed on a rotavaporator to obtain a residue. This residue was dissolved in water, acidified to pH 3, and passed through the H+ form of the cation exchange resin Dowex~ 50W-X8 (50-100 mesh) to remove the excess ionic zinc. As the solution passed through the resin, it was immediately neutralized with sodium hydroxide to avoid decomposition - of the acidic compound to zinc ions and the unmetallated porphine sulfonate. Yield was 0.96 g. tetra(4-sulfophenyl) porphine zinc, tetrasodium salt.

' lr~

~i~t4~5~

E~ampl'e II
Eighteen exemplary compositions of t~is invention are identified' on Ta~le'I. All contain com~inat~or~ of surractant, peroxy ~leach, and porphine ~leach within the scope of thi's invention. The individual components of these'compositions are'identified in the'~ootnotes which follow the'ta~le.' Composition num~ers 5, 12 and 15 are in liquid form, and the balance of each composition is water. ~ ;
The r~maining compositions are in solid form, and each composition contains 10% water with the balance sodium sulfate.
T~e~e compositions are tested in the manner described in Example'I. Washing temperatures are 90C.
for compositions 2, 3, 9, 12, 14 and 17, and 40C. for the remainder. In each case fabrics washed in the compo-sition of this invention show substantially greater stain remo~al than fabrics washed in compositions omitting either peroxy bleach or porphine bleach.

~, .,, ~ .
; - -61 -:. . . ,. . .. ., . .. , ; , .......

Si Ta~le I

Compo- - Pe~ox~ ` ` ~~ Perox~ oth-er sition SurL'ac~ Bleach Porphine Bleach - Compo~
5 No. tant P~V. Ox~ -~leach Activator Builder nents 1 5% Sa 4.596 Pa 0.004% pf - 1.5% Aa 30~ Ba 196 Oa 2 40 Sb 0 0 2 Pe O .-Olû pa 3 25 Sc 2 . 5 Ph ~010 pl 10 Bj ~.1 Ob 4 10 Sd 00 5 Pi 0. 022 pg 70 Ba lû Oc 10 - 10 Bh O . 5 Og ' 5 :16 Se 4.O Pg 0. aol p~ 15 ~ 10 (~c~

6 24 Sf 0,.~ Pn 0.50 pc 40 13d 0.5 Oa Q~l O~'
7 26 Sg 0.4 Pb 0.013 pk 1.0 Ae 20 B~ 0.5 Ok
8 50 Sh 3 . 5 Pj 0. 003 po 0 . 5 Od
9 20 Si O . 7 Pd 0. 007 pm 44 Bc 2 Oc 6 Bf . 10 18 Sj 2.0 Pm 0.002 ph 15 B~ 0.2 Oe .10 Bi 1.0 0~
11 35 Sk 0.6 Po 0.04 po 40 Bg 0.2 Ob . 12 12 Sl 3.0 Pc 0.30 pn 8 Oc 13 30 Sm 1. 5 Pk 0. 005 pd 25 Ba 10 Oh Bf - - - 14 45 Sn O . 3 Pf O . 20 pj - - O . 01 Of 12 C~c So 5. 0 Pl 0. 017 pq 0 .1 Oe 16 6 Sc 0.3 Pf 0.004 pr 1.0 Ac 14 Bg 6 S:E 6 Bf 17 10 Sa 3 . 5 Pb 0. 02 Pe 5 Sg 18 12 Sj 0.5 Pe 0.40 pi 3.0 Ad 30 Bd 3 Ok 8 Sk 3 0 Be :

. ,'i `~ ~
' ' ~ . .~. .
- .

~ootnot~s to ~able~
.. ... . ... ..
S-ur$actant~
Sa C12 branched chain-alkyl ~enzene'sulfonate ~ABS~, sodium salt S~ C12 linear alkyl ~enzene'sulfonate (LAS), sodium salt :
Sc coconut alkyl sul~ate, sodium salt Sd eth~l ester of C18 alpha sulfocarboxylate, sodium salt - ~
Se' tallow soap S~ alkyl polyethoxy-alcohol sulfate having ll carbon atoms . 10 in the alk~l group asd 2 mols ethylene'oxide per mol of alcohol, sodium salt Sg alkyl polyethoxy alcohol having 16 carbon atoms in the alkyl group and 25 mols ethylene oxide per mol of hlCOllOl Sh' polyethoxy polypropoxy-glycol ha~ing a molecular weight of 5000, half of which represents the polypropoxy base and half of which represents hydrophilic polyethoxylate Si dimethyl C12 amine oxide Sj C16 alkyl dimethyl ammonio propane sulfonate Sk coconut alkyl trimethyl ammoni~m chloride Sl ditallow dLmethyl ammonium chloride Sm trioctyl methyl ammonium chloride Sn stearoyl choline ester quaternary ammonium bromide .,, O O
So Br (CH3)3-N -(C~I2)2-o-c-(cH2)l2-c-o-(cH2)2-N~-cH3)3 Br - '~:-.~ .

