CA1126908A - Fabric bleaching and stain removal compositions - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
Improved fabric bleaching and stain removal are achieved by use of a composition comprising a photo-activator and a cationic substance. The photoactivator is a tetra-aza porphine, solubilized with anionic, nonionic and/or cationic substituent groups, and metal free or metallated with Zn(II), Cd(II), Mg(II), Sc(III), or Sn(IV). The cationic substance is preferably one that, in a la?dry bath, itself performs a desired function such as acting as fabric softener, electrostatic control agent, surfactant, or germicide.

Description

~Z~9~8 BACKGROUND OF THE INVENTION
This invention relates to household laundry processes having improved effectiveness for fabric bleachiny and for simultaneous removal of stains and fugitive dyes and is a divisional of Canadian Application Serial No. 319,431 filed January 10, 1979.

~.' 9~ .

.

-~269~)8 -! ITnited States Patent 3,927,967 granted to Speakman on December 23, 1975 related to a household washing and bleaching process for cotton fabrics utilizing photoactiva-ting compounds, principally sulfonated zinc phthalocyanine, in the presence of visible light and atmospheric oxygen.
Japanese Patent application OPI 50-113,479 assigned to The Procter & Gamble Company, laid open to the public on September 5, 1975, invented by Holcombe and Schultz, teaches the use of specific mixtures of sulfonated zinc phthalocya-nine species, principally tri- and tetra-sulfonates, as pre-ferred bleach photoactivators. In the foregoing references the detergent compositions utilizing sulfonated zinc phthalo-cyanine contained organic surfactant, anionic or nonionic and alkaline builder salt.
Belgian patent No. 840,348 invented by Wiers, granted on October 4, 1976 discloses the use of zinc phthalo-cyanine tri- and tetra-sulfonates as bleach photoactivators in unbuilt liquid detergent compositions containiny nonionic, anionic, zwitterionic, or ampholytic sur~actants.
British F'atent 1,372,036 invented by Speakman and available to the public on October 30, 1974 describes a wash--ing machine provided with a source of visible light which irradiates wash liquor containing phthalocyanine photoactiva-tor 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 certain porphines as catalysts for the photo-oxidation of olefins.

.

~Z690~

References to carboxylated porphines have appeared in U.S. Patent 2,706,199 issued 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, in-vented by Mayhew; and British patent ~76,691 published September 6, 1961, issued to Geigy A.G. See also Color Index Mo. 74350. Other substituted porphines are disclosed in Austrian patent 267,711 issued January 10, 1969, invented by Wimmer; French patent 1,266,094 published May 29, 1961, in-vented by Tartter et al; U.S. Patent 2,670,265 issued February 23, 1954, invented by Heyna et al; British Patent 471,418 accepted August 30, 1937, invented by Groves; and JCS 1938, 1-6 authored by Dent.

~269~8 Sakkab, U.S. Patents 4,256,597 and 4,256,598 disclose the use of many species of porphine photoactivators other than sulfonated phthalocyanines in combination with anionic, nonionic, semi-polar, ampholytic or zwitterionic surfactants.
The two patents referred to supra disclose new compos-itions that provide improved fabric whiteness by three different means: stain removal; oxygen bleaching of overall discoloration; and removal of fugitive dyes.
It has now been found that porphine photoactivators are especially useful in laundry baths in combination with cationic substances. These cationic substances are known to the laundry arts and, depending on the nature of their chemical structures, are useful in one or more of the following ways: as softeners or as electrostatic control agents for fabrics, as surfactants, or as germicidal or sanitation agents.
It is well known that cotton surfaces are negatively charged; and her,ce positively charged, i.e. cationic substances have a strong a~einity ~o~ cotton Çabrics and a strong tendency to adsorb or deposit thereon. In so doing they tend to bring down or co-adsorb other substances present in the laundry bath, such as the photoactivators of 1~269~8 this invention. Greater deposition of photoaetivator means greater effeetiveness of a given amount of photoactivator which represents an economic advantage to both producer and consumer and more efficient utilization of natural resourees, and which after use and waste disposal has a reduced impact upon the ecology of the environment.
The foregoing objects of this invention ean be accomplished by any convenient laundry process which involves exposure of fabrics to a composition of this invention, .
exposure to visible light and oxygen either simulaneously or thereater. For example, photoactivator and cationic surfaetant can be present together in the laundry pre-soak or alternatively in the laundry wash; or the photoactivator and a cationie fabrie softener or antistatie agent ean be present toc3ether in the laundry rinse; or the photoactivator and a eationie germieide ean be present together in one of the foregoing washes or in a separate treatment bath. Exposure to light and oxygen ean take place during the above reeited proeessiny step or ean oecur durincJ a separ,lte, subsequent, proeessing step such as drying out of doors, especially in direct sunlight as on a elothesline.

5 _ 1~1269~8 S UMMARY OF TH E I NVE NT I ON
This invention relates to a bleach composition com~
prising a cationic substance and from 0.001% to 0.5% by weight of the composition of a water soluble photo-activator having the formula R2 R.

S ~ ~ ) S
l ~`X~I~s R ~ r, 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, aralkyl, aryl, alkaryl or heteroaryl; wherein each R, indepen-dently, is hydrogen or pyrrole substituted a].kyl, cyclo alkyl, aralkyl, aryl, al.karyl or heteroraryl, or whereln adjacent pairs of ~'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), Ca(II), Cd(II), Mg(II), Sc(III), or Sn(IV); wherein B is an an.ionic, nonionic or cationic solubilizing group substituted into Y or R; wherein M is a counterion to the solubilizing groups; and wherein s is the number of solubilizing groups.

_ ~ _ Preferred cationic solubilizing groups are quaternary pyridinium and quaternary amrnonium groups.
Preferred anionic solubilizing groups are carboxylate, poly-ethoxy carboxylate, sulfate, polyethoxy sulfate, phosphate, polyethoxy phosphate, and sulfonate. Preferred nonionic solubilizing 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 polyethoxyla-te nonionic solubili~in~ groups -(C~l2CH20)nH, M is zero, s is ~rom 1 to about 8, and N =(sn)= the number o~ (condensed ethylene oxide molecules per porphine molecule) is from about 8 to about 50. For anionic groups M, the counterion, is cationic. For anionic groups attached to atoms no more than 5 atoms displaced from the porphine core, i.e. for "proximate" anionic groups as defined herein, s is from 3 to about 8. For anionic groups attached to atoms more than 5 atoms displaced from the porphlne core, i.e. for "r.emote" anionic groups as defined herein, s is from 2 to about 8. ~or sulfonate groups their nurnber is no greater than the number of aromatic and hat~_ocyclic 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 cati.onic, anionic, and/or nonionic solubilizing groups can be present on an individual photoactivator molecule.

1~6~

In the foregoing descripti.on, the term "alkyl" is defined.to.be not only ~ simple. carbon chain but also a carbon chain interrupted by other chain-formi.ng atoms, such as 0, N or S. Non-limiting examples of such interruptions are those of the following groups:
O
ether - O -, ester - CO -, 0 1~0 amide - C - NH -, and amino sulfonyl - NH - S -.
' The cationic substance which is a part of.the compositions of this invention is preferably one that, in a laundry bath, itself performs a desirecl function such as actiny as fabric softener, electrostatic control agent, sur-factant, or germicide.

1~269~
DETAILED DESCRIPTION OF THE INVENTION
The essential components of the instant invention are two in number. One is a cationic substance. The cationic substance is preferably used at levels from about 0.5% to about 50% of the composition by weight, more preferably at levels from about 2% to about 30%. The weight ratio of cationic substance to the photoactivator, the other essential component of this invention, is preferably from about 1/1 to about 50,000/1, more preferably from about 20/1 to about 5,000/1.
The cationic substance is preferably one that, in a laundry bath, itsel performs a desired function such as active as fabric softener, electrostatic control agent for fabrics, surfactant, or germicide. These functions are well known in the prior art, and one skilled in the art can select them in the usual manner. ;
Cationic substances having the capacity to _ondition fabrics as by softening and/or by controlling electrostatic effects on fabrics during laundering have been described in numerous patent disclosures, or example U.S. Patent 3,756,950 issued Gluck on September 4, 1973;
U.S. Patent 3,904,533 issued to Neiditch on September 9, 1975, and Okamoto et al, Japanese patent publication 42-15596 published August 28, 1967.
Preferred cationic fabric conditioners and anti-static agents include:
(a) quaternary ammonium salts having the following structure:
_ g _ ~Z69~8 f :
+

~ R3 Rl -- 'I R2 X

wherein Rl is hydrogen or an aliphatic group having from 1 to 22 carbon atoms; R2 is an aliphatic group having from 10 to 22 carbon atoms; R3 and R4 are each alkyl groups having from 1 to 3 carbon atoms; and X is an anion selected from the halogen, acetate, phosphate, nitrate and methylsulfate radicals.
Representative examples of quaternary ammonium softeners of the invention include tallow trimethyl ammonium chloride; ditallow dimethyl ammonium chloride; ditallow dimethyl ammonium methyl sulfate; dihexadecyl dimethyl ammon-ium chloride; di(hydrogenated tallow) dimethyl anmonium chloride; dioctadecyl dimethyl ammonium chloride; dieicosyl dimethyl ammonium chloride; didocosyl dimethyl ammonium chloride; di(hydrogenated.tallow) dimethyl ammonium methyl sulfate; dihexadecyl diethyl ammonium chloride; dihexadecyl dimethyl ammonium acetate; ditallow dipropyl ammonium phosphate; ditallow dimethyl ammonium nitrate, and di (coconut-alkyl) dimethyl ammonium chloride.

l~Z69t~8 An especially preferred quaternary ammonium fabric conditioning agent is ditallow dimethyl ammonium chloride that is commercially available from General Mills, Inc. under the trade mark ALIQUAT-2HT and from Ashland Oil, Inc. as ADOGEN 448.
(b) quaternary imidazolinium salts having the following structure:

_ +
.' H H

H - C - C - H O

N N - C2~4 - N - C - R7 X

wherein R6 is an alkyl group having from 1 to 4, prefer-ably from 1 to 2 carbon atoms, R5 is an alkyl group having from 1 to 4 carbon atoms or a hydrogen radical, R8 is an alkyl group having from 1 to 22, preerably at least 15 carbon atoms or a hydrogen radical, R7 i5 an alkyl group having from 8 to 22, preferably at least 15 carbon atoms, and X is an anion, preferably methylsulfate or chloride ions. Other suitable anions include those disclosed with reference to the cationic quaternary ammonium fabric antistat/softeners ~r~
, ~ lD

~lZ69~)8 described hereinbefore. Particularly preferred are those imidazoliniur,l compounds in which both R7 and R8 are alkyl groups having from 12 to 22 carbon atoms, e.g., l-met,hyl-l-[(stearoylamide)ethyl]-2-heptadecyl-4,5-dihydroimidazolin-ium methylsulfate and l-methyl-l-[(palmitoylamide)ethyl]-2-octadecyl-4,5-dihydroimidazolinium chloride.
An especially preferred quaternary imidazolinium fabric conditioning agent is 2-tallow-1-methyl-1-(tallow-amidoethyl) imidazoline methylsulfate having the structure:

- lla -,.~

~Z69~8 H C CH +
l ¦ O CH3SO4 ~ /\

R _ wherein R is an alkyl group derived from tallow. This material is commercially available from the Ashland Oil Co. under the trade mark VARISOFT-445.

(c) Polyamido quaternized biurets having the following structure:
_ . _ , :.

O A +

R - C - NH - (CH2)m - N - (CH2)m 11 C = O O X~
NH
O C=O O

. R - C - NH - (CH2)m - N - (CH2)m wherein R is an aliphatic hydrocarbyl group (saturated or unsaturated), a substituted aliphatic hydrocarbyl group, or an alkoxylated aliphatic hydrocarbyl group having from ,,..~1 ,., ~ .

~1269Q8 about 10 to 30 carbon atoms. Preferably, the number of carbon atoms is from about 12 to about 22 with R being an aliphatic hydrocarbyl group. Most preferably, R is derived from fatty acids, particularly from tallow fatty acid, which acid has predominately 16 to 18 carbon atoms.

A is a vicinal dihydroxy alkyl group containing at least 3 carbon atoms, preferably from 3 to about 8 carbon atoms; especially preferred is the 2,3- dihydroxy propyl group. Values of m range from 1 to about 8, preferably 2 or 3. X is an anion selected from the halogen, acetate, phosphate, nitrate and methylsulfate radicals.
Materials fitting the above-given formula where A
is 2,3-dihydroxy propyl, R is an alkyl group derived from tallow, m is 2, and X is Cl, and containing minor amounts of starting materials and other reaction products, are sold under the name TAFLO ~-320A by Daiichi Kogyo Seiyaku Co., Ltd. of Japan. The manufacture of such materials is described in Okamoto's Japanese Patent ~ublication 42-15596 referred to hereinbefore.
(d) alkyl (C12 to C22)-pyridinium chlorides, (e) alkyl (C12 to C22)-alkyl (Cl to C3)-morpholinium chlorides, and (f) ~uaternary derivatives of amino acids and amino esters.

_ l3 _ ,1~ . .

, ~Z69~8 AS disclosed in U.S. Patent 4,222,905, invented by Cockrell and U.S. Patent 4,259,217 invented by Murphy, under appropriate circumstances cationic surfactants are highly effective soil removal agents. As described in the two patents cited above, cationic surfactants can be advantageously used in combination with nonionic surfac-tants: this fact is however not material to the practice of the instant invention. The enhancement of photoactiv-ator deposition takes place in the presence of cationic surfactant and is essentially independent of the presence or absence of nonionic surfactants: for purposes of this invention the latter can therefore be considered merely an optional component.
The cationic surfactants of Cockrell and Murphy applicable to the instant invention have the formula RlmR2XYL Z

wherein each R1 is an organic group containing a straight or branched alkyl or alkenyl grôup optionally subs~ituted with up to 3 phenyl groups and optionally interrupted by up to 4 structures selected from the group consisting of O ~ , -C-O-, -O-C-, -C-N, -N-C-, -O-, _ l4 _ ,,, .~lE3~

l~Z69~8 and mixtures thereof, and which contains from about 8 to 22 carbon atoms, and which may additionally contain up to 20 ethoxy groups, m is a number from one to three, no more than one Rl in a molecule can have more than 12 carbon atoms when m is 3, each R2 is an alkyl or hydroxyalkyl group containing from 1 to 4 carbon atoms or a benzyl group with no more than one R2 in a molecule being benzyl, x is a number from 0 to 3, the remainder of any carbon, nitrogen, sulfur or phosphorus atom positions being filled by hydrogens, Y is selected from the group consisting of llZ6g~8 (1) - N

\ / I
(2) - N - C -- C j , ..
,.
N - C -

(3) - p+ _

(4) - S

(5) - N - , wherein p is from 1 to 20, (C2H4)pH

C

(6) C ~ N

C C
~ C
I

C

(7) N N
Il +l C C , and N

(8) mixtures thereof, L is a number from 1 to 10, Z is an anion in a number to give electrical neutrality.
- 15a -~Z~9~3 In cationic surfactants preferred in the practice of the instant in~ention, z is a halide, methylsulfate, toluene sulfonate, hydroxide or nitrate ion, particularly preferred being chloride, bromide or iodide anions. In certain pre-ferred cationic surfactants, L is equal to 1 and Y is as defined in paragraphs (1), (2) or (5) supra; in other pre-ferred cationic surfactants more than one cationic charge center is present and L is greater than 1, as in the substance In preferred cationic materials, described above, where m is equal to 1, it is preferred that x is equal to 3, and R2 is a methyl group. Preferred compositions of this mono-long chain type include those in which Rl is a C10 to C20 alkyl group. Particularly preferred components of this class include C16 (palmityl) trimethyl ammonium halide and C12 (coconut alkyl) trimethyl ammonium halide.
Where m is equal to 2 it is preferred that x i~ equal to 2, and that R2 i5 a methyl group. In this instance it is aLso preferred that Rl is a C10 to C20 alkyl group.
Particularly preferred cationic materials of this class include distearyl (C18) dimethyl ammonium halide and ditallow alkyl (C18) dimethyl ammonium halide materials.
Where m is equal to 3, only one of the Rl chains can be greater than 12 carbon atoms in length. The reason for this l~Z69~8 ; chain length restriction is the relative insolubility in water of these tri-long chain materials. Where tri-long chain materials are used, it is preferred that x i5 equal to l and that R2 is a methyl group. In these compositions it is preferred that Rl is a C8 to Cll alkyl group. Particularly preferred tri-long chain cationic materials include trioctyl (C8) methyl ammonium halide and tridecyl (C10) methyl ammon-ium halide.
Another particularly preferred type of cationic surfactant useful in the compositions of the present inven-tion is of the imidazolinium variety. A particularly pre-ferred surfactant of this type is one having the structural formula l N - CH

R - C~ ¦ Z

wherein R is ClO to C20 alkyl, particularly Cl~ to C20 alkyl.

Another type of preEerred cationic surfactant for use in the compositions of the present invention are the alkoxylated alkyl quaternaries. Examples of such compounds are given below:

~ R-N -(C2H4)pH H(OC H ) N+ (C H O) H Z~
R R

wherein p is from 1 to 20 and each R is a C10 to C20 alkyl group.

.~

~lZ69~8 A particularly preferred type of cationic component, which is described in U.S. Patent 4,260,529, Letton, has the formula:

R -(Z )a~(R3)n-Z2-(CH2)m~~ -R X

wherein Rl is Cl to C4 alkyl or hydroxyalkyl; R2 is C5 to C30 straight or branched chain alkyl or alkenyl, alkyl phenyl, or X Rl - N-(CH2)s; wherein s is from 0 to 5;
Rl R3 is Cl to C20 alkyl or alkenyl; a is 0 or 1; n is 0 or 1; m is from 1 to 5; zl and z2 are each selected from the group consisting of O O O O l-l H O O El H O
Il ll 11 il I 1 11 11 1 1 11 .
-C-O-, -O-C-, -O-, -O-C-O-, -C-N-, -N-C-, -O-C-N, -N-C-O-, and wherein at least one of said groups is an ester, reverse ester, amide or reverse amide; and X is an anion which makes the compound at least water-dispersible, preferably selected from the group consisting of halide, methyl sulfate, and nitrate, preferably chloride, bromide or iodide.

` ~ llZ~9~8 Other preferred cationic surfactants of this type are the choline ester derivatives having the following formula:

R -c-o-cEl2c~2-N -CE13 X

as w~ll as tho~e cormpound5 ~/hercin the ester lin]i.ye in the above formula is replaced with a reverse es-ter, amide or rt~vers~ amide linkacJe.
Particularly preferred exampl~s o.~ this type oE cationic surfactant, inclucle stearoyl choline ester qua-ternary ammoniutn halides (R2 = Cl7 alkyl), palmitoyl cholille ester qu~ternary amrnoniurn halides (R2 = Cl~ alkyl), my.ristoyl chol.:ine tster .cluatern~ry amrnon~ un ha'Licles ~R2 = C L3 a].1;yl), :Lauroyl choline et,ter amrnon:;urtl11alides (R~ - Cll al~;yL), and tallowyl .choline c~s~er qua~ern~ry a1nmonium halides (R2 - Cl5-Cl7 alkyl).
~ddit:lonal preEerred cationic components of the choline ester variel:y are cJiVen ~y the structur~l i.orrnulas ~elo~, wherein p may ~ fro1ll 0 to 20.

.. ~
O O Cfl R -O-C-(C112)p-C-o_cll2c~l2_N~-c113 X-c~3 1~269~8 CH3 l CH3 X- CH +N-CH -CH2-0-C- (CH2) p-C-O CH2 2 1 3 The preferred choline-derivative cationic sub-stances, discussed above, may be prepared by the direct esterification of a fatty acid of the desired chain length with dimethyl-aminoethanol, in the presence of an acid catalyst. The reaction product is then quaternized with a methyl halide, forming the desired cationic material. The choline-derived cationic materials may also be prepared by the direct esterification of a long chain fatty acid of the desired chain length together with 2-haloethanol, in the presence of an acid catalyst material. The reaction product is then used to quaternize trimethylamine, forming the desired cationic component.
Another type of novel, particularly preEerred ]5 cationic materia], described in U.~. Patellt 4,228,042, Letton, has the formula R2 Rl' R3-o[(CH)n]y~(Z )a~(R )t-Z -(CH2)m-N -R X
R

~,,,l~i l~Z69Q8 In the above formula, each Rl is a Cl to C~ al~yl or hydroxy-alkyl ~roup, preferably a methyl group. Each R2 is either hydrogen or Cl to C3 al~l, preferably hydrogen. R3 is a C~ to C30 straight or branched chain alkyl, al~enylene, or alkyl benzyl ~roup, preferably a C8 to C13 alkyl group, ~ost preferably a C12 al~l group. R4 is a Cl to C10 alkylene or alkenylene group. n is from 2 to 4, preferably 2; y is from 1 ~o 20, prcferably from about 1 to 10, most preferably about 7; a may be 0 or 1; t ma~ be 0 or 1; and m is from 1 to 5, preferably 2. ~. arld Z are each selected from the ~roup consistinc~ of O O O O El ~ O O 11 H O
Il 11 11 11 1 1 11 11 1 1 11 ~C-O-, -C , -O~, -O-C-O-,-C-N-, -N-C-, -O-C-N-, -N-C-O- , and wherein at leclst one of said groups is selected from the 'group consisting of es-ter, reverse ~ster, c~lnide canr~ revers~
amide. X is an ~ni.on wllich w.ill m~ke the colnpo~lrld rlt least water-dispersible, and is selectcd from the ~Jroup consisting o halides, methyl sulfate, and nitrate, particulclrly chloride, bromide and iocli.de. ~lixtures oE the above structures can also be used.
Preferred embodiments of this type of cationic component are the choline esters (Rl is a me-thyl group and %2 is an ester or reverse ester ~roup), particular exam}?les o~ which are ~iven helow, in which t i5 0 or 1 and y .~s ~rom 1 to 20.

