Note: Descriptions are shown in the official language in which they were submitted.
BACKGROUND OF THE INVENTION
This invention relates to household laundry
processes Eor combined washing and bleaching of fabrics,
and to simultaneous removal of stains and fugltive dyes
and is a divisional of Canadian application Serial No.
319,432, filed January 10, 1979.
~l~3~
,
,! .
United States Patent 3,927,9~7 yranted to
Spea~man on December 23, 1975 related to a household
washing and ~leachincJ proc~ss for c~tton Eabr1cs uLilizing phot
activa-ting compounds, principally sulfonated zinc phthalo-
5 cyanine, in the presence of visible light and atmospheric
o~ygen. Japanese Patent application OPI 50-113,479
assigned to The Procter & Gamble Co~pany, laid open to Lhe
public on September 5, 1975, teaches the use of specific
ntixtures of sulfonated ~inc phthalocyanine species, princi-
10 pally tri- and tetra-sulfonates, as pre~erred bleach photo-
activators. In each of the Eoregoing references the cl~r~ent
co~positions utilizing sulf~nated zinc ph-thalocyznine
contained bath orgclnic surfactant and alkaline builder
salt.
Belgian patent No. 840,348 lnven-ted by Wiers, yranted
on October 4, 1976 discloses the use of zinc phthalocyanine
tri- and tetra-sulfonates as bleach photoactivators in
unbuilt liquid detergent compositions.
British Patent 1,372,036 invented by Speakman and
available to the public on October 30, 1974 describes a
washing machine provided with a source of visible light
which irradiates wash liquor containing phthalocyanine
photoactivator and fabrics.
U.S. patents 2,951,797; 2,951,798; 2,951,799 and
2,951,800, assigned -to Monsanto Chemical Company and issued
on September 6, 1960 describe cer-tain por~hines as ca'alysts
for the photo-oxida-tion of olefins.
. ~
. . ,
~.~ 3~
,
References -to carboxylated porphines have appeared
in U.S. Patent 2,706,199 lssued April 12, 1955, invented
by Brentano et al, and C.R. Acad. Sci., Ser. C 1972,
275(11), 573-6 authored by Gaspard et al. See also Color
Index No. 74320. References to aminosulfonyl porphines are
West German OLS 2,057,194 laid open June 8, 1972, invented
by Von der Eltz et al; British patent 613,781 accepted
December 2, 1948, invented by Mayhew;and British patent
876,691 published Septe~ber 6, 1961, issued to Geigy A.G.
See also Color Index No. 74350. O~her substituted porphines
are disclosed in Austrian patent 267,711 issued January 10,
1969, inven~ed by Wimmer; French patent 1,266,094 published
May 29, 1961, invented by Tart-ter et al; U.S. Patent 2,670,265
issued February 23, 1954, invented by Meyna et al; British
- Patent 471,418 accepted August 30, 1937, invented by Groves;
and JCS 1938, 1-6 authored by Dent.
It has now been found that certain species of photo-
activators other than sul~onated phthalocyanines perform a
similar fabric bleaching function .in the presence of
visiblc light and atmosp~eric oxygen, and indeed under
some circumstances are superior thereto. These other photo-
activators provide .in fact not only stain removal. but also
improved whitening o~ the fabrics -in two other respects:
the first of these is an improvement in the general whiteness
of the fabrics, which is of~en referxed to as wh.iteness
maintenance; this improve~ent is not however accomplished in
the ordinary way by reducing the repxecipi~ation o~ dirt
upon cleaned fabrics, but rather by oxygen blea~hing oE the
overall fabric discoloration that is o~ten pres~nt in soiled
: fabrics even after washing ~ith ordinary detergent composi-
tions.
The second respect in which whiteness can be
improvea by the compositions o~ this invention is in the
removal of so-called fugitive dyes -- the tendency of some
colored fabrics to release-dye into the laundering solutions,
which dye is then :transferred during laundering onto other
~abrics being washed therewith. Dye transfer removal
using peroxy acids together with chemical activators is the
subject of U.S. Patent 3,822,114 granted on July 2, 1974 to
Montgomery and Jones and com~only assigned U.S. patent
2S 4,001,131 issued January 4, 1977
. . ~
tMont9omery)~ Dye transfer removal using peroxy compounds
such as hydrogen peroxide or sodium perborate catalyzed by
porphines and phthalocyanines chelated with iron, and only
iron, is the subject of U~S. Patent 4,Q77,768, issued
March 7, 1978 (Johnson and Tate).
The foregoing objects of this invention can be
conveniently ~ccomplished by a washing process which is
followed by drying out-of-doors, especially in direct
sunlight as on a clothesline. The common procedure of
lQ soak.ing fabrics in the wash/bleach solution prior to the
actual washing process is an especially effective way to
accomplish the objects of this invention.
SUMMARY OF T~E INVENTION
This invention relates to a detergent bleach
composition comprising an anionic, nonionic, semi-polar,
ampholytic, or zwitterionic surfactant and from 0.005~
to 0.5~ by weight of the composition of a water soluble
photoactivator having the formula
_
~ ~ X ~ R,, ~ (BM)
R8 ~` X~$ Rs
R7 R6
...
...... ..
~ ~3~2
wherein each X is (=N-) or (=CY-), and the total number
of (=N-) groups is ~; wherein each Y, independently, is
hydrogen or meso substituted alkyl, cycloalkyl, aralkyl,
aryl, alkaryl or heteroaryl; wherein each R, indepen-
dently, is hydro~en or pyrrole substituted alkyl, cyclo-
alkyl, aralkyl, aryl, alkaryl or heteroraryl, or wherein
adjacent pairs of R's are joined together with ortho-
arylene groups to form pyrrole substituted alicyclic or
heterocyclic rings; wherein A is 2(H) atoms bonded to
diagonally opposite nitrogen atoms, or Zn(II), Cd(II),
Mg(II), Sc(III), or Sn(IV); wherein M is a counterion
to the solubilizing groups; wherein s is the number of
solubilizing groups; and wherein substitutecl into Y or R
; is B, a solubilizing group seleeted from the group con-
sistiny of (a) cationic groups, where M is an anion and
s is from 1 to about 8; (b) polyethoxylate nonionie groups
-(C~12CH2O)nH, where M is zero, s is from 1 to about ~,
and sn (the number of condensed ethylene oxide
molecules per porphine molecule) is from about 8 to about
50; ~c) proximate anionic groups attached to atoms no more
than 5 atoms displaced from -the porphine core, where M is
cationic and s is from 3 to about ~; and (d) remote anionic
groups attached to atoms more than 5 atoms displaced from
the porphine core, where M is cationie and s is from 2 to
about 8; provided that anionic sulfonate groups are remote
and are no greater in number than the number of aromatic
and heterocyclic substituent yroups; wherein said alkyl
groups are comprised of simple carbon chains or carbon
chains interrupted by other chain-forming atoms.
'.~
~3~
Preferred cationic solubilizing groups are
quaternary pyridinium and quaternary ammonium groups.
Preferred anionic solubilizing groups are carboxylate, poly~
ethoxy carboxylate, sulfate, polyetho~y sulfate, phosphate,
polyethoxy phosphate, and remote sulfonate. Preferred
nonionic solubilizlng groups are polyethoxylates.
For cationic solubilizing groups M, the counterion,
is an anion such as halide and s is from 1 to about 8. For
polyethoxylate nonionic solubilizing groups -(CH2C~I2O)I~H,
M is æero, s is from 1 to about 8, and sn (the number
of condcnsed ethylene oxidc molecules per poxphine molecule)
is from about 8 to about 50. ~or anionic yroups M, the
count~rion, is cationic. For anionic groups attached to
a~oms no more than S atoms displaced ~rom the porphine core,
i.e. for "proximate" anionic groups as defined herein, s is
from 3 to about 8. For anionic groups attached to a~oms more
than 5 atoms displaced from the porphine core, i.e. for
"remote" anionic groups as defined herein, s is from 2 to
about 8. Sulfonate groups are remote and their number is no
greater than the number of aromatic or heterocyclic substi-
tuent groups.
The solubilizing groups on a given porphine
photoactivator of this invention can be, but need not be,
all alike; they can be different not only as to their
precise structure but also as to their electrical charge.
Thus cationic, anionic, and/or nonionic solubilizing
groups can be present on an individual photoactivator
molecule.
..
3~
In the foregoing description, the term "alkyl" is
defined to. be not only a simple carbon chain but also a
carbon chain interrupted by. o-ther chain-forming atoms, such
as 0, N or S. Non-limiting examples of such interruptions
are those of the following groups:
O
ether - O -, ester - CO -,
O ' ,0~
Il .
amide - C - NH -, and amino sulfonyl - NH - S -.
o
DET.~ILED D~scr~IpTIo-~r 0~ TH~ VE~IrIo~
The essential components of--the instaIlt invention
are -t~o in number. One i5 a surca`cta~t ~Ihich can be anionic,
nonionic, semi-polar, amp~lolytic, or z~litterionic in nature,
or can be mi:~tures thereo. Surfactar~ts can be used at
levels from about lOQo to about 50~ of the col~.position by
weight, preferably at levels rom about 15~; to about 30
by weight.
Preferred anionic non-soap surfactants are water
soluble salts of alXyl benzene sulfoilate~ alkyl sulfate,
alkyl polyetho ~ ether sulrate, paraffin sulonate, alpna-
oleEin sulfonate, alpha-sul0carboxylat~5 and t.heir estPrs,
alkyl glyceryl ether sul~onate, fattv acid monoglycericle
sulEates and sul~onates, alk~l phenol polye-tho.~y ether
sul~ate, 2-acyloxy-alkane-1-sulfonate, and be~a-alkylo~y
^ alkane sulfonate. Soaps are also preferred anionic surfac-
tants.
Especially preferred al~yl benzene sulfonates have
- about 9 to about 15 carbon atoms in a linear or branched
al~yl chain, more especially about 11 to about 13 carbon
atoms. Especially preferred alkyl sulfate has about 8 to
about 22 carbon atoms in the alkyl chain, more especially
from about 12 to about 18 carbon atoms. Especially preferred
alkyl polyethoxy ether sulfate has about 10 to about 18
carbon atoms in the alkyl chain and has an average of about
1 to about 12 -CH2CH20- groups per molecule, especially about
10 to about 16 carbon atoms in the al~yl chain and an average
of about 1 to about 6 -CH2CH20- groups per molecule.
~L~3~
Especially pref2rred paraf~in sulronat_s are
essentially linear and contain frcm about 8 to abo~t 2~
carbon atoms, more especially from about L~ to about lZ
carbon atoms. Especi~lly pre~crrecl aLpna-olerin sul~onate
has about 10 to about 24 carbon atom~ more especially
abou-t 1~ to abou-t 16 carbon a-toms; alpha-oleEin sulfonates
can be made by reaction with sulfur trioxide followed by
neutralization under conditons such that any sultones
present are hydroly~ed to the corresponding hydroxy alkane
sulEonates~ Especially preferred alpha-sulEocarbo~ylates
contain from about 6 to about 20 carbon a-toms; incluclecl
herein are not only the salts of alpha-sulfonated fatty
acids but also their esters made from alcohols containlng
abou-t 1 to about 14 carbon a-tom~.
Especially preferred alkyl glyceryl ethex sulfates
are ethers of alcohols having about lG to about 18 carbon
atoms, more especially those derived from coconut oil an~l
tallow. Especially preferred alkyl phenol polyethoxy
ether sulfate has about 8 to about 12 carbon atoms in the
alkyl chain and an average of about 1 to about 10 -CH2CH~O-
groups per molecule. Espec~ally preferred 2-acyloxy-alkane-
l-sulfona-tes contain from abou-t 2 to about 9 carbon atoms
in the aryl group and about 9 to about 23 carbon ato~s in
the alkane moiety. Especially preferred beta-alkyloxy
alkane sulfonate contains about 1 to about 3 carbon atoms
in the alkyl group and about 8 to about 20 carbon atoms in
the alkyl moiety.
1.~ 3~ ~Ip~
The alkyl chains of the foregoing non-soap anionic
surfactants can be derived from natural sources such as
coconut oil or tallow, or can be made synthetically as for
example using the Ziegler or Oxo processes. Water solubility
can be achieved by using alkali metal, ammonium, or alkanol-
amine cations; sodium is preferred. Magnesium and calcium
are preferred cations under circumstances described by Belgian
patent 843,636 in~ented by Jones et al, issued December 30,
1976. Mixtures of anionic surfactants are contemplated by
this invention; a preferred mixture contains alkyl benzene
sulfonate having 11 to 13 carbon atoms in the alkyl group
and alkyl polyethoxy alcohol sulfate having 10 to 16 carbon
atoms in the alkyl group and an average degree o ethoxylation
of 1 to 6.
Especially preferred soaps contain about 8 to about
24 carbon atoms, more especially about 12 to about 18 carbon
atoms. Soaps can be made by direct saponification of natural
fats and oils such as coconut oil, tallow and fish oil, or by
the neutralization of free fatty acids obtained from either
natural or synthetic SQurCes. The soap cation can be alkali
metal, ammonium or alkanolammonium; sodium is preferred.
Preferred nonionic surfactants are water soluble
compounds produced by the condensation of ethylene oxide with
a hydrophobic compound such as an alcohol, alkyl phenol, poly-
propoxy glycol, or polypropoxy ethylene diamine.
Especially preferred polyethoxy alcohols are thecondensation product of 1 to 30 mols of ethylene oxide with
1 mol of branched or straight chain, primary or secondary
aliphatic alcohol having from about 8 to about 22 carbon
atoms; more especially 1 to 6 mols of ethylene oxide
~'
condensed with 1 mol of straight or branched chain, primary
or secondary aliphatic alcohol having from about 10 to
about 16 carbon atoms; certain species of polyethoxy
alcohols are commercially available from the Shell Chemical
Company under the trade mark 'Neodol'. Especially pre-
ferred polyethoxy alkyl phenols are the condensation
product of about 1 to about 30 mols of ethylene oxide with
1 mol of alkyl phenol having a branched or straight chain
alkyl group containing about 6 to about 12 carbon atoms
certain species of polyethoxy alkyl phenols are commer-
cially available from the GAF Corporation under the trade
mark 'Igepal'.
