CA1139182A - Composition for combined washing and bleaching of fabrics - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE

Combined washing and bleaching of fabrics is accom-plished by use of a composition comprising surfactant and a photoactivator. The surfactant is anionic, nonionic, semi-polar, ampholytic, or zwitterionic in nature. THe photoactivator is a tetra-aza porphine, solubilized with anionic, nonionic and/or cationic substituent groups, and metal free or metallated with Zn(II), Ca(II), Cd(II), Mg(II), SC(III), or SN(IV).

Description

BACKGROUND OF THE INVENTION
This invention relates to household laundry processes Eor combined washing and bleaching of fabrics, and to simultaneous removal of stains and fugltive dyes and is a divisional of Canadian application Serial No.
319,432, filed January 10, 1979.

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United States Patent 3,927,9~7 yranted to Spea~man on December 23, 1975 related to a household washing and ~leachincJ proc~ss for c~tton Eabr1cs uLilizing phot activa-ting compounds, principally sulfonated zinc phthalo-5 cyanine, in the presence of visible light and atmospheric o~ygen. Japanese Patent application OPI 50-113,479 assigned to The Procter & Gamble Co~pany, laid open to Lhe public on September 5, 1975, teaches the use of specific ntixtures of sulfonated ~inc phthalocyanine species, princi-10 pally tri- and tetra-sulfonates, as pre~erred bleach photo-activators. In each of the Eoregoing references the cl~r~ent co~positions utilizing sulf~nated zinc ph-thalocyznine contained bath orgclnic surfactant and alkaline builder salt.
Belgian patent No. 840,348 lnven-ted by Wiers, yranted 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 available to the public on October 30, 1974 describes a washing machine provided with a source of visible light which irradiates wash liquor containing phthalocyanine photoactivator and fabrics.
U.S. patents 2,951,797; 2,951,798; 2,951,799 and

2,951,800, assigned -to Monsanto Chemical Company and issued on September 6, 1960 describe cer-tain por~hines as ca'alysts for the photo-oxida-tion of olefins.

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, References -to carboxylated porphines have appeared in U.S. Patent 2,706,199 lssued April 12, 1955, invented by Brentano et al, and C.R. Acad. Sci., Ser. C 1972, 275(11), 573-6 authored by Gaspard et al. See also Color Index No. 74320. References to aminosulfonyl porphines are West German OLS 2,057,194 laid open June 8, 1972, invented by Von der Eltz et al; British patent 613,781 accepted December 2, 1948, invented by Mayhew;and British patent 876,691 published Septe~ber 6, 1961, issued to Geigy A.G.
See also Color Index No. 74350. O~her substituted porphines are disclosed in Austrian patent 267,711 issued January 10, 1969, inven~ed by Wimmer; French patent 1,266,094 published May 29, 1961, invented by Tart-ter et al; U.S. Patent 2,670,265 issued February 23, 1954, invented by Meyna et al; British - Patent 471,418 accepted August 30, 1937, invented by Groves;
and JCS 1938, 1-6 authored by Dent.

It has now been found that certain species of photo-activators other than sul~onated phthalocyanines perform a similar fabric bleaching function .in the presence of visiblc light and atmosp~eric oxygen, and indeed under some circumstances are superior thereto. These other photo-activators provide .in fact not only stain removal. but also improved whitening o~ the fabrics -in two other respects:
the first of these is an improvement in the general whiteness of the fabrics, which is of~en referxed to as wh.iteness maintenance; this improve~ent is not however accomplished in the ordinary way by reducing the repxecipi~ation o~ dirt upon cleaned fabrics, but rather by oxygen blea~hing oE the overall fabric discoloration that is o~ten pres~nt in soiled : fabrics even after washing ~ith ordinary detergent composi-tions.

The second respect in which whiteness can be improvea by the compositions o~ this invention is in the removal of so-called fugitive dyes -- the tendency of some colored fabrics to release-dye into the laundering solutions, which dye is then :transferred during laundering onto other ~abrics being washed therewith. Dye transfer removal using peroxy acids together with chemical activators is the subject of U.S. Patent 3,822,114 granted on July 2, 1974 to Montgomery and Jones and com~only assigned U.S. patent 2S 4,001,131 issued January 4, 1977 . . ~

tMont9omery)~ Dye transfer removal using peroxy compounds such as hydrogen peroxide or sodium perborate catalyzed by porphines and phthalocyanines chelated with iron, and only iron, is the subject of U~S. Patent 4,Q77,768, issued March 7, 1978 (Johnson and Tate).

The foregoing objects of this invention can be conveniently ~ccomplished by a washing process which is followed by drying out-of-doors, especially in direct sunlight as on a clothesline. The common procedure of lQ soak.ing fabrics in the wash/bleach solution prior to the actual washing process is an especially effective way to accomplish the objects of this invention.
SUMMARY OF T~E INVENTION
This invention relates to a detergent bleach composition comprising an anionic, nonionic, semi-polar, ampholytic, or zwitterionic surfactant and from 0.005~
to 0.5~ by weight of the composition of a water soluble photoactivator having the formula _ ~ ~ X ~ R,, ~ (BM) R8 ~` X~$ Rs ...

...... ..

~ ~3~2 wherein each X is (=N-) or (=CY-), and the total number of (=N-) groups is ~; wherein each Y, independently, is hydrogen or meso substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or heteroaryl; wherein each R, indepen-dently, is hydro~en or pyrrole substituted alkyl, cyclo-alkyl, 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 M is a counterion to the solubilizing groups; wherein s is the number of solubilizing groups; and wherein substitutecl into Y or R
; is B, a solubilizing group seleeted from the group con-sistiny of (a) cationic groups, where M is an anion and s is from 1 to about 8; (b) polyethoxylate nonionie groups -(C~12CH2O)nH, where M is zero, s is from 1 to about ~, and sn (the number of condensed ethylene oxide molecules per porphine molecule) is from about 8 to about 50; ~c) proximate anionic groups attached to atoms no more than 5 atoms displaced from -the porphine core, where M is cationic and s is from 3 to about ~; and (d) remote anionic groups attached to atoms more than 5 atoms displaced from the porphine core, where M is cationie and s is from 2 to about 8; provided that anionic sulfonate groups are remote and are no greater in number than the number of aromatic and heterocyclic substituent yroups; wherein said alkyl groups are comprised of simple carbon chains or carbon chains interrupted by other chain-forming atoms.

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Preferred cationic solubilizing groups are quaternary pyridinium and quaternary ammonium groups.
Preferred anionic solubilizing groups are carboxylate, poly~
ethoxy carboxylate, sulfate, polyetho~y sulfate, phosphate, polyethoxy phosphate, and remote sulfonate. Preferred nonionic solubilizlng groups are polyethoxylates.

For cationic solubilizing groups M, the counterion, is an anion such as halide and s is from 1 to about 8. For polyethoxylate nonionic solubilizing groups -(CH2C~I2O)I~H, M is æero, s is from 1 to about 8, and sn (the number of condcnsed ethylene oxidc molecules per poxphine molecule) is from about 8 to about 50. ~or anionic yroups M, the count~rion, is cationic. For anionic groups attached to a~oms no more than S atoms displaced ~rom the porphine core, i.e. for "proximate" anionic groups as defined herein, s is from 3 to about 8. For anionic groups attached to a~oms more than 5 atoms displaced from the porphine core, i.e. for "remote" anionic groups as defined herein, s is from 2 to about 8. Sulfonate groups are remote and their number is no greater than the number of aromatic or heterocyclic substi-tuent groups.

The solubilizing groups on a given porphine photoactivator of this invention can be, but need not be, all alike; they can be different not only as to their precise structure but also as to their electrical charge.
Thus cationic, anionic, and/or nonionic solubilizing groups can be present on an individual photoactivator molecule.

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In the foregoing description, the term "alkyl" is defined to. be not only a simple carbon chain but also a carbon chain interrupted by. o-ther chain-forming atoms, such as 0, N or S. Non-limiting examples of such interruptions are those of the following groups:
O
ether - O -, ester - CO -, O ' ,0~
Il .
amide - C - NH -, and amino sulfonyl - NH - S -.
o DET.~ILED D~scr~IpTIo-~r 0~ TH~ VE~IrIo~
The essential components of--the instaIlt invention are -t~o in number. One i5 a surca`cta~t ~Ihich can be anionic, nonionic, semi-polar, amp~lolytic, or z~litterionic in nature, or can be mi:~tures thereo. Surfactar~ts can be used at levels from about lOQo to about 50~ of the col~.position by weight, preferably at levels rom about 15~; to about 30 by weight.
Preferred anionic non-soap surfactants are water soluble salts of alXyl benzene sulfoilate~ alkyl sulfate, alkyl polyetho ~ ether sulrate, paraffin sulonate, alpna-oleEin sulfonate, alpha-sul0carboxylat~5 and t.heir estPrs, alkyl glyceryl ether sul~onate, fattv acid monoglycericle sulEates and sul~onates, alk~l phenol polye-tho.~y ether sul~ate, 2-acyloxy-alkane-1-sulfonate, and be~a-alkylo~y ^ alkane sulfonate. Soaps are also preferred anionic surfac-tants.
Especially preferred al~yl benzene sulfonates have - about 9 to about 15 carbon atoms in a linear or branched al~yl chain, more especially about 11 to about 13 carbon atoms. Especially preferred alkyl sulfate has about 8 to about 22 carbon atoms in the alkyl chain, 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 -CH2CH20- groups per molecule, especially about 10 to about 16 carbon atoms in the al~yl chain and an average of about 1 to about 6 -CH2CH20- groups per molecule.

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Especially pref2rred paraf~in sulronat_s are essentially linear and contain frcm about 8 to abo~t 2~
carbon atoms, more especially from about L~ to about lZ
carbon atoms. Especi~lly pre~crrecl aLpna-olerin sul~onate has about 10 to about 24 carbon atom~ more especially abou-t 1~ to abou-t 16 carbon a-toms; alpha-oleEin sulfonates can be made by reaction with sulfur trioxide followed by neutralization under conditons such that any sultones present are hydroly~ed to the corresponding hydroxy alkane sulEonates~ Especially preferred alpha-sulEocarbo~ylates contain from about 6 to about 20 carbon a-toms; incluclecl herein are not only the salts of alpha-sulfonated fatty acids but also their esters made from alcohols containlng abou-t 1 to about 14 carbon a-tom~.

Especially preferred alkyl glyceryl ethex sulfates are ethers of alcohols having about lG to about 18 carbon atoms, more especially those derived from coconut oil an~l tallow. Especially preferred alkyl phenol polyethoxy ether sulfate has about 8 to about 12 carbon atoms in the alkyl chain and an average of about 1 to about 10 -CH2CH~O-groups per molecule. Espec~ally preferred 2-acyloxy-alkane-l-sulfona-tes contain from abou-t 2 to about 9 carbon atoms in the aryl group and about 9 to about 23 carbon ato~s 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 be derived from natural 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-amine cations; sodium is preferred. Magnesium and calcium are preferred cations under circumstances described by Belgian patent 843,636 in~ented by Jones et al, issued December 30, 1976. Mixtures of anionic surfactants are contemplated by this invention; a preferred mixture contains alkyl benzene sulfonate having 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 o 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 neutralization of free fatty acids obtained from either natural or synthetic SQurCes. The soap cation can be alkali metal, ammonium or alkanolammonium; sodium is preferred.
Preferred nonionic surfactants are water soluble compounds produced by the condensation of ethylene oxide with a hydrophobic compound such as an alcohol, alkyl phenol, poly-propoxy glycol, or polypropoxy ethylene diamine.
Especially preferred polyethoxy alcohols are thecondensation 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 oxide ~' condensed with 1 mol of straight or branched chain, primary 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 ~rom BASF-Wyandotte under the trade mark 'Pluronic'. ~specially 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 ami~e 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 contain-ing 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 hydroxvalkvl ~roups con-taining from about 1 to 3 carbon ~toms; ~nd ~at~r soluble sulfoxide detergents cont~ining one ~lkyl moiety of , ~ r ~ ~` ;`,, ~!

; ~ rom 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 suractants are water soluble S derivatives oE aliphatic secondary and tertiarty amines in which the aliphatic moiety can be straight chain or branched and wherein one of the aliphat:ic substituents contains from about 8 to 18 carbon atoms and one con~
tains an anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate, phosphate, or phosphonate.
Preferred zwitterionic surfactants are water soluble derivatives of aliphatic quaternary ammonium, phosphonium and sulfonium cationic compounds in which the aliphatic moieties can be strai~ht chain or branched, and wherein one of the aliphatic substituents contains from about to 18 carbon atoms and one contains an anionic water solubilizing group, especially 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 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 compoùnds and mixtures which can be used in the instant compositions, are representative of such materials but are not intended to be limiting.

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The other essential component of the instant invention i5 a photoactivator as described hereinbelow. This component can also be described as a photochemical activator, or as a photosensitizer: these terms are synonymous. Before describing the photoactivator in detail, a discussion of chemical nomenclature will be appropriate. The structure of the compound porphine is:
H

~ H ~ Prphine HC ~C

~C ~

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 - porphin or poxphyrin. This struc~ure is sometimes referred to herein as the porphine 'core', because the photoactivators 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 (=CH-) in porphine. As an example of conventional nomenclature, a compound having 3 aza groups and one methine group is referred to as triaza porphine.
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-1~3~ o~
tution by an aliphatic or aromatic group, or can be ort~ofused 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. ~he numbers designate the positions of pyrrole substitution according to conventional nomenclature.

[T]
N ~ phthalocyanine NH N
N~ ~ N

~ N ~

Another ~orm 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 &reek letters as illustrated on the phthalocyanine structure above.
Still another form of substitution is metallation by a heavy metal atom in a chelation structure: replacement 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.