1~269~8 O CII

3 2 2 y (2) t C O CEI2 CE12 I CH3 X

OCH

3 R (CEl2cH2) y~C~CE12~N -CH X

CE13-r~ ~ -O (CHC1-120) y~C--CE12~N~CH3 X

CE13 Cll 3 3 1 1 +
C~13--R -O (CllcH2O) y~ (CEI2 ) t~C-O-CH2-C112-N -Cll X
C~13 O O C~ll, r C113-~ -O (Ctl2(:E12O) - C- (Cll ) -C-O-CII Cll -N Cll X~
].~ C113 O I ~
Cl-l -R -O (CE~2cEl2cEr2cEl2O) y C C 2 1 3 O . -.. CEI
cH3-R -O (CEl2crl2cEl2cEr2o) y- (C~r2) t-c-o-cEl2cEl2-N --CEI3 X

11269~8 O ~1 ~1 0 C~l 3 ~ 11 1 3 CE13-R -O(C~12C1120) -C-C-C-C-O-CH C~ -N -Cll X~

. The preferred choline der.ivates, described above, may be p.repared by the reaction of a lon~ chain alkyl polyalko~y (preferably po].yethoxy) carboYylate, havin~ an al]~yl chain o~ d~s:Lred lenyth, w1.th oxalyl chloride, to form the corres-ponding acid chloride. I'he acicl chloxide is -then reacted with dimethylaminoethanol to form the appropriate am~ne ester, which is then quaternized with â methyl hali.de -to form the desired choline ester compound. ~nother way of preparing thesQ compour.ds is bv the direct esteri.fication of the appr~-priate long chain etho.Yylatt_d carboxylic acid to~ether with 2-haloethanol or d.imethyl aminot~thanol, irl th~ p~l3sence o~
heat and an ac;.d catalyst. 'l'he .~-~actlolt product EoJ:med is then quaterllizetl w:ith methylhalide or used to quaternize tr:i-methylamine to forrn the desired choline ester cornpound.

112~9~8 Cationic substances are also well known fGr their biological properties for control of microorganisms such as bacteria, fungi, algae, spores, viruses, protozoa, and the like.
Accordingly the prior art has taught the use of compositions containing cationic substances as germicides, bactericides, bacteristats, antiseptics, fungicides, etc. Typical disclosures of this kind are U.S. Patent 2,295,504 granted to Shelton on September 8, 1942; U.S. Patent 2,479,850 granted to Marks on August 23, 1949; U.S. Patent 2,666,010 granted to Stayner on ~anuary 12, 1954. The term antiseptic/germicide will he used here.inaf~er to broadly refer to all of the biological functions mentioned above.
Preferred cationic substances for the control of microorganisms are in categories:
(a) quaternary ammonium salts having the following structure 3 1 ~
¦R1 1 ~2 ¦ ~

where Rl has from about 9 to about 26 carbon atoms and is a hydrophobic group which is alkyl, aryl, alkaryl, aralkyl or alkyl heterocyclic; saturated or unsaturated; the alkyl chain of which is straight or branched; unsubstituted or substituted with ha].ogen, hydroxy, amino, ester, or ether groups;
where R2~ R3 and R4 each have from 1 to about 9 carbon atoms, and are the same or different, and have combined a total of from 3 to about 15 carbon 13 2~998 atoms in groups which are alkyl, aryl, alkaryl, aralkyl or heterocyclic; saturated or unsaturated;
the alkyl chains of which are straight or branched;
unsubstituted or substituted with halogen, hydroxy, nitro, amino, sulfonamide, ester or ether groups;
and where X is an anionic solubilizing group.
Especially preferred cationic substances in this category are those where Rl has from about 12 to about 20 carbon atoms and is straight chained;
wherc R2 and R3 are, lndependently, methyl or ethyl; where ~ is methyl, ethyl, benzyl or chlorobenzyl and where X is inorganic such as halide,.nitrate, sulfate, hydroxide, methyl sulfate, toluene sulfonate, and carbonate, phosphate or organic such as acetate, propionate, benzoate, tartrate, citrate, and salicylate.
By way of exemplification and not of limitation, among .the cationic substances in this category are N-myristyl-N-trimethyl ammonium chloride, N~cety:L--N-diet~hyl ammoniurn bromide, N-oleyl-N-hexyl~N-dime-thyl ammonium iodide, N-hydroxy stearyl-N-diethyl-N-methyl ammonium sulfate, N-decylbenzyl-N-dimethyl ammoniurm propionate, N-benzyl tetradecyl-N-diethy]. ammonium salicylate, N-dodecyl furyl-N-dimethyl ammonium methyl sulfate, N-methoxy palmityl-N-thioazyl-N-dimethyl ammonium nitrate, N-lauryl~N-dimethyl-N-benzyl ammonium hydroxide, N-behenyl-N-diethyl-N-chlorbenzyl ammonium phosphate, N-para-tertiaryoctylphenoxyethoxyethyl-N-dimethyl-N--benzyl ammonium chlor.ide, N-cetylaminophenyl-N-trimethyl arnmonium methosulfate, and N-cetyl-dimethyl-nitrobenzyl ammonium chloride.

l~Z6~8 (b) Quaternary salts having the structure _ _ +
C U
Rl - N = C

where R1 and X are the same as defined immediately hereinbefore in paragraph (a) and U is an unsaturated heterocyclic group, unsubstituted or substituted with a short chain alkyl group.
Especia].]y preferred cationic substances in this category are those where Rl has from about lO
to about 20 carbon atoms and is straight chained and where the heterocyclic group is pyridine, picoline, qu;noline, quinaldine, thioazole, pyrrole, imidazole, pyrazole, oxazole, pyrazine, pyridazine, or pyrimidine.
By way of exemplification and not of limitation, among the cationi.c substances in t}liS category are N-octyl picolinium chloride, N-tetracosyl imidazolinium bromide, and N-palmityl pyridinium benzoate;
(c) Quaternary salts having the structure Rl - N - C X

_ _ where R, R2 and X are the same as defined here-inbefore in paragraph (a); and S is a saturated heterocyclic group, unsubstituted or substituted with a short chain alkyl group.

l~Z69~8 Especially preferred cationic substances in this category are those where Rl has from about 10 to about 20 carbon atoms and is straight chained and where the heterocyclic group is piperidine, piperazine, pyrrolidine, indoline, imidazolidine, pyrazolidine, or morpholine.
By way of exemplification and not of limitation, among the cationic substances in this category are decyl methyl piperidinium chloride, stearyl hexyl indolinium acetate, and N-dodecyl-N-methyl mor-pholinium methyl sulfate.
It is readily apparent that the foregoing recitation of cationic substances having the function of fabric softener/
antistatic agent; surfactant; and ant.iseptic/germicide;
respectively, are not mu-tually exclusive. Certain cationic substances have the capability of performing two,or even three f these functions.

1~269Q~3 ( The other essential component of the instant inven-tion is a photoactivator as described hereinbelow. This com-ponent 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 [S]

porphine Nil N
llC CH
~ N HN ~
~`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 porphyrin. This structure is sometimes reEerred to herein as the porphine 'corc', because the photoactivators of this invention are species of subsituted porphines.
One form of substitution involves substituting 1, 2, 3, or 4 aza groups (=N-) for the methine groups (=C_-) in porphine. As an example of conventional nomenclature, a compound having 3 aza groups and one methine group is referred to as triaza porphine.

'~, ~1269~3 e - Another form of substitution involves substituting for one or more of the hydrogen atoms attached to the carbon atoms in the pyrrole rlngs of porphine. This can be substi-tution by an aliphatic or aromatic group, or can be ortho-fused polycyclic substitution as for example to form benzene or naphthalene ring structures. The compound having the com-mon 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 tetra-benzo tetraaza porphine, and has the structure which follows.
The numbers designate the positions of pyrrole substitution according to conventional nomenclature.

c~ ~ phthalocyanine NH N

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

Z69~8 ( replacement of the two hydrogen atoms attached to two diagonal-ly 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 sulfonate group into the photoactivator molecule.
The various forms of substitution described above can be illustrated by the compound 3-phenyl-2,7-disulfophenyl-~, y-diaza-~-benzofuryl- ~-sulfobenzofuryl porphine zinc, trisodium salt, which is within the scope of this invention:

SO3Na ~U]
~' .
N~ SO3Na n C 4 ~ SO3Na With the foregoing cxplanation as prelude, it is now possible to describe in detail the photoactivators of this invention. Referring to the structure shown hereinbefore in the SUMMARY OF THE INVENTION, effective photoactivators which are within the scope of this invention contain 0, 1, 2, 3 or 4 aza groups [and, according to the nomenclature defin-ed above, contain 4, 3, 2, 1 or 0 methine groups, respectively].

The groups designated as R's in the structural formula above can, independently, be hydrogen or pyrrole ii269i3 8 f substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl, or heteroaryl. Adjacent pairs of R's can also be joined togeth-er with ortho-arylene groups to form alicyclic or heterocy-clic rings. Benzo substitution is especially preferred; i.e.
Rl and R2, R3 and R6, and/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 10 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 prefer-red that Y is H, phenyl, naphtyl, thienyl, furyl, thioazyl, oxazyalyl, indolyl, benzothienyl, or pyridyl. No meso sub-stitution at all or tetra phenyl meso substitution are especially preferred.
In the foregoing description, the term "alkyl" is defined to be not only a simple carbon chain but also a 20 carbon chain interrupted by other chain-forming atorns, such as O, N or S. Non-limiting exarnples of such interruptions are those of the following groups:

~lZ69~8 o o o Il ,. ,, ether - 0 -, ester - C0 -, reverse ester - C0 -, carbonyl - C -, O O
1~ "
amide - C - NH -, reverse amide - NH - C -, amino sulfonyl - NH - S -, and sulfonamido - S - NH -.
Il O O

The photoactivating compounds of the instant invention can be unmetallated, A in the foregoing structural formula being comprised of two hydrogen atoms bonded to diayonally opposi.te inner nitrogen atoms of ~he pyrrole yroups in the molecule [The characteristic structure of unmetallated compounds is illustrated by compounds [S] and [T] illustrated hereinbefore; these compounds are not, ho~ever, within the scope of this invention because they lack essential substituent groups as herein described.]
~lternatively, the photoactivators of this invention can be metallated with zinc(II), cadmium(II), magnesium(II), scandium(III), aluminum(III), or ~in(IV). Thu~, ~ltogether, A can be 2(H) atoms bonded to diagonally opposite N atoms, or Zn(II), Ca(Ir)~ Cd(II), Mg(II), Sc(III), Al(III) or Sn(IV).
It is preferred that A be 2(ll) or Zn(II).
Solubilizing groups can be located anywhere on the porphine molecule other than the porphine core as 25 hereinbefore defined. Accordingly the solubilizing yroups can b described as substituted into Y or R as hereinbefore defined.
Solubilizing groups can be anionic, nonionic, or cationic in nature. Preferred anionic solubilizing groups are carboxylate 1l "
- C ~ ; sulfate - 0 ~ S - ~ ;

O

1~269~8 o o phosphate - O - P - O ; and sulfonate - S - O .

OH O

Other preferred anionic solubilizing agents are ethoxylated derivatives of the foregoing, especially the polyethoxysulfate group - (CH2CH20)nS03~ and the polyethoxy carboxy]ate group -(CH2CH2O)nCO ~ where n is an integer from l to about 20.
For anionic solubilizing groups, M the counterion is any cation that confers water solubility to the porphine moleoule. ~ monovalent cation is preferred, especially ammonium, ethanolammonium, or al~ali metal. Sodium is most preferred. For reasons described hereinafter the ~ mbe.
of anionic solubilizing groups operable in the ccmpositlons of this invention is a function of the location of such groups or the porphine molecule. A solubilizing group attached to a carbon atom of the photoactivator molecule displaced more than 5 atoms away from the porphine core is sometimes herein referred to as "remote", and is -to b~ distinguish~d from an attachment to a carbon atom displaced no more than 5 atoms from the porphine core, which is sometimes referred to herein as "proximate". For proximate solubilizing groups, the number of such groups per molecule, s, is from 3 to about 8, preferably from 3 to about 6, most preferably 3 or 4. Eor remote solubilizing groups, s is from 2 to about 8, preferably from 2 to about 6, most preferably 2 to 4.
Preerred nonlonic solubilizing groups are poly-ethoxylates -(CH2CH2O)nH. Defining s as the number of solubilizing groups per molecule, the number of condensed ethylene oxide molecules per porphine molecule is N = sn.

: .
.. , i , - ~ : - :: - -. ,:

~Z~9~8 The water soluble nonionic phbtoactivators of t~is invention 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 counterion and accordingly M is numerically equal to zero.
Preferred cationic soluhilizing groups are ~uaternary compounds such as quaternary ammonium salts ,~

Rl ,. R2 -- I
and quaternary pyridium salts ~ ~ R!
where all R's are alkyl or substituted alkyl groups.
For cationic solubilizing groups, M the counterion is any anion that confers water solubility to the porphine molecule. A monovalent anion is pre~erred, especially iodide, bromide, chloricle or toluene sul~ona~e Cl-13 ~ so3~ ' For reasons ~hat are described hereinafter, the number of cationic solubiliziny yroups can be from 1 to about 8, preferably from about 2 to about 6 r most preferably from 2 to ~-_ 3a _ ~lZ69~8 .Photoactivator usage in the compositions of this inven.ion can be from about 0.001% to aboutØ5% by weight of the com~osition~ Preferable usage :is from about 0.005 to about 0.1~ by weight of the composition.
Although it is not wishe~ to.be bound b~. theor-~, it is believed that.th~ nature oE this invention can be ~ore clearly understood by postulating the mechanism of hleac ~ using the instant photoactivators. Re~erring to ,scheme ~, the photoactivator in the upper :le~t hand corner .is ln a~ueous solution and is in its yround state~ Reaction (1), entitled 'adsorption', indicates that dissolved photo-activator is in part adsorbed on fabrics. Reaction (2) sugyests that photoac-tivator 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 surf ces.

~1269~38 Reaction Scheme A

MECHANISM OF BLEACHING
P/A = Photoactivator O = an Oxygen atom hv = visible light radiation ISC = intersystem crossing \dimerization dimer ground state;
in solution adsorption @~ .
adsorbed on fabric hv ~ \

1 ~ , excitation @~1 \
excited ~ C
singlet 3 ~ + 302 ~ ~ + 102 / excited ground ~round excited state;
/ state; state; sta-te singlet triplet triplet / STAIN
reactions ~ ~
chemical bleaching 1 , OXIDIZED
STAIN

- 35a -~Z69~!8 ~ eaction (3) illustrates that photoactivator in the ground state can be excited by visible light, hv, and thereby raised to the excited singlet state. From the excited singlet state the photoactivator can undergo intersystem crossing 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 with the ground state of atmospheric oxygen molecules, which are also in the triplet state, forming thereby according to reaction (5) the excited singlet state of oxygen and also regenerating photoactivator at its original ground state. Both the singlet and the triplet excited states of the photoactivator can enter into reactions other than the desired reaction with oxygen. For example, the singlet state can fluoresce, while the triplet state can phosphoresce, undergo radiationless decay, undergo electron transfer to photoactivator molecules in the ground state which results in deactivation of the photoactivator, or react with other components of the solution. From the standpoint o 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 is capable of reacting with stains as shown in reaction (7) to chemically bleach them to a colorless and usually water-soluble state, thereby accomplishing the purposes of this invention.
It will be instructive to consider the effect upon .~

~, . ~ , ....
, llZ~9(~8 bleaching brought about by the individual species of photo-activators that are within the scope of this invention.
This will be done in reference to the seven reactions appearing on Scheme A which have been described above.
The number of aza groups substituted for methine groups in the porphine core primarily affects (a) the lifetime of the triplet state, and (b) the side reactions.
The lifetime of the triplet state of metalloporphines [Grayushko et al, Opt. Spektrosk 31, page 548 (1971)] is substantially greater than that of corresponding metallo-phthalocyanines [Vincett et al, J. Chem. Physics 55, No. 8 page 4134, October 1971]. It is believed that introduction of each successive aza group shortens the lifetime, and it is apparent that a longer lifetime is desired to provide greater opportunity 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 countervailing factor is that side reactions tend to be greatest when 4 methine groups are present, and decrease progressively as successive aza groups are introduced. The foregoing effects work in opposite directions, and accordingly it is not possible to predict the relative effectiveness of the diferent species based on theoretical considerations alone. As described herein-after, porphines having 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, avail-ability, and performance under specific conditions of interest to him.

~1~69~8 This invention contemplates photoactivators that are metal free and also those that are metallated with certain metals. In general, the introduction of a metal atom into the photoactivator molecule causes a perturb-ation of the system which reduces the lifetime of the excited triplet states and increases side reactions, both of which are unwanted effects in relation to the instant invention. From this point of view unmetallated compounds are preferred photoactivators.
A countervailing factor is that manufacture of certain photoactivators is more readily accomplished when a metal is present to stabilize the molecule. This factor applies both to synthesis of a photoactivator compound by sulfonation of its unsulfonated precursor molecule, and also to synthesis of the precursor molecule itself.
Perturbation is especially great for metals which have unpaired electrons; hence paramagnetic metals are not satisfactory. Perturbation is also great for metals that are large in size. Data appearing in Vincett et al, op.
cit., suggest that the lifetime of the triplet state of zinc phthalocyanine is hundreds oP times longer than that of copper phthalocyanine (Cu i~ paramagnetic) and approaches a hundred times longer than that of platinum phthalocyanine (Pt is large).
Metallated photoactivators that are acceptable in the practice of this invention are those~containing relatively small, diamagnetic metals: zinc(II), cadmium (II), magnesium(II), scandium(III), aluminum(III), and tin(IV). Because the first five of these named metals have essentially constan~ valence, specific identification ~ lZ~9~8 of their valence states will sometimes be omitted herein.
Zinc is preferred because the triplet state of zinc metallated photoactivators is perturbed to a relatively low extent and hence its lifetime is relatively long.

All of the reactions described on Scheme A are predicated on solubility of the photoactivator in the laundry bath. Solubilization is accomplished by intro-ducing solubilizing groups into the molecule. It is entirely practical to make compounds having respectively, one, two, three, four and even indeed up to as many as twelve solubilizing groups per molecule, and all are to some extent photoactivators. However as each successive solubillzing group is added, changes occur monotonically in a number of properties which effect usefulness, as explained below.
An anionic macrocyclic photoactivator molecule in solution is present in dissociated ionic form having nega-tive charges around its periphery. The Coulombic effect of these negative charges is minimized by the counter ions in solution. The peripheral negative charges do, however, tend to localize the electron density o the ring near the center of the molecule and to enhance its basicity which leads to increased dimerization of the molecules as brought about by van der Waal forces [reaction 2, Scheme A]. This circumstance is increased by multiple solubïlizing groups, and loss of symmetry, and hence the tendency to dimerize in solution follows the order mono ' di ' tetra < tri ~
penta .... Dimerization being an undesirable reaction, a relatively small number of anionic solubilizing groups are preferred from this point of view.

1~69~8 The porphine photoactivators of this invention are especially useful in laundry baths in conjunction with cationic substances. Inasmuch as cotton surfaces are negatively charged, cationic substances have a strong affinity for cotton fabrics and a strong tendency to adsorb or deposit thereon. In so doing t~ey tend to bring down or co-adsorb other substances present in the laundry bath, such as the photoactivators of this invention.
The porphine photoactivators of this invention contain in their molecular structure certain chemical groups which solllbiliæe the photoactivator in an aqueous laundry bath.
As detailed hereinafter these groups can contain a formal electrical charge, either positive or negative, or can be electrically neutral overall; in which latter case they can contain partial charges of various degrees of strength. A
photoactivator molecule can contain more than one solubilizing group, which can be all alike or can be different from one another in respect to electrical charge.
The co-adsorption phellomenon discussed alone in relation to cationic substances assumes increasing importance in relation to photoactivators having, to some extent, an anionic or negative charge, whether a negative partial charge; a negative formal charge in an electrically neutral or even cationic molecule as a whole; or a multiplicity of negative charges in an anionic photoactivator molecule. The latter is a particularly strong effect which has been discovered to apply to the most common photoactivating bleach of the prior art, viz. zinc phthalocyanine sulfonate.
It will be remembered that the prior art, however, used this photoactivator in combination with anionic and not with _ 40 _ ~269~8 cationic substances, and hence failed to discover the improved, indeed synergistic effectiveness demonstrated by the compositions of the instant invention.