Especially preferred polyethoxy polypropoxy glycols
are commercially available ~rom BASF-Wyandotte under the
trade mark 'Pluronic'. ~specially preferred condensates
of ethylene oxide with the reaction product of propylene
oxide and ethylene diamine are commercially available from
BASF-Wyandotte under the trade mark 'Tetronic'.
Preferred semi-polar surfactants are water soluble
ami~e oxides containing one alkyl moiety of from about 10
to 28 carbon atoms and 2 moieties selected from the group
consisting of alkyl groups and hydroxyalkyl groups contain-
ing from 1 to about 3 carbon atoms, and especially alkyl
dimethyl amine oxides wherein the alkyl group contains
from about 11 to 16 carbon atoms; water soluble phosphine
oxide detergents containing one alkyl moiety of about 10
to 28 carbon atoms and 2 moieties selected from the group
consisting of alkyl groups and hydroxvalkvl ~roups con-
taining from about 1 to 3 carbon ~toms; ~nd ~at~r soluble
sulfoxide detergents cont~ining one ~lkyl moiety of
, ~ r ~ ~` ;`,, ~!
; ~ rom about 10 to 28 carbon atoms and a moiety selected
from the group consisting of alkyl and hydroxyalkyl
moieties of from 1 to 3 carbon atoms.
Preferred ampholytic suractants are water soluble
S derivatives oE aliphatic secondary and tertiarty amines
in which the aliphatic moiety can be straight chain or
branched and wherein one of the aliphat:ic substituents
contains from about 8 to 18 carbon atoms and one con~
tains an anionic water-solubilizing group, e.g. carboxy,
sulfonate, sulfate, phosphate, or phosphonate.
Preferred zwitterionic surfactants are water soluble
derivatives of aliphatic quaternary ammonium, phosphonium
and sulfonium cationic compounds in which the aliphatic
moieties can be strai~ht chain or branched, and wherein
one of the aliphatic substituents contains from about
to 18 carbon atoms and one contains an anionic water
solubilizing group, especially alkyl-dimethyl-ammonio-
~ propane-sulfonates and alkyl-dimethyl-ammonio-hydroxy-
; propane-sulfonates wherein the alkyl group in both types
contains from about 14 to 18 carbon atoms.
A typical listing of the classes and species of
surfactants useful in this invention appear in U.S. Patent
3,664,961 issued to Norris on May 23, 1972. This listing,
and the foregoing recitation of specific surfactant
compoùnds and mixtures which can be used in the instant
compositions, are representative of such materials but are
not intended to be limiting.
. ~
~ ~.
., .. , . _ . . ... ..... ... .... . . .
The other essential component of the instant
invention i5 a photoactivator as described hereinbelow. This
component can also be described as a photochemical activator,
or as a photosensitizer: these terms are synonymous. Before
describing the photoactivator in detail, a discussion of
chemical nomenclature will be appropriate. The structure of
the compound porphine is:
H
~ H ~ Prphine
HC ~C
~C ~
Porphine has a large closed ring designated as a
macrocyclic structure, and more specifically as a quadri-
dentate macrocyclic molecule. Porphine can be described as
tetramethine tetrapyrrole, and has also been designated as
- porphin or poxphyrin. This struc~ure is sometimes referred
to herein as the porphine 'core', because the photoactivators
of this invention are species of substituted porphines.
One form of substitution involves substituting 1,
2, 3, or 4 aza groups (=N-) for the methine groups (=CH-) in
porphine. As an example of conventional nomenclature, a
compound having 3 aza groups and one methine group is
referred to as triaza porphine.
Another form of substitution involves substituting
for one or more of the hydrogen atoms attached to the carbon
atoms in the pyrrole rings of porphine. This can be substi-
- 13 -
1~3~ o~
tution by an aliphatic or aromatic group, or can be ort~ofused
polycyclic substitution as for example to form benzene or
naphthalene ring structures. The compound having the common
name 'phthalocyanine' contains 4 ortho-fused benzene rings,
each substituted on a pyrrole ring of the porphine core; and
also contains 4 aza groups substituted for the methine
groups of the porphine core; it can therefore be designated
tetrabenzo tetraaza porphine, and has the structure which
follows. ~he numbers designate the positions of pyrrole
substitution according to conventional nomenclature.
[T]
N ~ phthalocyanine
NH N
N~ ~ N
~ N ~
Another ~orm of substitution involves substituting
for the hydrogen of the methine groups; this is conventionally
referred to as meso substitution, and the positions of
substitution are conventionally designated by &reek letters
as illustrated on the phthalocyanine structure above.
Still another form of substitution is metallation
by a heavy metal atom in a chelation structure: replacement
of the two hydrogen atoms attached to two diagonally opposite
inner nitrogen atoms of the four pyrrole groups by a heavy
metal atom bonded to all four inner nitrogen atoms.
- 14 -
Still another form of substitution is substitution
of a solubilizing group into the photoactivator molecule.
The various forms of substitution described above
can be illustrated by the compound 3-phenyl-2,7-dicarboxy-
phenyl-~,y-diaæa-~-benzofuryl-~-carboxybenzofuryl porphine
zincl trisodium salt, which is within the scope of this
invention:
C0~Na
~U]
N ~ C2Na
C ~n~ C
N
~~C02Na
With the foregoing explanation as prelude, it is
now possible to describe in detail the photoactivators of
this invention. Referring to the structure shown herein-
before in the SUMMARY OF THE INVENTION, effective photo-
activators which are within the scope o this invention
contain 0, 1, 2, 3 or 4 aza groups [and, according to the
nomenclature defined above, contain 4, 3, 2, 1 or O methine
groups, respectively].
- 15 -
~.~l3~
The groups designated as R's in the structural
formula above can, independently, be hydrogen or pyrrole
substi~uted alkyl, cycloalkyl, aralkyl, aryl, alkaryl, or
heteroaryl. Adjacent pairs of R's can also be joined
together with ortho-arylene groups to form alicyclic or
heterocyclic rings. Benzo substitution is especially
preferred; i.e., Rl and R2, R3 and R6, a~d/or R7 and R8 are
connected together pairwise by methylene groups to form
fused benzene rings. Other preferred forms of pyrrole
substitution are naphtho, pyrido, phenyl and naphthyl.
Substitutions can also be made for the hydrogen
atoms of the methine groups of the photoactivators of this
invention; thus each Y in the above structural formula can
independently be hydrogen or meso substituted alkyl, cyclo-
alkyl, aralkyl, aryl, alkaryl, or heteroaryl. It is pre~erred
that Y is H, phenyl, naphthyl, thienyl, uryl, thioazyl, oxa-
zyalyl, indolyl, benzo~hienyl, or pyridyl. No meso substi-
tution at all or tetra phenyl meso substitution are especially
preferred.
In the foregoing description, the term "alkyl" is
de~ined to be not only a simple carbon chain but al50 a
carbon chain interrupted by other chain-iorming atoms, such
as O, N or S. Non-limiting examples of such interruptions
are those of the following groups:
- 16 -
o o o
ether - O -, ester - CO ~, reverse ester - CO -, carbonyl - C -,
O O
~, "
amide - C - NH -, reverse amicle - NH - C -, amino sulfonyl
O O
,. ,.
- NH - S -, and sulfonamido - S - NH -.
11
O O
The photoactivating compounds of the instant
invention can be unmetallated, A in the ~oregoing structural
formula being comprised of two hydrogen atoms bonded to
diagonally opposite inner nitrogen atoms oE the pyrrole
groups in the molecule ~The characteristic s-tructure of
unmetallated compounds is illustrated by compounds [S~ and
[T] illustrated hereinbe~ore; these compounds are not,
however, within the scope of this invention because they
lack essential substituent groups as herein described.~
Alternatively, the photoactivators of this invention can be
metallated with zinc(II), ca~cium(II), cadmium(II), magnesium(II)
scandium(III), aluminum(III), or tin(IV). Thus, altogether, A
can be 2(H) atoms bonded to diagonally opposite N atoms, or
Zn(II), Ca(II), Cd(II), ~lg(II), Sc(III), Al(III), or Sn(IV).
It is pre~erred that A be 2(H) or Zn(II).
Solubilizing groups can be located anywhere on
the porphine molecule other than the porphine core as
hereinbefore defined. Accordingly the solubilizi~ng groups can b~
described as substituted into Y or R as hereinhefore defined.
Solubilizing groups can be anionic, nonionic, or
cationic in nature. Preferred anionic solubilizing groups
are carboxylate "
- C ~ , sulfate - O - S - O~ and
17
~`~3~
phosphate ~ O - P - O~. ~nother preferred anionic solu-
OH O
bilizing group is sulfonate - S - ~ providing this group
O
is attached to a carbon atom of the photoactivator molecule
that is displaced more -than 5 atoms away from the porphine
core. Such a location is sometimes her~in referred to as
"remote", and is ~o be distinguished from an attachment to a
carbon atom displaced no more than 5 atoms from the porphine
core, which is sometimes referred to herein as "pro~imate".
Other preferred ani.onic solubilizin~ agents are etho~ylat~d
derivatives of -the foregoiny, especially the polyethoxysulfa-te
group - tCH2C~I2O)nSO3~ and the polyethoxy carboxyl.ate group -
(CEI2C~I2O)nCO ~ where n is an .inteyer from 1 to about 20.
- For anionic solubilizing groups, M the counterion
is any cation that confers water solubility to the porphine
molecule. A monovalent cation is preferred, especially
ammonium, ethanolammonium, or alkali metal. Sodium is most
preferred. For reasons described hereinafter, for proxi-
mate solubilizing groups, the number of such groups per
molecule, s, is from 3 -to abou-t 8, preferably from 3 to about
6, most preferably 3 or 4. For remote solubilizing groups,
s is from 2 to about 8, preferably from 2 to about 6, most
preferably 2 to 4.
Preferred nonionic solubilizing groups are poly-
ethoxylates -(CH2CH20)nH. Defininy s as the number of
solu~ilizing groups per molecule, the number of condensed
ethylene oxide molecules per porphine mo].ecule is N = sn.
18
3~
The water soluble nonionic photoactivators of this
inventlon have a value of N between about 8 and about 50,
preferably from about 12 to about 40, most preferably from
about 16 to about 30. Within that limitation the separate
values of s and n are not critical.
For nonionic solubilizing groups, there is no counter-
ion and accordingly M is numerically equal to zero.
Preferred cationic solubilizing groups are quaternary
compounds such as quaternary ammonium salts
~3
- N - R3
Rl R2 _~ ~
and quaternary pyridinium sal~.s - ~ N - R,
where all ~'s are alkyl or substituted alkyl groups.
For cationic solubilizing groups, M the counterion is
any anion that confers water solubility to the porphine
molecule. A monovalent anion is preferred, especially
iodide, bromide, chloride or toluene sulfonate
' CH3~3-So3
For reasons that are described hereinafter, the number
of cationic solubilizing groups can be from 1 to about 8,
preferably from about 2 to about 6, most preferably from
2 to 4.
19
Photoactivator usage in th~ compositions of this
invention can be from about 0.005~ ~o about 0.5% by weight
of the composition. Preferc~ble usage i5 from about 0.01
to abou-t 0.1~ by weight of the composition. The weight
ratio of photoactivator to surfactant can be between about
1/10,000 and about 1/20, preferably between about 1/1000
and about 1/100.
A~though it is not wished to be bound by theory,
it is believed that the nat~e o~ this inven~ion carl be
more clearly understood b~ postulating the ~achanlsm o~
bleaching using the instant photoactivators. Referring to
Reaction Scheme A, the photoactivator in the upper left hand
corner is in aqueous solution and is in its ground state.
Reaction ~1), entitled 'adsorption', indicates that dissolved
photoactivator is in part adsorbed on fabrics. Reaction (2)
suggests that photoactivator can dimerize into a form which
- is not readily adsorbed and therefore is not available to
enter into the desired bleaching reactions on the fabric
surfaces.
1~39~L~
Reaction Scheme A
~CH~NISl~l OY B~AC~iIL~C
P/~ = Photo~ctivator
O = an Oxygen ato~
h~ = visible light r~diation
ISC = intersystem crossing
in solution \ dimeri~at~or dimer
:. (~;) ` \ '
~ ~ adso~tion
[~3 \
adsorbed on fabric
h~ ~
~ ~e~ ci ta tion
1 ~ ~1 ' \
e:icited state
singlet
/ 3¦ P/A ~ ~ 3 ~ ~ ~ lo~
/ excited statei c3round state; excited st~
~ f triplet triplet state in~le~
. side
~ea~tions
STAI~I
cnemicaZ
b ZeacrLing
.. '~ . ", . ' 1 ~ '
OXIDIZED
STAI~
,
. .
- 20a -
.~
\~
~ .
~ '`'`` .
. '
. Reaction (3) illustrates that photoactivator in
the ground state can be excited by visible light, hv, and
thereby raised to the e~cited singlet state. From the
excited singlet state the photoactivator c~n undergo
intersystem crossiny or ISC, reaction (4), to the
triplet state which is also excited but at a lower
energy level than -the singlet state. It is the excited
triplet state -that is desired because it is capable of
interacting wi-th the ground state of atmospheric o.~gen
molecules, which are also in the triplet s-tater forming
thereby according -to reaction (5) the excitecl sing].et state
oE o~yge~l and also reyeneraking pho-toacti~ator at its
original yround state. Both the singlet and the triplet
e~cited states of the pho-toactivator can enter in-to
.reactions other than the desired reac-tion t~ith oxygen.
For example, the singlet state can fluoresce, while the
triplet state can phosphoresce, undergo radiati.onle~s decay,
undergo electron transfer to photoacti.vator molecules in the
ground state which res~ults in deac-tivation or the photo-
activator, or react with other components of the so]u-tion.
From the standpoint of the desired bleaching these are
collectively designated as reaction (6), 'side reactions'.
The excited singlet oxygen, formed by reaction (5)
is the oxidative species that i5 capable oE reacting with
2S stains as shown in reaction (7) to chemically bleach them to
a colorless and usually water-soluble state, thereby accom-
plishing the purposes of this invention.
It will be instructive to consider the effect upon
~3~
bleaching ~rou(~ht about ~ the indi~ld~al species of photo-
activators that are ~/ithln -the scope-oE this invention.
This will be clone in reference -to the seven reac-tions
appearing on Scheme A which have been described above.