Still another form of substitution is substitution of a solubilizing group into the photoactivator molecule.
The various forms of substitution described above can be illustrated by the compound 3-phenyl-2,7-dicarboxy-phenyl-~,y-diaæa-~-benzofuryl-~-carboxybenzofuryl porphine zincl trisodium salt, which is within the scope of this invention:

C0~Na ~U]
N ~ C2Na C ~n~ C

N

~~C02Na With the foregoing explanation as prelude, it is now possible to describe in detail the photoactivators of this invention. Referring to the structure shown herein-before in the SUMMARY OF THE INVENTION, effective photo-activators which are within the scope o this invention contain 0, 1, 2, 3 or 4 aza groups [and, according to the nomenclature defined above, contain 4, 3, 2, 1 or O methine groups, respectively].

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The groups designated as R's in the structural formula above can, independently, be hydrogen or pyrrole substi~uted alkyl, cycloalkyl, aralkyl, aryl, alkaryl, or heteroaryl. Adjacent pairs of R's can also be joined together with ortho-arylene groups to form alicyclic or heterocyclic rings. Benzo substitution is especially preferred; i.e., Rl and R2, R3 and R6, a~d/or R7 and R8 are connected together pairwise by methylene groups to form fused benzene rings. Other preferred forms of pyrrole substitution are naphtho, pyrido, phenyl and naphthyl.
Substitutions can also be made for the hydrogen atoms of the methine groups of the photoactivators of this invention; thus each Y in the above structural formula can independently be hydrogen or meso substituted alkyl, cyclo-alkyl, aralkyl, aryl, alkaryl, or heteroaryl. It is pre~erred that Y is H, phenyl, naphthyl, thienyl, uryl, thioazyl, oxa-zyalyl, indolyl, benzo~hienyl, or pyridyl. No meso substi-tution at all or tetra phenyl meso substitution are especially preferred.
In the foregoing description, the term "alkyl" is de~ined to be not only a simple carbon chain but al50 a carbon chain interrupted by other chain-iorming atoms, such as O, N or S. Non-limiting examples of such interruptions are those of the following groups:

o o o ether - O -, ester - CO ~, reverse ester - CO -, carbonyl - C -, O O
~, "
amide - C - NH -, reverse amicle - NH - C -, amino sulfonyl O O
,. ,.
- NH - S -, and sulfonamido - S - NH -.

O O

The photoactivating compounds of the instant invention can be unmetallated, A in the ~oregoing structural formula being comprised of two hydrogen atoms bonded to diagonally opposite inner nitrogen atoms oE the pyrrole groups in the molecule ~The characteristic s-tructure of unmetallated compounds is illustrated by compounds [S~ and [T] illustrated hereinbe~ore; these compounds are not, however, within the scope of this invention because they lack essential substituent groups as herein described.~
Alternatively, the photoactivators of this invention can be metallated with zinc(II), ca~cium(II), cadmium(II), magnesium(II) scandium(III), aluminum(III), or tin(IV). Thus, altogether, A
can be 2(H) atoms bonded to diagonally opposite N atoms, or Zn(II), Ca(II), Cd(II), ~lg(II), Sc(III), Al(III), or Sn(IV).
It is pre~erred that A be 2(H) or Zn(II).
Solubilizing groups can be located anywhere on the porphine molecule other than the porphine core as hereinbefore defined. Accordingly the solubilizi~ng groups can b~
described as substituted into Y or R as hereinhefore defined.
Solubilizing groups can be anionic, nonionic, or cationic in nature. Preferred anionic solubilizing groups are carboxylate "

- C ~ , sulfate - O - S - O~ and ~`~3~

phosphate ~ O - P - O~. ~nother preferred anionic solu-OH O

bilizing group is sulfonate - S - ~ providing this group O

is attached to a carbon atom of the photoactivator molecule that is displaced more -than 5 atoms away from the porphine core. Such a location is sometimes her~in referred to as "remote", and is ~o be distinguished from an attachment to a carbon atom displaced no more than 5 atoms from the porphine core, which is sometimes referred to herein as "pro~imate".
Other preferred ani.onic solubilizin~ agents are etho~ylat~d derivatives of -the foregoiny, especially the polyethoxysulfa-te group - tCH2C~I2O)nSO3~ and the polyethoxy carboxyl.ate group -(CEI2C~I2O)nCO ~ where n is an .inteyer from 1 to about 20.
- For anionic solubilizing groups, M the counterion is any cation that confers water solubility to the porphine molecule. A monovalent cation is preferred, especially ammonium, ethanolammonium, or alkali metal. Sodium is most preferred. For reasons described hereinafter, for proxi-mate solubilizing groups, the number of such groups per molecule, s, is from 3 -to abou-t 8, preferably from 3 to about 6, most preferably 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. Defininy s as the number of solu~ilizing groups per molecule, the number of condensed ethylene oxide molecules per porphine mo].ecule is N = sn.

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The water soluble nonionic photoactivators of this inventlon have a value of N between about 8 and about 50, preferably from about 12 to about 40, most preferably from about 16 to about 30. Within that limitation the separate values of s and n are not critical.
For nonionic solubilizing groups, there is no counter-ion and accordingly M is numerically equal to zero.
Preferred cationic solubilizing groups are quaternary compounds such as quaternary ammonium salts ~3 Rl R2 _~ ~
and quaternary pyridinium sal~.s - ~ N - R, where all ~'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 ' CH3~3-So3 For reasons that are described hereinafter, 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.

Photoactivator usage in th~ compositions of this invention can be from about 0.005~ ~o about 0.5% by weight of the composition. Preferc~ble usage i5 from about 0.01 to abou-t 0.1~ by weight of the composition. The weight ratio of photoactivator to surfactant can be between about 1/10,000 and about 1/20, preferably between about 1/1000 and about 1/100.
A~though it is not wished to be bound by theory, it is believed that the nat~e o~ this inven~ion carl be more clearly understood b~ postulating the ~achanlsm o~
bleaching using the instant photoactivators. Referring to Reaction Scheme A, the photoactivator in the upper left hand corner is in aqueous solution and is in its ground state.
Reaction ~1), entitled 'adsorption', indicates that dissolved photoactivator is in part adsorbed on fabrics. Reaction (2) suggests that photoactivator can dimerize into a form which - is not readily adsorbed and therefore is not available to enter into the desired bleaching reactions on the fabric surfaces.

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Reaction Scheme A

~CH~NISl~l OY B~AC~iIL~C

P/~ = Photo~ctivator O = an Oxygen ato~
h~ = visible light r~diation ISC = intersystem crossing in solution \ dimeri~at~or dimer :. (~;) ` \ ' ~ ~ adso~tion [~3 \
adsorbed on fabric h~ ~
~ ~e~ ci ta tion 1 ~ ~1 ' \

e:icited state singlet / 3¦ P/A ~ ~ 3 ~ ~ ~ lo~
/ excited statei c3round state; excited st~
~ f triplet triplet state in~le~

. side ~ea~tions STAI~I

cnemicaZ
b ZeacrLing .. '~ . ", . ' 1 ~ ' OXIDIZED
STAI~
, . .

- 20a -.~
\~
~ .
~ '`'`` .

. ' . Reaction (3) illustrates that photoactivator in the ground state can be excited by visible light, hv, and thereby raised to the e~cited singlet state. From the excited singlet state the photoactivator c~n undergo intersystem crossiny or ISC, reaction (4), to the triplet state which is also excited but at a lower energy level than -the singlet state. It is the excited triplet state -that is desired because it is capable of interacting wi-th the ground state of atmospheric o.~gen molecules, which are also in the triplet s-tater forming thereby according -to reaction (5) the excitecl sing].et state oE o~yge~l and also reyeneraking pho-toacti~ator at its original yround state. Both the singlet and the triplet e~cited states of the pho-toactivator can enter in-to .reactions other than the desired reac-tion t~ith oxygen.
For example, the singlet state can fluoresce, while the triplet state can phosphoresce, undergo radiati.onle~s decay, undergo electron transfer to photoacti.vator molecules in the ground state which res~ults in deac-tivation or the photo-activator, or react with other components of the so]u-tion.
From the standpoint of the desired bleaching these are collectively designated as reaction (6), 'side reactions'.
The excited singlet oxygen, formed by reaction (5) is the oxidative species that i5 capable oE reacting with 2S stains as shown in reaction (7) to chemically bleach them to a colorless and usually water-soluble state, thereby accom-plishing the purposes of this invention.
It will be instructive to consider the effect upon ~3~

bleaching ~rou(~ht about ~ the indi~ld~al species of photo-activators that are ~/ithln -the scope-oE this invention.
This will be clone in reference -to the seven reac-tions appearing on Scheme A which have been described above.
The n~er or aza yroups substituted for met'nine groups in the po-phine core primarily affects (a) the lietime of the triple-t s-ta-te, and (~) the side reactions.
The lifetime of the triplet s-tate of metalloporphines ~Grayushko et alr Op-t. Spektrosk 31, page 548 ~1971)~ is ` substantially greater than -th~t of correspondinc3 metallo-p~thalocyanines EVince-tt e-t al, J. Chem. Physics 5'), No~ 8 page 4134, October 1971~. It is beLievecl that introduction of eac~l successive aza group shortens the lifetime, and it is apparent that a longer liEetime is dasired to provide greater o?portunity for reaction with oxygen molecules to form the active bleaching species. Hence from this point of view methine groups are preferred to aza groups. However a counter~
vailing factor is that slde reactions tend to be grea-test when 4 methine groups are present, and decrease proc~ressively as successive aza groups are in-troduced. The fore~Joing effects work in opposite directions, and accordingly it is not possible to predict the relative effectiveness of the difrerent species based on theoretical considerations alone.
As described hereinafter, porphines ha~ing 0, 1, 2, 3 and 4 aza groups are effective photoactivators, and the skilled artisan is free to select a photoactivator for reasons of cost, availability, and performance under specific condi-tions of interest to him.

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This invelltion conterllplates photoactivators that are metal rr2e and also those that a~e metallated ~lith certain metals. In general, the introduction of a metal atom into the photoac-tivator molecule causes a perturbation of the sys~em .7hich reduces the lifetime of the e~cited t~iplet states and increases side reactions, both of ~hich are un~anted e_fects in relation -to the instant invention.
From this point of view unmetallated compounds are preferred photoactivators~
~ countervailing factor ls -that manufacture o~
certain photoactivators is more readily a~cc)mpllshed ~hen a metal is present -to stabilize the molecule. Ilhis factor applies both to synthesis of a photoactivator compound by sulfonation of its unsulfonatecl pxecursor m~lecule r and also to synthesis of the precursor molecule itself.
Perturbation is especially yreat ~or metals ~hich have unpaired elec-trons; hence paramaynetic metals are not satisfactory. Perturbation is also grea-t for metals that are large in slze. Data appe~ring in Vince-tt et al., op. Clt~, suggest that the lifetime oE the triplet s-tate of ~inc phthalocyanine is hundreds of times longer ~han that of coppex phthalocyanine (Cu is par.amagnetic) and approaches a hundred times longer than that o~ platinum phthalocyanine (Pt is large).
~letallated photoactivators that are accepta~le in the practice of this invention are those containi.ng .. ..
~ relatively small, diamagnetic metals: zinc(II), calcium(II), , i magnesium(II), scandium(III), aluminum(III), and tin(IV).

Because the first six of these named metals have essentially ~.~3~

constant valence, specific ident~fication oE their valence states will sometimes be omitted herein. Zinc is preferred because -the triplet state of zinc me-tallated pho-toactivators is perturbed to a relatively low extent and hence its lifetime is relatively long. ~ ----- --- --------A11 of the reactions described on Scheme A are predicated on solubility of the photoactivator in the laundry bath. Solubiliza-tion is accomplished ~y introducin~
solubilizin~ groups-into the molecule. It is entirelv practical to maXe compounds having respec-tively, one, -two, three, ~our and even lndeed up to as many as twelve solu~ilizing ~roups per molecule, and all are -to some extent photoactivators.
However as each successive solubiliæing group is added, chanyes occur monotonically in a number of properties ~hich af~ect - usefulness, as explained below.
An anionic macrocyclic photoactivator molecule in solu-tion is present in dissociated ionic form having negative chargee around its ~eriphery. The Coulombic effect of these negative charges is minimized by the counter ions in SO]UtiO.l. The pèripheral negative charges do, however, tend to localize the electron density of the ring near the center of the molecule and to enhance its basicity ~hich leads to increased dimeri-zation of tne molecules as brought about by van der Waal forces [reaction 2, Scheme A]. This circu~mstance is increased by mul-tiple solubilizing groups and loss of symmetry, and hence the tendency to dimerize in solution follows the order mono cdi <tetra < tri < penta .... Dimerization being an undesirable reaction, a relatively small number of anionic solubilizing groups are preferred from this point of view.

24 ~-~3~

On a cotton surface, which is negatively charged, multiple negative charges at the periphery of the molecule cause s-trong Coulombic repulsions which follow the order mono ~ di < tri < te-tra ~ penta .... Hence adsorption, which is desired, is greatest for species having a small number of anionic solubilizing groups. Fur~hermore the adsorption which does take place tends, for the species having a small number of anionic solubilizing groups, to be closer to the fabric surface which also is desired.

Still another advant~age of a small number of anionic solubilizing groups is fewer side reactions o~ the triplet state.
However, once again there are countervailing factors. The Coulombic repulsions of species having a - relatively high number of anionic solubili~ing groups are widely distributed around the periphery of the adsorbed macrocyclic photoactivated molecule, which minimizes adsorp~ion of successive layers of photoactlvator on the fabric surface.
However molecules of species having a small number of anionic solubilizing groups can geometrically orient in such a way as to minimize Coulombic repulsions and-can build up multiple layers of photoactivator on the fabric surface These multilayers are not desired: -their intrinsic blue/green coloration becomes visible, and when irradiated by light they form singlet oYygen in a location sufficiently remote from the fabric surface that it is less effective for the desired stain removal. From these points of view desirability is in the order ... > penta > tri > tetra > di > mo Still another advantage of a large number of anionic solubilizin~ groups is increased solubility in water.