_ 4l _ llZ69~)~

"

Taking all the'above into consideration it has been found'that,. for anionic photoactivators haYing proximate solubilizing groups, the negative'factors of mono- and di-sulfonated photoactiva-tor mole.cules are so important that these species are unsatisfactory, and hence photoactivators of this invention have three or more proximate solubilizing groups per molecule. Compounds having more than about eight pro~imate solubilizing groups per molecu].e are often difficult to make and have no particular advantage. ~ence photoactiva-tors of this invention having proximate solubilizing groups have from three to about eight such groups per molecule;
compounds having three to six proximate solubilizing groups per molecule are preferred, and compounds having 3 or 4 proxi-mate solubiliziny groups per molecule are especially lS preferred as havlng an optimum balance of maximum bleaching effectiveness and minimum coloration.
The foregoing discussion rclates to anionic photo-activators having pro~imate solubil:izing groups. When -the solubilizing groups are in remote loc~tiolls, -the ~endency of the photoactiva-tor molecule to aggregate is reduced because of both elec-trical and steric reasons, with the result that less dimerization occurs, less buildup on the fabric occurs, and the solubilizing effect of individual solubilizing groups is enhanced. Accordingly, a minimum of 2 remotely located anionic solubilizing groups per photoactivator.molecule is satisfactory for the practice o~ this invention, wi-th 2 to about 6 being preEerred and 3 or 4 being especially preferred.
Nonionic solubilizing groups have a low tendency to aggregate because there is no electrical charge-density ~1269~8 effect and there is a particularly large steric effect reducing orderly association between photoactivator molecules.
Because solubilization o~ polyethoxy:1.ated pllotoactivator molecules occurs primarily be_ause of numerou.s ether ~roups in the polyethoYylate chains, it .i.s of little conse~uence whether there is a sinyle very :Long chai.n or a number o~
shorter chains. Accordingly, the solubility requiremellt as hereinbefore expressed is in terms o the number of condensed ethylene oxide molecules per porp]l;.ne molec~ Le, which .is from about 8 to about 50, pre~erab:1.y .from ~bout :1.2 to about ~0, most preferably from about 16 to about 30.
Photoactivators having cationic so].ubi.liz.i.1lg ~roups do not effectively aggregate a-t all because the elec~ro1l density in the ring is reduced. Direct substantivity on cotton .fabrics is great. Only one solubilizin~ ~roup is enou~h to accomplish the purposes of this invent:ior1, a].thouqh more are acceptable and indeed preferl:ed. Ac(:~rc1in~l:1.y t:he limi~i.ny numbers of solub.ilizing C.lti.OrliC CJLOUpC; aJ.e from 1 to abO11t: ~, preferably from abou~ 2 -to about 6, mos~ preEer.ab].y frorn 2 to ~.
~s stated hereinabove, the macromolecular structu*e comprising the porphine core contributes tlle e.ssen-tia]. photo~
activation properties oE the compounds o thi.s inventior1. It follows inexorab.ly that large nu~er.s of compounds having l:his macromolecular core, but with myriads of different substituent groups, are effective in the practice of this invention. One versed in the art will ~ecoynize the impracticab.ility of reduciny to writing all possibilities that can be envisioned by a skillful practioner. The embodiments which follow are therefore to be considered exemplary but not ex~haustive.

- ~3 -Photoactivators that are effective bleaching agents for fabrics and are within the scope of this invention are the following:
Tetrabenzo ~ tetrakis (4-N-ethyl) pyridyl porphine tetrachloride; tetrabenzo - ~, ~, y, ~ - tetrakis (N-trimethyl) aminoethyl porphine tetraiodide, tetrahcnzo -~, ~, y, ~ - tetrakis (~--carboxyphenyl) po~phine cad.r~,ium, tetrasodiwn salt; tetrabenzo - ~r ~r y, ~ etrakis ~4-sulfatophenyl) porphine zinc, tetrapotassium sa].t;
tetrabenzo - ~ - tetrakis (4-~u].fato pol~et.hoxy phenyl) porphine, te-trasodiuTn salt; tetra benzo -~, ~, y, ~ - tetrakis (~---carboxy po].ye~hoxy phenyl) porphine calcium, tetraamonium salt; tetrabenzo -~ , S - -tetrakis (4-phosphatophenyl) porphine, tetrapotassium salt; tetrabenzo ~ - tetrakis (~ phosphato polyethoxy phenyl) porphine zinc, tetra(mono-ethanolamine) sa].t; trans-dichloro, tetrabenzo - a, ~, y, ~ -tetrakis (4-polyethoxy phenyl) porphine tin (IV).
Tetrakis (N-rrlethyl) p~rido porphine ~.inc t~trcliodide;
tetralcis (N-trintethyl)- aminohen~o porphi.ne, tetra (tol.uene sulfonate) salt; trans-dibromo, tetrakis (carboxybenzo) porphine tin(IVj, tetra(diethallolamine) salt; tetralcis (sulato benzo) porphine zinc, tetrasodi.um salt; chloro, tetrakis (sulfato polyethoxy benzo) porphi.ne scandium, tetrammonium salt; tetrakis (carboxy polyethoxy benzo) porphine, tetrasodiwn salt; tetrakis (phosphato benzo) porphine zinc, tetrali-thium salt; tetrakis (phosphato polyethoxy benzo) porphine, tetra(triethanolamine) salt;
tetrakis (polyethoxy benzo) porphine; tetrabenzo -_ 44 _ ` 1~269!~)8 ~, ~, y, ~ - tetrakis-(-4 carboxyphenyl) porphine zinc, - tetrasodium salt.
Tetranaphtho ~ ~, ~, y, ~ - tetrakis - (4-phosphato polyethoxy phenyl) porphine, tetrasodium salt; tetrak.i.s (N-methyl) pyrido - a, ~, y, ~ - tetranaphthyl porphine tetrachloride;chloro, tetrakis (polye~xy naptho) ~ ~r ~, Yl ~ ~
tetra phenyl porphine aluminum, tetraki.s (N-di.etllyl-N~propyl) - aminobenzo - ~, ~, y, ~ - tetra}cis (4-~-meth~l) pyri.~1yl porphine magnesium, octabromi.de; tetrakis (carboxynaphkho) - ~, ~, y, ~ - tetrakis (4-carboxy phen~l) porp]-li.ne zinc, octa potassium salt; tetraki~ (polyethoxy benzo) -a, ~, y, ~ - tetra.kis (polyethoxy phenyl) porphine; trans-dichloro, 1, 3, 5, 7 - tetrakis (carboxy phenyl) -a, ~, 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, 5, 7 - tetrakis (phosphato phenyl) ~ , y, ~ -tetrakis (4-N-methyl) pyridyl porphine zinc, tetra socllum salt tetra chloride; 1, 3, 5, 7 - tetrakis (N trimethyl)aminobutyl ~, ~, y, ~ - tetrakis polyethoxy phenyl porphine, tetraiodide.
.... . .. . ... . . .
1, 3, 5, 7 - te~rakis (4-carboxy phenyl) - a, ~, y, - tetrakis - (4-carboxy phcnyl) porphine, octasodium salt;
1, 3, 4, 6 - tetrakis (carboxyethyl) - ~, ~, y, ~ - t:etrakis - (4-carboxy naphthyl) porphine, octasodium salt; ]., 2, 3, 4 - tetrakis (phosphato phenyl) - ~, ~, y, ~ - tet:ra phenyl porphine zinc, tetra(monoethanolamine) salt; 2, 3, 6, 7 -tetrakis (sulfatoethyl)-~, ~, y, ~ - tetra anthracyl _ 45 _ 11Z69~B

porphine, tetrammonium salt; dibenzo ~ , y, ~ -tetrakis -. (4-N-ethyl) pyridyl porphine cadmium tetra-iodide; dinaphtho - ~, ~, y, ~ - tetrakis - (4-carboxy . phenyl) porphine, tetrapotassi.um salt; di.(N-triethyl)-aminobenzo - ~, ~, y, ~ - tetra~is - (N~triethyl aminomethyl porphine zinc hexabromide; trans~ibromo, di(sul~atobenzo) ~ , y, ~ - tetrakis - (sulfatobenzo) porphine tin(IV), hexasodium salt; chloro,3, 5, 7 - tet.ra]cis (sulfato phcny].) -~ di(sulfato phenyl) porphlne scandium, hexaamoni.um salt; 1, 3, 5, 7 - tetrakis (polyethoxy phenyl) - a, ~ -di(polyethoxy phenyl) porphille magrlesiu~
Tetrakis - (carboxy benzo) - a, ~, y - tri (4-carboxy phenyl) porphine, heptasodium salt; tetrakis (phosphato benzo! - ~ - mono(phosphato phenyl) porphine, pentapotassium salt; 1, 5 - di(polyethoXy phenyl) -~, ~, y, ~ - tetrakis (polyethoxy phenyl) porphine; 1 - mono (polycarboxy phenyl) - a, ~, y, ~ - tetrakis (polycarboxy phenyl) porphine, pentasodium salt; ]., 3, 5, - tri(sulEato phenyl) - ~, ~, y, ~, - tetrakis (sulato phenyl) po.~phi.ne zinc, heptasodi~m salt; 1, 5 - di(carboxy phenyl) - a, ~ -di(carboxy phenyl) porphine, tetrasodium salt; 1, 3 -di(phosphato phenyl) - ~, ~, y - tri (phosphato pheny].) porphine, pentasodium salt; mono(carboxybenzo) -~, ~, Y - tri (4-c~rboxy phenyl) porphine, tetrasodiuM salt;
tetrakis - (carboxybenzo) - ~, ~, y, ~ - tetrakis (2-furyl) - porphine zinc, tetrasodium salt; tetrakis - (di.carboxy-benzo) - ~, ~, y - tri(4-pyridyl) - porphine, octasodium s~lt;

l~Z69~8 l, 2, 3, 4, 5, 6, 7, 8 - octa - (4-N-ethyl pyridyl) - ~, y - di(2-thioazyl) - porphine oc~aiodide;
l, 2, 3, 4, 5, 6, 7, 8 - octa - (4-sulfato phenyl) - ~ -(2-oxazolyl) - porphinel octasodium salt; l, ~, 3, ~, S, G, 7, 8 - octa - (4-polyethoxy phenyl) - ~, ~ - di(2 indo:lyl) -porphine; l, 2, 5, 6 - tetrakis - (4 carhoxy polyethoxy phenyl) - a, ~, y, 3 - tetrak.is ~metho~y phenyl) - porphine, tetrasodium salt; 1,3,5, 7 - tetraki5 - (4-carboxy phenyl) -a, ~, y, 3 - tetrakis (2-ben.zo thienyl) - porphi.ne, ~:etra-sodium salt; tetrakis (N-methyl p~rido) - ~, ~, y, ~ -tetraaza porphine tetraiodide; 1, 3, 5,.7 - tetrakis (N-trimethyl pyridyl) - ~, ~, y, 3 - tetraaza porphine æinc tetrachloride; tetrakis (N-methyl pyrido) - ~ -(N-methyl pyrido) - ~, y, 3 - triaza porphine cadmium pentaiodide; chloro, tetrakis (carboxybenzo) ~
di(4-carboxy phenyl) - y, 3 - diaza porphine aluminum, hexasodium salt; trans-dichloro, di~polyethoxybenzo) -~, y - di(polyethoxymethy~ -dia7cl porphine tin (~V).
Di(sulfatobenzo) - ~, ~, y - tri(sulfato phenyl) -3 - monoaza porphine calcium, penta-sodium salt; tetrakis (phosphato _ ~7 _ l~Z69~8 benzo) - ~ - mono naphthyl - ~, y, ~ - triaza porphine tetrasodium salt; mono (N-trimethyl amino ethyl benzo) -~, ~, y, ~5 - tetraaza porphine monoiodidej tribenzo - ~
(polyethoxy phenyl) - ~, y, ~ - triaza porphine; 1, 3 - di (polyethoxy ethyl) - ~, ~, y, ~5 - tetrakis (2-oxazolyl) porphine; di~N-methyl pyridyl benzo) - dibenzo ~ , (S - te~raaza porphine dibromide; tetrasulfo-benzo - ~, ~, y, ~ - tetrakis (5--sulfophenyl-n-amyl) porphine zinc, octasodium salt; 1,5 - di(6-sulfophenyl-n-hexyl) -~, ~, y, (S - te~rakis (sulfo-2-uryl) porphine, hexa-ammoni~n sal~ , y, ~ - tetrakis (dicarboxyethy~-phenyl(aminosulfonyl phenyl) porphine, octapotassiu~ salt.
Tri (sulfobenzo) monobenzo- a, ~, r, ~-tetraaza porphine zinc, trisodium salt; tetra (sulfobenzo)- ~, ~, y, ~-tetraaza porphine, tetrapotassium salt; tri (sulfobenzo) - tetraaza porphine, triarnmonium salt; tetra (sulfonaphtho) tetraaza porphine cadmium, tetra (mo;noethanolamine) salt; tetrasulfo dibenzo h ~c t~tr-~ D~r~h:r- ~

llZ691~

~, ~, y, ~ - tetrakis (sulfophenyl) porphine, tetra sodium salt; ~, ~, y - tri (sulfophenyl) - ~ (phenyl~
porphine zinc, tri ammonium salt; a, ~, y, ~ - tetrakis (2-thienyl, 5-sulfo~ porphine zinc, tetra sodium salt;
, ~, y - tri (2-thienyl, 5-sulfo) - ~ (2-thienyl) porphine magnesium, tri potassium salt; a, ~, y, ~ - tetrakis (2-furyl, 5-sulfo) porphine, tetra ammonium salt; a, ~, y - tri (2-~uryl, 5-sulfo) - ~ (2-furyl) porphine, tri ammonium salt;
trans-dichloro, ~, ~, y, ~ - tetrakis (2-thiazolyl, 3-sulfo) porphine tin (IV), tetra sodium salt; chloro, ~, r3, y, ~-tetrakis (2-thiazolyl, 4-3ulfo) porphine scandium, tetra lithium sa].t;
~, ~, y - tri (2-thiazolyl, ~-sulfo) - ~ (2-thiazolyl) porphine zinc, tri ammonium salt; , ~, y, ~ - tetrakis (2-oxazolyl, 4-sulfo) porphine, tetra (mono ethanol amine) salt;

, . , , ~, y, ~ - tetrakis (2-oxazciyl, 3-sulfo) por-phine magnesium,tetra sodium salt; ~ , Y - tri (2-oxa~olyl, 3-sulfo) - ~ (2-oxazolyl) porphine cadmillln, kri (krl ~hanol amine) salt; a, ~, y, ~ - tetraki.s ~4-I)yridyl, mono sulfo) porphine zinc, tetra ammonium salt; a, ~, y - tri (4-pyridyl, mono sulfo) - ~ (4-pyridyl) porphine, tri (di ethanol amine) salt; chloro, ~, r~ -tetrakis (2-pyridyl, mono sulfo~ porphine scandium, tetra potassium salt; trans-dichloro, , ~, y - tri (2-pyridyl, mono sulfo) - ~ (2-pyridyl) porphine tin (IV), tri ammonium salt; ~, ~, y, ~ - tetrakis (2-indolyl, mono-sulfo) porphine, tetra sodium salt; ~, ~, y - tri (4-hydroxy, monosulfo phenyl) - ~ (4-hydroxy phenyl) porphine, tri ammonium salt; 1, 2, 3, 4, 5, 6, 7, 8 - octamethyl - ~, ~, y, tetrakis (sulfophenyl) porphine, tetra sodium salt, 1, 2, 3, ----.
.

- ~12~9~8 4, 5, 6, 7, 8 - octae-thyl ~ , y - tri (2-furyl, 5-sulfo) -(2--furyl) porphine zinc, tri sodium salt.

1, 2, 3, 4, 5, 6, 7, 8 - octaisopropyl-a, ~, y, ~ -tetrakis (2-oxazolyl, 4-sulfo) porphine cadmium, tetra ammonium salt; 1,:'2, 3, 4, 5, 6, 7, 8 - octa n-butyl - ~, ~, y - tri (2-pyridyl, mono sulfo) - ~ (2-pyridyl) porphine, tri sodium salt; 1, 2, 3, 4, 5, 6, 7, 8 - octa sulfo phenyl porphine, octc sodium salt; 1, 2, 3, 4, 5, 6, 7, 8 - octa sulfo phenyl porphine, octa sodium salt; 1, 2, 3, 4, 5, 6, 7, 8 - octa sulfo phellyl porphine zinc, octa ammonium salt; 1, 2, ~
5, 6, 7, 8 - octa,'sulfo naphthyl porphine zinc, ~cta ammonium salt; ], 2, 3, 4, 5, 6, 7, 8 - octa sulfo naphthyl porphine zinc, octa a~moni~m salt; tetra sul~o benzo porphine, tetra (tri ethanol amine)salt; tetra sulfo benzo porphine zinc, tetra sodium salt.

, Trans-dibromo, tetra sulfo benzo porplline tin ~IV), tetra lithium salt; ben~o tri sulo hellzo porphina scandium, tri an~lonium salt; bromo, benzo tri sulfo benzo porphine tri (mor ethanol amine) salt; benzo tri sulfo benzo porphine magnesium, tri potassium salt; benzo tri sulfo benzo-meso-tetra phenyl porphine cadmiu;n, tri sodium salt; benzo tri sulfo benzo-meso-tetra phenyl porphine zinc, tri sodium salt; trans-dichloro, benzo tri sulfo benzo-meso-tetra naphthyl porphine tin (IV), tri (di ethanol amine) salt; chloro, tetra sulfo pyrido porphine aluminum, tetra sodium salt; tetra sulfo pyrido porphine, tetra ammonium salt; tctra sulfo pyrido porphine zinc, tetra sodium salt.
Tri sulfo pyrido porphine, tri ammonium salt; tri sulfo pyrido porphine calcium, tri a~nonium salt; tri sulfo .

~69~8 pyrido porphine, tri sodium salt; meso-disulfopyrryl-meso-disulfo phenyl porphine, tetra sodium salt; meso-disulfo-pyrryl-meso-disulfo phenyl porphine .zinc, tetra sodium salt;
meso-disulfopyrryl-meso-disulfo phenyl porphine, tetra sodium salt; 1, 2, 3, 4, 5, 6, 7, 8-octamethyl-meso-disulfopyrryl-mes.o-disulfo phenyl porphine, tetra ammonium salt; 1, 2, 3, 4, 5, 6, 7, 8-octa n-propyl -meso-disulfopyrryl-meso-disulfo phenyl porphine zinc, tetra sodium salt; disulfobenzo-meso-tetrasulfophenyl porphine, hexa sodium salt; disulfobenzo-mes.o-tetra(sulfo-~-pyridyl) porphine zinc, hexa soclium salt.

Dibenzo-meso-tetra-(2-thienyl-5-sulfo) porphine, tetra ammonium salt; dibenzo-meso-tetra-(2-furyl-5-su].fo) porphine zinc, tetra sodium salt; benzo~sulfobenzo meso-tetra-(2-thiazolyl-3-sulfo) porphine, penta sodium salt; benzo-tr.isulfobenzo-meso-tetra-(2-thiazolyl-3-sulfo) porphine zinc, hepta sodium salt; disulfobenzo-meso-di(2-oxazolyl-3-sul~o)w di(2-oxazolyl) porphine, tetra sodium saJ.t; cl:isulfohenzo-me.qo-di(2-oxazolyl-4-sulfo) porphino zinc, tetra sodium salt;
trisulfobenzo-a, ~, y-tri(sulo-2-pyridyl)-~-pyridyl porphine, hexa sodium salt; disulfobenzo-a, ~, y-tri(sulfo-2-indolyl)-~-indolyl porphine, penta ammonium salt; disulfobenzo-~, ~, y-tri(sulfo-4-11ydroxyphcnyl)-~-hydroxyphenyl porphine zinc, penta ammonium salt; tetrasulfo-naphtho porphine, tetra ammonium salt.
.. . ...
Trisulfo naphtho porphine zinc, tri ammonium salt;
disulfo benzo disulfo naphthyl porphine zi.nc, tetra ammonium salt; disulfo benzo sulfo naphthyl porphine, tri ammonium salt;
mono sulfo benzo disulfo naphthyl porphine, tri ammonium salt;
tetra sulfo benzo-meso-tetramethyl porphine, tetra ammonium salt trisulfo benzo-meso-tetraethyl porphine zinc, tri ammonium salt; tetrasulfo benzo-meso-tetraisopropyl porphine zinc, tetra ammonium salt; trisulfo benzo-meso-tetra n-butyl porphine, tri ammonium salt; tetrasulfo naphtho-~, ~, y-tri phenyl-~-sulfophenyl porphine, penta ammonium salt; trisulfo naphtho-meso sec-butyl porphine zinc, tri ammonium salt.