Perox~ ~leach~
~ Pa) sodium perborate monohydratff ; Pb) potassium perborate tetrahydrate Pc~ sodium perbo~'ate tetxahydrate Pd~ potassium per~orate monoh~drate Pe~ potassium percarbonate ~f~ potassium monopersulfate ~1 ' .

~ , ' ' ' , -, .

Pg~ sodium perphosph~te - ~ Ph~ urea peroxide Pi) diperazelaic acid Pj~ diperdodecanedioic acia Pk~ monoperoxy pht~alic acid Pll m-chloroperoxy benzoic acid Pm~ p-nitroperoxy benzoic acid Pn~ diperoxyisophthalic acid Po~ diperoxy terephthalic acid ...... .. ... ....
10 ' P~:' Bleaches ~pa) through (ph) are identified herein-before. The remainder are as ~ollows:
pil benzotrisulrobenzo monoaza porphine magnesium, trilithium salt pj~ tetrasulfo~enzo diaza porphine scandium, tetra~ethanol-amIne) salt ; pk~ trans-dichloro, trisulfobenzo-tri~sulfo-2-pyridyl)-2-pyridyl porphine tin(IV~, hexapotassium salt pl) . 1,2,3,4,5,6,7,8- octasulfophenyl porphine cadmium, octasodium salt pm) tetrabenzo~ , y, ~ - tetrakis ~4-N-methyl) pyridyl porphine tetraiodide pn~ . 1,3,5,7- tetrakis (sulfato polyethoxy phenyl) -, y, ~ - tetrakis (phosphato napthyl) porphine, octapotassium salt po) trans dichloro, di(N-methyl pyrido) - a, ~
tetrakis (carboxyphenyl) porphine tin(IV), tetra-ammonium salt pp) 1,3,5 - tri(4-polyethoxy) - ~ tri-(4-poly-ethoxy~-~-aza-porphine p~) bromo, tetrabenzo-a-(4-N-methyl) pyridyl-~pyridyl porphine scandium monobromide px~ 2,4,6,8 - Letrakis (sulfophenyl-n-heptyl~ tetraaza porphine, tetra Cmonoethanolamine~ salt .

4-~

..,. ~
. . .

Perox~:Bleac~ ~ctivators;
Aal N,N,N',N~-tetraacet~1 ethylene diamine A~ triacetyl cyanurate ACl tetraacetyl glycoluril Adl N~acetyl imidazole Ae~' sodium-p~acetoxy ~enzene'sulfonate' ..... ...... .
~u~ ers~
Ba sodium tripolyphosphate' -Bb sodium pyrophosphate Bc sodium nitrilotriacetate Bd citric acid Be sodium carbonate' Bf sodium silicate solids, 2.0 ratio SiO2/Na20 Bg sodium aluminosilicate Na12(A102 SiO2)12 27 H~O
Bh potassium tetraborate . Bi sodium orthop~osphate B; ethane-l-hydroxy-l,l-diphosphonate, sodium salt ' Ot~er ComPonents Oa polyeth.ylene glycol, molecular weight 6000 Ob perfume Oc potassium toluene sulfonate od sodium carboxymethylcellulose Oe optical brightener (fluorescer) ,~ Of colorant ; 25 Og protease Oh montmorrilonite clay . ,.. , ~.~ ~, j .
. . .

s~
Oi Gantre ~ AN, an equimolar copolymer of maleic anhydride and vinyl methyl ether, manufactured by the GAF Corp.
Oj "Glass H", a glassy phosphate having the formula Nax23P2164 manufactured by the FMC Corp.
Ok "Zeosy ~ 110SD", a precipitated silica manufactured by the J.M. Huber Corp.
EXAMPLE III
The following granular composition is prepared Cll 8 linear alkyl benzene 4%
suifonate, Na salt Diperdodecanedioic acid ~76% active) 21 Boric acid (anhydrous) 21 Zinc phthalocyanine tetrasulfonate, 0.01 tetrasodium salt Sodium sulfate 51 Optical brightener 0.6 Mineral oil Minors (carboxymethylcellulose, bluing, perfume, etc.) and miscellaneous 1.4 a .