Taking all the above into consideration it has been found that, for anionic photoactiva~ors h2viny proxima-te solubilizing groups, the negative factors of mono- and di-sulfonated photoaetivator molecules are so important that these speeies are unsatisfactory, and henee photoae,ivators of this invention have three or more proximate solubilizing groups per moleeule. Compounds having more than about eight pro~imate solubilizing groups per moleeule are often difficult to make and have no partieular advantage. Hence photoaetiva-tors of this invention having proxima-te solubilizincJ groups ~ have from three to about eight sueh groups per molecule;
eompounds having ~hree to slx proximate solubilizing groups per moleeule are pre~erred, and eompouncls having 3 or 4 proxi-mate solubilizing groups per molecule are espeeially preferred as having an optimum balance of maximum bleaching ef~ectiveness and minimum coloration.
The foregoing discussion relates to anionic photo-aetivators having proximate solubilizing groups. When the solubilizing groups are in remote loeations, the tendeney of 2~ the photoactivator moleeule to aggregate is redueed beeause of both eleetrieal and sterie reasons, with the result that less dimerization oeeurs, less buildup on the fabrie oeeurs, and the solub~lizing effeet of individual solubilizing groups is enhanced. Accordingly, a minimum of 2 remotely located anionic solubilizing groups per photoactivator molecule is satisfactory for the praetiee of this invention, with 2 to about 6 being preferred and 3 or 4 being espeeially preferred.
Nonionie solubilizing groups have a low tendency to aggregate beeause -there is no electrieal eharge-density 2~

3~

effect and tllere ls a particularly large steric effect reducing orderly association between photoactivator molecules.
Because solubilization o polyethoxylated photoactivator molecules occurs prima-ily because of numerous ether groups ,5 in the polyetho~ylate chains, it is of little consequence whether there is a single very long chain or a number of shorter chains. Accordingly, the solubility requirement as hereinbefore expressed is in terms of the number of condensed ethylene oxide molecules per porphine molecule, which is frQm about 8 to about 50, preerably from about 12 to about 40, most preferably from about 16 to about 30.
Pho~oclctivators having cationic solubili~iny groups do not effectively aggregate at all because the electron density in the ring is reduced. Substantivity on cotton fabrics is yreat. Only one solubilizing group is enough to -accomplish the purposes of this invention, although more are acceptable and indeed preferred. Accordingly the limiting numbers of solubilizin~ cationic groups are from l to about 8, preferably from about Z to about 6, most preferably from 2 to 4.
As stated hereinabove, the macromolecular structure comprislng the porphine core contributes the essential photo-activation properties of the compounds of this invention. It follows inexorably that large numbers of compounds having this macromolecular core, but with myriads of different substituent groups, are effective in the practice of this invention. One versed in the art will recognize the impracticability of reducing to writing all possibilities that can be envisioned by a skillful practioner. The embodiments which follow are therefore to be considered exemplary but not e~haustive.

Photoactivators that are eIfective bleachin~ agen-ts for fabrics and are within the scope of this invention are the following:
Tetrabenzo ~ , y, ~ - tetrakis (~-N-ethyl) pyridyl porphine tetrachloride; tetrabenzo - ~ tetrakis (N-trimethyl) aminoethyl porphine tetraiodide; tetrabenzo -- tetrakis (~-carboxyphenyl) porphine cadmillm, tetrasodium salt; tetrabenzo - ~ - tetrakis (4-sulfatophenyl) porphine zinc, tetrapotassium salt;
tetrabenzo - ~ te-trakis (~-sulfato polyethoxy phenyl) porphine, tetrasodium salt; -tetra benzo -.
~, ~, y, ~ - tetrakis (4-carboxy polyethoxy phenyl) porphine calcium, -tetraamonium salt; tetrabenzo -u, ~ - -tetrakis (4-phosphatophenyl) porphine, tetrapotassium salt; -tetrabenzo ~ , y, ~ - tetrakis .(4-phosphato polyethoxy phenyl) porphine zinc, tetra(mono-ethanolamine) salt; tran,-dichloro, tetrabenzo -tetrakis (~-polyethoxy phenyl) porphine tin(IV).
Tetrakis (N-methyl) pyrido porphine zinc tetraiodide;
tetrakis (N-trimethyl)- aminobenzo porphine, tetra ~toluene sulfonate) salt; trans-dibromo, tetrakis (carboxybenzo) porphine tin(IV), tetra(diethanolamine) salt; -tetrakis (sulfato benzo) porphine zinc, tetrasodium salt; chloro, tetrakis (sulfato polyethoxy benzo) porphine scandium, tetrammonium salt; tetrakis (carboxy polyethoxy benzo) porphine, tetrasodium salt; te-trakls (phosphato benzo) porphine zinc, tetralithium salt; tetrakis (phosphato polyethoxy benzo) porphine, tetra(triethanolamine) salt;
tetrakis (polyethoxy benzo) porphinei tetrabenzo -~.~L3d~

a, ~, y, ~ - tetrakis - (4-carbo~yphenyl) porphine zinc, tetrasodium salt.
Tetranaphtho - N, ~ r, ~ - tetrakis - (4-phosphato polyethoxy phenyl) porphine, tetrasodium salt; tetrakis tN-methyl) pyrido - a, ~, y, ~ - tetranaphthyl porphine tetra-chloride; chloro, tetrakis (polyethoxy naphtho) - N, ~, y, ~ -tetra phenyl porphine alumlnum, tetrakis (N-diethyl-N-propyl) - aminobenzo - N, ~ r, ~ - tetrakis (4-N-methyl) pyridyl porphine magnesium, octabromide; tetrakis (carboxynaphtho) ~ , y, ~ - -tetrakis (4-carboxy phenyl) porph.ine zinc, octa potassium salt; tetrakis (po].yethoxy benzo) -N, ~, y, ~ - tetrakis (polyethoxy phenyl) porphine; trans-dichloro, 1, 3, 5, 7 - tetrakis (carboxy phenyl) -N, ~, y, ~ - -tetrakis (polyethoxy phenyl) porphine tin(IV), tetra ammonium salt; 1, 3, 5, 7 - tetrakis (sul~ato polyethoxy phenyl) - ~, ~, y, ~ - tetrakis (carboxy naphthyl) porphine cadmium, octa di(ethanolamine) salt;
. 1, 3, S, 7 - tetrakis (phosphato phenyl) - ~r ~I Yl ~ ~
tetrakis (4-N-methyl) pyridyl porphine zinc, tetra sodium salt tetra chloride; l, 3, 5, 7 - tetrakis (N-trimethyl)aminobutyl N, ~, y, ~ - tetrakis polyethoxy phenyl porphine, tetraiodide.
1, 3, 5, 7 - tetrakis (4-carboxy phenyl~ - a, ~, y, ~ - tetrakis - (4-carboxy phenyl) porphine, octasodium salt;
1, 3, 4, 6 - -tetrakis tcarboxyethyl) - N, ~, y, ~ ~ tetrakis 25~ - (4-carboxy naphthyl) porphine, octasodium salt; 1, 2, 3,

4 - tetrakis (phosphato phenyl) - N, ~, y, ~ - tetra phenyl porphine zinc, tet~a(monoethanolamine) salt; 2, 3, 6, 7 -tetrakis (sul~atoethyl)-N, ~, y, ~ - tetra anthracyl porphine, tetrammonium salt; dibenzo - N, 3, '~
tetrakis - (4-N-ethyl) pyridyl porphine cadmium tetra-iodide; dinaphtho - a, ~, y, ~ - tetrakis - (4-carboxy phenyl) porphine, tetrapotassium salt; di(N-triethyl)-aminobenzo - ~, ~, y, ~ - te-trakls - (N-triethyl aminomethyl porphine zinc hexabromide; -transdibromo, di(sulfatobenzo) - a, ~, y, ~ - tetrakis - (sulfatobenzo) porphine tin(IV), hexa-sodium salt; chloro, l, 3, 5, 7 - tetrakis (sulfato phenyl) -~r ~ ~ di(sulfato phenyl) porphine scandium, hexaamonium salt; l, 3, 5, 7 - tetrakis (polyethoxy phenyl) - a, ~ -di(polyethoxy phenyl) porphine magnesium.
Tetraki.s - (carboxy benzo) - a, ~, y - tri(~-carboxy phenyl) porphine, heptasodium salt; tetrakis (phosphato benzo) - a - mono(phosphato phenyl) porph.ine, pentapotassium salt; l, 5 - di(polyethoxy phenyl) -, y, ~ - tetrakis (polyethoxy phenyl) porphine; l - mono (4-carboxy phenyl) - a, ~, y, ~ - tetrakis (4-carboxy phenyl) porphine, pentasodium salt; l, 3, 5, - tri(sulfato phenyl) - a, ~, y, ~, - tetrakis (sulfato phenyl) porphine zinc, heptasodium salt; l, 5 - di.(carbo~y phenyl) - a, ~ -di(carboxy phenyl) porphine, tetrasodium salt; 1, 3 -di(phosphato phenyl) - a, ~, y - tri (phosphato phenyl) porphine, pentasodium salt; mono(carboxybenzo) -a, ~, y - tri (4-carboxy phenyl) porphine, tetrasodium salt;
tetrakis - (carboxybenzo) - a, ~, y, o - tetrakis (2-furyl) - porphine zinc, tetrasodium salt; tetrakis - (dicarboxy-benzo) - a, ~, y - tri(4-pyridyl) - porphine, octasodium salt;

3~

1, 2, 3, 4, 5, 6, 7, ~ - oc~a - (4-N-ethyl pyridyl) ~ - di(2-thioazyl) - porphine octaiodide;
1, 2, 3, 4, 5, 6, 7, 8 ~ octa - (4--sulfato phenyl) - ~
- (2-oxazolyl) - porphine, octasodium salt; 1, 2j 3, 4, 5, 6, 7, 8 - octa - (4-polyethoxy phenyl) - a, ~ - di~?-indolyl) -porphine; 1, 2, 5, 6 - tetrakis - (4-carboxy polyethoxy phenyl) - a, ~ tetrakis (methoxy phenyl) - porphine, tetrasodium salt; 1,3,5, 7 - tetrakis - (4-carboxy pnenyl) -~, ~, y, ~ - tetrakis (2-benzo thienyl) - porphine, tetra-sodium salt; tetrakis (N-methyl pyrido~ - a, ~
tetraaza porphine tetraiodide; 1, 3, 5, 7 - tetrakis (N-trimethyl pyridyl) - ~, ~, y, ~ - tetraaza porphine zinc tetrachloride; tetrakis (N-methyl pyrido) - ~ ~
(N-methyl pyrido) - ~, y, ~ - triaza porphine cadmium ~pentaiodide; chloro,~tetrakis tcarboxybenzo) - ~
di(4-carboxy phenyl) - y, ~ - diaza porphine aluminum hexasodium salt; trans-dichloro, di(polyethoxybenzo) -a, y - di(polyethoxymethyl)~ -diaza porphine tin (IV).
Di(sulfatobenzo~ , r - tri(sulfato phenyl) -~ - monoaza porphine ca~cium, Ipenta-sodium salt; tetrakis (phosphato _ . .. _ . . . . _ _ _ . _ ~ 39~
A ~ ~

benzo)- ~ - mono naphthyl - ~ - triaza porphine tetrasodium salt; mono (N-trimethyl amino ethyl benzo) -- tetraaza porphine monoiodide; txibenzo - ~
(polyethoxy phenyl) - ~, y, ~ - triaza porphine; l, 3 - di (polyethoxy ethyl) - ~, ~, y, ~ - tetrakis (2-o~azolyl) porphine; di(~-methyl pyridyl benzo~ -dibenzo ~ - tetraaza porphine dibromide; tetrasulfo-benzo ~ - tetrakis (5-sulfophenyl-n-amyl) porphine æinc, octasodium salt; 1,5 - di(6-sulfophenyl-n-hexyl) -~, ~, y, ~ - tetrakis (sulfo-2-furyl) porphine, he~a-a~monium sa:Lt; ~, ~, y, ~ - tetrakis (dlcarbo~yethyl~-phenyl(aminosulfonyl phenyl) porphine, oc-tapotassium salt.

Each of the foregoin~ illustra-tive photoac-tivators is a specific chemical compound. It should be understood that alternative photoactivators, each within the scope of the instant invention, are those wherein substituted in each specific named compound are, inter alia:
a) instead of a specific ca-tion listed: sodium, - potassium, lithium, ammonium, monoethanolamine, diethanolamine, or triethanolamine salts.
b) instead of a specific anion listed: chloride, bromide, iodide, or toluene sulfonate salts.
c) instead of the metallation listed: zinc(II), calcium(I
cadmium(II), magnesium(II), scandium(III), aluminum(III
tin(IV), or metal free.
d) instead of the specific alkyl groups mentioned:
methyl r ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, or tertbutyl.
e) instead of the specific solubiliziny group mentioned: carboxyla-te, polyethoxy carboxylate, sulfate, polyethoxy sulfate,phosphate, polye-thoxy phosphate, remote sulfonate, quaternary pyridini~
quaternary ammonium, or polyethoxylate.
f~ instead of the number of solubilizing groups mentioned: any number of solubilizing groups that is not greater than the number of pyrrole-substituted aromatic or pyrido groups plus the number of meso-subst:ituted aroma-tic or heterocyclic groups c~nd tha~
0 i5 ~` for cationic or nonionic solubilizincJ groups, - from l to 8; for remote anionic solubili~ing groups, from 2 to 8; and for non-remote solubiliæing cJroups, from 3 -to~8.
g) instead of the specific pyrrole substituents mentioned: benzo, naphtho, pyrido, phenyl or naphthyl.
h~ instead of the specific meso substituents mentioned:
phenyl, naphthyl, thienyl, furyl, thioazyl, oxazyalyl, indolyl, benzothienyl, or pyridyl.
The alternatlve photoactivator compounds descrlbed above are to be considered eclually illustrative of the compounds of this invention as the compounds specifically named in the precediny list.
Additional embodiments of this invention are compounds hereinafter appearing numbered from II through XIII and from X~IV through XX~VIII, as well as compounds nu~bered from XIV through XXIII following conversion of hydroxy grc)ups to corresponding carboxy groups.