Tetrasulfo naphtho-meso tert-butyl porphine æinc, tetra ammonium salt; trisulfo naphtho-meso-n-propyl porphine, tri ammonium salt; tetra sulfo benzo triaza porphine, tetra sodium salt; tetrasulo benzo triaza porphine zinc, tetra sodium salt; tetrasulfo benzo triaza porphine, tetra ammonium salt; tctrasulfo benzo-~, ~, y-triaza-~-sulfophenyl porphine zinc, penta ammonium salt; tetrasulfo benzo cliaza porphine, tetra ammonium salt; tetrasulfo benzo diaza porphine zinc, tetra sodium salt; tetrasulfo benzo diaza porphine, ammonium salt; tetrasu~fo benzo diaza porphine zinc, tetra sodium salt.

Tetrasulfo benzo-~-aza-~, y, ~-triethyl porphine zinc, tetra ammonium salt; tetrasulfo benzo mono aza porphine, tctra sodium salt; tetLasulfo benzo mono aza porphine zinc, tetra ammonium salt; tetrasulfo benzo mono aza porphine, tetra sodium salt; trisulfo benzo triaza porphine, tri sodium salt;
trisulfo benzo triaza porphine zinc, tri sodium salt; tri-sulfo benzo diaza porphine zinc, tri sodium salt; trisulfo benzo-~ diaza-y, ~-disulfo naphthyl porphine, hexa sodium salt; trisulfo benzo monoaza porphine, tri sodium salt; tri-sulfo benzo monoaza porphine zinc, tri ammonium salt.

--l~Z69~8 Tetrasulfo naphtho triaza porphine zinc, tetra ammonium salt; tetrasulfo naphtho triaza porphine, tetra a~nonium salt; tetrasulfo naphtho diaza poxphine, tetra ammonium salt; tetrasulfo naphtho-~, y-diaza-~, ~-diphenyl porphine zinc, tetra ammonium salt; tetrasulfo naphtho monoaza porphine zinc, tetra ammonium salt; tetrasulfo naphtho monoaza porphine, tetra ammonium salt; trisulfo naphtho triaza porphine .
tri sodium salt; trisulfo naphtho diaza porphine zinc, tri sodium salt; trisulfo naphtho monoaza porphine zinc, tri ammoniurn salt; tetrasulfo dibenzo dinaphtho triaza porphine zinc, tctra sodium salt.

_.
Tetrasulfo dibenzo dinaphtho diaza porphine, tetra a~nonium salt; tetrasulEo benzo trinaphtho monoaza porphille, tetra ammonium salt; trisulfo tribenzo naphtho triaza por-phin~, tri ammonium sa].t; trisulfo dibenzo dinaphtho diaza porphine zinc, tri sodium salt; trisulfo dibenzo dinaphtho monoaza porphine zinc, tri sodium salt~ , y-trisulo pyrryl-~-sul~ophellyl porphine ~inc, tetra socl1um salt; y-sulo pyrryl-~, y, ~-trisulfo phenyl porphine, tetra sodium salt;
~-sulfo uryl-~, y, ~-trisulfo phenyl porphine zinc, tetra sodium salt; meso-disul~o pyrryl-meso-disulfo phenyl porphine zinc, tetra sodium salt; 1,3,5,7-tetra methyl~ , y, ~-tetrakis(sulfophenyl) porphine, tetra sodium salt.

1,3,5,7-tetra phenyl-~, ~, y, ~-tetrakis(2-o~azolyl, 4-sulfo) porphine ma~nesium, tetra sodium salt; sulfobenzo-~, ~, y-tri(2--thienyl-5-sulfo) porphine cadmium, tetra potassiun salt; trisulfobenzo-, ~, y-(2-furyl-5-sulfo) porphine, tetra 69~8 a~noniurn salt; 1,2,3,4,5,6,7,8-penta sulfo phenyl porphine zinc, penta sodiurn salt; 1,2,3,4,5,6,7,8-hexasulfo phenyl porphine, hexa sodium salt; chloro, heptasulfo naphthyl porphine aluminum, hepta sodium salt; tetrasulfo benzo-meso-disulfo phenyl porphine calcium, hexa sodium salt;
disulfo benzo-meso-tetrasulfo phenyl porphine, hexa sodium salt;
1,2,3,4,5,6,7,8-tetraphenyl-tetrasulfo phenyl-~, ~, y, ~-tetrakis-2-benzo thienyl porphine ZillC, tetra sodium salt;
, ~, y, ~-tetrakis(4-methoxy sulfo phenyl) porphine, tetra sodiurn salt.
, Each of the foregolng illustrative photoactivators is a specific chemical compound. It should be understood that alternative photoactivators, each within the scope of the instant invention, are those where.in substituted in ~ach specific named compound are, inter alia:
a) instead of a specific cation listed: sodium, potassium, lithium, arNnonium, monoethanolamine, diethanolamine, or triethanolamine salts.
b) instead oE a spe~ci~ic anion .Lisl:ed: chloride, bromide, iodide, or toluene sulfonate salts.
c) instead of the metallation listed: zinc(II), cadm.ium(II), maynesitlm(II), scandium(III), aluminum(III
tin(IV), or metal free.
d) instead of the specific al~yl groups mentioned:
methyl, etllyl, n-propyl, isopropyl, n-butyl, isobu-tyl, sec-butyl, or tertbutyl.
e) instead of the specific solubilizing ~roup _ 54 _ mentioned: carboxylate, polyethoxy carboxylate~
sulfate, polye~hoxy sulfate,phosphate, polyethoxy phosphate, sulfonate, quaternary pyridinium, quaternary ammonium, or polyethoxylate.
f) instead of the number of solubilizing groups mentioned: any nu~ber of solubilizing groups that is not greater than -the number of pyrrole-substituted aromatic or pyrido groups plus the number of meso-substituted aromatic or heterocyclic groups and that is, for cationic or nonionic solubilizing groups, from 1 to 8; for remote anionic soluhilizing groups, from 2 to 8; and for non-remote solubllizing groups, from 3 to 8.
g) instead of the specific pyrrole substituents lS mentioned: benzo, naphtho, pyrido, phenyl or . naphthyl.
h) instead of the specific meso substituents mention~d:
phenyl, naphtllyl, thlenyl, furyl, th.ioa~yl, o~a~yalyl, indolyl, benzothienyl, or pyridyl.
The alternative photoactivator compounds described above are to be considered equally illustrative of the compounds of this invention as the compounds specifically named in the preceding 11st.
Additional embodiments of this invention are .25 compounds hereinaf-ter appearing numbered from XXV through XXXVI and from XLVII through LXI; compounds numbered from XXXV:[I through XLVI fol].owing conversion of hydroxy groups to corresponding carboxy groups; and compounds numbered from I through XXI following sulfonation.

_ 55 _ 1~269~'8 The literature contains references to numerous means of ~reparation o~ porphine and its derivatives, i.e. to the photoactivators of this invention. One s~i~led in the art of porphine or pht~alocyanine chemistr~ will have no difficulty selecting a synt~esis appropriate for his particular purposes. Some of the synthesi~ reactions are accompanied ~y side reactions; in these cases conventional mea of separation and purification are needed,such as chromatograph techni~ues,in a manner also detailed in the literaturo al?d well known to the ski].lcd pr~ctitionex.
It may be said that there are two general preparative routes to make solubilized substituted porphines. The first route is to prepare the substituted porphine of choice and then solubilize it by introduction of appropriate solubilizing groups. This route is especially applicable to the preparation of sulfonated porphi.nes, and is illustrated hereinafter by the synthesis of divc.rs :i.ndiv.idual sul~onaLecl porphine species. The second routc is to prepare t.-.he solubilized porphine species of chance by using starting materials already containing the desired solubilizing groups as part of their own constitution. This route is especially applicable to thc preparation o~ porphines solubi].ized by groups other than sulfonate, and is illustrated herinafter by the synthesis of divers compounds of this type. It will be appreciated by one skilled in the art that these two preparat-.ve routes are by no means exclusive Eor these two types of compounds, respectively. Indeed it is possible, within the scope of this invention, to prepare porphine compounds having some solubilizing groups introduced by the first route and some - 56 - .

1~2~9~8 J
by the second route, with the two sets of solubilized groups (those introduced by the first route and the second route, respectively) being either the same or different.
Illustrative examples of these variations are also described hereinafter.
The first preparative route, as defined above, will now be discussed. One convenient way to prepare porphines is to react substituted or unsubstituted heterocyclic or aromatic carboxaldehydes with substituted or unsubstituted pyrroles.
By vaxyiny the substituent groups of one or tlle other or bot}l o~ these reactants, a great variety o~ porphine derivatives can be obtained. For example, ~I) , ~ ~ 0 Nl~ N~
IN~ ~ NJ ~ ~ C~ C ~ N
¢'~1 ' pyrrole4-pyridine ~,~,Y,~ -tetrakis(4-pyridyl)porphine lS carbo~aldehyde - 57 _ 11;~69~
/

The sta~ility of the ~uadridentate ~acromolecular structure is such that the reaction proceeds as described above. ~or convenience, the product is frequently and conventionally described ~ sho~ing only one ~uarter of this sym~netrical s~ructure. It will be apprecia-~ed this structure is stabili~ed by resonance, and the bonds of all four ~uarters of the structure are alike, even though conventionally they are dra~n in just one o the resonating .
structures. According].y, compound (I) above can be illustrated morc simply as:

- ~ (I) .. ,.. , .,. f ~ .
.
..

When pyrrole is reac~ed wi.th 2~thiophene caxbo~:aldehyde instead o~ ~-pyr:idine carboxaldehyde, the reacti.on proceeds (II) ~3 + ~CI~ ~C4~ ~

pyrrole 2-thiophene ~,~,Y,~ -tetra~is-(2-thienyl)porphln~
carboxaldehyde .

~269~i8 Othe~ compaxable re~ctions ~i.th py~role and ~ubstituted pyrrole are giYen beIo~. It will be understood t~at'.
substitutent groups which'are pres'ent on either of the ' reactants ~ill carry over into the corresponding porphine' 5' derivative, thereby maki.ng possible a great variety of compounds that have the'essential characterlstics necessary for the practice'of this invention~ The specific equations belo~7 are'therefore'exemplary and are not intended to be limiting~
~III) ' . .

pyrrole ~ ~;3 Cl10 C 40~
..

2--furan ~,e ,~ etrakis-carboxaldehyde (2-furyl)porphine V) ~yrrolO + ~ ~ CU~ 3 2-thiazole ~,~,y,~-tetrakis-carboxaldehyde (2-~hioazyl)porphine' _ 59 _ 1~269~8 ~

. .
(y) ~ ~o~c,~O ~3 isoindole2-oxazole ~,~,y,o-tetr~};is-[benzop~role]carbox~ldehyde (2-oxaæolyl)~e~rabenzo porphine .(VI) pyrrole ~ ~ CUo C ~

indole a,~,y,~-tetr~kis-2-carboxaldeh~de (2-indolyl)por~hin2 (VII) pyrrole ~ ~CI10 ~

~enzalde~yde ~,~,y,o-tetraphenyl porphir .

- ~ ~lZ69~8 (VI I I ) pyr~ole ~ CH30 ~ CHO ~ OCH3 .4-metho~.~y ~,~,y,~-te~rakis~-methox~
hen~aldehyde phenyl)porphille .
.
.. . .
,,' ' ' ' ' _. . . .

.,, ,, . .'.' ...... . .
,, .

- -. :;: .

1~269~8 .
(IX) ~ 3~ ~c~o~ ,C~

3,~-diphenyl . 2-benzo a,~,y,~-tetrakis-pyrrole thiophene (2-benzothienyl)~
carboxaldehyde 1,2,3,4,5,6,7,8-octaphenyl porphine .. (X) , ,:

lC113 IICC~ICt-13 C - C~
+ ~ c~o 3-isopxopyl 2-furan a,~,y,~-tetrakis-pyrrole c~rboxaldehyde (2-furvl)-1,3,5,7-tetra isopropyl porphin The above class o~ reactions can be carried out by refluxing propionic acid for about 30 to 60 minutes followed by ,~

llZ69~8 chromatographic purification. This method is described by Adler in J. Organic Chemistry, volume 32 page 476 (1967).
Any of the resultant metal-free compounds can be con-verted to the corresponding metallated compound by heating with a metal salt of Zn(II), Cd(II), Mg(II), Sc(III) or Sn(II) in an appropriate solvent. [The Sn(II) becomes oxidized in the process, such that the photoactivator is metallated by Sn(IV).]. For example, heating a,~
tetrakis(4-pyridyl) porphine in dimethylformamide in the presence of zinc acetate yields ~ -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, 1970).
Alternatively, a metallated derivative can be prepared by carrying out the synthesis reactions [e.g. (I) through (X) above] in the presence of a salt of the desired metal.
For example, if cadmium chloride is present while carrying out reaction (IV), the resultant photoactivator compound is ~ -tetrakis-(2-thioazyl)porphine cadmium. This reaction for producing a metallated compound may be pre-ferred because the presence of the metal tends to increase stability of the desired quadridentate structure and tends to minimize the formation of other reaction products.

.

llZ69~8 A completeIy different route to por~hine compounds having fused ring su~stitution on the pyrrole rin~s is . the condensation and rearrangement ol 4 molecules of cyano aromatic or cyano heterocyclic ketones to form a ~uadridentate structllre.This is done by heating in the presence of metallic zinc, cadmium, magnesiu~, scandium, aluminum or tin, or a metal salt o~ Zn(XI), Ca(II), Cd(II), Mg(II), Sc(III), Al(III) or Sn(IV), and yields the corresponding metallated porphine.
" ' .
n C - C112-R metal or CN metal salt I r N~
. ... A C - R ..

~here A is zinc (II), cadm~um (II), maynesium (II), scandium(III), alumlnum(III), or tin(IV) dnd where R is hydroaen, alkyl, aryl, or mi:~tures th(?reof . SpeciEi.c cxamples are:

~ (XI) 11 ,~\
er ~N ;
Mg & ~ H

o-cyano-acetonaphthone tetra naphtho porphine magnesium - 6~ -llZ69~8 (XII) ~ C~CIIz~ ~ zinc acet~te o-cyanophenyl-(naphthyl Tetrabenzo-meso-ttetra ethyl)ketone naphthyl methyl)-porphine zinc Similarly, condensation and rearrangement of :imidcs and aromatic vicinal dinitriles yields aza porphine structures as does condensation and rearrangement of aromatic vicinal dicarboY.ylic acids in the presence of ammonia. Molybdic or tungstic acid or metallic antimony can be employed, as desired, to accelerate the reactions.
For example:

O (XIII) C .
ll NH - ;' N ~
HC~ / ~N
lco maleimide tetra aza porphine llZ69~8 (XIV) N
/

1.
phthalimide tetrabenzo tetra aza porphine (XV) CN

N
~N

phthal~ di.nit:ri.le te-t-rabenzo.t:et:raaza porphine (XVI) ~ 0011 phthalic acid tetrabenzo tetraaza porphine llZ~9~8 ,, .

A mixture of metal cyanide together with a ketone whose two side groups are (alkyl or aryl) and (halo aryl or halo heterocyclic), respectively, yields a mixture o~ mono-and di-aza porphines. For example:

(XVII) o ~,cl ~
C-cll 3 t.etra~nzo N\ ~N
mon~a~a N Zn N
~ ~Z~ N), ---J~l-olp~ + ~ ~ ~

o-chloro zinc tetrabenzo diaza .acetophenone cyanide porphine zinc Similarly, a mixture of phthalonitrile and a ketone whose side groups.are (alkyl or ary.l.) and (cyano-aryl or cyanoheterocyclic), r~speckiv~.ly, ylc~lds a ~ix~urc of mono- and di- aza porphines. Substit:u~..ion o~ the mes.o-carbon atoms can be varied by appropriate cholce of ketone.

(XVIII) ~,C~
~ CN ~ -Cll2R

phthalo- o-cyano CH2R
dinitrile acetophenone tetrabenzo-~, y-dialkyl-~, ~- diazo porphine ~12t;9~8 /
An especially versatile method of preparing mono-, di-, and tri-aza porphines uses mixtures of pyrroles and carboxaldehydes [starting materials for porphines, as illustrated by equations (III) through (X) supra] together with dinitriles or imides ~starting materials for aza porphines, as illustrated by equations (XIII) through (XV) supra]. Throu~h suitable proportionation of the starting materials, mixtures of reaction products are obtained that are primarily mono-, di-, or tri-aza porphines, as desired.
If pure species are desircd, these reaction products can be purified by ordinary chromatocyraphic techniques.
Examples of the above reactions are:

~ (X~:X), 3 ~ ~ ~ C
N ~ N IIN
pyrido benzal- phthalo~
pyrrole dehyde nitrile / y C
\~,N

predominantly 1,2,3,4,5,6-tri-pyrido-7,8-benzo-~,y-tripheny monoaza porphine (X~) l~o ' -~ 5 HC -C ~
methyl 2-furan mal ~ N
pyrrole carboxalde- (excPss) ~ N~
hyde predominantly 2-methyl-~(2-furyl)-~,y,~-triaza porphine ~269~8 A mixture of phthalonitrile, a metal salt, and methylene phthalimidene or phthalimideneacetic acid yields triazaporphine, as shown below. Varying the substituent groups forms substituted triaza porphines according to usual chemical principles.

(XXI) 1 2 ~ C

CN ~C

phthalo- stannous phtha.limidene trans-dichloro, nitrile chloride acetic acid tetrabenzo triaza porphine tin (IV) When the foregoing condensation method is used, unmet-allated derivati.ves can be prepared by treatment with concentrated sul.furic acid followed by dilute al.kall with cooling, as described by Helberger in Annalen 529, 305 (1937).

Many of the reactants used in the foregoing methods of preparation are commonly known and readily available to the skilled organic chemist. Certain general methods of synthesis can be described below, as follows:

~ .

~269~8 Substituted pyrroles can be prepared by heating 1,4 dicarbonyl compounds (diacids or keto acids~ with ammonia.
For example, HC = O N~3 1~ C
HC ~ ~ ~-2Hzo~
HC = o H

diphenyl pyrrole ~ leterocyclic 2-aldehydes containing hetero or oxYgen atoms can be prepared rrom pentos~ns by hydrolysis to pentoses followed hy dehydration and oxidation. For example, .

ll2o Il(l-o ~-3 ll2~ ~
(CSIIY2) ~ (liCOil)3 ~ ~ O Cl~O

H

EIeteroc~clics containinc3 sul~ur or nitrogen hetero a-toms can he converted into 2-aldehydes by re~cting ~/ith ~ICl and ~ICN, followed by hydrolyzing ~7ith ~7ater. Two examples follow:

_ 70 _ .

.

~lZ69~8 1. HCl, HCN
2. H20 ~

2-benzothiophene carboxaldehyde ~ 1. HCl, HCN ~

2-pyrryl carboxaldehyde In ~le fore~oing equations, each ~uadridentate porphine macxomoIccule is comprised of 4 identical quar-ters.
For example, reactiny pyrrole ¢~
N

~ith 4-pyridine carboxaldehyde forms compound I which is ,~ tetra]cis(~-pyridyl)porphine. Rr-~acting a substituted pyrrole, isoindole ~N
~T

with 4-py-idine carboxaldehyde, forms in an analoyous manner the com~o~nd te-tra benzo-r,~,y,ô-tetra~is(4-T~yridyl) ~;Z69~)8 porphine. Reacting a mixture of pyrrole and indole with 4-pyridine carbox.aldehyde forms the monobenzo, dibenzo, or tribenzo deriva'ives of ~,~,y,~-tetrakis(4-pyridyl) porphine, depending upon the proportions of reactants used.
This technique of reacting mixtures is widel~ appliable to the reactions illustrated hereinbefore.
It is also possible to prepare poxphines having 4 non-identical ~uarters by cornbining reactions of the type illustrated ~y equations I - X with those illustrated by ]o ~quations XI - XV. ~or example, o-acylnaphthonitrile, pyrrole, And an aldehyde re'act in such'a way as to form porphi'nes with 1 to 3'naphtho groups.
Sulfonation of the'substituted porphines' described herein~efore'can be accomplishe'd by ordinary methods such as are familar to the skillea chemist. Sulfuric acid, oleum, chlorosulfonic acid and the like are'effective sulfonating agents~ As usual, higher degrees of su]fonation are obtained by increasing reac~ion ~ime or ~empera~ure or by selection o a stronger sulfona~ing agent.
Sulfonation occurs principally on benzo, naphtho, or other aromatic groups fused directly onto the pyrrole rings or on arornatic groups such as phenyl or naphthyl sub-stituted on the pyrrole rings; and also on phenyl, naphthyl, or other aromatic groups in the meso position. Sulfonation can also occur on pyrido, pyrryl and furan heterocyclic groups, and on aromatic rinys fused onto hetero rings; however the pyridine/SO3 salt is often used for these sulfonations.
Often a maximum of 4 locations is possible for each of these two types of substitution, making an overall maximum .