`` 1;~C~4~S~ .

SUPPLEMENTARY DISCLOSURE
The present invention as originally described relates to a bleach composition comprising three components: (a) a surfactant, (b) a peroxy bleach, and (c) a porphine bleach.
The porphine bleach had the general formula:

~X ,A~

10 ~U X

wherein eaah X is t=N-) or (=CY-), and the total number of (=N-) groups is 0, 1, 2, 3 or 4; wherein each Y, independently, is hydrogen or meso substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or heteroaryl; wherein each R, independently, is hydrogen or pyrrole substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or heteroraryl, or wherein adjacent pairs of R's are joined together with ortho-arylene groups to form pyrrole substituted alicyclic or heterocyclic rings;
wherein A is 2(H) atoms bonded to diagonally opposite nitro-gen atoms, or Zn(II), Cd(II), Mg(II), Sc(III), or Sn(IV);
wherein B is an anionic, nonionic, or cationic solubilizing group substituted into Y or R; wherein M is a counterion to the solubilizing groups; and wherein s is the number of solubilizing groups.
It has now been found that in the above formula A
can also have the meanings Ca(II) and Al(III). Such materials have the same utility as those originally described.
Thus, the invention in its broadest aspect relates to a detergent bleach composition comprising (a) surfactant, (b) peroxy bleach and (c) porphine bleach, in which the ~49L~;~

surfactant and peroxy bleach are the ones described above, while the porphine bleach has the general formula:

~ R X 6 wherein each X is (=N-) or (=CY-), and the total number of (=N-) groups is 0, 1, 2, 3 or 4; wherein each Y, independent-ly, is hydrogen or meso substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or heteroaryl; wherein each R, independently, ; i8 hydrogen or pyrrole substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or heteroraryl, or wherein adjacent pairs of R's are joined together with ortho-arylene groups to form pyrrole substituted alicyclic or heterocyclic rings; wherein A is 2(H) atoms bonded to diagonally opposite nitrogen atoms, or Zn(II), Cd(II), Mg(II), Ca(II), Al~III), Sc(III), or Sn(IV); wherein B is an anionic, nonionic or cationic solu-bilizing group substituted into Y or R; wherein M is a counter-ion to the solubilizing groups; and wherein s is the number of solubilizing groups.
Composition 111] is prepared like composition 11]
of the original disclosure except that 0.010% aluminum phthalocyanine tetrasulfonate, tetrasodium salt is added.
This material is prepared by a method analogous to that of the corresponding Zn derivative; i.e. using Al rather than Zn dust. Stain removal tests show composition [11] to be more comparable to composition [2] than to composition [1].
Composition ~12] is prepared like composition [1]

, - 68 -'''~ ' .

': `'' :

li~44Sl of the original disclosure except that 0.010% calcium phthalo-cyanine tetrasulfonate, tetrasodium salt is added. This material is prepared by a method analogous to that of the cor-responding Zn derivative, i.e. using Ca rather than Zn dust.
Stain removal tests show composition [12] to be more comparable to composition [2] than to composition [1].

~ :
.. , ., .

"

3Q ~:

.,

Claims (38)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A detergent bleach composition comprising the following components, (a) surfactant, (b) peroxy bleach, and (c) porphine bleach;

where the surfactant is from 5 to 50 wt.% based on the weight of the composition and is anionic, nonionic, semi-polar, ampholytic or cationic;

where the peroxy bleach has an available oxygen content of from 0.2 to 5.0 wt.% based on the weight of the composi-tion and is an inorganic peroxyhydrate, urea peroxide, or an organic peroxy acid or anhydride or salt thereof having the general formula where R is an alkylene group containing from 1 to 20 carbon atoms or a phenylene group and Y is hydrogen, halogen, alkyl, aryl or any group which provides an anionic moiety in aqueous solution;