The n~er or aza yroups substituted for met'nine
groups in the po-phine core primarily affects (a) the
lietime of the triple-t s-ta-te, and (~) the side reactions.
The lifetime of the triplet s-tate of metalloporphines
~Grayushko et alr Op-t. Spektrosk 31, page 548 ~1971)~ is
` substantially greater than -th~t of correspondinc3 metallo-
p~thalocyanines EVince-tt e-t al, J. Chem. Physics 5'), No~ 8
page 4134, October 1971~. It is beLievecl that introduction
of eac~l successive aza group shortens the lifetime, and it is
apparent that a longer liEetime is dasired to provide greater
o?portunity for reaction with oxygen molecules to form the
active bleaching species. Hence from this point of view
methine groups are preferred to aza groups. However a counter~
vailing factor is that slde reactions tend to be grea-test
when 4 methine groups are present, and decrease proc~ressively
as successive aza groups are in-troduced. The fore~Joing
effects work in opposite directions, and accordingly it is
not possible to predict the relative effectiveness of the
difrerent species based on theoretical considerations alone.
As described hereinafter, porphines ha~ing 0, 1, 2, 3 and 4 aza
groups are effective photoactivators, and the skilled
artisan is free to select a photoactivator for reasons of
cost, availability, and performance under specific condi-
tions of interest to him.
22
.
~ 3~
This invelltion conterllplates photoactivators that
are metal rr2e and also those that a~e metallated ~lith
certain metals. In general, the introduction of a metal
atom into the photoac-tivator molecule causes a perturbation
of the sys~em .7hich reduces the lifetime of the e~cited t~iplet
states and increases side reactions, both of ~hich are
un~anted e_fects in relation -to the instant invention.
From this point of view unmetallated compounds are
preferred photoactivators~
~ countervailing factor ls -that manufacture o~
certain photoactivators is more readily a~cc)mpllshed ~hen
a metal is present -to stabilize the molecule. Ilhis factor
applies both to synthesis of a photoactivator compound by
sulfonation of its unsulfonatecl pxecursor m~lecule r and
also to synthesis of the precursor molecule itself.
Perturbation is especially yreat ~or metals ~hich
have unpaired elec-trons; hence paramaynetic metals are not
satisfactory. Perturbation is also grea-t for metals that
are large in slze. Data appe~ring in Vince-tt et al., op. Clt~,
suggest that the lifetime oE the triplet s-tate of ~inc
phthalocyanine is hundreds of times longer ~han that of
coppex phthalocyanine (Cu is par.amagnetic) and approaches
a hundred times longer than that o~ platinum phthalocyanine
(Pt is large).
~letallated photoactivators that are accepta~le
in the practice of this invention are those containi.ng
.. ..
~ relatively small, diamagnetic metals: zinc(II), calcium(II),
, i
magnesium(II), scandium(III), aluminum(III), and tin(IV).
Because the first six of these named metals have essentially
23
~.~3~
constant valence, specific ident~fication oE their valence
states will sometimes be omitted herein. Zinc is preferred
because -the triplet state of zinc me-tallated pho-toactivators
is perturbed to a relatively low extent and hence its lifetime
is relatively long. ~ ----- --- --------
A11 of the reactions described on Scheme A are
predicated on solubility of the photoactivator in the
laundry bath. Solubiliza-tion is accomplished ~y introducin~
solubilizin~ groups-into the molecule. It is entirelv practical
to maXe compounds having respec-tively, one, -two, three, ~our
and even lndeed up to as many as twelve solu~ilizing ~roups
per molecule, and all are -to some extent photoactivators.
However as each successive solubiliæing group is added, chanyes
occur monotonically in a number of properties ~hich af~ect
- usefulness, as explained below.
An anionic macrocyclic photoactivator molecule in solu-
tion is present in dissociated ionic form having negative chargee
around its ~eriphery. The Coulombic effect of these negative
charges is minimized by the counter ions in SO]UtiO.l. The
pèripheral negative charges do, however, tend to localize the
electron density of the ring near the center of the molecule
and to enhance its basicity ~hich leads to increased dimeri-
zation of tne molecules as brought about by van der Waal
forces [reaction 2, Scheme A]. This circu~mstance is increased
by mul-tiple solubilizing groups and loss of symmetry,
and hence the tendency to dimerize in solution follows
the order mono cdi <tetra < tri < penta .... Dimerization
being an undesirable reaction, a relatively small number
of anionic solubilizing groups are preferred from this
point of view.
24 ~-
~3~
On a cotton surface, which is negatively charged,
multiple negative charges at the periphery of the molecule
cause s-trong Coulombic repulsions which follow the order
mono ~ di < tri < te-tra ~ penta .... Hence adsorption,
which is desired, is greatest for species having a small
number of anionic solubilizing groups. Fur~hermore the
adsorption which does take place tends, for the species
having a small number of anionic solubilizing groups, to be
closer to the fabric surface which also is desired.
Still another advant~age of a small number of
anionic solubilizing groups is fewer side reactions o~ the
triplet state.
However, once again there are countervailing
factors. The Coulombic repulsions of species having a
- relatively high number of anionic solubili~ing groups are
widely distributed around the periphery of the adsorbed
macrocyclic photoactivated molecule, which minimizes adsorp~ion
of successive layers of photoactlvator on the fabric surface.
However molecules of species having a small number of anionic
solubilizing groups can geometrically orient in such a way
as to minimize Coulombic repulsions and-can build up multiple
layers of photoactivator on the fabric surface These
multilayers are not desired: -their intrinsic blue/green
coloration becomes visible, and when irradiated by light
they form singlet oYygen in a location sufficiently remote
from the fabric surface that it is less effective for the
desired stain removal. From these points of view
desirability is in the order ... > penta > tri > tetra > di > mo
Still another advantage of a large number of anionic
solubilizin~ groups is increased solubility in water.
Taking all the above into consideration it has
been found that, for anionic photoactiva~ors h2viny proxima-te
solubilizing groups, the negative factors of mono- and di-
sulfonated photoaetivator molecules are so important that
these speeies are unsatisfactory, and henee photoae,ivators
of this invention have three or more proximate solubilizing
groups per moleeule. Compounds having more than about eight
pro~imate solubilizing groups per moleeule are often difficult
to make and have no partieular advantage. Hence photoaetiva-
tors of this invention having proxima-te solubilizincJ groups
~ have from three to about eight sueh groups per molecule;
eompounds having ~hree to slx proximate solubilizing groups
per moleeule are pre~erred, and eompouncls having 3 or 4 proxi-
mate solubilizing groups per molecule are espeeially
preferred as having an optimum balance of maximum bleaching
ef~ectiveness and minimum coloration.
The foregoing discussion relates to anionic photo-
aetivators having proximate solubilizing groups. When the
solubilizing groups are in remote loeations, the tendeney of
2~ the photoactivator moleeule to aggregate is redueed beeause
of both eleetrieal and sterie reasons, with the result that
less dimerization oeeurs, less buildup on the fabrie oeeurs,
and the solub~lizing effeet of individual solubilizing groups
is enhanced. Accordingly, a minimum of 2 remotely located
anionic solubilizing groups per photoactivator molecule is
satisfactory for the praetiee of this invention, with 2 to
about 6 being preferred and 3 or 4 being espeeially preferred.
Nonionie solubilizing groups have a low tendency
to aggregate beeause -there is no electrieal eharge-density
2~
3~
effect and tllere ls a particularly large steric effect
reducing orderly association between photoactivator molecules.
Because solubilization o polyethoxylated photoactivator
molecules occurs prima-ily because of numerous ether groups
,5 in the polyetho~ylate chains, it is of little consequence
whether there is a single very long chain or a number of
shorter chains. Accordingly, the solubility requirement
as hereinbefore expressed is in terms of the number of
condensed ethylene oxide molecules per porphine molecule,
which is frQm about 8 to about 50, preerably from about 12
to about 40, most preferably from about 16 to about 30.
Pho~oclctivators having cationic solubili~iny groups
do not effectively aggregate at all because the electron
density in the ring is reduced. Substantivity on cotton
fabrics is yreat. Only one solubilizing group is enough to
-accomplish the purposes of this invention, although more
are acceptable and indeed preferred. Accordingly the limiting
numbers of solubilizin~ cationic groups are from l to about 8,
preferably from about Z to about 6, most preferably from 2 to 4.
As stated hereinabove, the macromolecular structure
comprislng the porphine core contributes the essential photo-
activation properties of the compounds of this invention. It
follows inexorably that large numbers of compounds having this
macromolecular core, but with myriads of different substituent
groups, are effective in the practice of this invention. One
versed in the art will recognize the impracticability of
reducing to writing all possibilities that can be envisioned
by a skillful practioner. The embodiments which follow are
therefore to be considered exemplary but not e~haustive.
Photoactivators that are eIfective bleachin~ agen-ts for
fabrics and are within the scope of this invention are
the following:
Tetrabenzo ~ , y, ~ - tetrakis (~-N-ethyl) pyridyl
porphine tetrachloride; tetrabenzo - ~ tetrakis
(N-trimethyl) aminoethyl porphine tetraiodide; tetrabenzo -
- tetrakis (~-carboxyphenyl) porphine cadmillm,
tetrasodium salt; tetrabenzo - ~ - tetrakis (4-
sulfatophenyl) porphine zinc, tetrapotassium salt;
tetrabenzo - ~ te-trakis (~-sulfato polyethoxy
phenyl) porphine, tetrasodium salt; -tetra benzo -.
~, ~, y, ~ - tetrakis (4-carboxy polyethoxy phenyl)
porphine calcium, -tetraamonium salt; tetrabenzo -
u, ~ - -tetrakis (4-phosphatophenyl) porphine,
tetrapotassium salt; -tetrabenzo ~ , y, ~ - tetrakis
.(4-phosphato polyethoxy phenyl) porphine zinc, tetra(mono-
ethanolamine) salt; tran,-dichloro, tetrabenzo -
tetrakis (~-polyethoxy phenyl) porphine tin(IV).
Tetrakis (N-methyl) pyrido porphine zinc tetraiodide;
tetrakis (N-trimethyl)- aminobenzo porphine, tetra ~toluene
sulfonate) salt; trans-dibromo, tetrakis (carboxybenzo)
porphine tin(IV), tetra(diethanolamine) salt; -tetrakis
(sulfato benzo) porphine zinc, tetrasodium salt; chloro,
tetrakis (sulfato polyethoxy benzo) porphine scandium,
tetrammonium salt; tetrakis (carboxy polyethoxy benzo)
porphine, tetrasodium salt; te-trakls (phosphato benzo)
porphine zinc, tetralithium salt; tetrakis (phosphato
polyethoxy benzo) porphine, tetra(triethanolamine) salt;
tetrakis (polyethoxy benzo) porphinei tetrabenzo -
28
~.~L3d~
a, ~, y, ~ - tetrakis - (4-carbo~yphenyl) porphine zinc,
tetrasodium salt.
Tetranaphtho - N, ~ r, ~ - tetrakis - (4-phosphato
polyethoxy phenyl) porphine, tetrasodium salt; tetrakis
tN-methyl) pyrido - a, ~, y, ~ - tetranaphthyl porphine tetra-
chloride; chloro, tetrakis (polyethoxy naphtho) - N, ~, y, ~ -
tetra phenyl porphine alumlnum, tetrakis (N-diethyl-N-propyl)
- aminobenzo - N, ~ r, ~ - tetrakis (4-N-methyl) pyridyl
porphine magnesium, octabromide; tetrakis (carboxynaphtho)
~ , y, ~ - -tetrakis (4-carboxy phenyl) porph.ine zinc,
octa potassium salt; tetrakis (po].yethoxy benzo) -
N, ~, y, ~ - tetrakis (polyethoxy phenyl) porphine; trans-
dichloro, 1, 3, 5, 7 - tetrakis (carboxy phenyl) -
N, ~, y, ~ - -tetrakis (polyethoxy phenyl) porphine tin(IV),
tetra ammonium salt; 1, 3, 5, 7 - tetrakis (sul~ato
polyethoxy phenyl) - ~, ~, y, ~ - tetrakis (carboxy
naphthyl) porphine cadmium, octa di(ethanolamine) salt;
. 1, 3, S, 7 - tetrakis (phosphato phenyl) - ~r ~I Yl ~ ~
tetrakis (4-N-methyl) pyridyl porphine zinc, tetra sodium salt
tetra chloride; l, 3, 5, 7 - tetrakis (N-trimethyl)aminobutyl
N, ~, y, ~ - tetrakis polyethoxy phenyl porphine, tetraiodide.
1, 3, 5, 7 - tetrakis (4-carboxy phenyl~ - a, ~, y,
~ - tetrakis - (4-carboxy phenyl) porphine, octasodium salt;
1, 3, 4, 6 - -tetrakis tcarboxyethyl) - N, ~, y, ~ ~ tetrakis
25~ - (4-carboxy naphthyl) porphine, octasodium salt; 1, 2, 3,
4 - tetrakis (phosphato phenyl) - N, ~, y, ~ - tetra phenyl
porphine zinc, tet~a(monoethanolamine) salt; 2, 3, 6, 7 -
tetrakis (sul~atoethyl)-N, ~, y, ~ - tetra anthracyl
29
porphine, tetrammonium salt; dibenzo - N, 3, '~
tetrakis - (4-N-ethyl) pyridyl porphine cadmium tetra-
iodide; dinaphtho - a, ~, y, ~ - tetrakis - (4-carboxy
phenyl) porphine, tetrapotassium salt; di(N-triethyl)-
aminobenzo - ~, ~, y, ~ - te-trakls - (N-triethyl aminomethyl
porphine zinc hexabromide; -transdibromo, di(sulfatobenzo)
- a, ~, y, ~ - tetrakis - (sulfatobenzo) porphine tin(IV), hexa-
sodium salt; chloro, l, 3, 5, 7 - tetrakis (sulfato phenyl) -
~r ~ ~ di(sulfato phenyl) porphine scandium, hexaamonium
salt; l, 3, 5, 7 - tetrakis (polyethoxy phenyl) - a, ~ -
di(polyethoxy phenyl) porphine magnesium.