:

~1269~8 of 8 sites per molecule readily available for sulfonation.
For example, tetrabenzo-meso-tetraphenyl porphine can be reacted to form mono-, di-, tri-, . . . . . penta-, and octa-sulfonate derivatives. However a photoactivator such as 1,2,3,4,5,6,7,8 octaphenyl-meso-tetraphenyl porphine can possibly have up to 12 sites of sulfonation. Tetra benzo porphine and meso tetra phenyl porphine, each of which has only 4 aromatic substituent groups, are examples of por-phines which can be effectively reacted only to form mono-, di-, tri-, and tetra-sulfonate derivatives. Attempting to go beyond this degree of sulfonation destabilizes the molecule.
A preferred photoactivator of this invention is sulfon-ated phthalocyanine. This compound metallated with zinc is especially preferred, the tri- and tetra-sulfonated species of the compound are more especially preferred, and the sodium salts thereof are most especially preferred.
This photoactivator is discussed in U.S. Patent 3,927,967, Japanese OPI 50 113,479, Belgian Patent 840,348 and British Patent ],372,036.
The prior art method o~ preparation of zinc phthalo-cyanine sulfonat:e is the reaction of oleum upon zinc phthalocyanine, and old and commercially available start-ing material. The structure of zinc phthalocyanine tetrasulfonate, tetrasodium salt is closely related to that of compound [T] disclosed hereinbefore and is as follows:

_ 73 _ 1~269~8 NaO3S
s03Na ! XXII

inc phthalocyanine tetrasulfonate, tetrasodium salt. [Alternatively named N ~ tetra(sulfoben~o)~
, ~ tetraaza porphine zinc, ~ ~ I tetrasodium salt.]
NaO3 SO3Na A convenient syn-thesis for zine phthalocyanine tetra-sulfonate is the condensation of 4 molecules of phthalonitrile into a single quadridentate molecule in a solution of ethylene glycol in the presence of zinc dust and molybd acid as ca-talyst, followed by sulfonation with oleum and suhsequent neutralization. Variations in structure can be achieved, as usual, by using other metallating agents or none at all, by startincJ with substituted phthalonitriles, and by changes in sulfonatiorl concditions. Yields are relatively low ( 25%) for unmetallated phthclayanines, but purification by chromatographic separation can be employed in the customary manncr if such compound should he desired.
Sulonation in remote sites can be brought about by ].5 certain reactions illustrated infra in additi.on to the reactions described supra. It is of course contemplated that sulfonation can, and frequently will, take place on both pro~imate and remote sites. Condensing and rearranging a substituted maleimide leads to the following:

~269~8 CH2(CH2)3CH

H N
5-phenyl-n-pentyl maleimide oleum ~ (XXIII) ~_ CH2 ( CH2 ) 3CH2 ~ .

~N ~ SO3 2,4,6,8 - tetrakis-(sulfo-phenyl-n~pentyl) tetraza porphine Also, as described in Groves hereinbefore cited, reactions of the following form can be utilized:

~CI12-CI12-C - O 112N - C - CN

10~C~12-C:112-C ~ O ~ 11 ;, di(phenylethyl) ~etone d' .
Lamlno malelc acid dinitrile _ 75 _ ~26908 -CH2-c c - CN
I ll conden~ation H2-C~I2-C~ C - CN and rearrangement 4-5 di(phenylethyl pyrazine) -2,~ dicarboxylic acid dinitrile (X~IV) C~12-Cil2 ~

N ~-c~2-C~-I
slllEation ~ N

(oleum) ~
~N ' The second preparative route for making solubilized substitute~d porphines w.ill now be described. As stated hereinbeEorc, this route is to prepare the solubilized porphine species of ciloice by using starting materials already containing the described solubilized groups as part of their own consti-tution.

11269~)8 I~Jhen compound (I), a substituted pyridine, is reacted with an alkyl halide such as C~13I, 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 porphine derivatives adsorb directly and strongly upon cotton fabrics because of their opposite charge. This is desirable; however a countervailing factor is the yellowish color of many such compounds which tends to remain on the fabric after washing.
'rhe methyl ester oE toluene sulfonate rnay be used instead of methyl iodide as a quaternizing salt, leading to the following synthesis:
(I) (XXV) + ~ ~C ~ --C~

~, ~, y, ~ - tetrakis methyl ester ~, ~, y, ~ - tetrakis (4-pyridyl) p~rphineof toluene (4-~-methyl pyridyl)porph sulfonate tetra(4-toluene sulfonate ~hen substituted pyrroles are reacted with pyridine 4-carboxy-aldehyde, and the reaction product reacted with an alkyl halide, a nur~er of different pyridiniwn salts are formed~
20Non-limiting examples are:

~) I .
(XXVI) tetrabenzo - , ~, y, ~ -N tetrakis - (4-N-alkyl H pyridyl) - porphine, tetra halide salt isoindole [benzopyrrole]

_ 77 _ :

.

112~

(XXVII) p ___ octaphenyl ~ , y, ~ -h ~ tetrakis - (4-N-alkyl pyridyl) - porphine, H tetra halide salt 3,4-diphenyl pyrrole (X"VIII) 1, 3, 5, 7 - tetrakis ~ __ ~ ___ (4-N-alkyl pyridyl) // \\ ~, ~, y, ~ - tetrakis --N-al}~yl pyridyl) -N porphine, tetra ha].ide salt 3 - pyridyl pyrrGle Statements made hereLnbefore in relati.on to the preparation of compounds I through X also apply to the preparation of compounds XXVI through XXVIII in relation to isopropionic acid reflex and methods o.~ mc~dllatiorl, which ~re yenera].ly applicable to ~he photoactivators of -this inven-tion, whatever the solubili~ing groups may he.
~ za pyridini~n salts can be made by condensiny and re.~rrancJi.ny pyrido-sub~c;tituted imides or dinitriles, or by condensing and rearranyiny pyrido-substituted aromatic vicinal dicarhoxylic acids in -the presence of ammonia. For example, 1~269~8 1/ \~ N

pyrido phthalodinitrile +C~131 (XXIX) N +I~ ¦

/
tetrakis (N-methyl-6, 7 - quinolinediyl) te~traaza porphine, tetra.iod:idQ s~lt (XX~C) _ C1-13 C00~1 COOII ~ U9I N +1 . tetrakis (N-methyl pyridyl benzo) tetraaza porphine, tetraiodide salt _ 79 _ llZ69~8 Mono-, di-, and tri-aza pyridinium salts can be prepared by using mixtures of starting materials 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:

~LZ69~)8 -~CHO
3 e~;~+ 3 ~ ~[CN C~HsBr ( XXXI ) ¢~ ,C21-ls f~

predornlnat~ly a, ~ ~NII ~
tri. (N-e thyl pyridyl) - N C J~N
monoaz a porph:ine, ~ / \=~
tribromide salt ~C ~ _ C2Hs -~3 13 C2lls C~lo O

,Nll ~ ~ Ç
() ~ C3117 predom.incl. te~ly 2, G-dim~! thyl~
3,~,7,~- di(N-p:ror~yl I)~f.ridyl ~J l~o l~(-3nzo) -a, y. - di (benzo- HJc i /~\l/ N
N-propyl pyridyl)- ,B, ~ - ~;C ~ // \~ C3117 diaza porphine, tetra- \ I ~1 >~
chloride salt ,~NII ,~ N ~

~l ,C3~ ~ ~ ~ C113 +4 ClB

l~Z69~8 By suitable changes in starting materials, quaternary a~nonium salts can be prepared in a manner sirnilar to tha-t of the pyridinium sal-t illustrated as compound (XXV). For example, reac-ting pyrrole with a tertiary amino aldehyde, followed by quaternizing, leads to (XX.YIII) R~ - N - R2 R3X/ ~ ~N\ ~ +

a, ~, y, ~ - tetrakis -'- ' trial]cyl 4-amino phenyl) porphine, tetra hali.de salt ~ s heL'orc, ll'ir! oE substi~ute-l pyr.roles leclds to pyrrole-substitul-ed porphines, while var:iations in the tertiary amino c;roup lead to corresponding variations in the meso substitution.

ï5 ~ completely di,iierent route to quaternized porphinc compounds having fuscd ring substitution on thc pyrrole rings is the condensation anc' rearranc,ement of 4 molecu]es of cyano aromatic or cyano heterocyclic ketones to form a quadridentate structure. This is analogous to thc metl-lods hereinbefore described for the preparation of compounds (XI) and (XII).

l~Z69~8 To utilize this method to make quaternary ammonium salts it is only necessary to start with a compound having a tertiary amino group in the R moiety, and then quaterni.ze the resultant porphine as be~ore. For example, O
~,C-CH 2 - ( CH 2 ) n~N -R 2 l?,n ~lust ~ 11 , . . ~ C~lor Zn acetate ~N ~ R~
Zn &-(C~12)n-N-R2 +R3I

(XXXIV) ~C-(CH2) -~N~ + I

c~ n - 2, u, P" y, c) - tetraki~ ~
(~-trialkyl amino eth~l) porphine ZillC, tetra iodide :

l~Z69~8 Quaternary a~nonium aza porphines can be made by adaptation of the methods of equations ~XTX and ~X supra, as for example:

(XXXV) (H3C) -N-C2Hs (1'3C) N ~ CN C2Hsl , ~ (CH3)Z

N
. ' I
S tetrakis - di-(N-dimethyl-N-ethylamino) benzo - a, ~, ~, ~ - tetraaza porphine, octaiodide salt Quaternary ammonium mono-, di-, and tri-aza porphines can be made by su.i~able cho.icc o~ mixed startln~
matericlls, in a manner analacJous ko the way anala~ous pyridinium compounds can be made as explained hereinabove.
Mixed quaternary ammonium/pyridinium porphine compounds are readily prepared, as for example:

- 8~ -~Z69~8 ¢ ~ ~ ~ 'N ~ CH3I

(C2Hs)2 (l2~1s)2 1-13C - N~ 1 (XXXVI) pr~lominately 2-(N-diethyl-N~
methyl amino ~ N
benzo)-,B,y,~- \ I
tri~N-methyl H ~ k- N~1 N ~ /==~
pyridyl)-~- 3C- ~ C Ç ~\ N -C1-1 monoaæa porph.ine, ~ N 11N~
tetra iodide sa1t ~ + 4 1 .

~I~Z69~8 ., Among the preferred nonionic and anionic solubi-li2ing groups of the photoactivators of this invention and polyethoxylates, sulfates, polyethoxysulfates, carboxylates, polyethoxy carboxylates, and phosphates. A suitable S preparative method for introducing all such groups into the porphine structure is to first make the corresponding poly-hydroxy porphine, and then convert the hydroxy groups to the solubilizing groups of choice. ~ccordingly, methods o~ preparing hydroxy porphines will be described below, ~ollowing which rneans of convertiny these compounds to poly-ethoxylates, sul~ates, etc. will be discussed.
One method of making polyhydrox~ porphin-es is the reaction of pyrro]e and substituted pyrroles with hydroxy-sub~tituted aromatic aldehydes. This is analagous to the preparation o~ cationic solubilizing groups illustrated by compounds (XXV), (XXVI), (XXVII), (XXVIII), and (~XXIII) gb :

~1269~8 Ho (XxXVII) ~9 + ~CI~O ~ ~ ~0.'1 ~

indole -~- hydrox~ ,y,~ - tetrakis -2-carboxaldehyde ¢5-hydroxy - 2-indolyl) porphine (XXXVIII) C110 ~

~ ~/c ~ ~(cH2)noH
H (CH2) OH

a,~,y,~ - tetrakis -(hydroxy alkaryl) tetrabenzo porphine , . Mixtures o~ khe above startin~ materia].s y~ield porphine structure~ 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 mixture of pyrrole and benzo-pyrrole with benzaldehyde to yield dlbenzo meso tetraphenyl porphine.

~ lternatively, hydroxy-substituted pyrroles can be reacted with aromatic aldehydes:

1~269~8 (XXXIX) OH
HO OH --~

H

3,4-di(~-hydroxy benzo 1,2,3,4,5,6,7,8 -phenyl) pyrrole thiophene -2- octa(hydroxy phenyl)-caxboxaldehyde ~ tetrakis ~2-benzothienyl) porphine .

(XL) ' Cl-l1 CI~C~I20 C~{CI-I 2 0~
~ ¢~CII() 3-hydro~y iso- 2-furan 1,3,5,7 - tetra propyl pyrrole carboxaldehyde hyclroxyisopropyl-~,~,y,~ - tetrakis -(2-furyl) porphine ~lZ69~!8 In a manner analagous to the preparation of cationic compound (XXXIV), hydroxy cyano aromatic or hydroxy cyano heterocyclic ketones can be condensed and rearranged to foxm the stable porphine quadridentate structure. For example:

(XLI) 1' powdered Mg ~ OH

CN

,Mg~N ~CIl tt ~i ~ Zn acetate (XLII) ' C-C~12 ~/
N ~ ~ ~C-CII
~ I .
. .

(XLIII) C-CI~ ~ Zn accta~e ~
N z , N -C~i~ ~ OH

Mix~ures of the above starting materials yield porphine structures wherein the 4 quarters of the quadri-dentate molecules have non-identical structures, according 1~2S9~8 J

to the proportions used.
Hydroxy-substituted aza porphines can be made in a manner analagous to that used to prepare compounds (~;XIX) and (xxxl; i.e. by condensation and rearranyement of hydroxy-substituted aromatic vicinal dicarboxylic acids in the presence of a~nonia. For ex~nple:

( XLTV) llO ~ COOII Nll ~ O~l /
hydroxy phthalic acid ~ mixture o~ po:Lyllydroxy mono- and di-aza porphines results from usingr as starting materials, a mixture o~ a metal cyanide with a ketone whose two side groups are, respectively, (al];yl or aryl) and (halo aryl or halo heterocyclic), where one or the other or both side yroups 1~ of the ~etone have a hydroxyl yroup substituted therein.
For example, _ 90 _ 11269~
O ( XLV
HO ~ C-CH2-CH20H
+ Zn(CN) 2 Cl OH OH

tetra (hydro~ybenzo) - ~ ,C ~H
Zn N
a, ~, r - tri(hydroxy- ~ `C

methyl)-~ - monoaza HO ~ C~12 ~
Oll OH
porphine zlnc tetra (hydroxybenzo) - a,y -di(hydroxymethyl) -diaza porphi.ne zinc Alternatively, using mixtures of starting materlals described abov~:

" , ' . .
CHO

~3 + ~ t' 3 ~ . ~_ (XLVI) Clt2oll oll tri(dihydroxybenzo)-~, C~OH a- (hydroxymethyl N N ~ phenyl) - ~,y,~ -N ~ OH triaza p~rphine O , 1~

~1269~!8 The hydroxy groups of the foregoing hydroxy substituted porphines can be converted to solubilizing groups of this invention according to the fol].owing well known chemical reaction procedures:
_ _ - CH20H +n CH~ ~ CH2 ;~ -CH2 [ O - CEr2 - CH2] n polyethoxylate - CH20H ~ oleum _ CE120S03~3 sulfate 2 2 2 n 3 polyethoxysu].fate - CII20H ~ Ki~nO~ - CO ~
- carboxylate -- CH2011 1- ClCll2COOEl ~_ -- CEI20CI12COC~) met}loxy earboxylate ~ CEr2 ( Crl2cEl2 )nII+KMn~ ~ -Cf r2 (CH2cEl2 ) n ] Cll2coo(~
polyethoxy earboxylate 22 2)nClCE12COOH -Crr2 (OCH2CH2) OCrl2COO(~) polyethoxy carboxylate --CH20Er+ E13PO4 2 1 2 0 OEI phosphate - CE12 (OCH2CEl2)nOll+H3po4 ~ C 2 ( 2 2 n I
OH
polyetho~y phosphate 69Q~

~ CO ~+n ~CE12CEI2~ ( 2 2)nOH
polyethoxylate ester To exemplify how these procedures can be used:

~ .

, ~- ~ CI~OII
C ~y ~ (XLVII) ~ . ''.

. . N C ~ CH2(OCII2CH2)zoOH
/

tetrabenzo -~,~,y,~ - tetra(4-polyetho~ymethyl-phenyl) porphine ~ (XLVIII) G~\_Oll ~ OCH 2 C()~

-~ ClC~zCOOII
N N
~N N

2,4,6,8 - tetrakis (carboi:y methoxy) -~,R,y,~ - tetraaza porphine It will be appreciated that one skilled in the chemical arts, and particularly in -the color and dye arts, can apply the foregoiny principles to make his photoactivator of choice according to this invention.

~126~

Alternative ways of making carboxy porphines are evident modifications of the chemistry hereinbefore described:

(XLIX) COo~l ~ I Cl{O ~Coo~

2-(4-carboxy henæaldehyde ~ - tetraphenyl -phenyl) pyrrole . 1,3,5,7 tetra(4-carboxy-phenyl) porphine Cllo 1 (L) C ~ COO~I
I Coo~
pyrrole 4-carhoxy ~ tetrakis benzaldehyde ~4-carboxyphenyl) porphine I (LI) C~Otl ,[~C-OII 1~113 ~
IIO-C C-O~I N
o o 7 ( LI I ) Cl Cl /~_ COCl coo~3 N ~"_ ~ H 2 Cl / N

_ 94 _ :

.~, . .

1~Z69~

,, .

Varying proportions o~ the above starting materials in mixtures yield mono-, di-, and tri-aza compounds. For example:

HOOC Cllo 3~ ~ 3 1~3 ~ ~ CN
(/ ~ C
N

(LIII) COOil ~3~0011 l~OOC ~ / ' ~C ~
k rll~ N ~ ~ C()t)ll >~r~ nN~
, <~c~ I
COOH

COoll : predominately 1,3,5 - tri(~-carboxyphenyl) - ~,~,y -trit4-carbo~Yyphenyl.) - ~ - aza - porphine _ 95 _ ~26~8 Using mixtures of starting materials which have different solubilizing groups, followed by appropriate sequential reaction, yields corresponding porphine deriva-tives, which may be entirely anionic, entirely nonionic, or may be zwitterionic in nature. For example:

3.3~26~8 HO OH

=coo~ ~

m CH\ ~CIl2 ~(CH2CH O) H (LIV) ~>
~ Coo(cH2cH2o) C()O~
~ CllO

CH201-l Cl12OH

o lium ( LV ) ~ COO~ ' ' / ~CH2 _ 97 _ 6~

COO
~ooc COO~ ~ ~
~COO~ ~

' Coo ¦(LVI) ~,COO~ ~

C ~ ~-CII3 t As usual, var:iations in starting materials make po~sible thce pl.eparat:i.on of aza derivatives and metallated derivatives to suit.
r~emote sites are preferred fo.r the solubilizing groups of this invention. Porphine structures solubilized at remote sites have a reduced tendency to aycJregate into multilayers on Eabric surEaces because they tend to have more bulk and less crystal order, hence the intensive blue/green coloration of these substances is imparted to Q~

.
the fabrics in reduced ~nount. Also, remotely solubilized porphines participate to a relatively small degree in the side reactions designated by numeral 7 on Scheme A ; -thus the excited singlet state of such compounds is converted more efficiently to the excited triplet state 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 XXXIV supr~ where n is 5 or grcater; compound XXXV~II where n is 2 or greater;
compound XL with 4 or more methylene groups interposed between the hydroxy group and the pyrrole ring; compound XXX with 3 or more methylene groups interposed betwcen -the pyridine and pyrrole riny; compound XXXIII with 2 or more methylene groups interposed between the meso carbon atom and the benzene ring; etc.
Especially preferred photoactivators are remotely sulfated amino sulEonyl yorphines. '~hese comyounds not only have the benefits discussed supra or remotely solu-bilized porphines generally, but also have the added beneEit of substantivity to synthetic fibers as well as cotton fibers. These compounds can be prepared by a provess involving the ollowing sequential steps:

_ 99 _ ~:24i~

1) Preparing a porphine without solubilizing groups.
This step is illustrated by the preparation of all cationic porphines exemplified hereinbefore, omitting the quaterni~ation step; and by t:he prepara-tion of all hydroxy porphines exempli~ied hereinbe~ore, where the starting materials are analagous non-hydroxy-substituted compounds.
2) Reacting with chlorosulfonic acid and thionyl chloride to form the corresponding ch].orosulfona~ed porphine.
3) Condensing with an amino alcoholt using an aqueous medium and a temperature at which may be at, above~
or be].ow normaL a~bient~

9) Sulfonal-ing with oleum.
Illustrative examples oE this preparative method are:

_ 100 _ - ~2~i9~8 ~Ho ~3 ~ C~ 5O2Cl (I,VII) H2N ~ OH
UJ~rY~ - tetrakis (4-sulfato-phenyl ~mino sulfonyl phenyl) porphine ~ ' C

SO2NI-I_~OSO3 SO2NH ~ 011 ¢~CN ~ CISOJH H2NCII2CH201-l ,Zn N

(LVIII ) ~ ~1,2,3,~,5,6,7,8 - tetrakis ole~lm ~N / (2-sulfatoethyl amino-~ -~ sulfonylbenzo)-tetraaza Zn N porphine zinc _ 101 _ ~z~

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-2,3-propane diol.
~ general method of preparing amino hydro~y alcoholsis as follows, where the R's may be H, alkyl, or substituted alkyl:

RlCI~O ~ }I(-i~ ~ Rl - C - C - R

~reduction R ~ C - C - R

The amirlo~lllEonyl colltpound~ discu)~.ecl supra con-tain the - S - N -Il l O El group interruptiny the chain of atoms linkiny the -OSO
solubilizing group and the porphine core. It is also con-templated that many other non-methylene groups can be interrupting groups, as explained hereinbefore.