where the porphine bleach is from 0.001 to 0.5 wt.% based on the weight of the composition and has the general formula wherein each X is (=N-) or (=CY-), and the total number of (-N-) groups is 0, 1, 2, 3 or 4; wherein each Y, indepen-dently, is hydrogen or meso substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or heteroaryl; wherein each R, independently, is hydrogen or pyrrole substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or heteroraryl, or wherein adjacent pairs of R's are joined together with ortho-arylene groups to form pyrrole substituted alicyclic or heterocyclic rings; wherein A is 2(H) atoms bonded to diagonally opposite nitrogen atoms, or Zn(II), Cd(II), Mg(II), Sc(III), or Sn(IV); wherein B is an anionic, nonionic or cationic solubilizing group substituted into Y or R; wherein M is a counterion to the solubilizing groups; and wherein s is the number of solubilizing groups;

wherein, when B is cationic, M is an anion and s is from 1 to about 8; when B is nonionic, B is polyethoxylate, M is zero, s is from 1 to about 8, and the number of condensed ethylene oxide molecules per porphine molecule is from about 8 to about 50; when B is anionic and proximate, M is cationic and s is from 3 to about 8; when B is anionic and remote, M is cationic and s is from 2 to about 8; and when B is sulfonate the number of sulfonate groups is no greater than the number of aromatic and heterocyclic substituent groups.
2. The composition of claim 1 wherein the available oxygen content of the peroxy bleach is from 0.2 to 0.7 wt.%
based on the weight of the composition.
3. The composition of claim 1 wherein the available oxygen content of the peroxy bleach is from 0.2 to 0.5 wt.%
based on the weight of the composition.
4. The composition of claim 1 wherein the porphine bleach is from 0.003 to 0.022 wt.% based on the weight of the composition.
5. The composition of claim 1 where the porphine bleach is a compound other than zinc phthalocyanine sulfonate.
6. The composition of claim 1 wherein the surfac-tant is from 10% to 30% by weight of the composition and, where the surfactant is anionic, is soap or a water-soluble salt of alkyl benzene sulfonate, alkyl sulfate, alkyl polyethoxy ether sulfate, paraffin sulfonate, alpha-olefin sulfonate, alpha-sulfocarboxylates and their esters, alkyl glyceryl ether sulfonate, fatty acid monoglyceride sulfates and sulfonates, alkyl phenol polyethoxy ether sulfate, 2-acyloxy-alkane-1-sulfonate, and beta-alkyloxy alkane sulfonate; where the surfactant is nonionic, is a poly-ethoxylate of an alcohol, alkyl phenol, polypropoxy glycol, or polypropoxy ethylene diamine; where the surfactant is semi-polar, is amine oxide, phosphine oxide or sulfoxide; where the surfactant is ampholytic, is a water-soluble derivative of an aliphatic secondary or tertiary amine in which the aliphatic moiety is 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; where the surfactant is zwitterionic, is a water-soluble derivative of an aliphatic quaternary ammonium, phosphonium or sulfonium cationic compound in which the aliphatic moieties are 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; and where the surfactant is cationic, has the formula wherein each R1 is an organic group containing a straight or branched alkyl or alkenyl group optionally subsituted with up to 3 phenyl groups and optionally interrupted by up to 4 structures selected from the group consisting of , , ,,, -O-, (1) , (2) , (3) , (4) , (5) , wherein p is from 1 to 20, (6) , (7) , and (8) mixtures thereof, L is a number from 1 to 10, Z is an anion in a number to give electrical neutrality.
7. The composition of claim 1 wherein the peroxy bleach is an alkali metal salt of perborate, percarbonate, persulfate, persilicate, perphosphate or perpolyphosphate;
urea peroxide; or diperazeleic acid, diperdodecanedioic acid, monoperoxyphthalic acid, diperoxyterephthalic acid, 4-chlorodiperoxyphthalic, the monosodium salt of diperoxy-terephthalic acid, m-chloroperoxybenzoic acid, p-nitroperoxy-benzoic acid, or diperoxyisophthalic acid.