3~
The litera-ture contains references to numerous means of pre~aration of porphine and its derivatives, i.e., to the photoactivators of this invention. One skilled in the art of porphine or phthalocyanine chemistry will have no difficulty selecting a synthesis appropriate for his particular purposes.
Some of the synthesis reactions are accompanied by side reactions; in these cases conventional means of separation and purification are needed, such as chromatographic techniques, in a manner also detailed in the literature and well known to the skilled practitioner.
One convenient way to prepare porphines is to react substituted or unsubstituted heterocyclic or aromatic carbox-aldehydes with substituted or unsubstituted pyrroles. By varying the substituent groups of one or the other or both of these reactants, a great variety of porphine derivatives can be obtained. For example, ~I) H
C 2 0 ~C ~?

~C~

N

Pyrrole 4-pyridine a,~,y,~-tetrakist4-pyridyl)porphine carboxaldehyde ~, The stability of the quadridentate macromolecular structure is such that the reaction proceeds as described above. For convenience, the product is frequently and conventionally described by showing only one quarter of this symmetrical structure. It will be appreciated this structure is stabilized by resonance, and the bonds of all four quarters of the s~ructure are alike, even though conventionally they are drawn in just one of the resonating structures. Accordingly, compound ~I) above can be illustrated more simply as:

(I) ~C ~ N

~, When compound (I), a substituted pyridina, is reacted with an alkyl halide such as CH3 , a quaternary pyridinium salt is formed which is an effective photoactivating bleach of this invention providing the other requirements are met as set forth herein. Quaternary porph:ine derivatives adsorb especially strongly upon cotton fabrics because of their opposite charge. This is desirable; however a counter-vailing factor is the yellowish color of many such compounds which tend to remain on the fabric after washing.
The methyl ester of toluene sulfonate may be used instead of methyl iodide as a quaternizing salt, leading to the following synthesis:
(I) (II) C ~ ~3~H~ ~C ~ _c~3 s~3 a, ~, y, ~ - tetrakis methyl ester a, 15 (4-pyridyl) porphine of toluene (4-N-methyl pyridyl)porphine, sulfonate tetra(4-toluene sulfonate) salt When substituted pyrroles are reacted with pyridine 4-carboxy-aldehyde, and the reaction product reacted with an alkyl halide, a number of different pyridinium salts are formed.
20 ~on-limiting examples are:

(III) tetrabenzo - a, ~, y, ~
isoindole tetrakis - (4-N-alkyl pyridyl) Cbenzopyrrole~ - porphine, tetra halide salt 39~

(IV) octaphenyl ~ , y, ~ -N tetrakis - (4-N-alkyl pyridyl) - porphine, tetra halide salt 3,4-diphenyl pyrrole ~-N (V) >--~- 1,3,5,7 ~ tetrakis 4-pyridyl) ~, ~, y~ ~ -i 10 ~N tetrakis -(4-N-alkyl pyridyl) - porphine, tetra halide salt ! 3 - pyr idyl : pyrrole The above-class of reactions between substituted pyrroles and pyridine 4-carboxaldehyde can be carried out by refluxing in isopropionic acid for about 30 to 60 minutes followed by chromatographic purification. This method is described by Adler in J. Organic Chemistry, 32, p~ 4~6 : (1967) Any of the resultant metal-free compounds illustrated by compounds (TI~ through (V) above can be converted to the corresponding metallated compound by heating with a metal salt of Zn(II), Ca(II)~ Cd(II), Mg~II), Sc(III), Al~III) or Sn (II) in an appropriate solvent. ~The Sn(II) becomes oxidized in ~he process, such that the photo-activator is metallated by Sn(IV)~ For example, heating ~, B, y, ~ -tetrakis ~4-pyridyl) porphine in dimethyl-- formamide in the presence of zinc acetate yields Z

, ~- r~ ~ ~ tetrakis ~4-pyridyl) porphine zinc. This method is described by Adler in J. Inorganic Nuclear Chemistry, volume 32, pages 2443-5 (Pergamon Press Inc., Great Britain, 1~70j.

Alternatively, a metallated derivative can be prepared by-~arrying out the synthesis reaction in the pres-ence of a salt of the desired metal. For example, if cadmium chloride is present while carxying out reaction (IV), the res~ltant photoactivator compound is 1, 2, l, 4,

5, ~, 7, 8 - octaphenyl ~, ~, y, ~ - tetrakis ~ N alkyl pyridyl) porphine cadmium, tetrahalide salt. This reaction for producing a metallated compound may be preferred because the presence of the metal tends to increase stahility of the desired quadridentate structure and tends to minimize the ~ormation of other reaction products.
The metallation processes described abo~e are generally applicable to the photoactivators of this inven-tion, whatever the solubilizing groups may be.
Aza pyridinium salts can be made by condensing and rearranging pyrido-substituted imides or dinitriles, or by condensing and rearranging pyrido-substituted aromatic vicinal dicarboxylic acids in the presence of ammonia.
Molybdic or tungstic acid or metallic antimony can be employed, if desired, to accelerate the reactions. For example. - ---~ 3~
N~ ~ CN N

pyrido phthalodinitrile H3I

.
,.' (VI) N +~9 , -tetrakis (N-methyl-

6, 7 - quinolinedyl) tetraaza porphine, tetraiodide salt (VII) ~13 ~ 007~ J~
~ OoH NH3~ ___ __~ N ~

tetrakis (N-methyl pyridyl benzo) tetraaza porphine, tetraiodide salt ~3~

Mono-, di-, and tri-aza pyridi~ium salts can be prepared by using mixtures o~ star-ting ma-terials which yield mixtures of reaction products according to the proportions of the reactants. If pure species are desired, they can be purified by chromatographic techniques. Non-limiting examples are:

... . . _ . . . _ _ .. . . . ._ : .. .

3 ~

CHO

3 ~ -t 3 ~ ~ CN~ - C~HsB~
(VIII) C2Hs ~3 predominately tri (N-ethyl pyridyl~ - ~NH N
~ monoaza porphine, N C _ ~
tribromide salt ~ HN ~ ~ ~C2Hs ~N~ -~3 Br C~HO
H ~ _ _ C3H7Cl ~ C3H7 predominately 2,6-dimethyl~ N
3,4,7,8- di(N-propyl pyridyl benzo)-~, y - di (benzo- `~ ~1 N-propyl pyridyl)~ - H3C / ~ ~ ~=J \C3H7 diaza porphine, tetra- ~ ~C
chloride salt NH N
~ N HN~

H 7C 3N-- ~ +~ C

~ ~ C 3~ 7 ~3~

By suitable changes in starting materials, quaternary ammonium salts can be prepared in a manner similar to that of -the pyridinium salt illustra-tecl as compound (II). For e~ample, reacting pyrrole with a tertiary amino aldehyder followed by quaternizing, leads to (X) CHo ~I Rl- N - R2 R3 ~, ~, y, ~ - tetrakis -trialkyl, 4-amino phenyl) - porphine, te~ra halide salt As ~efore, use of substituted pyrroles leads to pyrrole-substitu-ted porphines, while variations in the tertiary amino group lead to corresponding variations in the meso substitution.
A completely different route to porphine compounds having fused ring substitution on the pyrrole rings is the condensation and rearrangement of 4 molecules of cyano aroma-tic or cyano heterocyclic ketones to form a quadridentate structure. This is done by heating in the presence of metallic z1nc, calcium, cadmium, magnesium, scandium, aluminum or tin, or a metal salt of Zn(II), Ca(II), Cd(II), Mg(II), Sc(III), Al(III), or Sn(II), and yields the corresponding metallated porphine.

~2 Il Cll2-R
metal or CN metal salt ~ ~
A C - R

where A is zinc (II), calcium ~II), cadmium ~II), ma~nesium (II) scandium (III), aluminum (III) or tin (IV) and where R is hydrogen or substituted or unsubstituted a].]cyl, aryl, or mix-tures thereoE. To utilize -this method -to ma~ce quaternary ammonium salts it is only necessary to s-tar-t with a compouncl having a tertiary amino group in the R moiety, and then quater-, nize the resultant porphine as bercore. For e,xample, ' O R
C-CH2-(CH2) -N-R
7N ~_.s~
CN or Z~ acetate N ~ R
Zn C-(CH2)n-N-R2 + R3I

~Zn C-(Cllz) -N\ ~ + 1~3 ~ R3 where n = 2, ~ f, ~ - -tetrakis -(N-trialkyl amino ethyl) porphine zinc, tetra iodide ~3 ~3~

Quaternary ammonium aza porphines can be made by adaptation of the methods of equations VI and VII supra, as for example:

~XII) . (H3C~ 2-N-C211s ~ ~ ' .
(~3c)2N ~ CN ~ C2HsI ~ ~ N-(CH3)2 ~H3C)2N ~ CN ~ ~ ` C H

: - ` M

.~ 5 '~ tetrakis - di-(N-dimethyl-N-ethylamino) benzo ~
r . ~ - tetraaza porphine, octaiodide sal-t , . .
Quaternary ammonium mono-, di , and tri-aza porphines can be made by suitable choice of mixed starting materials, in a manner analagous to the way analagous pyridinium compounds can be made as explained hereinabove.
Mixed quaternary ammonium/pyridinium porphine compounds are readily prepared, as fox example:

CHO
c~

H (C2Us)2 (C2Ws)2 \ 113C - N ~ (XIII) predominately 2-(N-diethyl-N~
methyl amino I ~ ~ ~N
S .benæo)-~,y,~-tri(N-methyl ~ fi~ NH N ~ ~ ~
pyridyl)-~- ~ H3C - ~ ~ c C ~ ~y - CW3 monoaza porphlne,~
tetra iodide salt~ <
J~
+ 4 I
~N
Z ~ CH3 ~s Among the pre~erred nonionic and anionic solubi-lizing groups of the photoactivators of this invention and polyethoxylates, sulfates, polyethoxysulfates, carboxylates, polyethoxy carboxylates, and phospha-tes. A suitable preparative method for in-troducing all such groups into the - porphine structure is to first make the corresponding poly-hydroxy porphine~ and then convert the hydrox~ groups to the solubilizing groups of choice. Accordingly, methods of preparing hydroxy porphines will be described below, following which means of converting these compounds to poly-ethoxylates, sulfates, etc. will be discussed.
One method of making polyhydroxy porphines i5 the reac-tion o:E pyrrole and substituted pyrroles with hydroxy-substituted aromatic aldehydes, This is analagous to the preparation o~ cationic solubilizing groups illustrated by compounds (II), (III), (IV), (V) and (X) supra. For example, _ . ~.. _ ., _, ....... . . ~ _ . ____ ...

, . (XIV

CHO C
H H H
indole -5~ hydroxy~ ,y,~ - tetrakis -2--carboxaldehyde (5-hydroxy-2-indolyl)porphine (~V) ~ ~ -N ) OH C {~ (CII~)nOII

~ r ~ ~ Y ~ te-traki5 -(hydroxy al~ar~l) - tetrabenzo porphine Mixtures of the above starting materials yield porphine structures wherein the 4 quarters of the quadri-dentate molecules have non-identical structures, according to the proportions used. This method of preparation can be exemplified by the use of a mix-ture of pyrrole and benzo-pyrrole with benzaldehyde to yield dibenzo meso tetraphenyl porphine.
Alternatively, hydroxy-substituted pyrroles can be reacted with aromatic aldehydes:

:

.
J

(XVI) 0~1 CHO

3,4-di (4-hydroxy benzo 1,2,3,4,5,6,7,8 -phenyl) pyrrole thiophene-2- octa(hydroxy phenyl)-carboxaldehyde a,~,y,~ - tetrakis (2-benzo-thienyl) porphi.ne (XVII) + ~ CHO ~;3 3-hydroxy iso-~ 2-furan 1,3,5,7 - tetra propyl pyrrole carboxaldehyde hydroxyisopropyl-~,~,y,~ - tetrakis -. (2-furyl) porphine In a manner analagous to the preparation of eationie compound (XI), hydroxy eyano aromatic or hydroxy eyano heterocyelic ketones can be condensed and rearranged to form the stable porphine quadridenta-te s-tructure. For exarnple:

(XVIII) , . ,~,o~

- C113 powdered Mg ~Mg 5H

C;-CH~-~ Z,n aceLate `~UH

~C-CHg Zn .~cetate jn ,~C-cH2~-c~ - oH

Mixtures of the above starting materials yield porphine struetures wherein the 4 quarters of the quadri dentate moleeules have non-identieal struetures, aeeording to the proportions used.
Hydroxy-subs-tituted aza porphines can be made in a manner analagous to that used -to prepare compounds (VI) and (VII); i.e. by condensation and rearrangement of hydroxy-substituted aromatic vicinal dicarboxylic acids in thepresence of ammonia. For example:

(XXI) HO ~ COOH NH3 ~ 0~1 COOH ~ N
N

hydroxy phthalic 10 'b acid - A mixture of polyhydroxy mono- and di-aza porphines results ~rom using, as starting materials, a mixture of a metal cyanide with a ketone whose two side groups are, respectively, (alkyl-or aryl) and (halo aryl or halo heterocyclicj, where one or the other or both side groups of the ketone have a hydroxyl group substituted therein.
For example, .... .. . . . ~ .. . _ _ ~_ __ _ ~:~3~
( XXI I ) C-CH~ -CH? OH
. . 110 ~
~Cl + Zn(CN) 2 pH OH
~ CH ~ OH

tetra (hydroxybenzo~ N ~N~

cl~,y - tri(hydroxy- + ~ Zn ~`C~
methyl)-3 - monoaza Ho ~ CH2 ~
OH Oll porphine zinc te-tra (hydxoxyberl~:o) - Cl,y -~di(hydroxymet~lyl) -diaza porphine zinc Alternatively, usiny mixtures of startin~ materia].s described above:

C~lO
HO~cooH NH3 . H CH20H

: (~XIII) OH

~ ~ OH tri(dihydroxybenzo)-~ C ~ c~-(hydroxymethyl N ~ phenyl) - ~,y,~ _ ~ N N ~ triaza porphine HO 4~ ~ OH
O (3H

The hydroxy groups of the foreyoincJ hydroxy substituted porphines can be conver-ted to solubilizing groups or this invention according to the following well known chemical reaction procedures:

- CH20H +n ~CH~ /C 2] -CH2 [o - CrI2 CH2] n polyethoxylate - CE120H + oleum ~ CH2oSo3(3 sulfate .
- CH2(OCH2cH2)nOH + oleum- ~ C~12( 2 2 n 3 polyethoxysulfate - CH20H + KMnO~ ~ ~ CO ~
carboxylate ..