Whatever the nature of the interrupting group, the solubilizing yroup can be any of those discussed herein. Preparative methods for such compounds fall within the ordinary skill of the art supplemel~ted by the disclosure herein. For example, - .

~69~

C~10 NH2 , C ~3 NH2 O=C=~ COO~ ~

4-carboxyphenyl isocyanate (LIX) -C-N ~ Coo~

. CN ~ NH2CHO

ll2N ~ CN ~ t ,Mg N~ OH

(LX) ~ H

+ 9 CH~-C~

OH Mg N
/ ~ 0(CH2CH2O)sH

9~

Opti _ al inqredients of the compositions of this inven~
tion, their processes of preparation, and their methods of use are conventional in nature except for the necessary exposure to oxygen and visible light. In general, this invention in its processing aspect comprises removing stains from textiles by treating the textiles, in the presence of visible light and oxygen, with an aqueous solution of a composition of this invention.
The specific optional ingredients, processes of prepara-ti.on, and methods of use are a function of the type of laundry products that are desired and the types of cationic substances that are employed. These matters will now be addressed seriatim for fabric conditioniny/bleach compostions, for detergent/bleach compositions, and for gerrnicidal/bleach cornpositions.
One form of fabric conditioning/bleach composition is liquid; more specifically an emulsion i.n water. Numerous prior art refcre:nces and commercial products are in the form of liquid fabric conditioners formulated with cationic substances as their primary active ingredients. This .inventiOn in ~he form of a liquid fabric conditioner/bleach composition maintainS ~he fabric softening and electrostatic control purposes and benefits, compositions, processes and uses of the prior art fabric conditioners; contributes the stain removal functions and benefits previously disclosed in the prior art as obtainable only by the use of zinc phthalcyanine sulfonate photoactivator in detergent compo-sitions; contributes overall fabric bleaching and fugitive dye removal not disclosed by the prior art; while is abl.e .
:

g~B

to use smaller amounts of photoactivator to accomplish these purposes and benefits because of the hereinbefore discussed interaction between photoactivator and cationic fabric conditioner.

In addition to fabric conditioner, photoactivator and water, this type of fabric conditioning/bleach product can contain minor amounts of colorants, perfumes, preservatives, optical brighteners, opacifiers, pH buffers, viscosity modifiers, fabric conditioning agents in solid form such ac: clay, emulsifiers, stabilizers, shrinkage controllers, 5potting agents, yermicides, fungicides, anti-corrosion agents, etc. Urea, protonated diethoxylated monoalkyl amine, or solventS such as alcohols, glycols and glycol ethers can be uscd to control physical stability and visco5ity of the product.
Nonionic ~abric conditioning agents can be used, if desired, together with the cationic fabric conditioners in combination with photoactivator. This category of nl?tionll in~redients includes sorbitan esters, fatty alcohols, mono- and di-glycerides containing at least one free hydroxyl group, mono- and di-ether alcohols such as glycerol-1,3-distearyl ether; and diamine s ~
Liquid fabric conditoner/bleach compositions of the present invention can be prepared by conventional methods.

~lomogenizing is not necessary. A convenient and satisfactory method is to mix the components together batchwise at about 60-65~C, using a marine propeller for agitation. It is preferred to dilute the quaternary softeners with water before adding to the remainder of the composition. Temper-ature-sensitive optional components can be added after the - l05 -~2~

fabric conditioning/bleach composition is cooled to room temperature or thereabouts.
The liquid fabric conditioning/bleach compositions of this invention are used by adding to the rinse cycle of conventional home laundry operations. Generally, rinse water has a temperature of from about 5C. to about 60C. The concentration of fabric conditioning/bleach composition in the rinse water is typically about 0.05 to about 0.10%, and the concentration of the cationic fabric conditioners ]0 of this invcntion is gellerally from about 2 ppm to about 200 ppm, rnore commonly from about 10 ppm to about 100 ppm, by weight of the aqueous rins1ng ba-th. --It has been stated hereinbefore that photoactivator usage is from about 0.001% to about 0.5% by weight based on the fabric conditioning/bleach composition, preferably from about 0.005% to about 0.5%. Combining these figures with the foregoi:ng concentrations of fabric conditioner/
bleach composit:ion in water yi~ld~ the re~ult thclt the photoac-tivator concentrations in water range ~rom ahout 0.005 parts per million (ppm) to about 5 ppm. Within this range, from about 0.1 to about 1 ppm are preferred. The lower side of the foregoing ranges are effective especially when the fabric is exposed to photoactivator for a relatively long time, when drying takes place in brilliant sun~ight, and when the photoactivator adsorbs especially well upon the fabric.
In general, laundry practice embodying the present invention in its fabric conditioning/bleach aspect comprises the following steps:

t`

(i) washing fabrics with a detergent composition, (ii) rinsing the fabrics, (iii) adding during the rinsing step the above-described amounts of liquid fabrie conditioner/bleach, (iv) drying the fabrics, and (v) providing exposure to visible light and oxygen during step (iii) or step (iv).
When multiple rinses are used, the fabric condi-tioning/
bleach eomposition is preferably added to the final rinse.
Rinsing -time, duriny whieh fabries are exposed to the photoac-tivated bleach solutiol~ is typically short; often less than 10 Minutes and Erequently as little as 3 minutes.
Inasmuch as photoactivatorad~orption on the fabric is a function of time, in this type formulation it is extraordinarily important -tha-t adsorption be rapid.
It is convenient to provide light and oxygen by drying out-of~doors, especially in direct sunlight as on a clothesline. It is also possiblo to eotlcluct th:i~ drylng skep in an i]J.uminatecl dryer.
~nother form of fabric conditioniny/bleach composition is solid; more specifically a releasable deposition of fabric conditioner and photoactivator upon a substrate. This depositiorl can be prirnarily a coa-ting upon the surface of the subslrate or can be primarily an impregnation into the interstices of the substrate. The substrate can be a sheet of paper or of woven or nonwoven cloth or of foamed plastic.
Certain prior art references and commercial products exist in the form of cationic fabric conditioners deposited on a substrate. This invention in the form of a fabrie ~269~

conditioner/bleach deposited on a substrate maintains the fabric softening and electrostatic control purposes and benefits, compositions, processes and uses of the prior art articles while it contributes the stain removal, fabric bleaching and fugitive dye removal benefits of photoactivated bleach.
The substrate portion of this type of fabric condition-ing/bleach product is fully described in Japanese laid open application OPI 53-111,197 published September 28, 1978, and U.S. Patent 3,686,025 issued August 22, 1972 invented by Morton. Preferred methods of applying the fabric conditioner to the substrate are described in the above references, and the photoactivator bleach of this invention can be conveniently added by mixing with the fabric conditioner prior to application to the substrate.
Preferred methods include passing the substrate through a fan or trough containing the fabric conditioner in liquid form (melted or dissolved in a solvent) followed by removal of excess liquid by squecze-rolls, cooling or evaporation Pf solvent Oe necessary, olding, cutting, and packaging;
and spraying the fabric conditioner in liquid form upon the substrate, followed by removal of excess by squeeze-rolls or a doctor-knie, cooling or solvent evaporation of necessary, folding, etc. as before.
Optional ingredients for fabric conditioning/bleach compositions applied to a substrate are generally those hereinbefore described for liquid fabric conditioning bleach compositions; of course solvents will not be needed for reasons of controlling physical stability or viscosity, but may be desired for processing reasons.

The physical dirnensions of the sheet substrates herein can be varied to satisfy the desires of the manufacturer and the con-sumer. Convenient surface areas range from about 20 in.2 to 200 with the thickness of the sheet being set by the requirements of flexibility and softener loading. The amount of softener composition for purposes of supplying softness can conveniently be from about 0.2 to 16 grams on such sized sheets.
Fabric conditioning/bleach articles in substrate form can be used in the laundry rinse in the manner described hereinbefore for comparable products as ]iquid form.
~lterncltively, th~y can b~-~ added to a clothes dryer together with the damp fabrics to be treated. The fabric conditioning agents and the photoactivated bleach are released from the substrate in either the washing or the drying steps as the result o~ wa-ter, hea-t, and/or tumbling or rotating action.
Exposure to visible light and oxygen are provided during the drying step, or duriny the rinsing step if the photo-acti.vator is present at that time.
Detcrgent/bLeach colrlpos.itions o this invention contain a cationic surfactant and a porphine photoactivator as described hereinbefore. Such compositions maintain the cleaning purposes and henefits, compositions, processes and uses of prior art detergent compositions such as disclosed in Cockre].l and Murphy cited hereinbefore; contribute stain removal, overall fabric bleaching and fugitive dye removal; and accomplish these latter purposes and benefits at lower usacJe levels than known heretofore because of the hereinbefore discussed interaction between photoactivator and cationic surfactant.

_ 109 _ /

In addition to cationic surfactant and photoacti.vator, the degergent/bleach compositions of this invention optionally but preferably contain nonionic surfactants of the formula R(OC2H4)nOH

wherein R is a primary or secondary alkyl chain of from about 8 to about 22 carbon atoms and n is an average of from about 2 to about 9, and whereln said nonionic surfactant has an HLB from about 5 to about 17.
~s explained in Cockrell andin Murphy, these nonionic surfactants contribu-te substantially to the cleaning of cationic surfactants under certain conditions. Most preferred ratios of nonionic to cationic surfactant are from about 5:3 to about 300:1.
Coc];rell and Murphy teach advantages for detergent compositions containi.ng cat.ionic and nonionlc surfactallts so formulated as to produce, under aqueous laundry conditions, a noni.onic surfactant-rich phase boundary within about 20C of the desired washing temperature. I~hen such a phase-separating composition is used together with a photoactivator to formualte a detergent/bleach composition of this invention, it is preferred that the photoactivator be solubilized by nonionic and/or cationi.c solubilizing groups, most preferably by cationic solubilizing groups.

~Z6~

Another optional but preferable component is fatty amide having the formula 0 ~2 . R2 Rl_c_N or Rl_S~
\ 2 //~ \ 2 R O O R

whe~ein Rl is C8-C20 alkyl, alkenyl, alkyl phen~:l. C~l. a.l.]~y:l.
benzyl, preEera~ly C10-Cl~ alky.l., ancL MOS~ pre~erably Cl.
alkyl; ~nd each R2 i~s hydrogen, or Cl C~ alkyl or hydrc)xya:l.k.
pre~erably hydrogen.

- llOa -The detergent/bleach compositions of this invention should be reasonably free of anions which will render the eationic surfactant used in the composition non-dispersible in water. While this property is a function of the physieal and chemieal properties of each individual eationie surfaetant and each individual anion, in general it ean be said that it is preferred that the amounts of polyvalent anions from the following sourees be limited to a total of no more than about 4~ by weight of the eomposition: phosphates, silicate, and polyearboxylate builder anions; earboxymethyl eellulose; and anionie surfactants.
Other components are optional, sueh as suds eontrol agents, either suds builders or suds suppressors such as the long ehain fatty aeids diselosed in ~.S. Patent 3,954,3~7 lS granted on September 27, 1960 to St. John, the silieone/
silica mixtures diselosed in U.S. Patent 3,933,672 granted on January 20, 1976 to Bartolotta et al, the mieroerystalline waxes diseloscd in BelcJicln Pa~ent 82~,2~3 granted on July 19, I.975 to ~ate et al., and fatty phosphate esters sueh as monostearyl phosphate.
Still other optional eomponents of -the detergent/bleaeh eompositions of this lnvention are bleaehing agents, bleaeh aetivators, soil suspending agents, corrosion inhibitors, dyes, fillers, op-tieal brighteners, ~ermieides, plI adjusting ac~ents, enzymes, enzyme stabilizing agents, perfumes, fabrie softening componen-ts, statie eontrol ac~ents, and the li~e. Ilowever, because of the numerous and diverse performance advantages of the cornposition of the present invention,separate addition of components such as static control agents, fabric softening agents and germieides will not usually be necessary.

_ 111 _ ~:69~tB

MonoValent electrolytes can be used if desired to buffer pH, add ionic strength, control viscosity, prevent jelling, etc. Insoluble builder such as aluminosilicate, dry particulate fabric softener such as smectite clay, anti-caking agents such as benzoates and succinates, anti-redeposition agents such as carbox~sethyl cellulose and polyethylene glycol, and hydrotropes such as toluene sulfonate and urea can be used to the extent that they are compatible with the eationic component of the formulation.
Granu]ar formulations enbodying the compositions of the present invention can be formed by any of the conven-tional techniyues i.e., by slurrying the individual compo-nents in water and then atomizing and spray-drying the resultant mi~ture, or by pan or drurn granula-tion of the components. A prcferred method of spray drying compositions in granule form is disclosed in U.S. Patents 3,629,951 and 3,629,955 issued to Davis et al on Decembcr 2~ 71.
Liquid deter~ents cosnpc~sitiolls embocl~lny the photoactivating compositions of the present invention can contain cationic surfactants and preferably nonionic surfactants and water. They preferably contain an alkalinity source which can be inorganic sueh as borate or carbonate or organic such as snono-, di-, or tri-alkanolasnine. They can contain a solubilization system containing various mixtures of water, lower alcohols and glycols, and hydrotropes; and can contain a detergency builder. They can be homogeneous sin~le-phase compositions orin multi-phase heterogeneous form which can contain viscosity modifiers and stabilizers to maintain stable emulsions or suspensions.

Compositions of this invention in the form of detergent laundry bars can be prepared as described in U.S. Patent 3,178,370 issued April 13, 1965 and British Patent 1,064,414 issued April 5, 1967, both to Okenfuss. A
preferred 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.
The detergent/bleach compositions of this invention can be incorporated if desired into substrate articles in the manner hereinbefore described for fabric conditioning/
bleach compositions. These articles consist of a water-insoluble substrate which releasably incorporates an effec-tive amount, preferably from about 3 to about 120 grams, of the detergent compositions described herein, plus an effective amount of photoactivating bleach as described herein.
Detergent/bleach formulations embodying the composi-tions of the present invention are commonly used in laundry practice at concentrations from abo~t 0.1 to about 0.6 weight percent in water. Within these approximate ranges are variations in typical usage from household to house-hold and from country to country, depending on washing conditions such as the ratio of fabric to water, degree of soiling of the fabrics, temperature and hardness of the water, method of washing whether by hand or by machine, specific formulation employed, etc.

_ ll3 _ ~69~3 It has been stated hereinbefore that photoactivator usage is from about 0.005~ to about 0.5% by weight based on the detergent/bleach composition, preferably from about 0.01% to about 0.1%. Combining those figures with the foregoing concentrations ofdetergent/bleach composition in ~ater yields the result that photoactivator 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 is preferred. The lower side of the foregoing ranges are especially effective when the laundry process involves exposing fabric to pho-toactivator for a relatively long time as for example during a 30 to 120 minute presoak followed by a 20 to 30 minute wash, and drying the fabric in brilliant sunlight. The higher side of the foregoing ranyes may be needed when the laundry process involves exposing fabric to photoactivator for a relatively short time, as for example during a short 10 minute wash, followed by drying in an illum-inated dryer, Oll a line indoors, or outdoors on a cloudy day. While exposure to oxyyen and visible liyht are essenti.11, the source, intensity and duration of exposure of the light affect merely the degree of bleaching achieved.
In general, laundry practice embodying the present .invention in its detergent/bleach aspect 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 of steps (i), (ii), or (iii). These steps are appropriate whatevel physical form of deteryent bleach may be employed (e.g. granule, liquid, bar, substrate) and whatever means of exposure to _ ll4 _ ~;~Z6~

light and oxygen are employed (e.g. outdoor washing, outdoor drying, illuminated washing machine, illuminated dryer).
Germicidal/bleaching compositions of this invention can be prepared by mere addition of the essenti.al components to water, followed by mixing. Product concentrations can be as high as about 30O by weight, while use concentrations are typically in the range of 10-1000 ppm,preferably 50-500 ppm. The use of solvents to promo-te product stability, the selection oE indivi.dual yermicides and photoactive bleaches and the selcction of appropriate use concentrations and rnethods of use of germicide and bleach, are all-matters within the capability of a skilled artisan. The disclosures of the Shelton, Marks and Stayner references cited herein-before are typical of the many references that may assist in the formulation and use of such compositions.

_ ll5 _ 1~26~8 E,~PLE I
A photoactivator of this invention, tetra(sulfobenzo) tetraaza porphine zinc, tetrasodium salt [zinc phthalocyanine tetrasulfonate-Na salt] was prepared by condensing phthalo-nitrile and zinc dust in the presence of zn and molybdic acid, followed by sulfonation with oleum according to the method of Japanese OPI 50-113,479 and Belgian Patent 840,348 cited hereinbefore.
More specifically, 64 parts of phthalonitrile, 8 parts of zinc dust, and 1 part of molybdic acid ~ere reacted in 400 parts of ethyl~ne glycol at 195C. for 2 hours, yielding 55 parts of zinc phthalocyanine [77~ yield,~ 98% pure].
Sulfonation was accomplished by reacting 1 part of zinc phthalocyanine with 5 parts of 20% oleum for 4 hours at 100-120C., followed by addition of 25 parts cold water and NaOH sufficient to neutralize to pH 7. Composition of the resultant product on a dry basis was zinc phthalocyanine sulfonate 7.0~; organic by-products 12.9~i and sodium sulfate 80.1%.
q~he zinc phthalocyanine sulfonale lcvel was determined spectrophotometr:ically using absorption at 667 nm and an extinction coeff:icient of 2.03 x 105 and also by zinc analysis. The oryanic by-products were identified by high pressure liquid chromatograplly and mass spectrocopy to be predominantly 4-sulfophthalic aci.d, 4-sulfophthalimide, phthali.c acid, and the two isomersof 4-sulfophthalamic acid.
Sodium sulfate was determined gravimetrically after extraction of the organlc component with methanol.
The zinc phthalocyani.ne sulfonate was formulated with cationic fabric softening/antistat agent into the following fabric conditioning/bleach composition in the form of a stable aqueous emulsion, Composition A as defined on Table I.

~2~9~8 TABLE I
Com~onent Weiqht Percent Composition Composition Composition A _ B D
Zinc phthalocyanine sulfonate-Na4 salt 0.73 - 0.18 Ditallowdimethylammonium chloride 5.25 5.25 5.25 Nonionic emulsifier 0.50 0.50 0.50 Color, perfurne, and optical brightener - 0.473 Water balance balance balance 100. 0 100. 0 100 . O
*Equal parts of C fatty alcohol condensed with 3 molcs of e~hylenelo~ide per mole of alcohol and C 5 fa-tty alcohol condensed with 12 moles of e~hy~ene o~ide per mole of alcohol Other compositions used in the comparative tests of E~amplc I
were Composition [B], a commercial liquid fabric softener/
antistat agent; and Composition [C], a granular detergent composition free from bleaches and optical brighteners wh.ich had a pH at use concent.ration in water of about 10.2 and is defined otl Table II.

~lZ~9~8 TAsLE II

Corn~onent I~Jt. % Com~osition C~.

C12 branched chain alk~l benzene sulfonate 20 Sodium tripo'yphosph2te 28 Sodium to].uene s~ onate 2 Silicate solids (2 0 ratio SiO2/Na2O) 5,~
Sodium sulfate 34 Sodium car~onate 0.. 17 ~ocl~ n carb~ yme~h~l c,e~llulose 0.~S
~erfur~e 0.1 Optical brightener ~none]
~isc~llaneous 1.38 Moisture _ 8.5 ~ Total dete~gent 100.00 A conlrnercial waslling maclllne was used Eor testing, specifically a Me~ican General Electric CONDESA wringer type machine having an ayitator speed of 25 cycles per minutes and a recommellded capacity of lG.5 U.S..gallons.
Water had a hardness of 9 grains per gallon, with a 3/1 ratio of Ca++ to Mg~+. Cloth load consisted of 12 cotton terry bath towels and 48 cotton muslin swatches whi.ch had been stained by passing through a boiling bath oE tea follow~d by squeezing, drying and aging. The entire cloth load was washed for 10 minutes in a 0.25% concentration of Composition [C] at 75F. Six bath towels and 24 swatches ~26g~8 were removed. [Treatment (1): washing only]. The remaining 6 towels and 24 swatches were rinsed for 3 minutes in the washing machine in a solution of 51 liters of water and 28 grams of Composition [A], which represents a concentration of 4 parts per million (ppm) zinc phthalocyanine sulfonate-Na4 salt and28.8 ppm. ditallowdimethyl ammonium chloride.
[Treatment (2): washing plus rinsing in a composition of this invention.]
A second,comparable, cloth load was similarly washed.
~ter removal o~ 6 towels and 24 swatches as before [Treatment (1): washin~ onl~__uplicate], the remaining 6 towels and 24 swatches were rinsed as before except in commercial fabric softener Composition [F] at a strength providing, as before, 28.8 ppm ditallowdimethyl ammonium chloride. [Treatment 3: wa6hing, plus rinsing in commercial softener].
After completion of the treatments described above,all towels were dried in an automatic dryer and all stalned swatches were dried out-of-doors Oll a sunli.t clothec,lille.
~he whiteness o the tca-stained swa-tches were measured before and after each of the 4 treatments described above, and their increase in whiteness corresponding to stain removal was measured on a Gardner XL-10 using the following equation:
/` w = l o o - J (100-L) + a + b Softness of the towels was graded by a panel of expert judges and graded on a 9-point Scheffé scale. Results were as follows:

_ 119 _ ~269~3 ,, TABLE III
Treatment Stain Removal Softness No. (~ W) (Panel score units) 1 5.7 -0.5 2 9.9 +0.5 l(dup.) 4.8 -0.6 3 5.3 +0.6 90~ LSD [1.0] [0.4]

I'he numerical result6 above show that significant stain removal as well as softening was accomplished by the fabric conditioning/bleach compositions of this invention.
Subjectively, both of these benefits were considered large.
However it was also observed that, before drying, the damp towels of Treatment 2 had a strong blue!green hùe, which hue had disappeared after drying. This test had used a concen-tration of plloto.lctivator considered ar~proE~riat:c whcll used in combination with an aniorlic detercJent composition typical of the prior art.
Allother test W~IS run to test for stain removal effectiveness at a lowcr concentration of photoactivator when used in the presence of a cationic substance.
The test described above was repeated with the following results, while [Trea-tment 2' is used to designate _ashing-plus rinsing with Composition [D] instead of Composition [A], with al] other factors hcld constant:

- 120 ~

~269~

TAsLE IV

Treatment Stain Removal Softness _No. _ (~ W) (Panel score units) l 2.8 -1.3 2' 4.7 +0.6 l(dup.~ * *
3 * +0.1 90% LSD [0.9] [0.5]
* not measured These numerieal results show that signifieant stain removal and softeniny was accomplished by e~tremely low levels of photoaetivator. Subjeetively, no appreciable blue/green hue was observed on the damp towels before drying.
zine phthalocyanine tetrasulfonate is also an effeetive photoaetivating bleaeh when formulated with distearyl dimethyl ar~lonium ehloride into a detergent/bleach composition and when formulated with N-octyl pieolinium bromide into a germieical/bleach eomposition.