8. The composition of claim 1 wherein A is 2(H) or Zn(II); and B is pyridinium, quaternary ammonium, poly-ethoxylate, sulfonate, carboxylate, polyethoxycarboxylate, sulfate, polyethoxysulfate, phosphate, or polyethoxyphos-phate.
9. The composition of claim 6 wherein the peroxy bleach is an alkali metal salt of perborate, percarbonate, persulfate, persilicate, perphosphate or perpolyphosphate;
urea peroxide; or diperazeleic acid, diperdodecanedioic acid, monoperoxyphthalic acid, diperoxyterephthalic acid, 4-chlorodiperoxyphthalic, the monosodium salt of diperoxy-terephthalic acid, m-chloroperoxybenzoic acid, p-nitroper-oxybenzoic acid, or diperoxyisophthalic acid;
A is 2(H) or Zn(II); and B is pyridinium, quaternary ammonium, polyethoxylate, sulfonate, carboxylate, polyethoxy-carboxylate, sulfate, polyethoxysulfate, phosphate, or poly-ethoxyphosphate.
10. The composition of claim 3 wherein the porphine bleach is from 0.003 to 0.022 wt.% based on the weight of the composition.
11. The composition of claim 3 where the porphine bleach is a compound other than zinc phthalocyanine sulfonate.
12. The composition of claim 9 wherein the available oxygen content of the peroxy bleach is from 0.2 to 0.7 wt.%
based on the weight of the composition.
13. The composition of claim 9 wherein the available oxygen content of the peroxy bleach is from 0.2 to 0.5 wt.%
based on the weight of the composition.
14. The composition of claim 9 wherein the porphine bleach is from 0.003 to 0.022 wt.% based on the weight of the composition.
15. The composition of claim 9 where the porphine bleach is a compound other than zinc phthalocyanine sulfonate.
16. The composition of claim 12 wherein the surfac-tant is alkyl benzene sulfonate.
17. The composition of claim 12 wherein the peroxy bleach is sodium perborate monohydrate or tetrahydrate.
18. The composition of claim 12 wherein the porphine bleach is zinc phthalocyanine sulfonate.
19. The composition of claim 12 wherein the porphine bleach is from 0.003 to 0.022 wt.% based on the weight of the composition.
20. The composition of claim 12 where the porphine bleach is a compound other than zinc phthalocyanine sulfonate.
21. The composition of claim 13 wherein the surfac-tant is alkyl benzene sulfonate, the peroxy bleach is sodium perborate tetrahydrate, and the porphine bleach is zinc phthalocyanine tetrasulfonate.
22. The composition of claim 13 wherein the porphine bleach is from 0.003 to 0.022 wt.% based on the weight of the composition.
23. The composition of claim 13 wherein the porphine bleach is from .005 to 0.017 wt.% based on the weight of the composition.
24. The composition of claim 13 where the porphine bleach is a compound other than zinc phthalocyanine sulfonate.
25. The composition of claim 22 additionally containing a peroxy bleach activator comprising an acylating agent selected from the following classes of compounds:
N-diacetylated amines; N-alkyl-N-sulfonyl carbonamide;
N-acyl hydantoins, eyelid N-acyl hydrazides; triacyl cyanurates; benzoic anhydrides; phthalic anhydrides;
O,N,N-trisubstituted hydroxyl amines; N,N'-diacyl sulfuryl-amides; 1,3-diacyl-4,5-dialyloxy-imidazolidines; acylated glycolurils; and carboxylic esters.
26. The composition of claim 22 additionally containing from 10 to 60% of a detergency builder selected from the group consisting of water-soluble alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates; water-soluble aminopolycarboxylates, salts of phytic acid, organic polyphosphonates, salts of polycarboxylate polymers and copolymers; and amorphorus and crystalline aluminosilicates.
27. The composition of claim 1 additionally containing an exotherm control agent which is present in the amount of at least 50% of the amount of organic peroxy bleach present.
28. A process for removing stains from cotton fabrics which comprises the steps of (a) treating the fabrics with an aqueous solution of the detergent bleach composition of claim 1; and (b) drying.
29. A process for removing stains from cotton fabrics which comprises the steps of (a) treating the fabrics with an aqueous solution of the detergent bleach composition of claim 1; and (b) drying; wherein both steps take place in darkness.