Tetraki.s - (carboxy benzo) - a, ~, y - tri(~-carboxy
phenyl) porphine, heptasodium salt; tetrakis (phosphato
benzo) - a - mono(phosphato phenyl) porph.ine,
pentapotassium salt; l, 5 - di(polyethoxy phenyl) -
, y, ~ - tetrakis (polyethoxy phenyl) porphine; l - mono
(4-carboxy phenyl) - a, ~, y, ~ - tetrakis (4-carboxy
phenyl) porphine, pentasodium salt; l, 3, 5, - tri(sulfato
phenyl) - a, ~, y, ~, - tetrakis (sulfato phenyl) porphine
zinc, heptasodium salt; l, 5 - di.(carbo~y phenyl) - a, ~ -
di(carboxy phenyl) porphine, tetrasodium salt; 1, 3 -
di(phosphato phenyl) - a, ~, y - tri (phosphato phenyl)
porphine, pentasodium salt; mono(carboxybenzo) -
a, ~, y - tri (4-carboxy phenyl) porphine, tetrasodium salt;
tetrakis - (carboxybenzo) - a, ~, y, o - tetrakis (2-furyl)
- porphine zinc, tetrasodium salt; tetrakis - (dicarboxy-
benzo) - a, ~, y - tri(4-pyridyl) - porphine, octasodium
salt;
3~
1, 2, 3, 4, 5, 6, 7, ~ - oc~a - (4-N-ethyl
pyridyl) ~ - di(2-thioazyl) - porphine octaiodide;
1, 2, 3, 4, 5, 6, 7, 8 ~ octa - (4--sulfato phenyl) - ~
- (2-oxazolyl) - porphine, octasodium salt; 1, 2j 3, 4, 5, 6,
7, 8 - octa - (4-polyethoxy phenyl) - a, ~ - di~?-indolyl) -
porphine; 1, 2, 5, 6 - tetrakis - (4-carboxy polyethoxy
phenyl) - a, ~ tetrakis (methoxy phenyl) - porphine,
tetrasodium salt; 1,3,5, 7 - tetrakis - (4-carboxy pnenyl) -
~, ~, y, ~ - tetrakis (2-benzo thienyl) - porphine, tetra-
sodium salt; tetrakis (N-methyl pyrido~ - a, ~
tetraaza porphine tetraiodide; 1, 3, 5, 7 - tetrakis
(N-trimethyl pyridyl) - ~, ~, y, ~ - tetraaza porphine
zinc tetrachloride; tetrakis (N-methyl pyrido) - ~ ~
(N-methyl pyrido) - ~, y, ~ - triaza porphine cadmium
~pentaiodide; chloro,~tetrakis tcarboxybenzo) - ~
di(4-carboxy phenyl) - y, ~ - diaza porphine aluminum
hexasodium salt; trans-dichloro, di(polyethoxybenzo) -
a, y - di(polyethoxymethyl)~ -diaza porphine tin (IV).
Di(sulfatobenzo~ , r - tri(sulfato phenyl) -
~ - monoaza porphine ca~cium, Ipenta-sodium salt; tetrakis
(phosphato
_ . .. _ . . . . _ _ _ . _
~ 39~
A ~ ~
benzo)- ~ - mono naphthyl - ~ - triaza porphine
tetrasodium salt; mono (N-trimethyl amino ethyl benzo) -
- tetraaza porphine monoiodide; txibenzo - ~
(polyethoxy phenyl) - ~, y, ~ - triaza porphine; l, 3 - di
(polyethoxy ethyl) - ~, ~, y, ~ - tetrakis (2-o~azolyl)
porphine; di(~-methyl pyridyl benzo~ -dibenzo
~ - tetraaza porphine dibromide; tetrasulfo-
benzo ~ - tetrakis (5-sulfophenyl-n-amyl) porphine
æinc, octasodium salt; 1,5 - di(6-sulfophenyl-n-hexyl) -
~, ~, y, ~ - tetrakis (sulfo-2-furyl) porphine, he~a-
a~monium sa:Lt; ~, ~, y, ~ - tetrakis (dlcarbo~yethyl~-
phenyl(aminosulfonyl phenyl) porphine, oc-tapotassium salt.
Each of the foregoin~ illustra-tive photoac-tivators
is a specific chemical compound. It should be understood
that alternative photoactivators, each within the scope of
the instant invention, are those wherein substituted in
each specific named compound are, inter alia:
a) instead of a specific ca-tion listed: sodium,
- potassium, lithium, ammonium, monoethanolamine,
diethanolamine, or triethanolamine salts.
b) instead of a specific anion listed: chloride,
bromide, iodide, or toluene sulfonate salts.
c) instead of the metallation listed: zinc(II), calcium(I
cadmium(II), magnesium(II), scandium(III), aluminum(III
tin(IV), or metal free.
d) instead of the specific alkyl groups mentioned:
methyl r ethyl, n-propyl, isopropyl, n-butyl,
isobutyl, sec-butyl, or tertbutyl.
e) instead of the specific solubiliziny group
32
mentioned: carboxyla-te, polyethoxy carboxylate,
sulfate, polyethoxy sulfate,phosphate, polye-thoxy
phosphate, remote sulfonate, quaternary pyridini~
quaternary ammonium, or polyethoxylate.
f~ instead of the number of solubilizing groups
mentioned: any number of solubilizing groups that
is not greater than the number of pyrrole-substituted
aromatic or pyrido groups plus the number of meso-
subst:ituted aroma-tic or heterocyclic groups c~nd tha~
0 i5 ~` for cationic or nonionic solubilizincJ groups,
- from l to 8; for remote anionic solubili~ing groups,
from 2 to 8; and for non-remote solubiliæing
cJroups, from 3 -to~8.
g) instead of the specific pyrrole substituents
mentioned: benzo, naphtho, pyrido, phenyl or
naphthyl.
h~ instead of the specific meso substituents mentioned:
phenyl, naphthyl, thienyl, furyl, thioazyl,
oxazyalyl, indolyl, benzothienyl, or pyridyl.
The alternatlve photoactivator compounds descrlbed above
are to be considered eclually illustrative of the compounds
of this invention as the compounds specifically named in
the precediny list.
Additional embodiments of this invention are
compounds hereinafter appearing numbered from II through
XIII and from X~IV through XX~VIII, as well as compounds
nu~bered from XIV through XXIII following conversion of
hydroxy grc)ups to corresponding carboxy groups.
3~
The litera-ture contains references to numerous means
of pre~aration of porphine and its derivatives, i.e., to the
photoactivators of this invention. One skilled in the art of
porphine or phthalocyanine chemistry will have no difficulty
selecting a synthesis appropriate for his particular purposes.
Some of the synthesis reactions are accompanied by side
reactions; in these cases conventional means of separation
and purification are needed, such as chromatographic
techniques, in a manner also detailed in the literature and
well known to the skilled practitioner.
One convenient way to prepare porphines is to react
substituted or unsubstituted heterocyclic or aromatic carbox-
aldehydes with substituted or unsubstituted pyrroles. By
varying the substituent groups of one or the other
or both of these reactants, a great variety of porphine
derivatives can be obtained. For example,
~I)
H
C 2 0 ~C ~?
~C~
N
Pyrrole 4-pyridine a,~,y,~-tetrakist4-pyridyl)porphine
carboxaldehyde
- 34 -
~,
The stability of the quadridentate macromolecular
structure is such that the reaction proceeds as described
above. For convenience, the product is frequently and
conventionally described by showing only one quarter of
this symmetrical structure. It will be appreciated this
structure is stabilized by resonance, and the bonds of all
four quarters of the s~ructure are alike, even though
conventionally they are drawn in just one of the resonating
structures. Accordingly, compound ~I) above can be
illustrated more simply as:
(I)
~C ~ N
~,
When compound (I), a substituted pyridina, is
reacted with an alkyl halide such as CH3 , a quaternary
pyridinium salt is formed which is an effective photoactivating
bleach of this invention providing the other requirements are
met as set forth herein. Quaternary porph:ine derivatives
adsorb especially strongly upon cotton fabrics because of
their opposite charge. This is desirable; however a counter-
vailing factor is the yellowish color of many such compounds
which tend to remain on the fabric after washing.
The methyl ester of toluene sulfonate may be used
instead of methyl iodide as a quaternizing salt, leading to
the following synthesis:
(I) (II)
C ~ ~3~H~ ~C ~ _c~3 s~3
a, ~, y, ~ - tetrakis methyl ester a, 15 (4-pyridyl) porphine of toluene (4-N-methyl pyridyl)porphine,
sulfonate tetra(4-toluene sulfonate)
salt
When substituted pyrroles are reacted with pyridine 4-carboxy-
aldehyde, and the reaction product reacted with an alkyl
halide, a number of different pyridinium salts are formed.
20 ~on-limiting examples are:
(III)
tetrabenzo - a, ~, y, ~
isoindole tetrakis - (4-N-alkyl pyridyl)
Cbenzopyrrole~ - porphine, tetra halide salt
36
39~
(IV)
octaphenyl ~ , y, ~ -
N tetrakis - (4-N-alkyl
pyridyl) - porphine, tetra
halide salt
3,4-diphenyl
pyrrole
~-N (V)
>--~- 1,3,5,7 ~ tetrakis
4-pyridyl) ~, ~, y~ ~ -
i 10 ~N tetrakis -(4-N-alkyl pyridyl)
- porphine, tetra halide salt
! 3 - pyr idyl
: pyrrole
The above-class of reactions between substituted pyrroles
and pyridine 4-carboxaldehyde can be carried out by
refluxing in isopropionic acid for about 30 to 60 minutes
followed by chromatographic purification. This method is
described by Adler in J. Organic Chemistry, 32, p~ 4~6
: (1967)
Any of the resultant metal-free compounds illustrated
by compounds (TI~ through (V) above can be converted to
the corresponding metallated compound by heating with a
metal salt of Zn(II), Ca(II)~ Cd(II), Mg~II), Sc(III),
Al~III) or Sn (II) in an appropriate solvent. ~The Sn(II)
becomes oxidized in ~he process, such that the photo-
activator is metallated by Sn(IV)~ For example, heating
~, B, y, ~ -tetrakis ~4-pyridyl) porphine in dimethyl-
- formamide in the presence of zinc acetate yields
Z
, ~- r~ ~ ~ tetrakis ~4-pyridyl) porphine zinc. This
method is described by Adler in J. Inorganic Nuclear
Chemistry, volume 32, pages 2443-5 (Pergamon Press Inc.,
Great Britain, 1~70j.
Alternatively, a metallated derivative can be
prepared by-~arrying out the synthesis reaction in the pres-
ence of a salt of the desired metal. For example, if
cadmium chloride is present while carxying out reaction
(IV), the res~ltant photoactivator compound is 1, 2, l, 4,
5, ~, 7, 8 - octaphenyl ~, ~, y, ~ - tetrakis ~ N alkyl
pyridyl) porphine cadmium, tetrahalide salt. This
reaction for producing a metallated compound may be
preferred because the presence of the metal tends to
increase stahility of the desired quadridentate structure
and tends to minimize the ~ormation of other reaction
products.
The metallation processes described abo~e are
generally applicable to the photoactivators of this inven-
tion, whatever the solubilizing groups may be.
Aza pyridinium salts can be made by condensing
and rearranging pyrido-substituted imides or dinitriles,
or by condensing and rearranging pyrido-substituted aromatic
vicinal dicarboxylic acids in the presence of ammonia.
Molybdic or tungstic acid or metallic antimony can be
employed, if desired, to accelerate the reactions. For
example. - ---
~ 3~
N~ ~ CN N
pyrido
phthalodinitrile H3I
.
,.'
(VI)
N +~9
,
-tetrakis (N-methyl-
6, 7 - quinolinedyl)
tetraaza porphine,
tetraiodide salt
(VII)
~13
~ 007~ J~
~ OoH NH3~ ___ __~ N ~
tetrakis
(N-methyl pyridyl benzo)
tetraaza porphine,
tetraiodide salt
39
~3~
Mono-, di-, and tri-aza pyridi~ium salts can be prepared by
using mixtures o~ star-ting ma-terials which yield mixtures
of reaction products according to the proportions of the
reactants. If pure species are desired, they can be
purified by chromatographic techniques. Non-
limiting examples are:
... . . _ . . . _ _ .. . . . ._ : .. .
3 ~
CHO
3 ~ -t 3 ~ ~ CN~ - C~HsB~
(VIII)
C2Hs
~3
predominately
tri (N-ethyl pyridyl~ - ~NH N
~ monoaza porphine, N C _ ~
tribromide salt ~ HN ~ ~ ~C2Hs
~N~ -~3 Br
C2H5
C~HO
H ~ _ _ C3H7Cl
~ C3H7
predominately 2,6-dimethyl~ N
3,4,7,8- di(N-propyl pyridyl
benzo)-~, y - di (benzo- `~ ~1
N-propyl pyridyl)~ - H3C / ~ ~ ~=J \C3H7
diaza porphine, tetra- ~ ~C
chloride salt
NH N
~ N HN~
H 7C 3N-- ~ +~ C
~ ~ C 3~ 7
41
~3~
By suitable changes in starting materials,
quaternary ammonium salts can be prepared in a manner
similar to that of -the pyridinium salt illustra-tecl as
compound (II). For e~ample, reacting pyrrole with a
tertiary amino aldehyder followed by quaternizing, leads
to
(X)
CHo
~I Rl- N - R2 R3
~, ~, y, ~ - tetrakis -
trialkyl, 4-amino phenyl)
- porphine, te~ra halide salt
As ~efore, use of substituted pyrroles leads to
pyrrole-substitu-ted porphines, while variations in the
tertiary amino group lead to corresponding variations in
the meso substitution.
A completely different route to porphine compounds
having fused ring substitution on the pyrrole rings is the
condensation and rearrangement of 4 molecules of cyano
aroma-tic or cyano heterocyclic ketones to form a quadridentate
structure. This is done by heating in the presence of
metallic z1nc, calcium, cadmium, magnesium, scandium,
aluminum or tin, or a metal salt of Zn(II), Ca(II), Cd(II),
Mg(II), Sc(III), Al(III), or Sn(II), and yields the
corresponding metallated porphine.