- l2l -- ~ , .

~z~

~LE II
~ y, c~ ' tet'rakis :(4-carbox~enyl) porphine was prepared by reflu~ing a propionie acid solution, 0.24 molar in both 4-carboxybenzaldehyde and pyrrole, ~or 2 hours. Upon cooliny the reaeti.on mixture, purple erystals of c~, ~, y, o - tetrakis (~-eaxbox~phenyl) porphine~ preci-pitated. Yield was 32'~. The product was puri~ied by recrystallization from methano]./ehloroform so~utions.
The foregoing method of preparation is simi.lar to that deseribed by I,onc3O et al., J. Me~eroeyclic Chem. G, 927(1969) and the follo~J;ng sl~ectral ana].ysis perforrned on a Caxy 14 speetrophotometer in pyridine solution acJree vcry well with Longo's and Datta-Guptals ~indinys, J. Heterocyclie Chem., 3, 195(1966): ' Wave lenyth A(nm) ~23 517 552 591 646 ExtiIletiorl loy 5.25 4.15 3. 85 3. 65 3. ~8 coefficient Metal:Lation waC; aeeomplislled as ~ollo~ one gram of tetr~.lkic;(~-e.lrI.)o~ypllc~nyl) poll?ll:irl~ was reactecltli~h a 105' e~xcess of zinc acetate in reflu~inc~ climet:lly]. ~ormami.de fox one hour. ~Eter eornpletion of the reaetion, the solvent was removed on a vitoperator to obtain a re~idue. This resiclue was dissolved in water, aeidified to prl 3, and passed throucJh the l~ for~ of the cation exehanye resin Dowex 5DIY-X8(50~100 mesh) to remove the excess ionic zinc.
The residue after evaporation yeilded a red crystalline produet ~ith about 98c yie~.d. Spectral analysls on a Cary 1~ speetr.oL7hotometer in methanol ayreed very t~/ell with published date for ~, ~, y, ~7 - tetrakis (~ earbo~yphenyl) porphine zine, Lonyo ct al., J. Heteroeyclie Cnem. 6, 927(1969~:

1~269~

~1ave length ~(nm) 429 517 556 596 E~tinction log 5.54 3.46 ~.15 3.75 coefficient The acid form of photoactivator, prepared as described above, ~las converted to the tetra sod;.um SAl.t upon addition to alkaline (pll ~ 10) deter~ent solution, the cations of which were predominantly sodium.
a, ~, y, ~ - tetrakis (4-caîhoxyphenyl) porplline tetrasodium salt, both unmetallated and metallated ~ h zinc, are efective photoactivated bleaches. Each is formulated into detergent/bleach, softener/bleach, and germicide/bleach compositions of this invention by mixing with myristoyl choline ester quaternary ammonium chloride, palmityl trimethyl ammonium bromide, and N-lauryl-N-dimethyl-N-benzyl ammonium hydroxide, respec-tively.

1~69fOB

~X~MPLE III

ti,''~ ', c,''-''tetrik:i's''l'4-N'-methYl pv'ridvL) p-or~hine',''t-etra: (4-'t'ol'uen-e:sul'fona'te')''s'alt ~7as prepared as follo~Js: a propionic acid solution~ 0.2~ molal^ in ]~o~
pyridine 4-carboxaldehydt-~ and pyrrolel was ref:LuY~ed for ~5 min. The solvent tJas .~las~led off and the res;.due i~as washed with dimethylformamide to dissolve the t:arry by--products leaving purple crystals of tetra.(~-pyridyJ.) '.
porphine. Yield ~Jas 22. 5'5 L~nd tlle product s~ectrcll char~icteristics ~ert3 .in Sl~)S t~lnti~l acJreemt~ t ~ h t~ ose oh~e~rved b~ l.e:ish~r, :~ntJry. Cllem.' 1, 493(1962) The tetra (fi-pyrid~l) porphine (~.25 mo.l) was then reflu~.ed with sodium ~-toluene sulfonate (1.]. mol~ over-' night in dimethyl formamide. The reaction was ~hen cooled in an ice bath ancl the product was removed by 1-iltr~ltion.
'The collected violet crystals of Ct, ~, y, ~ - tetra ~N-methyl pyridyl) porpllirle, tetra ~-t-oluene sulfon~ltc s~lt:~/e.rt.
t~Jas~led ~lith ~lt,t~tone ~irl~ i.c~d urld~ V.IC,'~ .it-~:Ld ~ldS ~2~.
SpecLr~il ancilysis :in t/at~.r al pll 6--7 on a ~'LIry 1~ spect:roJ?hoto-meter ayreed very Jell with published data, ~a-;tern~lck et a].. , J. ~ner. Chem. Soc., 9~, fi511~1972):
~'7~ lencjtl~ (nrn) ~i22 518 551 58~ 6~il ~tinct:ion loy S.17 3.96 3.83 3.57 3.07 coefficient Elemental ancllysis yielded the followiny calculated and found values for the empirical formula C72ll66N~3S~O12:
C ~I N S
Ccllc: ~3.~2 ~.~8 8.22 9.~1 Eound: 63.15 5.03 8.~1 9.1 12~ -~269`~B

Metallation was accomplished in a manner similar to that described above for the tetracarboxy porphine of Example 1, with purification accomplished by chromato-graphic chloroform solutions on alumina. The metallation was done prior to quaternization with 4-toluene sulfonate.
~, ~, y, ~ - tetrakis (4-N-methylpyridyl) porphine, tetra (4-toluene sulfonate) salt, unmetallated metallated with aluminum and metallated with calcium, are effectlve photoactivated bleachec Each is formulated into detergent/bleach, softener/bleach, and germicide/bleach compositi.ons of this invention by mixing wi-th coconut alkyl trime-thyl ammonium chloride, l-methyl-l-[(palmitoylàmide)ethyl]-2-octadecyl-4,5-dihydroimidazolinium chloride, and N-dodecyl-N-methyl morpholinium methyl sulfate, respectively.

- ~25 -EX~MPLE IV

' Tetra''(2-'sulfatoethvl sul'fonamido benz'o) 'tetra-aza ~or~hine zinc' tetrasodium salt was prepared as fol]ows:
t~7enty parts of tetrasulfo tetrabenzo tetraaza porphine zinc, ~etrasodium salt were added to 200 parts of ch]oro-sulfonic acid wikh agitation and the mixture is heated to 60C. At this temperature, 30 parts of tllionyl chloride were added dropwise and the mixture was then hea~ed ~or 4 hours at 80C. The reaction mixture was ~hen cooled and added with acJita~ion to 200 parts of cold water from ~hich the tetrachloro sulo tetra~enzo tetraaza porphine z;inc was separated by filtration and subsequently ~ashed with 1000 parts of cold water. The tetrachlorosulfo tetrabenzo tetraaza porphine paste was then suspended in 300 parts of cold water and mi~ed with 30 parts of 2-aninoethanol for 20 hours at 20C. I'he suspension was then acidified ~tith hydrochloric acid to obtain ~I precipitat~
which was ~Eiarated by filt:r.l~ion, wasl-led ~7ith ~/cl~er alld dried. Twenty parts o~ the alr~ady ol~t.~ ed ethano]sulfon-amide deri.~tative of tetrabenzo tetraaza porphine zinc were then mixed for 12 hours at 20C with 100 parts of 10 ole~n. Tilc solution was then poured in a solution oE 100 parts of sodium chloride into 1700 oE ~Jat~r,and ~00 p.lrts of ice ~7ere adcled. A blue/green precipitate was formed and ~as separated by filtration and was washed with a solution of soclium chloride in water and ethyl alcohol until it was neutral to Conyo rcd. The blue/grcen powder obtained was then dried at 105C. for 2 hours. The product was purificd by six successive precipitations from ~ ~6i9~

aqueous solution by the addition of four volumes of acetone. Yield was 28~.
Substitution on all sulfo 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.
Examination of the spectrum of 1, 2, 3, 4, 5, 6, 7, 8 - tetrakis (2-sulfato-ethyl sulfonamido benzo) ~,~,y,~
- tetraaza porphine zinc, tetrasodium salt, in H2O at pH
9.5, using a Cary 14 spectrophotometer, yielded the following results:
Wave length ~(nm) 686 672 653 Extinction log 4.46 4.64 3.91 Coefficient Analysis of the zinc content by atomic absorption yielded 4.32% zinc vs. 4.40% theoretical on the basis of the empirical formula C40H36N12s8o22 4 2 Tetra (2-sulfatoethyl sulfonamido benzo) tetraaza por-phine zinc, tetrasodium salt is an effective photoactivated bleach in detergent/bleach, softener/bleach, and germicide/
bleach compositions when formulated with appropriate cationic substances.

Bl 9~
EXAMPLE V

Tetra~enzo triaza Porphine was prepared as follows:
A so~.ution of meth~l m~gnesium iodide was prepared from 2.4 ym. of magnesium and 6 5 ml. of me-thyl iodide in 100 ml. of ether; this ~7as decanted from the residual metal and ad~ed to a mixture of 12~8 gm o finely powder~d ph-thalonitrile and S0 ml. of ether. Upon addition, the liquid at once turned reddish-hrown, the nitrile dissolvin~, the ether gen-tly boiling, and a tarry mass forming. i~fter three hours at ~oom temperat~re, the remaincler oE the ether was relnovecl on a steam hat:h and the tarry residue ~as rapidly heated to 200C. Three ml. of I~2O were adde~ dropwise, liberating first white fumes and then iodine ~apor. AEter a furthe~ 1/2 hour at 200C, the powde-y residue was cooled, crushed and repeatedly e~tr2cted with a mixture of alcohol and 10% concentrated hydrochloric acid until the.e~-tract was no lonyer bro;~Jn in color. The res~due was then washed i~h 500 ml. oE absolut~ ~hal1ol and ~l~.iecl in ~n ov~n at 105C fo~ one hour. 'l'lle procluct was ~eed ~.rom macJnes~ n by dissolving it in concentrated sulfuric acid (150 ml.), followed by filtration and precipitation oE the pi~ment with ice. The grcerl precipi-ta-te ~as then collected on a filter and was washed with hot water containing 54 a~nonium hydro~ide. It was then dried at 105C and crystal-lized from chloronaphthalene. Yield was ~.2 gm. of tetra-benzo triaza porphine in -the form of purple neeclle~ e crystals.
Elemental analysis of the product yielded -the followin~ resul-ts:

~C %H %N
C33H19N7 requires: 77.2 3.7 19.1 ~ound: 77.3 3.6 19.3 A quantitative ei;amination of the spectrum of the pi~nent in chloronaphthalene, using a Cary 14 spectrometer, gave the following results:

Wave lenyth ~ (nm,) 694 652 G38 622 592 'i70 Extinction coef, loy. ~ 5,19 5,03 ~,75 ~.G6 ~.~3 ~0 The fore~oing method of prepara-tion is.similar to that described in Barrett et al, J. Chem. Society, pages 1809-1~20, and the spectrum reported above i.s iclentical to that Eound by Barrett.

Tetrabenzo tria.za porphine was Tnetallated to tetrabell7,0 tri.aza por~h.ine ~inc }~y the ~oll.o~:i.ng proceC;s 20~ ml. o~
reayent yrane N,N' dirnethylform.lrnide was brought to reLlux in a 2 1. flask on a stirring hot plate. Tetrabenzo triAza porphine (2 gm,) was then added, 1 minute allowed for complete solution to occur, and then a 10~ excess of the stoichiometric amount of zinc acetate was added (.8~ gm.) and reaction was allowed to proceed under reflux for one hour. The reaction vessel was then removed from the hot plate and cooled in an ice-wa-ter bath for 15 rninutes. 200 ml, of chilled distilled wate.r ~Jas t:hen added, and the resulting partially crystalline precipitate was filtered, ~7ashed with water, and air-dried.
The product was then recr~stallized from chloronaphthalene.
Yield ~7as 1.9 gm. in the form of purplish crystals.

Elemental analysis yielded the following results:
%C H %N
C33lll7N7Zn requires 68.8 ~ 95 11~
found: 69.2 3.10 11.1 ~ quantitative e~amination of the spectru~ of tetrabenzo triaza por~hi.ne zinc in chloronaphthalene, using a Cary 14 spectrometer, gave the following results.
~nm): 677 654 625 614 599 ~.o~ ~ 5.2~ 5~05 4.~2 ~.43 ~.~9 These values compare very ~e.ll with the results of Barrett et al, op. cit.
Sulfonation of tekrabenzo triaza porphine zi.nc led to the compound tetrasulfobenzo triaza ~or~hine tetra-sodium saLt, w.ith demetallation occurring simultaneously:
. . .
One yram of -tet:rabenzo triaza porphine zinc and 20 ml o~
concentrated ~I~SO~ werc ~.round in~o a hoT~.ocJc~rleous paste with a mortar and pe~tle. ~'h~ pa~t~ w~s then ~l-anse~red t:o a 250 ml. beaker and 50 additioslal ml. or concentrated 112SO~
were admixed. The mixture was then heated on a steam ba-th for ~ hour~, .removed and allowed to stand at roorn tempera-~ure Eor ~8 hours, and filtered to remove unreac~ed pigment.
'rhe filtrate was then diluted with two volumes of ~120 to precipitate the bric~ht yreen HSO~ salt of the sul~onated material, whi.ch was filtered and washed with acetone and then dissolved in alkaline .nethanol (5% NaOH in CH301--'). The sulfonated porphine ~/as then precipitated as the sodium.
salt by addition of 3 volumes of acetone ~fter the product ~tas then dried, it was extractcd with hot rnethanol to remove Na2SO~ residues After ex'raction, the porphine ~269~8 was dissolved in H2O, acidified to pH 3, and passed through the H+ form of the cation exchange resin Dowex 50W-X8 (50-100 mesh) to remove ionic zinc. Pure tetra-sulfobenzo triaza porphine in the form of a fine green powder was then isolated from a pH 5 so]ution by the addition of four volumes of acetone.
Elemental analysis yielded the following results:

%C %H %N %S

C33H15N7S4l2Na4 requires: 42.99 1.63 10.64 13.91 found : 43.2 1.69 10.68 13.76 The absence of zinc was verified by atomic absorption spectroscopy. Tetrasulfonation 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.
Examination of the spectrum of tetrasulfobenzo triaza porphine, tetrasodium salt, in ~12O at p~l 9.5, using a Cary 14 spectrometer, yielded the ~ollowing results:
~ (nm) : 694 666 645 634 618 589 log E : 4.56 5.15 4.92 4.63 4.24 3.71 Tetrasulobenzo triaza porphine, tetrasodium salt is an effetive photoactivated bleach in detergent/bleach, softener/bleach, and germicide/bleach compositions when formulated with appropriate cationic substances.

_ l3l _ ~. .

EXAMPLE VI
Tetra(4-sulfo?henyl) porphine, tetraa~r~onium salt ~as prepared as follo-,~s: T~o grams o~ tetraphenyl p~rphine, obtained from the ~ldrich Chemical Com,~any, Milt~au~ee, ~isconsin, U.S.~ as sulfonated in the manner described in E,~ample I for tetrabenzo triaza porphin~ with tile e}:cep-tion tha~ neutralization ~as done with methanolic am~onia (5%). Yield was 2.5 ym. of tetra(4-sulfophenyl) porphine tetraa~onium salt. Con~irmation that the porphine ~7as tetr2sulfonated was o~tained through the chrornatogra~hic t~chnique described above. Confinnation that the sul~ona-' tions too~ place in the 4 posîtion was done by nucle~r magnetic resonance (nmr): the nmr spectr~m of the sulfonated compound in D2O shows an absorption due 'to the pvrro:Le protons at r - 2.19 referred to a 3(trimethilsyl~1) propzne ' sulfonic acid referenc~,arld two doublets due to the phenyl protons c~ntcred at ~ = 2.79 and 1.~1 with a collplins between thern o~ ~ cps. The in-tecJr.at.cd a~ea o~ 'the phen,yl protons to p~rrole protol-ls cJa~e the expec~ed 2:1 ratio.
Further confirmatinn of the purity of the ~ateria]
was done by spec-tral analysis on a Cary 14 spectrometer:

~ (nm) ~11 515 552 5S0 633 Log ~ ~.72 3.21 2.82 ?..79 2.57 The ~oregoing method of preparation is similar to that described in Fleisher, J. ~ner. Chem. Soc. 93, 3162 (1971), and the spectr-lm reported above agrees very well ~Jith that found by Fleisher.
~letallatlon ~as accomplished in a manner similar to - :

that described in Example I. One gram of tetra(4-sulfo-phenyl) porphine, tetraammonium salt was reacted with a

10% excess of zinc acetate in refluxing dimethyl formamide for one hour. However isolation of the product was accomplished by a different procedure. After completion of the reaction, the solvent was removed on a rotavaporator to obtain a residue. This residue was dissolved in water, acidified to pH 3, and passed through the H+ form of the cation exchange resin Dowe ~ 50W-X8 (50-100 mesh) to remove the excess ionic zinc. As the solution passed through the resin, it was immediately neutralized with sodium hydroxide to avoid decomposition oE the acidic compound to zinc ions and the unmetallated porphine sulfonate. Yield was 0.96 g. tetra(4-sulfo~hen~ orphine zlnc, tetra-sodium salt.
Spectral analysis yielded the following results:
~ (nm) 517 557 595 630 Log ~ 2.88 3.28 2.84 1.81 Analysis of the zinc content by atomic absorption yielded 6.47% zinc vs. 6.50% theoretical on the basis of the empirical formula C44H28N4S4Ol4ZnNa4 whlch includes 2 moles of water of hydration.
Tetra(4-sulfophenyl) porphine, tetraammonium salt and its metallated derivative tetra(4-sulfophenyl) porphine zinc, tetrasodium salt are effective photoactivated bleaches in detergent/bleach, softener/bleach, and germicide/bleach compositions when formulated with appropriate cationic substances.

_ l33 _ .B~ .

i~Z~8 /

_XAMPLE VII
A number of exemplary compositions of this invention are identified on Table V. All contain pho-toactivators of this invention and all contain cationic substances of this invention.
Those compositions, the cationic substance of which is fabric softener, are tested in the manner des_ribed in Example I. Yabrics are rinsed in laundry baths containing 50 ppm of each composition, and are dried on a clothesline in ~irect sunligh-t. In comparison with fabrics rinsed in comparablc compositions except for the absence of photo-activator, test fabrics are equally soft and static free, while whiteness in each instance is improved by bleaching, especially of stains and fugitive dyes.
Those compositions, the cationic substance of which is surfactant, are tested by washing fabrics in laundry baths containing 0.5 weight percent of each composition, rinsed in plai.n water, and dricd on a clotheslinr~ in di.rect SUIl-liyht. In comparision with fabrics washecl in comparable compositions except for the absence of photoactivator, the whiteness of test fabrics is in each instance improved by blcaching, especially of stains and fugitive dyes.
Those compositions, the catlonic substance of which is germicide, are tested by rinsing articles containing 30 ppm of each composition, and are dried in direct sunlicjht. In comparison with comparable art~cles rinsed in cornparable compositions except for the absence of photo-activator, test articles are equally germ-free, while whiteness is in each instance improved by bleaching, especially of stains and fugitive dyes.