Claims Supported by Supplementary Disclosure
30. A detergent bleach composition comprising the following components, (a) surfactant, (b) peroxy bleach, and (c) porphine bleach;
where the surfactant is from 5 to 50 wt.% based on the weight of the composition and is anionic, nonionic, semi-polar, ampholytic or cationic;
where the peroxy bleach has an available oxygen content of from 0.2 to 5.0 wt.% based on the weight of the composition and is an inorganic peroxyhydrate, urea peroxide, or an organic peroxy acid or anhydride or salt thereof having the general formula where R is an alkylene group containing from 1 to 20 carbon atoms or a phenylene group and Y is hydrogen, halogen, alkyl, aryl or any group which provides an anionic moiety in aqueous solution;
where the porphine bleach is from 0.001 to 0.5 wt.% based on the weight of the composition and has the general formula wherein each X is (=N-) or (=CY-), and the total number of (=N-) groups is 0, 1, 2, 3 or 4; wherein each Y, independently, is hydrogen or meso substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or heteroaryl; wherein each R, independently, is hydrogen or pyrrole substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or heteroaryl, or wherein adjacent pairs of R's are joined together with orthoarylene groups to form pyrrole substituted alicyclic or heterocyclic rings; wherein A is 2(H) atoms bonded to diagonally opposite nitrogen atoms, or Zn(II), Cd(II), Mg(II), Ca(II), Al(III), Sc(III), or Sn(IV); wherein B is an anionic, nonionic or cationic solubilizing group substituted into Y or R; wherein M is a counterion to the solubilizing groups, and wherein s is the number of solubilizing groups, wherein, B is cationic, M is an anion and s is from 1 to about 8; when B is nonionic, B is polyethoxylate, M is zero, s is from 1 to about 8, and the number of condensed ethylene oxide molecules per porphine molecule is from about 8 to about 50; when B is anionic and proximate, M is cationic and s is from 3 to about 8; when B is anionic and remote, M is cationic and s is from 2 to about 8; and when B is sulfonate the number of sulfonate groups is no greater than the number of aromatic and heterocyclic substituent groups.
31. The composition of claim 30 wherein A is Ca(II) or Al(III).
32. The composition of claim 1 wherein the avail-able oxygen content of the peroxy bleach is from 0.2 to 0.7 wt.% based on the weight of the composition.
33. The composition of claim 1 wherein the avail-able oxygen content of the peroxy bleach is from 0.2 to 0.5 wt.% based on the weight of the composition.
34. The composition of claim 1 wherein the porphine bleach is from 0.003 to 0.022 wt.% based on the weight of the composition.
35. The composition of claim 1 wherein the surfactant is from 10 % to 30 % by weight of the composition and, where the surfactant is anionic, is soap or a water-soluble salt of alkyl benzene sulfonate, alkyl sulfate, alkyl polyethoxy ether sulfate, paraffin sulfonate, alpha-olefin sulfonate, alpha-sulfocarboxylates and their esters, alkyl glyceryl ether sulfonate, fatty acid monoglyceride sulfates and sulfonates, alkyl phenol polyethoxy ether sulfate, 2-acyloxy-alkane-1-sulfonate, and beta-alkyloxy alkane sulfonate; where the surfactant is nonionic, is a polyethoxylate of an alcohol, alkyl phenol, polypropoxy glycol, or polypropoxy ethylene diamine; where the surfactant is semi-polar, is amine oxide, phosphine oxide or sulfoxide where the surfactant is ampholytic, is a water-soluble derivative of an aliphatic secondary or tertiary amine in which the aliphatic moiety is 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; where the surfactant is zwitterionic, is a water-soluble derivative of an aliphatic quaternary ammonium, phosphonium or sulfonium cationic compound in which the aliphatic moieties are 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; and where the surfactant is cationic, has the formula wherein each R is an organic group containing a straight or branched alkyl or alkenyl group optionally substituted with up to 3 phenyl groups and optionally interrupted by up to 4 structures selected from the group consisting of , , , , , -O-, (1) , (2) , (3) , (4) , (5) , wherein p is from 1 to 20, (6) , (7) , and (8) mixtures thereof, L is a number from 1 to 10, z is an anion in a number to give electrical neutrality.
36. The composition of claim 1 wherein the peroxy bleach is an alkali metal salt of perborate, percarbonate, persulfate, persilicate, perphosphate or perpolyphosphate;
urea peroxide; or diperazeleic acid, diperdodecanedioic acid, monoperoxyphalic acid, diperoxyterephthalic acid, 4-chloridiperoxyphthalic, the monosodium salt of diperoxy-terephthalic acid, m-chloroperoxybenzoic acid, p-nitroperoxy-benzoic acid, or diperoxyisophthalic acid.
37. A process for removing stains from cotton fabrics which comprises the steps of (a) treating the fabrics with an aqueous solution of the detergent bleach composition of claim 30 or 31; and (b) drying.
38. A process for removing stains from cotton fabrics which comprises the steps of (a) treating the fabrics with an aqueous solution of the detergent bleach composition of claim 30 or 31; and (b) drying; wherein both steps take place in darkness.
CA297,842A 1978-02-28 1978-02-28 Detergent bleach composition and process Expired CA1104451A (en)