~2
Il Cll2-R
metal or
CN metal salt ~ ~
A C - R
where A is zinc (II), calcium ~II), cadmium ~II), ma~nesium (II)
scandium (III), aluminum (III) or tin (IV) and where R is
hydrogen or substituted or unsubstituted a].]cyl, aryl, or mix-
tures thereoE. To utilize -this method -to ma~ce quaternary
ammonium salts it is only necessary to s-tar-t with a compouncl
having a tertiary amino group in the R moiety, and then quater-
, nize the resultant porphine as bercore. For e,xample,
'
O R
C-CH2-(CH2) -N-R
7N ~_.s~
CN or Z~ acetate N ~ R
Zn C-(CH2)n-N-R2
+ R3I
~Zn C-(Cllz) -N\ ~ + 1~3
~ R3
where n = 2,
~ f, ~ - -tetrakis -
(N-trialkyl amino ethyl)
porphine zinc, tetra
iodide
~3
~3~
Quaternary ammonium aza porphines can be made
by adaptation of the methods of equations VI and VII supra,
as for example:
~XII)
. (H3C~ 2-N-C211s
~ ~ ' .
(~3c)2N ~ CN ~ C2HsI ~ ~ N-(CH3)2
~H3C)2N ~ CN ~ ~ ` C H
: - ` M
.~ 5 '~ tetrakis - di-(N-dimethyl-
N-ethylamino) benzo ~
r . ~ - tetraaza porphine,
octaiodide sal-t
, . .
Quaternary ammonium mono-, di , and tri-aza
porphines can be made by suitable choice of mixed starting
materials, in a manner analagous to the way analagous
pyridinium compounds can be made as explained hereinabove.
Mixed quaternary ammonium/pyridinium porphine compounds
are readily prepared, as fox example:
CHO
c~
H (C2Us)2
(C2Ws)2
\ 113C - N ~ (XIII)
predominately
2-(N-diethyl-N~
methyl amino I ~ ~ ~N
S .benæo)-~,y,~-
tri(N-methyl ~ fi~ NH N ~ ~ ~
pyridyl)-~- ~ H3C - ~ ~ c C ~ ~y - CW3
monoaza porphlne,~
tetra iodide salt~ <
J~
+ 4 I
~N
Z ~ CH3
~s
Among the pre~erred nonionic and anionic solubi-
lizing groups of the photoactivators of this invention and
polyethoxylates, sulfates, polyethoxysulfates, carboxylates,
polyethoxy carboxylates, and phospha-tes. A suitable
preparative method for in-troducing all such groups into the
- porphine structure is to first make the corresponding poly-
hydroxy porphine~ and then convert the hydrox~ groups to
the solubilizing groups of choice. Accordingly, methods
of preparing hydroxy porphines will be described below,
following which means of converting these compounds to poly-
ethoxylates, sulfates, etc. will be discussed.
One method of making polyhydroxy porphines i5 the
reac-tion o:E pyrrole and substituted pyrroles with hydroxy-
substituted aromatic aldehydes, This is analagous to the
preparation o~ cationic solubilizing groups illustrated by
compounds (II), (III), (IV), (V) and (X) supra. For example,
_ . ~.. _ ., _, ....... . . ~ _ . ____ ...
,
. (XIV
CHO C
H H H
indole -5~ hydroxy~ ,y,~ - tetrakis -
2--carboxaldehyde (5-hydroxy-2-
indolyl)porphine
(~V)
~ ~ -
N ) OH C {~ (CII~)nOII
~ r ~ ~ Y ~ te-traki5 -
(hydroxy al~ar~l)
- tetrabenzo porphine
Mixtures of the above starting materials yield
porphine structures wherein the 4 quarters of the quadri-
dentate molecules have non-identical structures, according
to the proportions used. This method of preparation can be
exemplified by the use of a mix-ture of pyrrole and benzo-
pyrrole with benzaldehyde to yield dibenzo meso tetraphenyl
porphine.
Alternatively, hydroxy-substituted pyrroles can
be reacted with aromatic aldehydes:
47
:
.
J
(XVI)
0~1
CHO
3,4-di (4-hydroxy benzo 1,2,3,4,5,6,7,8 -
phenyl) pyrrole thiophene-2- octa(hydroxy phenyl)-
carboxaldehyde a,~,y,~ - tetrakis
(2-benzo-thienyl)
porphi.ne
CH3
(XVII)
CHCH20H
+ ~ CHO ~;3
3-hydroxy iso-~ 2-furan 1,3,5,7 - tetra
propyl pyrrole carboxaldehyde hydroxyisopropyl-
~,~,y,~ - tetrakis -
. (2-furyl) porphine
48
In a manner analagous to the preparation of
eationie compound (XI), hydroxy eyano aromatic or hydroxy
eyano heterocyelic ketones can be condensed and rearranged
to form the stable porphine quadridenta-te s-tructure. For
exarnple:
(XVIII)
, . ,~,o~
- C113 powdered Mg
~Mg 5H
C;-CH~-~ Z,n aceLate `~UH
~C-CHg Zn .~cetate jn ,~C-cH2~-c~ - oH
Mixtures of the above starting materials yield
porphine struetures wherein the 4 quarters of the quadri
dentate moleeules have non-identieal struetures, aeeording
to the proportions used.
Hydroxy-subs-tituted aza porphines can be made in
a manner analagous to that used -to prepare compounds (VI)
and (VII); i.e. by condensation and rearrangement of hydroxy-
substituted aromatic vicinal dicarboxylic acids in thepresence of ammonia. For example:
(XXI)
HO ~ COOH NH3 ~ 0~1
COOH ~ N
N
hydroxy
phthalic
10 'b acid
- A mixture of polyhydroxy mono- and di-aza porphines
results ~rom using, as starting materials, a mixture of a
metal cyanide with a ketone whose two side groups are,
respectively, (alkyl-or aryl) and (halo aryl or halo
heterocyclicj, where one or the other or both side groups
of the ketone have a hydroxyl group substituted therein.
For example,
.... .. . . . ~ .. . _ _ ~_ __ _
~:~3~
( XXI I )
C-CH~ -CH? OH
. . 110 ~
~Cl + Zn(CN) 2
pH OH
~ CH ~ OH
tetra (hydroxybenzo~ N ~N~
cl~,y - tri(hydroxy- + ~ Zn
~`C~
methyl)-3 - monoaza Ho ~ CH2 ~
OH Oll
porphine zinc te-tra
(hydxoxyberl~:o) - Cl,y -
~di(hydroxymet~lyl) -
diaza porphine zinc
Alternatively, usiny mixtures of startin~ materia].s described
above:
C~lO
HO~cooH NH3
. H CH20H
: (~XIII)
OH
~ ~ OH tri(dihydroxybenzo)-
~ C ~ c~-(hydroxymethyl
N ~ phenyl) - ~,y,~ _
~ N N ~ triaza porphine
HO 4~ ~ OH
O (3H
The hydroxy groups of the foreyoincJ hydroxy
substituted porphines can be conver-ted to solubilizing
groups or this invention according to the following well
known chemical reaction procedures:
- CH20H +n ~CH~ /C 2] -CH2 [o - CrI2 CH2] n
polyethoxylate
- CE120H + oleum ~ CH2oSo3(3
sulfate
.
- CH2(OCH2cH2)nOH + oleum- ~ C~12( 2 2 n 3
polyethoxysulfate
- CH20H + KMnO~ ~ ~ CO ~
carboxylate ..
- CH20H + ClCH2COOH ~ - CH20C112COO(~) '
methoxy carboxylate
lS _ C~I2(ocH2cH2)noH+KMno4 2( 2 2)n_lCH2COo
polyethoxy carhoxylate
- CH2(CH2CH2)no~+clcH2cooH ~ 2( 2 2)n 2
polye-thoxy carboxylate
- CH20H + H3PO4 2 lo
OH phosphate
- CH2(ocH2cH2)noH+H3po4~ CH2( 2 2 n j
OH
polyethoxy phosphate
- CO ~+n [C~I2CH2~ C(OCll2c~I2) 0~l
O polyethoxylate ester
To exemplify how these procedures can be used:
CH~2 -~CH2
C _~_,CH2 OU
~ C ~ C~l2(C~-I2C~I2)2oOH
tetrabenzo - .
~ - tetra(4-polyethoxymethyl-
phenyl) porphine
(XXV)
OH ~)CH 2 COO
N ~ + ClCH2COOH
N
2,4,6,8 - tetrakis
(carboxy methoxy) -
a,~ - tetraaza
porphine
It ~ill be appreciated that one skilled in the
chemical arts, and particularly in the color and dye arts,
can apply the foregoing principles to make his photoactivator
of choice according to this inven-tion.
53
,
Alternative ways oE making carboxy porphines are evident
modi~ications of the chemistry hereinbefore described:
Cool-l (XXVI)
2-(4-carboxy benzaldehyde ~,~,r ~ tetraphenyl -
phenyl) pyrrole 1,3,5,7 tetra(~-carboxy-
phenyl) porphine
O (XXVII)
coo~1
H COOH
: pyrrole 4-carboxy ~ I ~ r ~ tetrakis
benzaldehyde (4-carboxyphenyl)
porphine
- . COOH ~ XXVI I I )
,[~ C OH ~N 3 ~S
HO-C C-OH N
0 0
(XXIX)
Cl Cl /~_COCl /~ COO~
H2 0 _~
N .N
Cl
54
Varying proportions of the above starting materials
.
ln mix~tures yield mono-, di-, and -tri-aza compounds. For
example:
HOOC CEiO
3 ~ ~ 3 ~ ~ ~ C~
~ COOH
H
-
(XX~)
COOH COOH
~)~
HOOC /~
~_~C ~
~I N ~ ~
N C ~ ~ COOH
HN ~ ~=J
~`C~'~
~ ~COOH
~J
COOH
predominately
1,3,5 - tri~4-carbo~yphenyl) - ~,~,y -
tri(4-carbox~yphenyl) - ~ - aza - porphine
~L13~
Using mixtures o~ starting materials which have
different.solubilizing groups, followed by appropriate
sequential reaction, yields corresponding porphine deri.va-
tives, which may be entirely anionic, entirely nonionic, or
. may be zwitterionic in nature. For example:
_ . _ . _ . . _ _ . . _ _ _ _ . _ . .
- o~
o
COO C ~COO
H m CH2-CH2
O ( Cl~ 2 CH 2 ) nH
(YX~I )
~ COO(C1-12CH .O) H
..
.~ "' ' ' .
.
: coo~3,
~=~ CHO 9
CH20H CH20H
+ 'I( XXXI I )
ol~um
~ COOa
C ~ CH
CH20SO3
.
~l ~L. 3 L3 ~
- COO
~00 COo~
~0 ~C~O~
~0
- [I ,1
~ , COO~
~ ~ (XXXIII)
N_~ // ~ t~
C- ~ N - CH3
:
As usual, variations in starting materials mal~e
possible the preparation of aza derivatives and metallated
derivatives -to suit.
The sulfonate group as encompassed by this inven-
tion is limited to a "remote'l location on the photoactivator
molecule; i.e~ displaced more than 5 atoms away from the
porphine core. Remote sulfonation can prererably occur on
aryl or heterocyclic groups or on relatively large alkyl
groups themselves substituted into either the meso position
58
~-~3'~
or the pyrrole rings. These alkyl groups need not be
simple carbon chains, but can be carbon chains interrupted
by other groups such as those described hereinbefore.
Sulfonation of substituted porphines can be
accomplished by ordinary methods such as are familiar to
the skilled chemist. Sulfuric acid, oleum, chlorosulfonic
acid and the like are effective sulfonating agents. As
usual, higher degrees of sulfonation are obtained by increasing
reaction time or temperature or by selection of a stronger
sulfonating agent. For example, by condensing and rearranging
a substituted maleimide,
' ~ :
CH2CH2CH2CH2CH2 ~
~2 (C~12) 3C~2~3
O ~
_ H ,
5-phenyl-n-pentyl
maleimide oleum
~: '' ' 1
(XXXIV)
--~&H~(CU~) 3CH~
2,4,6,8 - tetrakis ~sulfo-
phenyl-n-pentyl~ tetraza
porphine
59
~3~
.
~lso, as described in Gro~es hereinbefore cited,
: reactions of the following form can be utilized:
~: :
CH2-CH2-C ~= 0 H2N - C - CN~
. ~ CH2-CH2-C = o : H2N - C - CN
`; di(~phenylethyl) ketone ~; d~lamino malelc;acid dinltrile
CU2-CHz~C N~ GN~
condensation
Cd ~ Uz-C~ C - ;CN ~ Dd ~ re~r~m3ement
2,3 d~ ~r~ th}~ zi~e~
C3 CH; 4
C-CH2-
~s u l f a t i o n ~
(oleum) ~ SCz
;10~ ~ : It~is~of~ course`contemplated that sulfonatian~can,:~
and ~requently~w~ take place~on both~re~ote and praxlma~t~e~
; sites.
` : ; 60 ':
~3~
Remote sites are not excluded for the solubilizing
groups of this invention other than sulfonate. ~ndeed,
remote sites are preferred. Porphine structures solubilized
at re~ote sites have a reduced -tendency to aggreyate into
multilayers on fabric surfaces because they tend to have
more bulk and less crystal order; hence the intensive
blue/green coloration of these substances is imparted to
the fabrics in reduced amount. Also, remotely solubilized
porphines participate to a relatively small degree in the
side reactions designa-ted by numeral 7 on Scheme A; thus
the excited singlet state of such compounds is converted
more efficiently to the excited triplet s-tate which reacts
with oxygen to bring about the intended bleaching of stains.
This is an economic advantage.
Porphines having remote solubilizing groups
are, for example, compound XI supra where n is 5 or
greater; compound ~YV where n is 2 or greater; compound XVII
with 4 or more methylene groups interposed between the
hydroxy group and the pyrrole ring; compound VII wi-th 3 or
more methylene groups interposed between the pyridine and
pyrrole rings; compound X with 2 or more methylene groups
interposed between the meso carbon atom and the benzene
ring; etc.
Æspecially preferred photoac-tivators are remotely
su]fated amino sulfonyl porphines. These compounds not
only have the benefits discussed supra for remotely solu-
bili~ed porphines generally, but also have the added benefit
of substantivity to synthetic fibers as well as cot-ton
fibers. These compounds can be prepared by a provess involving
the following sequential steps:
61
1~ Preparing a porphine without solubilizing groups.
This step is illustrated by the preparation of all
cationic porphines exemplified hereinbefore, omi-tting
; the qua-ternization step; and by the preparation of
all hydroxy porphines exemplified hereinbefore,
where the starting ma-terials are analagous non-
hydroxy-subs-tituted compounds.