- CH20H + ClCH2COOH ~ - CH20C112COO(~) ' methoxy carboxylate lS _ C~I2(ocH2cH2)noH+KMno4 2( 2 2)n_lCH2COo polyethoxy carhoxylate - CH2(CH2CH2)no~+clcH2cooH ~ 2( 2 2)n 2 polye-thoxy carboxylate - CH20H + H3PO4 2 lo OH phosphate - CH2(ocH2cH2)noH+H3po4~ CH2( 2 2 n j OH
polyethoxy phosphate - CO ~+n [C~I2CH2~ C(OCll2c~I2) 0~l O polyethoxylate ester To exemplify how these procedures can be used:

CH~2 -~CH2 C _~_,CH2 OU

~ C ~ C~l2(C~-I2C~I2)2oOH

tetrabenzo - .
~ - tetra(4-polyethoxymethyl-phenyl) porphine (XXV) OH ~)CH 2 COO
N ~ + ClCH2COOH
N

2,4,6,8 - tetrakis (carboxy methoxy) -a,~ - tetraaza porphine It ~ill be appreciated that one skilled in the chemical arts, and particularly in the color and dye arts, can apply the foregoing principles to make his photoactivator of choice according to this inven-tion.

, Alternative ways oE making carboxy porphines are evident modi~ications of the chemistry hereinbefore described:

Cool-l (XXVI) 2-(4-carboxy benzaldehyde ~,~,r ~ tetraphenyl -phenyl) pyrrole 1,3,5,7 tetra(~-carboxy-phenyl) porphine O (XXVII) coo~1 H COOH
: pyrrole 4-carboxy ~ I ~ r ~ tetrakis benzaldehyde (4-carboxyphenyl) porphine - . COOH ~ XXVI I I ) ,[~ C OH ~N 3 ~S
HO-C C-OH N

(XXIX) Cl Cl /~_COCl /~ COO~
H2 0 _~

N .N
Cl Varying proportions of the above starting materials .
ln mix~tures yield mono-, di-, and -tri-aza compounds. For example:

HOOC CEiO

3 ~ ~ 3 ~ ~ ~ C~
~ COOH
H
-(XX~) COOH COOH

~)~

HOOC /~
~_~C ~
~I N ~ ~
N C ~ ~ COOH
HN ~ ~=J
~`C~'~
~ ~COOH
~J
COOH

predominately 1,3,5 - tri~4-carbo~yphenyl) - ~,~,y -tri(4-carbox~yphenyl) - ~ - aza - porphine ~L13~

Using mixtures o~ starting materials which have different.solubilizing groups, followed by appropriate sequential reaction, yields corresponding porphine deri.va-tives, which may be entirely anionic, entirely nonionic, or . may be zwitterionic in nature. For example:
_ . _ . _ . . _ _ . . _ _ _ _ . _ . .

- o~
o COO C ~COO
H m CH2-CH2 O ( Cl~ 2 CH 2 ) nH

(YX~I ) ~ COO(C1-12CH .O) H

..
.~ "' ' ' .
.
: coo~3, ~=~ CHO 9 + 'I( XXXI I ) ol~um ~ COOa C ~ CH

.

~l ~L. 3 L3 ~

- COO
~00 COo~
~0 ~C~O~

~0 - [I ,1 ~ , COO~
~ ~ (XXXIII) N_~ // ~ t~
C- ~ N - CH3 :

As usual, variations in starting materials mal~e possible the preparation of aza derivatives and metallated derivatives -to suit.
The sulfonate group as encompassed by this inven-tion is limited to a "remote'l location on the photoactivator molecule; i.e~ displaced more than 5 atoms away from the porphine core. Remote sulfonation can prererably occur on aryl or heterocyclic groups or on relatively large alkyl groups themselves substituted into either the meso position ~-~3'~

or the pyrrole rings. These alkyl groups need not be simple carbon chains, but can be carbon chains interrupted by other groups such as those described hereinbefore.

Sulfonation of substituted porphines can be accomplished by ordinary methods such as are familiar to the skilled chemist. Sulfuric acid, oleum, chlorosulfonic acid and the like are effective sulfonating agents. As usual, higher degrees of sulfonation are obtained by increasing reaction time or temperature or by selection of a stronger sulfonating agent. For example, by condensing and rearranging a substituted maleimide, ' ~ :

CH2CH2CH2CH2CH2 ~
~2 (C~12) 3C~2~3 O ~
_ H , 5-phenyl-n-pentyl maleimide oleum ~: '' ' 1 (XXXIV) --~&H~(CU~) 3CH~

2,4,6,8 - tetrakis ~sulfo-phenyl-n-pentyl~ tetraza porphine ~3~
.

~lso, as described in Gro~es hereinbefore cited, : reactions of the following form can be utilized:
~: :

CH2-CH2-C ~= 0 H2N - C - CN~

. ~ CH2-CH2-C = o : H2N - C - CN

`; di(~phenylethyl) ketone ~; d~lamino malelc;acid dinltrile CU2-CHz~C N~ GN~
condensation Cd ~ Uz-C~ C - ;CN ~ Dd ~ re~r~m3ement 2,3 d~ ~r~ th}~ zi~e~

C3 CH; 4 ~s u l f a t i o n ~
(oleum) ~ SCz ;10~ ~ : It~is~of~ course`contemplated that sulfonatian~can,:~
and ~requently~w~ take place~on both~re~ote and praxlma~t~e~
; sites.

` : ; 60 ':

~3~

Remote sites are not excluded for the solubilizing groups of this invention other than sulfonate. ~ndeed, remote sites are preferred. Porphine structures solubilized at re~ote sites have a reduced -tendency to aggreyate into multilayers on fabric surfaces because they tend to have more bulk and less crystal order; hence the intensive blue/green coloration of these substances is imparted to the fabrics in reduced amount. Also, remotely solubilized porphines participate to a relatively small degree in the side reactions designa-ted by numeral 7 on Scheme A; thus the excited singlet state of such compounds is converted more efficiently to the excited triplet s-tate which reacts with oxygen to bring about the intended bleaching of stains.
This is an economic advantage.
Porphines having remote solubilizing groups are, for example, compound XI supra where n is 5 or greater; compound ~YV where n is 2 or greater; compound XVII
with 4 or more methylene groups interposed between the hydroxy group and the pyrrole ring; compound VII wi-th 3 or more methylene groups interposed between the pyridine and pyrrole rings; compound X with 2 or more methylene groups interposed between the meso carbon atom and the benzene ring; etc.
Æspecially preferred photoac-tivators are remotely su]fated amino sulfonyl porphines. These compounds not only have the benefits discussed supra for remotely solu-bili~ed porphines generally, but also have the added benefit of substantivity to synthetic fibers as well as cot-ton fibers. These compounds can be prepared by a provess involving the following sequential steps:

1~ Preparing a porphine without solubilizing groups.
This step is illustrated by the preparation of all cationic porphines exemplified hereinbefore, omi-tting ; the qua-ternization step; and by the preparation of all hydroxy porphines exemplified hereinbefore, where the starting ma-terials are analagous non-hydroxy-subs-tituted compounds.
2) Reacting with chlorosul~onic acid and thionyl chloride to form the corresponding chlorosulfonated porphine.
3) Condensing with an amino alcohol, using an aqueous medium and a temperature at which may be at, above, or below normal amblent.
4) Sulfonating with oleum.
Illustrative examples o~ this preparative method are:

:
.
~:

' .~ .

11 ~L 3 L~

C l S O ~

SO2Cl (XXXV~ El2N ~ OH
~,~,r,~ - tetrakis (4-sulfato- .-phenyl amino sulfonyl phenyl~
porphine ~ `

/ SO2NH ~ OSo3 So2MEI ~ , - ~ ClSO3H ; H2NCH2C~I20H

CN ~ znON SOC12 ~XXXVI) ~ 1,2,3,4~5,6,7,8 - tetrakis oleum ~ N ~ ¦(2-sulfa-toethyl amino-f ~ Isulfonylbenzo~-tetraaza Zn N ¦ porphine zinc 3~

Among the amino alcohols that are operable in these reactions may be mentioned 2-amino~2-methyl-1,3 propane diol, 2~amino-2-ethyl-1,3-propane diol, tri(hydroxymethyl) amino methane, l-amino glucose, 2-amino glucose, and 1-methylamino-~,3-propane diol.
The aminosulfonyl compounds discussed supra contain the O
- S - N -Il I
O H
group interrupting the chain of atoms linking the -oso3~3 solubilizing group and the porphine core. It is also con-templated that many other non-methylene groups can be interrupting groups, as exp1ained hereinbefore.
Whatever the nature of the interrupting group, the solubilizing group can be any of -those discussed herein. Preparative methods for such compounds fall within the ordinary skill of the art supplemented by the disclosure hereln. For example, .. _ _ .. . _ . _ . . . . . _ . .

C~10 ¢~
& ~ 2 O=C=N ~3coo 4-carboxyphenyl isocyanate ` ~ (XXXVII) ~ i .
N~
~N C-N ~3 COO~

H N ~CN ~
;~g ~ OH

_~H ~ (XXXVIII) H

~g ~ 9 CH2-cH2 ~ ~J ~

OH Mg / O(CH2CH20) gH

Many of the reactants.used.in the Eoregoing methods of preparation are commonly known and readily available to the skilled organic chemist. Certain general methods of synth~sis can be described below, as follows:
Substituted pyrroles can be prepared by heating 1,4 dicarbonyl compounds (diacids or keto acids) with ammonia. For example, HC a O
Hc - ,~ ` NH
HC - ~ [-~l20]
HC = o . .
- diphenyl pyrrole Heterocyclic 2-alde~n~des con~ aining hetero or 5 oxygen atoms can be prepared :Erom pen-.0s2ns bi~ hydrolysis to pen~oses follo~7ed by dehydra~ n and oxidat:ion For exam~le, ~IC=O
(CsE~302)~ H20 (HCOII) 3 [-_H20] ~ CHO
Il HCOH
H

- He~erocyclics con1:aining sulru. or nitrocJen he~2ro atom.s c~n bz converted into 2-alde'~yc~s by ~eac'~ g ~ rIC
arld HCN, follo~ed by hydrolyzing with ~later, T~lo exæ~.ples follow:

.
1. HCl,HCN ~

S 2. H~o ~ CHO
2-benzo-~:hiophene carboxaldehyde ~ 1. HCl, ~CN
N 2. H20 N CHO
2- f uran carboxald~hyd_ ~7 Z

A general method of preparing amino hydroxy alcohols is as follows, where the R's may be H, alkyl, or substituted alkyl:

0~ 1 12 RlCHO ~ HC-R3 - ~ ~1 1 3 ~: ~ freduction : .
. OH R2 ; Rl - C - C - R3 ~: NH

:: : : ` ~: `

: ' .
... .

, j , . . . ~ ~
` ' , :

.. . . . .