_ l34 _ /

It will be appreciated that, because many cationic substances exhibit both or all of these separate properties, test fabrics in certain instances are not only bleached but also cleaned and/or softened and/or rendered more free from germs.
Compositions specified to be in substrate form comprise the compositions as defined on Table V impreanated on a towel as follows: An 8" x 11" sheet of a Scott 8050 Industrial towel, having an air permeability of about 13.0 cu. ft./min/scl.ft., a basis weight of about 77.5 grn./sq.yd., and a thickness of 4~ mils, is impregnated with about 50 grams of composition.
An alternative method of making an article having comparable performance ls as follows: An 11" x 11" sheet of melt-blown polypropylene, having a thickness of about 29 mils, a basis weight of about 58.5 gms./sq.yd., and an air permeability of about 66 cu.ft./min.scI.ft. is coatccl one one sidc with about G0 c~rcltns oE composition; c~n identical subs-trate sheet is placed ovcr the coated sheet;
and the edges of the two substrates are heat-sealed to enclose the composition within the article.

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Photoactivators pa Tetra(sulfobenzo)tetraaza porphine zinc, tetrasodiurn salt pb ~, ~, r, ~ - tetrakis (4-carboxyphenyl) porphine, tetra-sodium salt pc ~, ~, y, ~ - tetrakis (4-carboxyphenyl) porphine zinc, tet sodium salt pd ~, ~, y, ~ - tetrakis (4-N-methylpYridyl) porphine zinc, tetra (4-toluene sulfonate) salt pe Tetra (2-sulfatoethyl sulfonamido benzo) tetraaza porphine zinc, tetrasodium salt pf Tetrasulfobenzo triaza porphine, tetrasodium salt pg Tetra (4-sul.fophenyl) porphine, tetraammonium salt ph Tetra (4-sulfophenyl) porphine zinc, tetrasodium salt pi Trans-dichloro, tri (sulfobenzo)-monobenzo-tetraaza porphine tin (IV), tri potassium salt pj tetrabenzo - , ~, y, ~ - tetrakis (4-N-methyl) pyridyl porphine tetraiodide pk tetrakis tcarhoxyhenzo) porphine zinc, tetrasodium salt pl tetrakis (polyethoxy naphtho) - ~, ~, `f, ~ - tetraphenyl porphine cadmium tetra-ammonium salt pm l, 3, 5, 7 - tetrakis (sulfato polyethoxy phenyl) -, ~, y, ~ - tetraki.s (carboxy naphthyl) porphine, oc tapotassium salt 2 pn l, 2, 3, 4 - tetrakis (pllospha~o phenyl) ~ , y, ~ -tetraphenyl porphine, tetra(triethanolamine) salt po dinaphtho - ~, ~, y, ~ - tetrakis (phosphatobenzo) porphine magnesium, tetralithium salt pp l, 3, 5, 7 - tetrakis (polyethoxy phenyl) - ~, y -di (polyethoxy phcnyl) porphine pq mono (polyethoxy henzo) - tribenzo - ~, ~, y, ~ -tetraphenyl porphine pr Bromo, tetrabenzo - ~ - (4-N-methyl) pyridyl - ~, y, ~ -pyridyl porphine scandium monobromide ps 2, 4, 6, 8 - tetrakis (sulfophenyl-n-heptyl) tetraaza porphine, tetra (monoethanolamine) salt pt tetrakis - (2-sulfatoethyl aminosulfonylbenzo) - tetraaza porphine zinc, tetrasodium salt pu Trans dichloro, di (N-methyl pyrido) - 1, ~, y, ~ -tetrakis (carboxyphenyl) porphine tin(IV), tetrasodium salt pv 1, 3,5 - tri (4-polyethoxy) - ~, ~, y - tri - (4-poly-ethoxy) - ~ - aza - porphine pw 2, 4, 6, 8 - tetrakis (carboxy methoxy) - ~, ~, y, ~ -tetraaza porphine, tetra(diethanolamine) salt px tri (diphosphatobenzo) - ~ - (phosphatomethylbenzyl) -~, y, ~ - triaaza porphine, tetrasodium salt py tetra (carboxybenzo) - ~, y - di(carbo-~benzo) -~, ~ - diaza porphine zinc, hexasodium salt pz trisulfobenzo-meso-tetraphenyl porphine, trisodium salt pA tetrasulfopyrido-meso-tetraphenyl porphine zinc, tetra-potassium salt pB tetrasulfonaphtho monoaza porphine, te_rasodium salt pC benzotrisulfobenzo monoaza porphine macnesium, trisodium salt pD benzotrisulfobenzo diaza porphine, trilithium salt pE tetrasulfobenzo diaza porphine scandium, tetradi-ethanolamine salt pF 1,2,3,~,5,6,~,8-octasulfophenyl porphine, octasodium salt pG trans-dichloro, trisulfobenzo-tri(sulfo-2-pyridyl)-2-pyridyl porphine tin (IV), hexasodium salt pll ~, ~, r, ~ - tetra]~is (2-furyl, 5 sulfo) porphine zinc, tet:rasodium salt pI tetrasulfonaphtho-meso-tetraethyl porphine, tetra-potassiunl salt p.J meso-sulfopyrryl-meso-trisulfophenyl porphine, tetrasodium salt :~2~i9~

Cationic Substances ca tallow trimethyl ammonium chloride cb ditallowdimethyl ammonium methyl sulfate cc di(coconut alkyl) dime-thyl ammonium chloride cd ditallow dimethyl ammonium chloride ce l-methyl-l-[(stearoylamide)ethyl]-2-hepta~ecyl-4,5-di-hydroimidazo.linium methyl sulfate cf l-methyl~l-[(palmitoylamide) ethyl]-2-oct~decyl-4,5-di-hydroimidazOlinium chloride cg TAFLON-320A
ch C14 pyridinium chloride ci N-dodecyl-N-methyl morpholinium methylsulfate cj -trioctyl methyl ammonium chloride c~ coconut alkyl trimethyl ammonium chloride cl N-octyl picolinium toluene sulfonate cm cetyl methyl piperidinium cn rnyristyl quinolinium bromide cc stearoyl choline ester quaternary ammonium bromide o cp 1~ 29 (Cll2cll2o)7 C112 C-O-CII~CIi2-N -(Cl13)3 C19 O O
cq Br~ 3 3 ( 2)2 C (cH2)l2-c-o-(cH2)2~N~-cl~ ) Bre O
cr 20~l41 0(Cll2CH2C112CH20)3-C-o-CH2CH2-N -(CH3)3 I9 cs octadecyl dimethyl dichlorbenzyl ammonium chloride ct para-tetiaryoctylphenoxyethoxyethyldimethyl benzyl ammonium chloride cu 2-phenyl-3-p-sulfamido-phenyl-5-undecyltetrazolium chloride O O
Il 11 cv 16 33 ( 2)4 NH CH2 N (C2H5)3 C13 _ l4l _ llZ~

Other Comporents oa C 5 al~yl polyethoxylate containing an average of o~ 4 moles ethylene oxide per mole ob alkyl glyeryl ether having the formula oc Nonyl ?henol polyethoxylate containing an average of 15 moles ethylene oxide per mole od sodium tripolyphosphate oe sodi~ pyrophosphate of sodiur.,nitrilotriacetate og sodiu~ carbonate oh sodiur, sulfate oi monoet~anolamine oj sodium silicate solids, 2.4 ratio sio2/Na2o ok Sodium aluminosilica-te Nal2(AlO2 SiO2)12 27l-l2O
ol ethane-l-hydroxy-l, l-diphosphonate, sodium salt om polyeth;~lene glycol, molecular weight 6000 on perfume oo potassi~m toluene ~ul.fonat~
op sodium car:boxymethylcellulose oq optical brightener (fluorescer) or colorant os protease ot montmorrilonite clay ou sodium ?erborate ov ;ethanol ow urea - l42 -

Claims (44)

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

1. A bleach composition comprising a cationic substance and from 0.001% to 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, aralkyl, aryl, alkaryl or heteroaryl; wherein each R, independently, is hydrogen or pyrrole substituted alkyl, cycloalkyl, aralkyl, aryl, alkaryl or heteroraryl or wherein adjacent pairs of R's are joined together with ortho-arylene groups to form pyrrole substituted alicyclic or heterocyclic rings; wherein A is 2(H) atoms bonded to diagonally opposite nitrogen atoms, or Zn(II), Cd(II), Mg(II), Sc(III), or Sn(IV), wherein B is an anionic, nonionic or cationic solubilizing group substituted into Y or R; wherein M is a counterion to the solubilizing groups; and wherein s is the number of solubilizing groups.

2. The composition of Claim 1 wherein, when B is cationic, M is an anion and s is from 1 to about 8; when B is nonionic, B is polyethoxylate, M is zero, s is from 1 to about 8, and the number of condensed ethylene oxide molecules per porphine molecule is from about 8 to about 50; when B is anionic and proximate, M is cationic and s is from 3 to about 8; when B is anionic and remote, M is cationic and s is from 2 to about 8; and when B is sulfonate the number of sulfonate groups is no greater than the number of aromatic and heter -acyclic substituent groups.

3. The composition or Claim 2 wherein B is quaternary pyridinium, quaternary ammorium, polyethoxylate, carboxylate, polyethoxy carboxylate, sulfate, polyethoxy sulfate, phosphate, polyethoxy sulfonate, or mixtures thereof.

4 . The compositicn of Claim 1 wherein the cationic substance comprises from about 0.5% to about 50% by weight of the composition, and the ratio of cationic substance to photoactivator is from about 1/1 to about 50,000/1.

5. The composition cf Claim 4 wherein the photoactivator comprises from 0.005% to about 0.1% by weight of the composition, the cationic substance comprises from about 2% to about 30%
by weight of the composition, and the ratio of cationic substance to photoactivator is from about 20/1 to about 5,000/1.

6. The composition of Claim 1 wherein the cationic substance is R1mR2xYL Z

wherein each R1 is an organic group containing a straight or branched alkyl or alkenyl group optionally subsituted with up to 3 phenyl groups and optionally interrupted by up to 4 structures selected from the group consisting of , , , , , -O-, and mixtures thereof, and which contains from about 8 to 22 carbon atoms, and which may additionally contain up to 20 ethoxy groups, m is a number from one to three, no more than one R1 in a molecule can have more than 12 carbon atoms when m is 3, each R2 is an alkyl or hydroxyalkyl group containing from 1 to 4 carbon atoms or a benzyl group with no more than one R2 in a molecule being benzyl, x is a number from 0 to 3, the remainder of any carbon, nitrogen, sulfur or phosphorus atom positions being filled hydrogens, Y is selected from the group consisting of (1) , (2) , (3) , (4) , (5) , wherein p is from 1 to 20, (6) , (7) , and (8) mixtures thereo , L is a number from 1 to 10, Z is an anion in a number to give electrical neutrality.

7. The composition of Claim 6 wherein, in the catlonic substance, L is equal to 1 and Y is .

8. The composition of Claim 7 wherein, in the cationic substance, m is equal to 1, X is equal to 3, R1 is C10-C20 alkyl, and R2 is methyl.

9. The composition of Claim 7 wherein, in the cationic substance, m is equal to Z, X is equal to 2, R1 is C10-C20 alkyl, and R2 is methyl.

10. The composition of Claim 7 wherein, in the cationic substance, m is equal to 3, X is equal to 1, R1 is C8-C11 alkyl, and R2 is methyl.

11. The composition of Claim 1 wherein the cationic substance is selected from the group consisting of (a) quaternarv ammonium salts having the following structure where R1 has from about 9 to about 26 carbon atoms and is a hydrophobic group which is alkyl, aryl, alkaryl, aralkyl or alkyl heterocyclic; saturated or unsaturated; the alkyl chain of which is straight or branched; unsubstituted or substituted with halogen, hydroxy, amino, ester, or ether groups;
where R2, R3 and R4 each have from 1 to about 9 carbon atoms, and are the same or different, and have combined a total of from 3 to about 15 carbon atoms in groups which are alkyl, aryl, alkaryl, aralkyl or heterocyclic; saturated or unsaturated;
the alkyl chains of which are straight or branched;
unsubstituted or substituted with halogen, hydroxy, nitro, amino, sulfonamide, ester or ether groups;
and where X is an anionic solubilizing group;
(b) Quaternary salts having the structure where R1 and X are the same as defined immediately hereinbefore in paragraph (a) and U is an unsaturatec heterocyclic group, unsubstituted or substituted with a short chain alkyl group;

(c) Quaternary salts having the structure where R, R2 and X are the same as defined here-inbefore in paragraph (a); and S is a saturated heterocyclic group, unsubstituted or substituted with a short chain alkyl group; and (d) polyamido quaternized biurets wherein R is an aliphatic hydrocarbyl group (saturated o?
unsaturated), a substituted aliphatic hydrocarbyl group, or an alkoxylated aliphatic hydrocarbyl group having from about 10 to 30 carbon atoms; A is a vicinal dihydroxy alkyl group containing at least 3 carbon atoms, m is 1 to about 8, and X is an anion selected from the halogen, acetate, phosphate, nitrate and methylsulfate radicals.

12. The composition of Claim 11 wherein the cationic substance has the structure where R1 has from about 12 to about 20 carbon atoms and is straight chained;
where R2 and R3 are, independently, methyl or:
ethyl; where R4 is methyl, ethyl, benzyl or chlorobe and whers X is an organic or inorganic anion.

13. The composition of Claim 11 wherein the cationic substance has the structure R1 has from about 10 to about 20 carbon atoms and is straight chained and where the heterocyclic group is pyridine, picoline, quinoline, quinaldine, thioazole, pyrrole, imidazole, pyrazole, oxazole, pyrazine, pyridazine, or pyrimidine.

14. The composition of Claim 11 wherein the cationic sub-stance has the structure R1 has from about 10 to about 20 carbon atoms and is straight chained and where the heterocyclic group is piperidine, piperazine, pyrrolidine, indoline, imidazolidine, pyrazolidine, or morpholine.

15. The composition of Claim 11 wherein the cationic substance has the structure where R has from about 12 to about 22 carbon atoms, A
has from 3 to about 8 carbon atoms, and m is 2 or 3.

16. The composition of claim 6 additionally containing a nonionic surfactant comprising an alkyl polyethoxylate having the formula R(OCH2CH2)nOH where R is a primary or secondary alkyl chain having from about 8 to about 22 carbon atoms, and the average value of n is from about 2 to about 9, said nonionic surfactant having an HLB from about 5 to about 17.

17. The composition of Claim 3 wherein the cationic substance is R1mR2xYL Z

wherein each R1 is an organic group containing a straight or branched alkyl or alkenyl group optionally subsituted with up to 3 phenyl groups and optionally interrupted by up to 4 structures selected from the group consisting of , , , , , -O-, and mixtures thereof, and which contains from about 8 to 22 carbon atoms, and which may additionally contain up to 20 ethoxy groups, m is a number from one to three, no more than one R1 in a molecule can have more than 12 carbon atoms when m is 3, each R2 is an alkyl or hydroxyalkyl group containing from 1 to 4 carbon atoms or a benzyl group with no more than one R2 in a molecule being benzyl, x is a number from 0 to 3, the remainder of any carbon or nitrogen atom positions being filled by hydrogens, Y is selected from the group consisting of (1) , (2) , (3) , (4) (5) , wherein p is from 1 to 20, (6) , (7) , and (8) mixtures thereof, L is a number from 1 to 10, is, Z is an anion in a number to give electrical neutrality.

18. The composition of Claim 17 wherein, in the cationic substance, L is equal to l and Y is .

19. The composition of Claim 3 wherein the cationic substanc is selected from the group consisting of (a) quaternary ammonium salts having the following structure where R1 has from about 9 to about 26 carbon atoms and is a hydrophobic group which is alkyl, aryl, alkaryl, aralkyl or alkyl heterocyclic; saturated or unsaturated; the alkyl chain of which is straight or branched; unsubstituted or substituted with halogen, hydroxy, amino, ester, or ether groups;
where R2, R3 and R4 each have from 1 to about 9 carbon atoms, and are the same or different, and have combined a total of from 3 to about 15 carbon atoms in groups which are alkyl, aryl, alkaryl, aralkyl or heterocyclic; saturated or unsaturated;
the alkyl chains of which are straight or branched;
unsubstituted or substituted with halogen, hydroxy, nitro, amino, sulfonamide, ester or ether groups;
and where X is an anionic solubilizing group;
(b) Quaternary salts having the structure where R1 and X are the same as defined immediately hereinbefore in paragraph (a) and U is an unsaturated heterocyclic group, unsubstituted or substituted with a short chain alkyl group;
(c) Quaternary salts having the structure where R, R2 and X are the same as defined here-inbefore in paragraph (a); and S is a saturated heterocyclic group, unsubstituted or substituted with a short chain alkyl group; and (d) polyamido quaternized biurets wherein R is an aliphatic hydrocarbyl group (saturated ?
unsaturated), a substituted aliphatic hydrocarbyl group, or an alkoxylated aliphatic hydrocarbyl group having fr?
about 10 to 30 carbon atoms; A is a vicinal dihydroxy alkyl group containing at least 3 carbon atoms, m is 1 to about 8, and X is an anion selected from the halogen, acetate, phosphate, nitrate and methylsulfate radicals.

20. The composition of Claim 19 wherein the cationic substance has the structure where R1 has from about 12 to about 20 carbon atoms and is straight chained;
where R2 and R3 are, independently, methyl or ethyl; where R4 is methyl, ethyl, benzyl or chlorobe and where X is halide, nitrate, sulfate, hydroxide, methyl sulfate, toluene sulfonate, and carbonate, phosphate, acetate, propionate, benzoate, tartrate, citrate, and salicylate.

21. The composition of Claim 19 wherein the cationic substance has the structure R1 has from about 10 to about 20 carbon atoms and is straight chained and where the heterocyclic group is pyridine, picoline, quinoline, quinaldine, thioazole, pyrrole, imidazole, pyrazole, oxazole, pyrazine, pyridazine, or pyrimidine.

22. The composition of Claim 19 wherein the cationic sub-stance has the structure R1 has from about 10 to about 20 carbon atoms and is straight chained and where the heterocyclic group is piperidine, piperazine, pyrrolidine, indoline, imidazolidine, pyrazolidine, or morpholine.

23. The composition of Claim 19 wherein the cationic substance has the structure where R has from about 12 to about 22 carbon atoms, A has from 3 to about 8 carbon atoms, and m is 2 or 3.

24. The composition according to any of claims 1, 5 or 6, wherein B is imidazolinium or quaternary ammonium.

25. The composition according to any of claims 1, 5 or 6, wherein B is polyethoxylate.

26. The composition according to any of claims 1, 5 or 6, wherein B is carboxylate, polyethoxycarboxylate, sulfate, polyethoxysulfate, phosphate, sulfonate, or mixtures thereof.

27. The composition according to any of claims 1, 5 or 6, wherein the photoactivator is zinc phthalocyanine sulfonate, tri- or tetra-sulfonate salt.

28. The composition according to any of claims 1, 5 or 6, wherein the composition is incorporated into substrate articles.

29. 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 bleach composition of any of claims 1, 5 or 6.

30. The composition according to any of claims 1, 5 or 6, wherein the composition is incorporated into substrate articles and wherein the photoactivator is zinc phthalocyanine sulfonate, tri- or tetra-sulfonate salt.

31. The composition according to any of claims 11, 17 or 20, wherein B is imidazolinium or quaternary ammonium.

32. The composition according to any of claims 11, 17 or 20, wherein B is polyethoxylate.

33. The composition according to any of claims 11, 17 or 20, wherein B is carboxylate, polyethoxycarboxylate, sulfate, polyethoxysulfate, phosphate, sulfonate, or mixtures thereof.

34. The composition according to any of claims 11, 17 or 20, wherein the photoactivator is zinc phthalocyanine sulfonate, tri- or tetra-sulfonate salt.

35. The composition according to any of claims 11, 17 or 20, wherein the composition is incorporated into substrate articles.

36. 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 bleach composition of any of claims 11, 17 or 20.

37. The composition according to any of claims 11, 17 or 20, wherein the composition is incorporated into substrate articles and wherein the photoactivator is zinc phthalocyanine sulfonate, tri- or tetra-sulfonate salt.

38. The composition according to any of claims 21, 22 or 23, wherein B is imidazolinium or quaternary ammonium.

39. The composition according to any of claims 21, 22 or 23, wherein B is polyethoxylate.

40. The composition according to any of claims 21, 22 or 23, wherein B is carboxylate, polyethoxycarboxylate, sulfate, polyethoxysulfate, phosphate, sulfonate, or mixtures thereof.

41. The composition according to any of claims 21, 22 or 23, wherein the photoactivator is zinc phthalocyanine sulfonate, tri- or tetra-sulfonate salt.

42. The composition according to any of claims 21, 22 or 23, wherein the composition is incorporated into substrate articles.

43. 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 bleach composition of any of claims 21, 22 or 23.

44. The composition according to any of claims 21, 22 or 23, wherein the composition is incorporated into substrate articles and wherein the photoactivator is zinc phthalocyanine sulfonate, tri- or tetra-sulfonate salt.