2) Reacting with chlorosul~onic acid and thionyl
chloride to form the corresponding chlorosulfonated
porphine.
3) Condensing with an amino alcohol, using an aqueous
medium and a temperature at which may be at, above,
or below normal amblent.
4) Sulfonating with oleum.
Illustrative examples o~ this preparative method are:
:
.
~:
'
.~ .
11 ~L 3 L~
C l S O ~
SO2Cl
(XXXV~ El2N ~ OH
~,~,r,~ - tetrakis (4-sulfato- .-
phenyl amino sulfonyl phenyl~
porphine ~ `
/ SO2NH ~ OSo3 So2MEI ~ ,
- ~ ClSO3H ; H2NCH2C~I20H
CN ~ znON SOC12
~XXXVI)
SO2NEICH2CH20SO3
~ 1,2,3,4~5,6,7,8 - tetrakis
oleum ~ N ~ ¦(2-sulfa-toethyl amino-
f ~ Isulfonylbenzo~-tetraaza
Zn N ¦ porphine zinc
3~
Among the amino alcohols that are operable in these reactions
may be mentioned 2-amino~2-methyl-1,3 propane diol, 2~amino-
2-ethyl-1,3-propane diol, tri(hydroxymethyl) amino methane,
l-amino glucose, 2-amino glucose, and 1-methylamino-~,3-
propane diol.
The aminosulfonyl compounds discussed supra
contain the O
- S - N -
Il I
O H
group interrupting the chain of atoms linking the -oso3~3
solubilizing group and the porphine core. It is also
con-templated that many other non-methylene groups can be
interrupting groups, as exp1ained hereinbefore.
Whatever the nature of the interrupting group,
the solubilizing group can be any of -those discussed
herein. Preparative methods for such compounds fall
within the ordinary skill of the art supplemented by the
disclosure hereln. For example,
.. _ _ .. . _ . _ . . . . . _ . .
C~10
¢~
& ~ 2
O=C=N ~3coo
4-carboxyphenyl isocyanate
` ~ (XXXVII)
~ i .
N~
~N C-N ~3 COO~
H N ~CN ~
;~g ~ OH
_~H ~ (XXXVIII) H
~g ~ 9 CH2-cH2 ~ ~J ~
OH Mg / O(CH2CH20) gH
Many of the reactants.used.in the Eoregoing methods
of preparation are commonly known and readily available to
the skilled organic chemist. Certain general methods of
synth~sis can be described below, as follows:
Substituted pyrroles can be prepared by heating
1,4 dicarbonyl compounds (diacids or keto acids) with
ammonia. For example,
HC a O
Hc - ,~ ` NH
HC - ~ [-~l20]
HC = o
. .
- diphenyl
pyrrole
Heterocyclic 2-alde~n~des con~ aining hetero or
5 oxygen atoms can be prepared :Erom pen-.0s2ns bi~ hydrolysis
to pen~oses follo~7ed by dehydra~ n and oxidat:ion For exam~le,
~IC=O
(CsE~302)~ H20 (HCOII) 3 [-_H20] ~ CHO
Il HCOH
H
- He~erocyclics con1:aining sulru. or nitrocJen he~2ro
atom.s c~n bz converted into 2-alde'~yc~s by ~eac'~ g ~ rIC
arld HCN, follo~ed by hydrolyzing with ~later, T~lo exæ~.ples
follow:
.
1. HCl,HCN ~
S 2. H~o ~ CHO
2-benzo-~:hiophene
carboxaldehyde
~ 1. HCl, ~CN
N 2. H20 N CHO
2- f uran carboxald~hyd_
~7
Z
A general method of preparing amino hydroxy alcohols
is as follows, where the R's may be H, alkyl, or substituted
alkyl:
2 OH R
0~ 1 12
RlCHO ~ HC-R3 - ~ ~1 1 3
2 - NO2
~: ~ freduction
: .
. OH R2
; Rl - C - C - R3
~: NH
:: : : ` ~: `
: ' .
... .
, j , . . . ~ ~
` ' , :
.. . . . .
The foregoing description concerns compositions
containing only surfactant and photoactivator, which are
the essential elements of this invention. They are unbuilt
compositions. Other componen-ts are optional, as the photo-
activators of this invention are useful in a great varie-ty
of othe~ise con~entional compositions.
For instance, conventional alkaline detergent
builders, inorganic or organic, can be used at levels up to
about 80go by weight of the composition, i.e. from 0 to about
80%. For bu'iit compositions, levels from about 10~ to abou-t
60o are preferred, and levels from about 20% to about ~0g
are especially preferred. I~he weight ratio of surfactant
to total builder in built compositions can be ~rom about
5:1 to about 1:5, preferably from about 2:1 to about 1:2.
Examples of suitahle inorganic alkaline detergency
builder salts useful in this invention are water soluble
alkali metal carbonates, bora-tes, phosphates, polyphosphates,
bicarbonates and silicates. Specific examples of such
salts are sodium and potassium tetrabora-tes, perborates,
bicarbonates, carbonates, tripolyphosphates, pyrophosphates,
orthophosphates, and hexametaphosphates.
Examples of suitable organic alkaline detergency
builder salts are: (1) Water-soluble aminopolycarboxylates,
e.g. sodium and potassium ethylenediaminetetraacetates,
nitrilotriacetates and N-(2-hydroxyethyl)-nitrilodiacetates;
(2) Water-soluble salts of phytic acid, e.g., sodium and
potassium phytates -- See U.S. Pat. No. 2,739,942; (3) Water-
soluble polyphosphonates, including specifically, sodium,
potassium and lithium salts of ethane-l-hydroxy-l,l-diphos-
phonic acid; sodium, potassium and lithium salts of methylene
~9
diphosphonic acid; sodium, potassium and :Lithium salts ofethylene diphosphonic acid; and sodium, potassium and lithium
sal-ts of ethane-1,1.,2-triphosphonic acicl. ~ther examples
include -the alkali metal salts oE ethane-2-car~oxy-1,1-diphos-
phonic acid, hydroxymethanediphosphonic acid, carbonyldiphos-
phonic aeid, ethane-l-hydroxy-1,1,2-triphosphonie aeid, ethane-
2-hydroxy-1,1,2-triphosphonie aeid, propane-1,1,3,3--tetra
phosphonie aeid, propane-1,1,2,3-tetraphosphonie aeid, and
propane-1,2,2,3-te-traphosphonic aci.d; (~) Water-soluble salts
of polycarboxylate polymers and copolymers as clescxibed in
U.S. Pat~ No. 3,30~,067.
A use:Eul detergent builder which may be employed
in the presen-t invention eo~prises a water-soluble salt of
a polymerie aliphatic polyearboxylic aeid having the followiny
struetural relationships as to the position of the earboxylate
groups and possessing the following prescribed physical
charaeteristies: ~aj a minimum moleeular wei.ght of abou-t
350 calculated as to the acid form; (b) an equivalen-t weigh-t
of about 50 -to about ~0 calcula-ted as to acid form;-(e) at
least ~5 mole percent of -the monomerie species havin~ at
least two carboxyl radieals separated from each other by
no-t more than two carbon atoms; (d) the site of attachment
of the polymer chain of any carboxyl-containin~ radical
being separated by not more than three earbon atoms along
the polymer ehain from the si-te of attachment of the next
earboxyl-eon-tainin~ xadieal. Specifie examples of the above-
deseribed builders inelude polymers of itaconic acid, aeonitie
acid, maleie aeid, mesaeonic aeid, fumarie acid, methylene
malonie aeid and citraeonie aeid and eopolymers with them-
selves~
In addition, other polyearboxylate builders wllich
ean be used satisfaetorily inelude water-soluble salts of
mellitie aeid, eitric acid, pyromellitie aeid, benzene
pentaexaboxylie aeid, oxydiaeetie aeid, carboxymethyloxy-
suceinie aeid and o~ydisuceinic aeld.
Certain zeolites or aluminosilieates enhaneQ the
funetion o~ the alkaline metal pyrophosphate and add
building eapacity in that the aluminosilieates se~uester
ealeium hardness. One such ?.luminosilieate whieh is useful
in the eompositions of the invention is an amorphous water-
insoluble hydrated eompound of th~ formula Nax(xAl02^SiO2),
wherein x is a number from 1.0 to 1.2 ancl y is 1, sai~
amorphous material being further eharaeteri2ed by ~ l~lg
exehange eapaeity of from about 50 mg eq. CaCO3/g. to
about 150 mg eq. CaCO3/g. and a partiele diameter o from
about 0.01 microns to about 5 microns. Thls ion exchange
huilder is more fully described in British patent No.
1,470,250 invented by B. ~. Ged~e et al, published April 14,
1977.
2~ A second water-insoluble synthetie aluminosilicate
ion exchanye material useful herein is erystalline in nature and
has the ~ormula NazlAlo2)z-tsio2)]x~l2ot wherein z and y are
integers of at least 6; the molar ratio of z to y is in the
ran~e from 1.0 to about 0.5, and x is an integer from about
15 to about 264; said aluminosilicate ion exchange material
having a partiele size diameter from about 0.1 micron to
about 100 microns; a ealcium ion exchange capacity on an
anhydrous basis of at least about 200 milligrams equivalent
., _ ~ ,_. _. . . . . _ . . _._
of CaC03 hardness per gram; and a calcium ion exchange rate
on an anhydrous basis of at least about 2 ~rains/yallon/
minute/gram. These synthetic aluminosilicates are more
fully described in British Patent No. 1,429,14~ published
March 24, 1976, invented by Cor~ill et al.
For nominally unbuilt compositions, it is contem-
plated that compositions can contain minor amounts, i.e. up to
about 10%, of compounds that, while commonly classified as
detergent bullders, are used primarily for purposes otllex
than reducing free hardness ions; for eYample electrolytcs
used to buffer pll, add ionic s-tren~th, control viscosity,
prevent gelling, etc.
It is to be understood that the detergent bleach
compositions of the present invention can contain other
components commonly used in detercJent compositions. Soil
suspending agents such as water-soluble salts of carboxy-
methylcellulose, carboxyhydroxymethylcellulose, copolymers
of maleic anhydride and vinyl ethers, and polyethylene glycols
having a molecular weight of about 400 to 10,000 are common
components of the detergent compositions of the present inven-
tion and can be used at levels of about 0.5% to about 10%
by weight. Dyes, pigments, optical brighteners, and perfumes
can be added in varying amounts as desired.
Other materials such as ~luorescers, antiseptics,
germicides, enzymes in minor amounts, and anti-ca~ing ayents
such as sodium sulfosuccinate and sodium benzoate may also
be added. Other materials use~ul in detergent compositions
are clay, especially the smectite clays disclosed in U.S.
Pat. No. 3,915,882, suds boosters, suds depressants, fillers
72
such as sodium sulfate, plI buffers, and hydrotropes such as
sodium toluene sulfonate and urea.
Pero~ygen bleaches such as sodium perborate can
optionally be used in the compositions of this invention;
they are however effective only at relatively high tempera-
tures such as approximately 160F. and above. In conjunc-
tion ~herewith, conver.tio~al chemical activators can be used
to bleach more effectively at low temperatures~ such as
the anhydrides, esters and amides di.sclosed by Gilbert ir.
Detergent Age, June 1967 pages 18-20, July 1967 pages 3~-33,
and August 1967 pa~es 26-~7 and 67. It is generally
believed that these activators func-tion by means o~ a
chemical reaction that requires usage in approxima~ely a 1:1
mol ratio wi~h the peroxygen compound. Catalytic pho~oactiva-
tors for peroxy bleaches can also be used, such as the iron
porphines, haemin chlorides and iron phthalocyanines disclosed
in U.S. ~atent No. 4,077,768.
It should be understood that, as described in
detail hereinbefore, the instant photoactivators do not
function by activating perborate or other peroxygell compounds;
the mechanism by which the instant photoactivators accomplish
their purpose is by activa-ting atmospheric oxygen. Never-
theless, formulations are not precluded that contain components
which bleach by two different mechanisms operating independently.
Granular formulations embodyin~ the compositions
of the present invention may be formed by any of the conven-
tional techniques i.e., by slurrying the individual compo-
nents in water and then atomizing and spray-drying the
l?' '
:.......................................... ....... .... . ..
resultant mixture, or by pan or drum granulation of the
components. A preferred me-thod of spray drying composi.tions
in granule ~orm is disclosed in U.S. Patents 3,629,951 and
3,629,955 issued to Davis et al on December 28, 1971.
Liquid detergents embodying the photoac-tivating
compositions of the present invention can contain builders
or can be unbuilt. If unbuilt, they can con'ain about 10
to about 50% surfactan-t, from 1 to about 15% of an organic
base such as mono-, di-, or -tri alkanolamine, and a
solubilization system containing var.ious mixtures of
water, lower alcohols and glycols, and hydrotropec;.
Built liquid single-phase composi-tions can contain about
10 to about 25% sur:Eactant, from about 10 to about 20%
builder which can be inorganic or organic, about 3 to about
10% hydrotrope, and water. Built liquid compositions in
multi-phase heterogeneous form can contain comparable
amounts of surEactant and builder together with viscosity
modifiers and stabilizers to maintain stable emulsions or
suspensions. _ _ . _ ~ -- - -- --~~--~~
Compositions of the invention in the form of
detergent laun~ry bars can be prepared as described in U.S.
Patent 3,178,370 issued April 13~ 1965 and British Paten~
1,064,414 issued April 5, 1967, both to Okenfuss. A pre~
ferred process, called "dry neutralization", involved
spraying the surfactant in liquid, acid form upon an
agitated mixture of alkaline components such as phosphates
and carbonates, followed by mechanically working as by
milling; extruding as in a plodder, and forming into bars.
i 10 The detergent bleach composi~ion of this inven-
tion can also be incorporated if desired into substrate
articles. These articles consist of a water-insoluble
substrate which releasably incorporates an effective
amount, preferably from about 3 to about 17.0 grams, of
the detergent composition described herein, plus an
I effective amount of photoactivating hleach as described
j herein.