The foregoing description concerns compositions containing only surfactant and photoactivator, which are the essential elements of this invention. They are unbuilt compositions. Other componen-ts are optional, as the photo-activators of this invention are useful in a great varie-ty of othe~ise con~entional compositions.
For instance, conventional alkaline detergent builders, inorganic or organic, can be used at levels up to about 80go by weight of the composition, i.e. from 0 to about 80%. For bu'iit compositions, levels from about 10~ to abou-t 60o are preferred, and levels from about 20% to about ~0g are especially preferred. I~he weight ratio of surfactant to total builder in built compositions can be ~rom about 5:1 to about 1:5, preferably from about 2:1 to about 1:2.
Examples of suitahle inorganic alkaline detergency builder salts useful in this invention are water soluble alkali metal carbonates, bora-tes, phosphates, polyphosphates, bicarbonates and silicates. Specific examples of such salts are sodium and potassium tetrabora-tes, perborates, bicarbonates, carbonates, tripolyphosphates, pyrophosphates, orthophosphates, 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, sodium, potassium and lithium salts of ethane-l-hydroxy-l,l-diphos-phonic acid; sodium, potassium and lithium salts of methylene ~9 diphosphonic acid; sodium, potassium and :Lithium salts ofethylene diphosphonic acid; and sodium, potassium and lithium sal-ts of ethane-1,1.,2-triphosphonic acicl. ~ther examples include -the alkali metal salts oE ethane-2-car~oxy-1,1-diphos-phonic acid, hydroxymethanediphosphonic acid, carbonyldiphos-phonic aeid, ethane-l-hydroxy-1,1,2-triphosphonie aeid, ethane-2-hydroxy-1,1,2-triphosphonie aeid, propane-1,1,3,3--tetra phosphonie aeid, propane-1,1,2,3-tetraphosphonie aeid, and propane-1,2,2,3-te-traphosphonic aci.d; (~) Water-soluble salts of polycarboxylate polymers and copolymers as clescxibed in U.S. Pat~ No. 3,30~,067.
A use:Eul detergent builder which may be employed in the presen-t invention eo~prises a water-soluble salt of a polymerie aliphatic polyearboxylic aeid having the followiny struetural relationships as to the position of the earboxylate groups and possessing the following prescribed physical charaeteristies: ~aj a minimum moleeular wei.ght of abou-t 350 calculated as to the acid form; (b) an equivalen-t weigh-t of about 50 -to about ~0 calcula-ted as to acid form;-(e) at least ~5 mole percent of -the monomerie species havin~ at least two carboxyl radieals separated from each other by no-t more than two carbon atoms; (d) the site of attachment of the polymer chain of any carboxyl-containin~ radical being separated by not more than three earbon atoms along the polymer ehain from the si-te of attachment of the next earboxyl-eon-tainin~ xadieal. Specifie examples of the above-deseribed builders inelude polymers of itaconic acid, aeonitie acid, maleie aeid, mesaeonic aeid, fumarie acid, methylene malonie aeid and citraeonie aeid and eopolymers with them-selves~

In addition, other polyearboxylate builders wllich ean be used satisfaetorily inelude water-soluble salts of mellitie aeid, eitric acid, pyromellitie aeid, benzene pentaexaboxylie aeid, oxydiaeetie aeid, carboxymethyloxy-suceinie aeid and o~ydisuceinic aeld.
Certain zeolites or aluminosilieates enhaneQ the funetion o~ the alkaline metal pyrophosphate and add building eapacity in that the aluminosilieates se~uester ealeium hardness. One such ?.luminosilieate whieh is useful in the eompositions of the invention is an amorphous water-insoluble hydrated eompound of th~ formula Nax(xAl02^SiO2), wherein x is a number from 1.0 to 1.2 ancl y is 1, sai~
amorphous material being further eharaeteri2ed by ~ l~lg exehange eapaeity of from about 50 mg eq. CaCO3/g. to about 150 mg eq. CaCO3/g. and a partiele diameter o from about 0.01 microns to about 5 microns. Thls ion exchange huilder is more fully described in British patent No.
1,470,250 invented by B. ~. Ged~e et al, published April 14, 1977.
2~ A second water-insoluble synthetie aluminosilicate ion exchanye material useful herein is erystalline in nature and has the ~ormula NazlAlo2)z-tsio2)]x~l2ot wherein z and y are integers of at least 6; the molar ratio of z to y is in the ran~e from 1.0 to about 0.5, and x is an integer from about 15 to about 264; said aluminosilicate ion exchange material having a partiele size diameter from about 0.1 micron to about 100 microns; a ealcium ion exchange capacity on an anhydrous basis of at least about 200 milligrams equivalent ., _ ~ ,_. _. . . . . _ . . _._ of CaC03 hardness per gram; and a calcium ion exchange rate on an anhydrous basis of at least about 2 ~rains/yallon/
minute/gram. These synthetic aluminosilicates are more fully described in British Patent No. 1,429,14~ published March 24, 1976, invented by Cor~ill et al.

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 bullders, are used primarily for purposes otllex than reducing free hardness ions; for eYample electrolytcs used to buffer pll, add ionic s-tren~th, control viscosity, prevent gelling, etc.
It is to be understood that the detergent bleach compositions of the present invention can contain other components commonly used in detercJent compositions. Soil suspending agents such as water-soluble salts of carboxy-methylcellulose, carboxyhydroxymethylcellulose, copolymers of maleic anhydride and vinyl ethers, and polyethylene glycols having a molecular weight of about 400 to 10,000 are common components of the detergent compositions of the present inven-tion and can be used at levels of about 0.5% to about 10%
by weight. Dyes, pigments, optical brighteners, and perfumes can be added in varying amounts as desired.
Other materials such as ~luorescers, antiseptics, germicides, enzymes in minor amounts, and anti-ca~ing ayents such as sodium sulfosuccinate and sodium benzoate may also be added. Other materials use~ul in detergent compositions are clay, especially the smectite clays disclosed in U.S.
Pat. No. 3,915,882, suds boosters, suds depressants, fillers such as sodium sulfate, plI buffers, and hydrotropes such as sodium toluene sulfonate and urea.
Pero~ygen bleaches such as sodium perborate can optionally be used in the compositions of this invention;
they are however effective only at relatively high tempera-tures such as approximately 160F. and above. In conjunc-tion ~herewith, conver.tio~al chemical activators can be used to bleach more effectively at low temperatures~ such as the anhydrides, esters and amides di.sclosed by Gilbert ir.
Detergent Age, June 1967 pages 18-20, July 1967 pages 3~-33, and August 1967 pa~es 26-~7 and 67. It is generally believed that these activators func-tion by means o~ a chemical reaction that requires usage in approxima~ely a 1:1 mol ratio wi~h the peroxygen compound. Catalytic pho~oactiva-tors for peroxy bleaches can also be used, such as the iron porphines, haemin chlorides and iron phthalocyanines disclosed in U.S. ~atent No. 4,077,768.

It should be understood that, as described in detail hereinbefore, the instant photoactivators do not function by activating perborate or other peroxygell compounds;
the mechanism by which the instant photoactivators accomplish their purpose is by activa-ting atmospheric oxygen. Never-theless, formulations are not precluded that contain components which bleach by two different mechanisms operating independently.
Granular formulations embodyin~ 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 then atomizing and spray-drying the l?' ' :.......................................... ....... .... . ..

resultant mixture, or by pan or drum granulation of the components. A preferred me-thod of spray drying composi.tions in granule ~orm 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 photoac-tivating compositions of the present invention can contain builders or can be unbuilt. If unbuilt, they can con'ain about 10 to about 50% surfactan-t, from 1 to about 15% of an organic base such as mono-, di-, or -tri alkanolamine, and a solubilization system containing var.ious mixtures of water, lower alcohols and glycols, and hydrotropec;.
Built liquid single-phase composi-tions can contain about 10 to about 25% sur:Eactant, from about 10 to about 20%
builder which can be inorganic or organic, about 3 to about 10% hydrotrope, and water. Built liquid compositions in multi-phase heterogeneous form can contain comparable amounts of surEactant and builder together with viscosity modifiers and stabilizers to maintain stable emulsions or suspensions. _ _ . _ ~ -- - -- --~~--~~

Compositions of the invention in the form of detergent laun~ry bars can be prepared as described in U.S.
Patent 3,178,370 issued April 13~ 1965 and British Paten~
1,064,414 issued April 5, 1967, both to Okenfuss. A pre~
ferred process, called "dry neutralization", involved spraying the surfactant in liquid, acid form 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.
i 10 The detergent bleach composi~ion of this inven-tion 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 3 to about 17.0 grams, of the detergent composition described herein, plus an I effective amount of photoactivating hleach as described j herein.
; Detergent bleach formulations em~odying the compositions of the present invention are commonly used in laundry practice at 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 countryt 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 oE washing whether by hand or by machine, specific formulation employed, etc.

74a ~ ~ 3~

It has been stated hereinbefore that photoactivator usage is from about 0.005~s to about 0.';% b~ weight based on the detergent bleach compositi.on, preferab:Ly from about 0~01 to about 0.1~. Combining those figures wi-th the foregoing detergent bleach concentratlons in water yields the result that photoacti~ator concentrations in water range from about 0.05 parts per million (ppm) to about 30 ppm. Within this range, from about 0.25 to about 5 ppm. are preerred~ The lower side of the foregoing ranges are especial.ly efEectivc when khe laundxy process lnvolves e~posing fabric to photo~
- 10 activa-tor for a relative1;y: long time, as :Eor exam21e during a 30 to 120-minute presoak followed by a 20 to 30-minute wash, and drying the fabri.c in brilliant s~mli~ht. The higher side oF the foregoing ranges are needed when the laundry process i.nvolves exposing fabric to photoac-tivator for a relatively short time, as for e~ample during a short 10-mlnute wash followed by drying in an .illuminated dryer, on a line indoors, or outdoors on a cloudy day. While - exposure to ox~gen and visible light are essential, the source, intensit~ and duration of exposure of the light affect merely the degree of bleaching achieved.
In general, laundry practice embodying the present invention in i-ts processing aspect comprises removing stains from cotton textiles by treating the textiles, in the presence of visible light and oxygen, with an aqueous solu-tion of a composition of this invention. More particularly,the process comprises the following steps: (i) washing fabrics with a detergent bleach composition, (ii) rinsing the fabrics, (iii) drying the fabrics, and (iv) providing exposure -to visible light and oxygen during any o:E steps 74b (i), (ii) or (iii). These steps are appropriate whatever physical form detergent bleach may be employed (e.g. granule, liquid, bar, substrate) and whatever means of exposure to lig~t and oxygen are employed (e~g. ou-tdoor washing, S outdoor drying, illuminated washing machine, illuminated dryer).

~P~LE I
~ y, ~ - tetrakis (4-carboxv~henY1) ~orPhine was prepared by re~luxing a propionic acid solution, 0.24 molar in both 4-carboxybenzaldehyde and pyxrole, for 2 hours. Upon cooling the reaction mi~ture, purple crystals o ~, ~, y, ~ - tetrakis t4-carbo~yphenyl) porphine preci-pitated. Yield was 32go~ The product was purified by recrystallization from methanol/chloroform solutions.
The foregoing method of preparation is similar to that described by Longo et al., J. Heterocyclic Chem. 6 927(19~9) and the following spectral analysis performed on a Cary 14 spectrophotometer in pyridine solution agree very well with Lonso's and Datta~Gupta's findings, J. Heterocyclic Chem., 3, 195(19~G):
W~ve length ~nm) 423 517 552 591 646 Extinction log ~ 5.25 4.15 3.85 3.65 3.~8 coeficient Metallation was accomplished as follows: one gram of tetrakis(4-carboxyphenyl) porphine was reacted with a 10~ excess of zinc acetate in refluxing dimethyl formamide for one hour. After completion of the reaction, the solvent was removed on a rotav~ora-tor to obtain a residue. This residue was dissolved in water, acidified to pH 3, and passed through the ~ form of the cation èxchange resin Dowex Dl~-X8~50-100 mesh) to remove the excess ionic æinc.
The xesidue after evaporation yielded a red crystalline product ~ith about 98~ yield. Spectral analysis on a Cary 14 spectrophotometer in methanol agreed very well with published date for ~ tetrakis (4 carboxyphenyl) porphine æinc, Longo et al., J. Heterocyclic Chem. 6, 927(1969):

Wave lengtll ~(nm) 429 517 556 596 Extinction log 5.54 3.46 ~I.15 3.75 coefficient The acid form of photoactivator, prepared as described above, was converted to the tetra sodium salt upon addition to alkaline (pI-I ~ 10~ detergent solution, the cations of which were predominantly sodium.
~ , ~, y, ~ - tetra~is (4-carboxyphenyl) porphine tetrasodium salt, bo-th unmetallated and me-tall.ated with zinc~ were evaluated as photoactive bleaches in conjunction Wit}l a granular detergent ha~ing the followiny composition identified hereln as Composi.tion [E] which has a pH clt ~lse concentra-tion in wa-ter of about 10.2.

Component llt. 5. Compositio~ [E~

C branched chain alkyl 12 benzene sulronate 20 Sodium tripo'yphosphate 28 Sodium toluene sulonate 2 Silicate solids (2~0 ratio SiO2/Na2O) 5.4 Sodium sulfate 34 Sodium carbonate 0.17 Sodium carboxymethyl cellulose 0.45 Perf~me 0.1 Optical brightener [none]
~iscellaneous 1.38 Moisture 8.5 ~otal detergent 100.00 ~L~3~2 Tcergotometer tests were run as follows: to each l-gal. tub was added lO00 ml. of water havir.g a hardness of 7 cfrains/c~allo;
with a Ca/Mg ratio of 3/l, and 2.$ ym. of. detergent composi-tion [E] defined above; the concentration of deteryent in S the solution ~7as accordinc~ly O.~.r~%. Photoacti.vator was adcled to certain of tshe solutions, as described in Table I. The cloth load in each tub was 5.3 ym. in weisht and consisted of six cotton swatches 2-l/2 x 2-l/2 inches in size, ~ of which had ~en previously stained with tea and 3 with wine.
~Staininy had been accomplished by passing cotton muslin through a bolled tea or wine bat}l, respectively, follo~.~ed bY
~ squeeyeeiny, drying and ayincJ.I ~he swatche.~.: were ~lashecl in ;~ ~ the Terc30tometer for lO minutes at 7~F~ h a xot.or speecl ~ o~ 110 rp~.;:r,lere rinsed by hancl .or l min~e ak 70F. in a ; ~ ~ 15 beaker containing 500 ml. of water haviny the same hardness as that used for washlng, and were line-dried ou,doors in the sun for l hour. After drying, the swatches were read ~-~;h on a Gardner XL-lO Color Difference Met~r and the resulcant L, a and b values were calculated irto ~lhiteness according to the formula J - .. ...._.
W = lO0 ~ ~ (lO0 - L)2 + a2 + b These values of whiteness were compared with those of s~ained ~: swatches beiore the Teryotometer treatment to ob-tain ~
values which measure the extent of blezching accom~lished by the photoactivators. Results are gi~-en in Table I, and are ~iscussed hereinafter~

: . 77 r,~}

Table I
BLEACHING/STAIN REMOVAL (~W) Buil-t DetercJent Composition ¦E~ 0.25 ~G

Type o Stain ll Wine ¦ Tea __ . _ __ _ Conc. of Photoactivator (ppm.) . 1 10 ¦ 1 10 _ . __ _, Type of Photoactivatox None - 8.6 8.6 7.7 7.7 Tetrasulfobenzo tetraaza porphine zinc, tetrasodium salt11.21~.1. 8.2 9.8 ~, ~, y, ~ - tetrakis (4-carbo~y~
phenyl) porphine, tetrasocl;.um salt 10~8 11.3 8.~L 8.5 ~, ~, y, ~ - tetrakis (4-carboxy-phenyl) porphine zinc, tetra-sodium sal-t :LO.9 9.2 7.4 7.0 ~, ~, y, ~ ~ tetrakis (4-N-rnethyl pyridyl~ porphine zinc, tetra (4-toluene sulfonate) salt 9.9 10.0 7.3 7.3 ~90% LSD - 0.4]
,.