Priority Applications (17)

Application Number Priority Date Filing Date Title
CA297,842A CA1104451A (en) 1978-02-28 1978-02-28 Detergent bleach composition and process
PH22189A PH15828A (en) 1978-02-28 1979-02-13 Detergent bleach composition and process
EP79200082A EP0003861A1 (en) 1978-02-28 1979-02-19 Detergent bleach composition and process for removing stains from cotton fabrics
NLAANVRAGE7915006,A NL187494C (en) 1978-02-28 1979-02-19 METHOD FOR REMOVING STAINS FROM COTTON FABRIC
DE19792948923 DE2948923A1 (en) 1978-02-28 1979-02-19 BLEACHING DETERGENT AND METHOD OF USE
BEBTR51A BE51T1 (en) 1978-02-28 1979-02-19 COMPOSITION AND METHOD FOR DETERGENT BLEACHING
GB8008028A GB2042005B (en) 1978-02-28 1979-02-19 Detergent bleach composition and process for removing stains from cotton fabrics
BR7901212A BR7901212A (en) 1978-02-28 1979-02-23 WHITE DETERGENT COMPOSITION AND PROCESS FOR THE REMOVAL OF SPOTTINGS FROM TISSUE CLOTHS
US06/015,677 US4240920A (en) 1978-02-28 1979-02-27 Detergent bleach composition and process
AU44613/79A AU524329B2 (en) 1978-02-28 1979-02-27 Detergent bleach composition
MX176757A MX150169A (en) 1978-02-28 1979-02-28 IMPROVED DETERGENT WHITENING COMPOSITION
JP54023282A JPS5858394B2 (en) 1978-02-28 1979-02-28 Cleaning bleaching compositions and methods
IE564/79A IE48257B1 (en) 1978-02-28 1979-08-08 Detergent bleach composition and process
FR8000103A FR2443500A1 (en) 1978-02-28 1980-01-02 COMPOSITION AND METHOD FOR DETERGENT BLEACHING
SE8001309A SE437533B (en) 1978-02-28 1980-02-19 LAUNDRY AND WHITING COMPOSITION AND WASTE TO REMOVE SPOTS FROM COTTON MATERIAL
IT86212/80A IT1148214B (en) 1978-02-28 1980-03-05 DETERGENT-BLEACHING COMPOSITION AND PROCESS FOR REMOVING STAINS FROM COTTON FABRICS
JP58017295A JPS594479B2 (en) 1978-02-28 1983-02-04 How to wash and bleach fabrics

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JP (2) JPS5858394B2 (en)
AU (1) AU524329B2 (en)
BE (1) BE51T1 (en)
BR (1) BR7901212A (en)
CA (1) CA1104451A (en)
DE (1) DE2948923A1 (en)
FR (1) FR2443500A1 (en)
GB (1) GB2042005B (en)
IE (1) IE48257B1 (en)
IT (1) IT1148214B (en)
NL (1) NL187494C (en)
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JPS54160403A (en) 1979-12-19
NL187494C (en) 1991-10-16
FR2443500B1 (en) 1983-11-25
BE51T1 (en) 1980-04-11
AU4461379A (en) 1979-09-06
JPS5858394B2 (en) 1983-12-24
GB2042005B (en) 1982-08-18
SE437533B (en) 1985-03-04
EP0003861A1 (en) 1979-09-05
FR2443500A1 (en) 1980-07-04
IE790564L (en) 1979-08-28
GB2042005A (en) 1980-09-17
AU524329B2 (en) 1982-09-09
SE8001309L (en) 1980-02-19
DE2948923A1 (en) 1980-05-29
IE48257B1 (en) 1984-11-14
PH15828A (en) 1983-04-08
IT1148214B (en) 1986-11-26
JPS594479B2 (en) 1984-01-30
NL7915006A (en) 1980-05-30
US4240920A (en) 1980-12-23
DE2948923C2 (en) 1988-09-01
IT8086212A0 (en) 1980-03-05
JPS58150000A (en) 1983-09-06
BR7901212A (en) 1979-10-02

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