; Detergent bleach formulations em~odying the
compositions of the present invention are commonly used in
laundry practice at concentrations from about 0.1 to about
0.6 wt. % in water. Within these approximate ranges are
variations in typical usage from household to household and
from country to countryt depending on washing conditions
such as the ratio of fabric to water, degree of soiling of
the fabrics, temperature and hardness of the water, method
oE washing whether by hand or by machine, specific
formulation employed, etc.
74a
~ ~ 3~
It has been stated hereinbefore that photoactivator
usage is from about 0.005~s to about 0.';% b~ weight based on
the detergent bleach compositi.on, preferab:Ly from about 0~01
to about 0.1~. Combining those figures wi-th the foregoing
detergent bleach concentratlons in water yields the result
that photoacti~ator concentrations in water range from about
0.05 parts per million (ppm) to about 30 ppm. Within this
range, from about 0.25 to about 5 ppm. are preerred~ The
lower side of the foregoing ranges are especial.ly efEectivc
when khe laundxy process lnvolves e~posing fabric to photo~
- 10 activa-tor for a relative1;y: long time, as :Eor exam21e during
a 30 to 120-minute presoak followed by a 20 to 30-minute
wash, and drying the fabri.c in brilliant s~mli~ht. The
higher side oF the foregoing ranges are needed when the
laundry process i.nvolves exposing fabric to photoac-tivator
for a relatively short time, as for e~ample during a short
10-mlnute wash followed by drying in an .illuminated dryer,
on a line indoors, or outdoors on a cloudy day. While
- exposure to ox~gen and visible light are essential, the
source, intensit~ and duration of exposure of the light
affect merely the degree of bleaching achieved.
In general, laundry practice embodying the present
invention in i-ts processing aspect comprises removing stains
from cotton textiles by treating the textiles, in the
presence of visible light and oxygen, with an aqueous solu-
tion of a composition of this invention. More particularly,the process comprises the following steps: (i) washing
fabrics with a detergent bleach composition, (ii) rinsing
the fabrics, (iii) drying the fabrics, and (iv) providing
exposure -to visible light and oxygen during any o:E steps
74b
(i), (ii) or (iii). These steps are appropriate whatever
physical form detergent bleach may be employed (e.g. granule,
liquid, bar, substrate) and whatever means of exposure to
lig~t and oxygen are employed (e~g. ou-tdoor washing,
S outdoor drying, illuminated washing machine, illuminated
dryer).
~P~LE I
~ y, ~ - tetrakis (4-carboxv~henY1) ~orPhine
was prepared by re~luxing a propionic acid solution, 0.24
molar in both 4-carboxybenzaldehyde and pyxrole, for 2
hours. Upon cooling the reaction mi~ture, purple crystals
o ~, ~, y, ~ - tetrakis t4-carbo~yphenyl) porphine preci-
pitated. Yield was 32go~ The product was purified by
recrystallization from methanol/chloroform solutions.
The foregoing method of preparation is similar to
that described by Longo et al., J. Heterocyclic Chem. 6
927(19~9) and the following spectral analysis performed
on a Cary 14 spectrophotometer in pyridine solution agree
very well with Lonso's and Datta~Gupta's findings,
J. Heterocyclic Chem., 3, 195(19~G):
W~ve length ~nm) 423 517 552 591 646
Extinction log ~ 5.25 4.15 3.85 3.65 3.~8
coeficient
Metallation was accomplished as follows: one
gram of tetrakis(4-carboxyphenyl) porphine was reacted with
a 10~ excess of zinc acetate in refluxing dimethyl formamide
for one hour. After completion of the reaction, the solvent
was removed on a rotav~ora-tor to obtain a residue. This
residue was dissolved in water, acidified to pH 3, and
passed through the ~ form of the cation èxchange resin
Dowex Dl~-X8~50-100 mesh) to remove the excess ionic æinc.
The xesidue after evaporation yielded a red crystalline
product ~ith about 98~ yield. Spectral analysis on a Cary
14 spectrophotometer in methanol agreed very well with
published date for ~ tetrakis (4 carboxyphenyl)
porphine æinc, Longo et al., J. Heterocyclic Chem. 6, 927(1969):
Wave lengtll ~(nm) 429 517 556 596
Extinction log 5.54 3.46 ~I.15 3.75
coefficient
The acid form of photoactivator, prepared as
described above, was converted to the tetra sodium salt
upon addition to alkaline (pI-I ~ 10~ detergent solution,
the cations of which were predominantly sodium.
~ , ~, y, ~ - tetra~is (4-carboxyphenyl) porphine
tetrasodium salt, bo-th unmetallated and me-tall.ated with
zinc~ were evaluated as photoactive bleaches in conjunction
Wit}l a granular detergent ha~ing the followiny composition
identified hereln as Composi.tion [E] which has a pH clt ~lse
concentra-tion in wa-ter of about 10.2.
Component llt. 5. Compositio~ [E~
C branched chain alkyl
12 benzene sulronate 20
Sodium tripo'yphosphate 28
Sodium toluene sulonate 2
Silicate solids (2~0 ratio SiO2/Na2O) 5.4
Sodium sulfate 34
Sodium carbonate 0.17
Sodium carboxymethyl cellulose 0.45
Perf~me 0.1
Optical brightener [none]
~iscellaneous 1.38
Moisture 8.5
~otal detergent 100.00
~L~3~2
Tcergotometer tests were run as follows: to each l-gal. tub
was added lO00 ml. of water havir.g a hardness of 7 cfrains/c~allo;
with a Ca/Mg ratio of 3/l, and 2.$ ym. of. detergent composi-
tion [E] defined above; the concentration of deteryent in
S the solution ~7as accordinc~ly O.~.r~%. Photoacti.vator was adcled
to certain of tshe solutions, as described in Table I. The
cloth load in each tub was 5.3 ym. in weisht and consisted
of six cotton swatches 2-l/2 x 2-l/2 inches in size, ~ of
which had ~en previously stained with tea and 3 with wine.
~Staininy had been accomplished by passing cotton muslin
through a bolled tea or wine bat}l, respectively, follo~.~ed bY
~ squeeyeeiny, drying and ayincJ.I ~he swatche.~.: were ~lashecl in
;~ ~ the Terc30tometer for lO minutes at 7~F~ h a xot.or speecl
~ o~ 110 rp~.;:r,lere rinsed by hancl .or l min~e ak 70F. in a
; ~ ~ 15 beaker containing 500 ml. of water haviny the same hardness
as that used for washlng, and were line-dried ou,doors in
the sun for l hour. After drying, the swatches were read
~-~;h on a Gardner XL-lO Color Difference Met~r and the resulcant
L, a and b values were calculated irto ~lhiteness according
to the formula
J - .. ...._.
W = lO0 ~ ~ (lO0 - L)2 + a2 + b
These values of whiteness were compared with those of s~ained
~: swatches beiore the Teryotometer treatment to ob-tain ~
values which measure the extent of blezching accom~lished by
the photoactivators. Results are gi~-en in Table I, and are
~iscussed hereinafter~
: . 77
r,~}
Table I
BLEACHING/STAIN REMOVAL (~W)
Buil-t DetercJent Composition ¦E~ 0.25 ~G
Type o Stain ll Wine ¦ Tea
__ . _ __ _
Conc. of Photoactivator (ppm.) . 1 10 ¦ 1 10
_ . __ _,
Type of Photoactivatox
None - 8.6 8.6 7.7 7.7
Tetrasulfobenzo tetraaza porphine
zinc, tetrasodium salt11.21~.1. 8.2 9.8
~, ~, y, ~ - tetrakis (4-carbo~y~
phenyl) porphine, tetrasocl;.um
salt 10~8 11.3 8.~L 8.5
~, ~, y, ~ - tetrakis (4-carboxy-
phenyl) porphine zinc, tetra-
sodium sal-t :LO.9 9.2 7.4 7.0
~, ~, y, ~ ~ tetrakis (4-N-rnethyl
pyridyl~ porphine zinc, tetra
(4-toluene sulfonate) salt 9.9 10.0 7.3 7.3
~90% LSD - 0.4]
,.
78
Exam le II
~ r ~ - te`tra~is (4~N-meth~ _dy~
pol~hlne,~-te-tra (4-toluene su`]fonate) ~salt was prepared as
follows: a propionic acid solution, 0.24 molar in both
pyridine 4-carboxaldehyde and pyrrole r was refluxed for
45 min. The solvent was flashed off and the residue was
washed with di~ethylformamide to dissolve -the tarry by-
products leaving purple crystals of tetra (4-pyridyl)
porphine. Yield was 22.5~ and the pxoduct spectral
characteristics were in substantial agreement with those
observed by Fleisher, Inorg. Chem. 1, 493(1962).
The tetra (4~pyridyl) porphine (~.25 mol~ was then
refluxed with sodium 4-toluene sulfonate (1.1 mol) over-
night in dimethyl formamide. The reaction was then cooled
in an ice bath and the product was removed by filtration,
The collected violet crystals of a, ~ tetra ~N-methyl
pyridyl) porphine, tetra 4~toluene sulfonate salt were
washed with acetone and dried under vacuum. Yield was 92%.
- Spectral analysis in wa-ter at pH 6-7 on a Cary 14 spectrophoto
meter agreed very well with published data, Pasternack et al.,
J. Amer. Chem. Soc., 94, 4511(1972):
Wave length ~(nm) 422 518 551 58S 641
Extinc-tion log ~ 5.17 3.96 3.83 3.57 3.07
coefficient
Elemental analysis yielded the following calcula-ted and found
values for the empirical formula C72H66N8S4O12:
C H N S
Calc: 63.42 4.88 8.22 9.41
Found: 63.15 5.03 8.41 9.14
79
'a~3~
.~
Metallation was accomplished in a manner similar
. to that described above :for the tetracarboxy porphine o
Example 1, with puriication accomplished by chroma-to-
graphic chloroform solutions on alumina. The metallation
was done prior to quaternization with 4-toluene sulfonate.
Tergotometer tes-ts made as described in Example I
were run on the metallated derivative ~, ~, r, ~ - tetrakis
~4-N-methylpyridyl) porphine zinc, tetra (4-toluene sulfonate)
salt~ Results are given in Table I, and are discussed
hereinafter.
.. . ._._ . .. .. _ .. .. .. .. . .
Table I presents bleaching, i.e. stain removal,
data for aqueous solutions of a built detergent composition
described hereinbefore containing four different photoacti-
va~ors and a control, respectively. All numbers appearing
in the table represent the average of duplicate tests.
Whiteness improvement during treatment is presented for
~wo concentrations, each, ~or wine stains and for tea
stains.
The first composition contained no photoactivator
and was the con~rol composikion for reference purposes.
The second composition contained ~he photoa~tivator
disclosed by Holcombe and Schult~ in Japanese patellt appli-
cation OPI 50-113,q79 re~erred to hereinbe~ore.
The third, fourth, and flfth compositions are
compositions according to ~his invention. It is apparent
that fabrics washecl in compositions containing the unmetal-
lated photoactivator of this invention are, or every test
condition~ more white than those washed in comparable
compositions containing no photoactivator. Fabrics washed
in compositions containing metallated photoactivators were
effective bleaches for wine stains but were not effective
~or tea stains. For all tests xeported herein, ~eference
to photoactivator usage is on a 100% active basis as
determined chromatographically~ _ _
r~x~
E`xample III
Tetra (2-sulfatoeth~l sulronamido henzo? tet~a-
aza porphine zinc, -tetrasodiu~ salt was prepared as rollows:
twenty parts of te-trasulfo tetrabenzo tetraaza porphine
zinc, tetrasodium salt were added to 200 parts of chloro-
sulfonic acid with agitation and the mixture is heated to
60C. At this temperature, 30 parts of thionyl chloride -
were added dropwise and the mixture was then heated for
4 hours a-t 80C. The reac-tion mixture was then cooled
and added with agitation to 200 parts o~ cold wa~er from
whi.ch the tetrachloro sulfo tetrabenzo tetraaza porphine
zinc was separated by Eiltration and subseqllently
washed with 1000 parts of cold water. The tetrachlorosulfo
tetrabenzo tetraaza porphine pas-te was then suspended in
300 parts of cold water and mixed with 30 parts of
2-aminoethanol for 20 hours at 20~C. The suspension was
then acidified wi-th hydrochloric acid to obtain a precipitate
which was separa-ted by filtration, washed with water and
dried. Twenty parts of the already obtained ethanolsulfon-
amide der vative of te-trabenzo tetraaza porphine zinc
were -then mixed for 12 hours at 20C with 100 parts of 10%
oleum. The solution was -then poured in a solution of 100
parts of sodium chloride into 1700 of water,and 400 parts
of ice were added. A blue/green precipitate was formed
and was separated by filtration and was washed with a
solution of sodium chloride in water and ethyl alcohol until
it was neutral to Congo red The blue/green powder
obtained was then dried at 105C. for 2 hours. The
product was purified by six successive precipitations from
82
~:~L3~
aqueous solution hy the addition of four volumes of acetone.
I Yield was 28~.
Substitution on all sul~o groups was confirmed by
the chromatographic techniques described in Japanese
patent application laid open to the public as OPI 50-113,479
on September 5, 1975 which c~rrespands to Canadian Patent
No. 1,031,652
Examination of the spectrum of 1, 2, 3, 4, 5, 6, 7,
8 - tetrakis ~2-sulfatooethyl sulfonamido benzo) ~,~,y,~ -
tetraa2a porphine zinc, tetrasodium salt, 1n ~2 at pH 9.5,
using a Cary 14 spectrophotometer, yielded the followin~
result5
Wave length A(nm) 686 672 653
Extinction loy ~ 4.46 4.64 3.91
15 . coef~i~ient
Analysis o~ the zinc content by atomic absorption
yielded 4.32~ zinc vs. 4.40~ theoretical on the basis of
the empirical formula C40~l36Nl2s8o22 4 2 ~
The test.re~or-ted in Ta~le II involved photo-
activator used together with unbuilt~de-tercJent composi-
tions in liquid.form. The ingredients for these composi-
tions are:
Com~onent ~`1t. -~ Com~osit.ion ~F]
C~ 5 alkyl polyethoxy ether
having an average of 7 mols
of ethylene oxide per nlol of
alcohol 33
Sodium C12 alXyl benzene sulfonate 22
Oleic acid ~ l.0
Triethanol amine 5.5
Ekhanol . 4.7
Electrolyte (0.9 ~OH; 0.l ci-tr:ic ac.id) l,0
Perfume, color and brighkener 0.7
~ater and Miscellaneous . 3? .1
- 100. 0
pH at use conc. in H20 ~ 8.5
... .. . _ .. _ _ _ . . ... _ . .. . ... . _ _ . . . ...