Exam le II
~ r ~ - te`tra~is (4~N-meth~ _dy~
pol~hlne,~-te-tra (4-toluene su`]fonate) ~salt was prepared as follows: a propionic acid solution, 0.24 molar in both pyridine 4-carboxaldehyde and pyrrole r was refluxed for 45 min. The solvent was flashed off and the residue was washed with di~ethylformamide to dissolve -the tarry by-products leaving purple crystals of tetra (4-pyridyl) porphine. Yield was 22.5~ and the pxoduct spectral characteristics were in substantial agreement with those observed by Fleisher, Inorg. Chem. 1, 493(1962).
The tetra (4~pyridyl) porphine (~.25 mol~ was then refluxed with sodium 4-toluene sulfonate (1.1 mol) over-night in dimethyl formamide. The reaction was then cooled in an ice bath and the product was removed by filtration, The collected 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%.
- Spectral analysis in wa-ter at pH 6-7 on a Cary 14 spectrophoto meter agreed very well with published data, Pasternack et al., J. Amer. Chem. Soc., 94, 4511(1972):
Wave length ~(nm) 422 518 551 58S 641 Extinc-tion log ~ 5.17 3.96 3.83 3.57 3.07 coefficient Elemental analysis yielded the following calcula-ted and found values for the empirical formula C72H66N8S4O12:
C H N S
Calc: 63.42 4.88 8.22 9.41 Found: 63.15 5.03 8.41 9.14 'a~3~
.~

Metallation was accomplished in a manner similar . to that described above :for the tetracarboxy porphine o Example 1, with puriication accomplished by chroma-to-graphic chloroform solutions on alumina. The metallation was done prior to quaternization with 4-toluene sulfonate.

Tergotometer tes-ts made as described in Example I
were run on the metallated derivative ~, ~, r, ~ - tetrakis ~4-N-methylpyridyl) porphine zinc, tetra (4-toluene sulfonate) salt~ Results are given in Table I, and are discussed hereinafter.

.. . ._._ . .. .. _ .. .. .. .. . .

Table I presents bleaching, i.e. stain removal, data for aqueous solutions of a built detergent composition described hereinbefore containing four different photoacti-va~ors and a control, respectively. All numbers appearing in the table represent the average of duplicate tests.
Whiteness improvement during treatment is presented for ~wo concentrations, each, ~or wine stains and for tea stains.
The first composition contained no photoactivator and was the con~rol composikion for reference purposes.
The second composition contained ~he photoa~tivator disclosed by Holcombe and Schult~ in Japanese patellt appli-cation OPI 50-113,q79 re~erred to hereinbe~ore.

The third, fourth, and flfth compositions are compositions according to ~his invention. It is apparent that fabrics washecl in compositions containing the unmetal-lated photoactivator of this invention are, or every test condition~ more white than those washed in comparable compositions containing no photoactivator. Fabrics washed in compositions containing metallated photoactivators were effective bleaches for wine stains but were not effective ~or tea stains. For all tests xeported herein, ~eference to photoactivator usage is on a 100% active basis as determined chromatographically~ _ _ r~x~

E`xample III
Tetra (2-sulfatoeth~l sulronamido henzo? tet~a-aza porphine zinc, -tetrasodiu~ salt was prepared as rollows:
twenty parts of te-trasulfo tetrabenzo tetraaza porphine zinc, tetrasodium salt were added to 200 parts of chloro-sulfonic acid with agitation and the mixture is heated to 60C. At this temperature, 30 parts of thionyl chloride -were added dropwise and the mixture was then heated for 4 hours a-t 80C. The reac-tion mixture was then cooled and added with agitation to 200 parts o~ cold wa~er from whi.ch the tetrachloro sulfo tetrabenzo tetraaza porphine zinc was separated by Eiltration and subseqllently washed with 1000 parts of cold water. The tetrachlorosulfo tetrabenzo tetraaza porphine pas-te was then suspended in 300 parts of cold water and mixed with 30 parts of 2-aminoethanol for 20 hours at 20~C. The suspension was then acidified wi-th hydrochloric acid to obtain a precipitate which was separa-ted by filtration, washed with water and dried. Twenty parts of the already obtained ethanolsulfon-amide der vative of te-trabenzo tetraaza porphine zinc were -then mixed for 12 hours at 20C with 100 parts of 10%
oleum. The solution was -then poured in a solution of 100 parts of sodium chloride into 1700 of water,and 400 parts of ice were added. A blue/green precipitate was 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 obtained was then dried at 105C. for 2 hours. The product was purified by six successive precipitations from ~:~L3~

aqueous solution hy the addition of four volumes of acetone.
I Yield was 28~.
Substitution on all sul~o groups was confirmed by the chromatographic techniques described in Japanese patent application laid open to the public as OPI 50-113,479 on September 5, 1975 which c~rrespands to Canadian Patent No. 1,031,652 Examination of the spectrum of 1, 2, 3, 4, 5, 6, 7, 8 - tetrakis ~2-sulfatooethyl sulfonamido benzo) ~,~,y,~ -tetraa2a porphine zinc, tetrasodium salt, 1n ~2 at pH 9.5, using a Cary 14 spectrophotometer, yielded the followin~
result5 Wave length A(nm) 686 672 653 Extinction loy ~ 4.46 4.64 3.91 15 . coef~i~ient Analysis o~ the zinc content by atomic absorption yielded 4.32~ zinc vs. 4.40~ theoretical on the basis of the empirical formula C40~l36Nl2s8o22 4 2 ~

The test.re~or-ted in Ta~le II involved photo-activator used together with unbuilt~de-tercJent composi-tions in liquid.form. The ingredients for these composi-tions are:

Com~onent ~`1t. -~ Com~osit.ion ~F]
C~ 5 alkyl polyethoxy ether having an average of 7 mols of ethylene oxide per nlol of alcohol 33 Sodium C12 alXyl benzene sulfonate 22 Oleic acid ~ l.0 Triethanol amine 5.5 Ekhanol . 4.7 Electrolyte (0.9 ~OH; 0.l ci-tr:ic ac.id) l,0 Perfume, color and brighkener 0.7 ~ater and Miscellaneous . 3? .1 - 100. 0 pH at use conc. in H20 ~ 8.5 ... .. . _ .. _ _ _ . . ... _ . .. . ... . _ _ . . . ...

Com~onent ~t. ~ Co~osi~ on [G]
~mon.iurl salt of coconut alkyl polyetho~y ether sulfate havin~
an av~rage of 3 mols of ethylene o~ide per mol of alcohol 25 Sodium salt of Cl~_l6 al~yl poly-e-thoxy ether sulfate having an average of 2 mols of ethylene oxide per mol of alcohol 5 Sodium salt of coconut alkyl glyceryl ether sulfonate 4 Potassium toluene sul~onate . 0~5 Ethanol . 6.9 . Electrolytes (2.5 KCl; 0.5 H3PO~;
0.5 potassium toluene sulEonate;
0.1 citric acid) 3.6 Citric acid, perfume and opacifier 1.2 Ethylene glycol distearate 1.0 ~later and miscellaneous . 52.8 ''' ` i00. 0 pH at use conc. in H2O ~ 7~0 .. , .. . . ... ., .. .. .. . ... . ~

;39;~

TercJotometer test~ were run in a manner which i.nvolved a soal;ing process followed b~ a washing process as follows: to each l~gal. tub was added 1000 ml. oE water having a hardness of 9 grains/ga.llon with a Ca~rlg ratio ol 3/1 S and 3.~ ~rn. of detergent composition ([FJ o.~ ~G]) defined above; the concentration of detergent in the`solution was accordingly 0.36%. Photoactiva-kor was added to certain of the solutions, as described in Table II. The cloth load in each tub consisted of 2-1/2-inch square swatches, 2 of which were cotton.muslin previously s-tained with -tea in the manner herein~e~o.re described, plus 8 clean te.rry cloJh s~atches to make a total cloth load o:E 9.9 ~rams~ ~:ll swa-tches were soakecl for 1-1/2 hours at -~0F~, following which 4 terry swatches were removed after the soakincJ solution clinging thereto had been squeezed back into the tubs. The remaining swatches ~ere washed for 10 minu-tes at 110 rpm. and rinsed by hand under the tap (city ~a-ter; a~out 6 gr./yal.). After line-drying in the sun for 1 hour, the stained, soaked and . washed swatches were read on the Gardner ~L-10 as before.
Values o~ W were obtained as compared with the W for stained swatches read prior to the soaking, washing and sun dxying trea-hnent.. Differential values aw which axe given in Table II measure the ex-tent of bleaching which was accomplished by the photoactivator.

$' Table II
Bl,E~C~ G/ST~LN RE'MOVAL (~W) Unhuilt Detergent Compositions 0.36%
Tea Stains 5Photoactivator Conc. 3.5 ppm.

T~-pe of'Ph'o'toa'c-ti'vator Com~osition F Com~osition G
. . . .. _ _ . _ -- , _ .. . _ , .
None ' 2.~ '~.7 y, ~ - tetrakis (~-carboxyphenyl) porphine, te-tra sodium salt 4.7 ~.1 Tctra(2-sulfato-eth~l sulEon amido ben~o~ tetra~
aza zinc, tetra sodiu~ salt 4.2 5.6 [90~ LSD = 1.3]

Table II presents bleaching, i.e. stain removal, ' data for two liquid compositions described hereinbefore, each containing photoactiva-tors of this invention, in comparison with a control. It is apparen-t that in one of these unbuilt detergents the compositions containing both photoactivators exhibit significant bleaching eEfects.
Other soaking/washing Tergo-tometer tests were run in the manner described in the preceding paragraphs with certain impor-tan-t changes: The de-tergent used was composition [E] as hereinbefore defined. Detergent concen-tration in solution was 0. 6Qo and photoac-tivator concentra-tion in solution was 0.3 ppm. In addition to the tea ~7 ~3~3~t~

stained and whi-te terry swatches previously described were 8 similarly sized swatches cu-t from a bolt of yellow fabric purchased in Mexico. After sQa~ing, washing, and sun dryiny as hereinbefore described, i-t was found that, as compared to the control composi-tion, the composition containing photoactivator not only bleached the tea stains but also bleached the yellow dye that had bled from the yellow fabric and had deposited upon the originally white terry swatches. This effect was ~easured by the Gardner b value which is a measure of yellowness~ These results are yiven in Table III and described -thereaf-ter.
No change in -thc appearance o;E the yellow fabrics themselves was observed to be caused by the photoactivator.
Comparable -tests were also run, -the swatches of lS which were dried in a dark room instead of in sunlight.
No bleaching took place in the absence of light, and the fabrics treated with photoactiva-tor solution were in fact pale blue/~reen in color due to the intrinsic blue/green color of the photoactivator compound. This color dis~ppeared upon later exposure of the fabrics to l:Lght.
Other comparable tests were run using the yellow Me~ican fabrics in solutions of detergent compositions [F]
and [G] with and without photoactivator. As with composi-tion [E], the photoactivator bo-th bleached the tea stains and reduced transfer of yellow dye to the originally white terry fabrics.

r~

Table III

BL~ACHIMG/STAIN ~EMOV~I. (Q~) and DY~ TR~NSFER REMOVAL (b) 5 Built Detergent Composition [E] 0.6 Pho-toactivator Conc. 0.3 ppm.

Type of swatch ¦ Tea-stained White muslin terry . ~ . ....... ... __ - . ,, Test purpose Bleaching/Dye Transfer Stain Removal Removal ~ ~ _ . ,_ _ Type of photoactivator ... _ . .. . _ .
None QW = 6.6 b - 1~73 tetrakis (4-carboxyphenyl) porphine, tetra sodium salt ~W = 8.8 ~ = 0.97 Tetra(2-sulfatoethyl sulf-amido benzo) tetxaaza zinc~ tetra sodium salt QW = 8.0 b = 0.43 .
[90~ LSD] [0.6] [0.7]

Table III presents, for a built detergent compo-sition described hereinbefore, data for both bleaching and dye transfer removal brought about by two photoactivators of this invention in comparison with a control. It is apparent that bo-th photoactivators are significantly effective in both respects.

` ~J~Z

E~'~LE ~
Detergent bleach compositions of this invention are prepared as described in Table IV ~hich ~ol]or~s. Compo-sitions 12, 15 and 16 are in li~uid form while the remainder are in granular rorm. When tested for bleaching in the manner described in E~ample I they are effective.
~11 figures in the table are weight percent of the compositions, and identification of the components specified in the table appears thereaEter. For all compositions the balance no-t speciFisd is compr:ised o~
~ sodi~Lm sulfate.
Compositions 17, 18 and 19 are prepared like composi-tions 2, 11 and 16, respectively, except that the porphine derivatives are metallated with aluminum instead oE ~inc.
Compositions 20, 21 and 22 are similarly prepared except ... .
they are metallated with calcium. When tested for bleaching in the manner described in E~ample I they are effective.