Com~onent ~t. ~ Co~osi~ on [G]
~mon.iurl salt of coconut alkyl
polyetho~y ether sulfate havin~
an av~rage of 3 mols of ethylene
o~ide per mol of alcohol 25
Sodium salt of Cl~_l6 al~yl poly-
e-thoxy ether sulfate having
an average of 2 mols of ethylene
oxide per mol of alcohol 5
Sodium salt of coconut alkyl
glyceryl ether sulfonate 4
Potassium toluene sul~onate . 0~5
Ethanol . 6.9
. Electrolytes (2.5 KCl; 0.5 H3PO~;
0.5 potassium toluene sulEonate;
0.1 citric acid) 3.6
Citric acid, perfume and opacifier 1.2
Ethylene glycol distearate 1.0
~later and miscellaneous . 52.8
''' ` i00. 0
pH at use conc. in H2O ~ 7~0
.. , .. . . ... ., .. .. .. . ... . ~
;39;~
TercJotometer test~ were run in a manner which
i.nvolved a soal;ing process followed b~ a washing process
as follows: to each l~gal. tub was added 1000 ml. oE water
having a hardness of 9 grains/ga.llon with a Ca~rlg ratio ol 3/1
S and 3.~ ~rn. of detergent composition ([FJ o.~ ~G]) defined
above; the concentration of detergent in the`solution was
accordingly 0.36%. Photoactiva-kor was added to certain of
the solutions, as described in Table II. The cloth load in
each tub consisted of 2-1/2-inch square swatches, 2 of which
were cotton.muslin previously s-tained with -tea in the manner
herein~e~o.re described, plus 8 clean te.rry cloJh s~atches to
make a total cloth load o:E 9.9 ~rams~ ~:ll swa-tches were soakecl
for 1-1/2 hours at -~0F~, following which 4 terry swatches
were removed after the soakincJ solution clinging thereto
had been squeezed back into the tubs. The remaining swatches
~ere washed for 10 minu-tes at 110 rpm. and rinsed by hand
under the tap (city ~a-ter; a~out 6 gr./yal.). After line-
drying in the sun for 1 hour, the stained, soaked and
. washed swatches were read on the Gardner ~L-10 as before.
Values o~ W were obtained as compared with the W for
stained swatches read prior to the soaking, washing and
sun dxying trea-hnent.. Differential values aw which axe
given in Table II measure the ex-tent of bleaching which was
accomplished by the photoactivator.
$'
Table II
Bl,E~C~ G/ST~LN RE'MOVAL (~W)
Unhuilt Detergent Compositions 0.36%
Tea Stains
5Photoactivator Conc. 3.5 ppm.
T~-pe of'Ph'o'toa'c-ti'vator Com~osition F Com~osition G
. . . .. _ _ . _ -- , _ .. . _ , .
None ' 2.~ '~.7
y, ~ - tetrakis
(~-carboxyphenyl)
porphine, te-tra
sodium salt 4.7 ~.1
Tctra(2-sulfato-
eth~l sulEon
amido ben~o~ tetra~
aza zinc, tetra
sodiu~ salt 4.2 5.6
[90~ LSD = 1.3]
Table II presents bleaching, i.e. stain removal,
' data for two liquid compositions described hereinbefore,
each containing photoactiva-tors of this invention, in
comparison with a control. It is apparen-t that in one of
these unbuilt detergents the compositions containing both
photoactivators exhibit significant bleaching eEfects.
Other soaking/washing Tergo-tometer tests were
run in the manner described in the preceding paragraphs
with certain impor-tan-t changes: The de-tergent used was
composition [E] as hereinbefore defined. Detergent concen-
tration in solution was 0. 6Qo and photoac-tivator concentra-
tion in solution was 0.3 ppm. In addition to the tea
~7
~3~3~t~
stained and whi-te terry swatches previously described were
8 similarly sized swatches cu-t from a bolt of yellow fabric
purchased in Mexico. After sQa~ing, washing, and sun dryiny
as hereinbefore described, i-t was found that, as compared
to the control composi-tion, the composition containing
photoactivator not only bleached the tea stains but also
bleached the yellow dye that had bled from the yellow
fabric and had deposited upon the originally white terry
swatches. This effect was ~easured by the Gardner b
value which is a measure of yellowness~ These results are
yiven in Table III and described -thereaf-ter.
No change in -thc appearance o;E the yellow fabrics
themselves was observed to be caused by the photoactivator.
Comparable -tests were also run, -the swatches of
lS which were dried in a dark room instead of in sunlight.
No bleaching took place in the absence of light, and the
fabrics treated with photoactiva-tor solution were in fact
pale blue/~reen in color due to the intrinsic blue/green
color of the photoactivator compound. This color dis~ppeared
upon later exposure of the fabrics to l:Lght.
Other comparable tests were run using the yellow
Me~ican fabrics in solutions of detergent compositions [F]
and [G] with and without photoactivator. As with composi-
tion [E], the photoactivator bo-th bleached the tea stains
and reduced transfer of yellow dye to the originally white
terry fabrics.
88
r~
Table III
BL~ACHIMG/STAIN ~EMOV~I. (Q~)
and
DY~ TR~NSFER REMOVAL (b)
5 Built Detergent Composition [E] 0.6
Pho-toactivator Conc. 0.3 ppm.
Type of swatch ¦ Tea-stained White
muslin terry
. ~ . ....... ... __ - . ,,
Test purpose Bleaching/Dye Transfer
Stain Removal Removal
~ ~ _ . ,_ _
Type of photoactivator
... _ . .. . _ .
None QW = 6.6 b - 1~73
tetrakis
(4-carboxyphenyl)
porphine, tetra sodium
salt ~W = 8.8 ~ = 0.97
Tetra(2-sulfatoethyl sulf-
amido benzo) tetxaaza
zinc~ tetra sodium salt QW = 8.0 b = 0.43
.
[90~ LSD] [0.6] [0.7]
Table III presents, for a built detergent compo-
sition described hereinbefore, data for both bleaching and
dye transfer removal brought about by two photoactivators
of this invention in comparison with a control. It is
apparent that bo-th photoactivators are significantly
effective in both respects.
89
` ~J~Z
E~'~LE ~
Detergent bleach compositions of this invention
are prepared as described in Table IV ~hich ~ol]or~s. Compo-
sitions 12, 15 and 16 are in li~uid form while the
remainder are in granular rorm. When tested for bleaching
in the manner described in E~ample I they are effective.
~11 figures in the table are weight percent of the
compositions, and identification of the components
specified in the table appears thereaEter. For all
compositions the balance no-t speciFisd is compr:ised o~
~ sodi~Lm sulfate.
Compositions 17, 18 and 19 are prepared like composi-
tions 2, 11 and 16, respectively, except that the porphine
derivatives are metallated with aluminum instead oE ~inc.
Compositions 20, 21 and 22 are similarly prepared except
... .
they are metallated with calcium. When tested for bleaching
in the manner described in E~ample I they are effective.
... ... ... . ...
_._ __ . ., ., _ _. . ., _
. 3 ~ rO
Tab le IV
Weight P_rc~nt_
C ompo-
sition Photo- S~lr.. - ~loi.s- O~'rc~r
No. activator ac~ant Builder ture Co~.~onents
__ _ __ .
0 . 20o pa 10% sa 44~ ba l~L% :l. % ocl
0.2 ob
2 oc
2 0 . 015 pb 15 sb 8 bb 10 0 . 5 oa
2 bg 0.1 ob
15 bh 1 od
3 0.005 pc15 sc 20 bb 5 0.1 ob
sm 10 bf 0 . 5 oe
10 hl
4 0.25-- pcl 20 sa22 bc 6 0.2 Oe
:1. 0 sd 8 bg
0 . 25 pa30 se10 hb 8 0.1. ob
O. 25 pe10 sli 10 bi
6 0 . 0:l.0pf ~0sb 10 bm 2 0.5 oa
sl
7 0 . 40 pg1.2 sf40 ba 10 1 oc
3 sn10 bj
bn
8 0.025 ph15 sa15 ba 4 0.1 o~
sg15 be 0 . 5 oh
bg 10 oj
9 0 . 0 2 pi 12sh 50 ha 6 0 . 2 ob
1~ '
~ 20 bk
0~15 pj2 sj 24 bd 7 10 oi
26 sp 4 bg
11 0.25 p~32 sc 0 11 1 oa
8 si 1 oc
12 0.05 pl14 sq 12 bn 61.3 0.5 ob
12 oc
0.1 o~
13 0.35 pm18 sc 0 12 0 .1 OI
4 so
14 0.0~ pn30 se --- 10 2 bj
0.1 ob
~.10 po17 sq 0 71.9 5 oc
om
16 0.20 pp8 sm 0 61,a 0.3 ob
sr 3 oc
O n O 1 0 cJ
1~) o~
91 2 ol
:~3~
Photoactivators
.
pa tetrabenzo - a, ~, y, ~ --
tetrakis (4-N~methyl) pyridyl porphine tetrai.odide
pb tetrakis (carboxybenzo)
porphine zinc, tetrasodium salt
pc tetrakis (polyethoxy naphtho~ -
a, ~, y, ~ - tetraphenyl porphine cadmium, -tetra-
ammonium salt
pd 1, 3, 5, 7 - tetrakis ~sulfato polyethoxy phenyl~ -
a, 3~ ~f~ ~ - tetrakis (carboxy naphtllyl) porphine,
octapotassium sal-t
pe 1, 2, 3, 4 - tetrakis (phosphato phenyl) - c~, ~, y, ~ ~
tetraphenyl porphine, tetra (triethano:Lamine) salt
pf dinaphtho - a, ~, y, ~S - tetrakis ~phos~.hat:o-
benzo) porphine maynesium, tetrallthium salt
pg 1, 3, S, 7 ~ tetraki.s (po:lyethoxy phenyl) - a, y ~
di(polyethoxy phenyl) porphine
ph mono (polyethoxy benzo) ~t~ibenzo -
a, ~, y, ~ -- tetraphenyl porphlne
pi bromo, tetrabenzo - a - (4-N-methyl)
... pyridyl - ~, y, ~ - pyridyl porphine scandium
monobrom.ide
pj 2, 4, 6, 8 ~ tetrakis (sulfophenyl-n~hep-tyl) tetraaza
porphine, tetra(monoe-thanolamine) salt
pk -tetrakis - (2-sulfatoethyl
aminosulfonylbenzo) ~ -tetraaza porphine zinc, tetra-
sodium salt
pl trans dichloro,- di (N-methvl ~vrido~ -
a, ~, y, ~ - tetra];is (4~carboxyphenyl) porphine
tin(IV), tetrasodium salt
pm 1, 3, 5 - tri (4-polyethoxy) ~ a, ~, y - tri ~ (4~poly~
ethoxy) - ~ - aza - porphine
pn 2, 4, 6, 8 ~ tetrakis (carboxy methoxy) ~ a, ~, y, ~ ~
tetraaza porphine, tetra(die-thanolamine) salt
po tri (diphosphatobenzo~ - a ~ (phos-
phatomethylbenzyl) - ~, y, ~ - triaaza porphine,
tetrasodium salt
pp tetra (carboxvbenzo) - a, y -
di(carboxybenzo) - ~ diaza porphine zinc, hexa~
sodium salt
92
3~
Surfactan~s
sa C~ branched chain alkyl benzene sulfonate (ABS)/
sodium salt
s~ C12 linear alkyl benzene sulronate (L~S), sodi.um salt
sc coconut alkyl sulfate, sodium salt
sd beta-alkoxy alkane sulfonate containing 2 carbon atoms
in the alkyl group and 16 carbon atoms in the alkane
moiety
se C16 paraffin sulfona-te, sodiu.m salt
sf Cl~ al~ha olefin sulEonate, sodium salt
sg Cl~ alpha sulEocarboxyla-te, sodium salt
sh ethyl est~r o:E Cl~ alpha sul.cocarbo~ylate, so~ u.l sa:lt
si -tallot~7 alkyl g:Lyce~.~yl ethex sul~onate, sod~um saLt
sj -tallo~7 soap
s~ alkyl polyethoxy alcohol sulfate having 11 carbon atoms
in t:he alkyl group and 2 mols ethylene oxide per mol
of alcohol, sodium sal-t
sl alkyl phenol polyetho~Yy alcohol sul:Fate having 9 carbon
atoms in the alkyl group and 10 mols ethylene oxide
20 . per mol of alkyl phenol 3 sodium salt
sm alkyl polyethoxy alcohol having 16 carbon atoms in the
alkyl group and 25 mols ethylene oxide per mol of
alcohol
sn ~olyethoxy polypropoxy glycol having a molecular ~7eisht
of 5000, half of ~7hich represents the polypropoxy base
and half o~ which represents hydrophilic polyethoxylate
so dimethyl C12 amine oxide
sp C16 alkyl dimethyl ammonio propan2 sulfonate
sq C12 linear alkyl benzene sulfonate (I~S), triethanol-
amine salt
sr coconut alkyl sulfate, potassium salt
~uilde~s
ba sodiun tripolyphosphclte
bb socli~ pyrophospha-te
bc sodi.um ni-tr:ilotriacetcLte
bd citric acid
be sodium carbonat2
bf sodium silicate solids, 2.0 ratio SiO2/Na2O
bg sodium silicate solids, 3.2 ratio SiO2/Na2O
bh sodium aluminosilicate ~;lal2(~1O2~SiO~)I2 ?.7 H,,O
bi potassium tetraborate
bj sodium bicarbona-te
bk potassium he~ametaphospha-te
bl sodiurn orthophospha-te
bm ethane-l~hydro,Yy~ diphosphonate, sodium salt
bn potassium pyrophosphate
Other ComPonents
oa polyethylene glycol, molecular weight 6000
ob perfurne
oc potassium toluene sulfonate
od sodium sul~osuccinate
oe sodium carboxymethylcellulose
of optical brightener (fluorescer)
oy colorant
oh protease
oi mon-tmorrilonite clay
oj sodiu.~ perborate
ok ethanol
ol diethylene ~lycol monoethyl ether
o,n triethanolarnine