... ... ... . ...
_._ __ . ., ., _ _. . ., _ . 3 ~ rO

Tab le IV
Weight P_rc~nt_ C ompo-sition Photo- S~lr.. - ~loi.s- O~'rc~r No. activator ac~ant Builder ture Co~.~onents __ _ __ .
0 . 20o pa 10% sa 44~ ba l~L% :l. % ocl 0.2 ob 2 oc 2 0 . 015 pb 15 sb 8 bb 10 0 . 5 oa 2 bg 0.1 ob 15 bh 1 od 3 0.005 pc15 sc 20 bb 5 0.1 ob sm 10 bf 0 . 5 oe 10 hl 4 0.25-- pcl 20 sa22 bc 6 0.2 Oe :1. 0 sd 8 bg 0 . 25 pa30 se10 hb 8 0.1. ob O. 25 pe10 sli 10 bi 6 0 . 0:l.0pf ~0sb 10 bm 2 0.5 oa sl

7 0 . 40 pg1.2 sf40 ba 10 1 oc 3 sn10 bj bn

8 0.025 ph15 sa15 ba 4 0.1 o~
sg15 be 0 . 5 oh bg 10 oj

9 0 . 0 2 pi 12sh 50 ha 6 0 . 2 ob 1~ ' ~ 20 bk 0~15 pj2 sj 24 bd 7 10 oi 26 sp 4 bg 11 0.25 p~32 sc 0 11 1 oa 8 si 1 oc 12 0.05 pl14 sq 12 bn 61.3 0.5 ob 12 oc 0.1 o~
13 0.35 pm18 sc 0 12 0 .1 OI
4 so 14 0.0~ pn30 se --- 10 2 bj 0.1 ob ~.10 po17 sq 0 71.9 5 oc om 16 0.20 pp8 sm 0 61,a 0.3 ob sr 3 oc O n O 1 0 cJ
1~) o~
91 2 ol :~3~

Photoactivators .
pa tetrabenzo - a, ~, y, ~ --tetrakis (4-N~methyl) pyridyl porphine tetrai.odide pb tetrakis (carboxybenzo) porphine zinc, tetrasodium salt pc tetrakis (polyethoxy naphtho~ -a, ~, y, ~ - tetraphenyl porphine cadmium, -tetra-ammonium salt pd 1, 3, 5, 7 - tetrakis ~sulfato polyethoxy phenyl~ -a, 3~ ~f~ ~ - tetrakis (carboxy naphtllyl) porphine, octapotassium sal-t pe 1, 2, 3, 4 - tetrakis (phosphato phenyl) - c~, ~, y, ~ ~
tetraphenyl porphine, tetra (triethano:Lamine) salt pf dinaphtho - a, ~, y, ~S - tetrakis ~phos~.hat:o-benzo) porphine maynesium, tetrallthium salt pg 1, 3, S, 7 ~ tetraki.s (po:lyethoxy phenyl) - a, y ~
di(polyethoxy phenyl) porphine ph mono (polyethoxy benzo) ~t~ibenzo -a, ~, y, ~ -- tetraphenyl porphlne pi bromo, tetrabenzo - a - (4-N-methyl) ... pyridyl - ~, y, ~ - pyridyl porphine scandium monobrom.ide pj 2, 4, 6, 8 ~ tetrakis (sulfophenyl-n~hep-tyl) tetraaza porphine, tetra(monoe-thanolamine) salt pk -tetrakis - (2-sulfatoethyl aminosulfonylbenzo) ~ -tetraaza porphine zinc, tetra-sodium salt pl trans dichloro,- di (N-methvl ~vrido~ -a, ~, y, ~ - tetra];is (4~carboxyphenyl) porphine tin(IV), tetrasodium salt pm 1, 3, 5 - tri (4-polyethoxy) ~ a, ~, y - tri ~ (4~poly~
ethoxy) - ~ - aza - porphine pn 2, 4, 6, 8 ~ tetrakis (carboxy methoxy) ~ a, ~, y, ~ ~
tetraaza porphine, tetra(die-thanolamine) salt po tri (diphosphatobenzo~ - a ~ (phos-phatomethylbenzyl) - ~, y, ~ - triaaza porphine, tetrasodium salt pp tetra (carboxvbenzo) - a, y -di(carboxybenzo) - ~ diaza porphine zinc, hexa~
sodium salt 3~

Surfactan~s sa C~ branched chain alkyl benzene sulfonate (ABS)/
sodium salt s~ C12 linear alkyl benzene sulronate (L~S), sodi.um salt sc coconut alkyl sulfate, sodium salt sd beta-alkoxy alkane sulfonate containing 2 carbon atoms in the alkyl group and 16 carbon atoms in the alkane moiety se C16 paraffin sulfona-te, sodiu.m salt sf Cl~ al~ha olefin sulEonate, sodium salt sg Cl~ alpha sulEocarboxyla-te, sodium salt sh ethyl est~r o:E Cl~ alpha sul.cocarbo~ylate, so~ u.l sa:lt si -tallot~7 alkyl g:Lyce~.~yl ethex sul~onate, sod~um saLt sj -tallo~7 soap s~ alkyl polyethoxy alcohol sulfate having 11 carbon atoms in t:he alkyl group and 2 mols ethylene oxide per mol of alcohol, sodium sal-t sl alkyl phenol polyetho~Yy alcohol sul:Fate having 9 carbon atoms in the alkyl group and 10 mols ethylene oxide 20 . per mol of alkyl phenol 3 sodium salt sm alkyl polyethoxy alcohol having 16 carbon atoms in the alkyl group and 25 mols ethylene oxide per mol of alcohol sn ~olyethoxy polypropoxy glycol having a molecular ~7eisht of 5000, half of ~7hich represents the polypropoxy base and half o~ which represents hydrophilic polyethoxylate so dimethyl C12 amine oxide sp C16 alkyl dimethyl ammonio propan2 sulfonate sq C12 linear alkyl benzene sulfonate (I~S), triethanol-amine salt sr coconut alkyl sulfate, potassium salt ~uilde~s ba sodiun tripolyphosphclte bb socli~ pyrophospha-te bc sodi.um ni-tr:ilotriacetcLte bd citric acid be sodium carbonat2 bf sodium silicate solids, 2.0 ratio SiO2/Na2O
bg sodium silicate solids, 3.2 ratio SiO2/Na2O
bh sodium aluminosilicate ~;lal2(~1O2~SiO~)I2 ?.7 H,,O
bi potassium tetraborate bj sodium bicarbona-te bk potassium he~ametaphospha-te bl sodiurn orthophospha-te bm ethane-l~hydro,Yy~ diphosphonate, sodium salt bn potassium pyrophosphate Other ComPonents oa polyethylene glycol, molecular weight 6000 ob perfurne oc potassium toluene sulfonate od sodium sul~osuccinate oe sodium carboxymethylcellulose of optical brightener (fluorescer) oy colorant oh protease oi mon-tmorrilonite clay oj sodiu.~ perborate ok ethanol ol diethylene ~lycol monoethyl ether o,n triethanolarnine

Claims (20)

The embodiments of the invention in which an exclusive property or privilege is claimed are defined as follows:

1. A detergent bleach composition comprising an anionic, nonionic, semi-polar, ampholytic, or zwitterionic surfactant and from about 0.005% to about 0.5% by weight of the composition of a water soluble photoactivator having the formula wherein each X is (=N-) or (=CY-), and the total number of (=N-) groups is 4; wherein each Y, independently is hydrogen or meso substituted alkyl, cycloalkyl, alkaryl, aryl, alkaryl or heteroaryl; wherein each R, independently, is hydrogen or pyrrole substituted alkyl, cycloalkyl, alkaryl 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 M is a counterion to the solubilizing groups; wherein s is the number of solubilizing groups; and wherein substituted into. Y or R is B, a solubilizing group selected from the group consisting of (a) cationic groups, where M is an anion and s is from 1 to about 8; (b) poly-ethoxylate nonionic groups -(CH2CH2O)nH, where M is zero, s is from 1 to about 8, and sn ( the number of condensed ethylene oxide molecules per porphine molecule) is from about 8 to about 50; (c) proximate anionic groups attached to atoms no more than 5 atoms displaced from the porphine core, where M is cationic and s is from 3 to about 8; and (d) remote anionic groups attached to atoms more than 5 atoms displaced from the porphine core, where M is cationic and s is from 2 to about 8; provided that anionic sulfonate groups are remote and are no greater in number than the number of aromatic and heterocyclic substituent groups;

wherein said alkyl groups are comprised of simple carbon chains or carbon chains interrupted by other chain-forming atoms.

2. The composition of claim 1 wherein the solubilizing groups are cationic and are quaternary pyridinium or quaternary ammonium.

3. The composition of claim 1 wherein the solu-bilizing groups are anionic and are carboxylate, polyethoxy carboxylate, sulfate, polyethoxy sulfate, phosphate, poly-ethoxy phosphate, or remote sulfonate.

4. The composition of claim 2 wherein 5 is from 1 to about 4 and M is halide or toluene sulfonate.

5. The composition of claim 3 wherein the solubilizing groups are proximate, s is from 3 to about 4, and M is an alkali metal, ammonium or ethanolamine salt.

6. The composition of claim 3 wherein the solubilizing groups are remote, s is from 2 to about 4, and M is an alkali metal, ammonium or ethanolamine salt.

7. The composition of claim 1 wherein the solu-bilizing groups are nonionic and sn is from about 12 to about 40.

8. The composition of claim 1 wherein the weight ratio of photoactivator to surfactant is from about 1/10,000 to about 1/20;

9. The composition of claim 5 wherein the weight percent of the photoactivator in the composition is from about 0.01% to about 0.1%, the weight ratio of photo-activator to surfactant is from about 1/300 to about 1/60 and the chain-forming atoms are selected from the group consisting of C, O, N and S.

10. The composition of claim 6 wherein the weight percent of the photoactivator in the composition is from about 0.01% to about 0.1%, the weight ratio of photo-activator to surfactant is from about 1/300 to about 1/60 and the chain-forming atoms are selected from the group consisting of C, O, N and S.

11. The composition of claim 7 wherein the weight percent of the photoactivator in the composition is from about 0.01% to about 0.1%, the weight ratio of photo-activator to surfactant is from about 1/300 to about 1/60 and the chain-forming atoms are selected from the group consisting of C, O, N and S.

12. The composition of claim 9 wherein the surfactant is from about 10% to about 50% by weight of the composition and is selected from the group consisting of water soluble salts 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-l-sulfonate, beta-alkoxy alkane sulfonate, and soap; water soluble compounds produced by the condensa-tion of ethylene oxide with an alcohol, alkyl phenol, polyproxy glycol or polyproxy ethylene diamine; water soluble amine oxides, phosphine oxides, and sulfoxides;
water soluble derivatives of aliphatic secondary and tertiary amines; and water soluble derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium cationic compounds.

13. The composition of claim 10 wherein the weight percent of the photoactivator in the composition is from about 0.01% to about 0.1%, the weight ratio of photo-activator to surfactant is from about 1/300 to about 1/60 and the chain-forming atoms are selected from the group consisting of C, O, N and S.

14. The composition of claim 11 wherein the surfactant is from about 10% to about 50% by weight of the composition and is selected from the group consisting of water soluble salts 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-l-sulfonate, beta-alkoxy alkane sulfonate, and soap; water soluble compounds produced by the condensa-tion of ethylene oxide with an alcohol, alkyl phenol, polyproxy glycol or polyproxy ethylene diamine; water soluble amine oxides, phosphine oxides, and sulfoxides;
water soluble derivatives of aliphatic secondary and tertiary amines; and water soluble derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium cationic compounds.

15. The composition of claim 12 additionally containing from about 10% to about 60% of an alkaline detergent builder selected from the group consisting of water soluble alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates; water soluble aminopolycarboxylates, phytates, polyphosphonates, and polycarboxylates; and water insoluble aluminosilicates.

16. The composition of claim 13 wherein the weight percent of the photoactivator in the composition is from ahout 0.01% to about 0.1%, the weight ratio of photo-activator to surfactant is from about 1/300 to about 1/60 and the chain-forming atoms are selected from the group consisting of C, O, N and S.

17. The composition of claim 14 additionally containing from about 10% to about 60% of an alkaline detergent builder selected from the group consisting of water soluble alkali metal carbonates, borates, phosphates, polyphosphates, bicarbonates and silicates water soluble aminopolycarboxylates, phytates, polyphosphonates, and polycarboxylates; and water insoluble aluminosilicates.

18. A process for removing stains from textiles which comprises treating the textiles, in the presence of visible light and oxygen, with an aqueous solution of the detergent bleach composition of any of claims 1, 4 or 8.

19. The composition of claim 9, 10 or 11 wherein the surfactant is from about 10% to about 50% by weight of the composition and is selected from the group consisting of water soluble salts of alkyl benzene sulfonate, alkyl sulfate, alkyl polyethoxy ether sulfate, paraffin sulfon-ate, alpha-olefin sulfonate, alpha-sulfocarboxylates and their esters, alkyl glyceryl ether sulfonate, fatty acid monoglyceride sulfates and sulfonates, alkyl phenol poly-ethoxy ether sulfate, 2-acyloxy-alkane-l-sulfonate, beta-alkoxy alkane sulfonate, and soap; water soluble compounds produced by the condensation of ethylene oxide with an alcohol, alkyl phenol, polyproxy glycol or polyproxy ethylene diamine; water soluble amine oxides, phosphine oxides, and sulfoxides; water soluble derivatives of aliphatic secondary and tertiary amines; and water soluble derivatives of aliphatic quaternary ammonium, phosphonium, and sulfonium cationic compounds.

20. A process for removing stains from textiles which comprises treating the textiles, in the presence of visible light and oxygen, with an aqueous solution of the detergent bleach composition of any of claims 15, 16 or 17.