U.S. patent application number 09/355154 was filed with the patent office on 2001-07-19 for low hue photobleaches.
This patent application is currently assigned to Alan David Willey. Invention is credited to WILLEY, ALAN DAVID.
Application Number | 20010008879 09/355154 |
Document ID | / |
Family ID | 21885471 |
Filed Date | 2001-07-19 |
United States Patent
Application |
20010008879 |
Kind Code |
A1 |
WILLEY, ALAN DAVID |
July 19, 2001 |
LOW HUE PHOTOBLEACHES
Abstract
Low hue photobleaching compositions comprising organotin (IV),
organogermanium (IV), organopaltinum (IV), organopalladium (IV),
organolead (IV) or organophosphorous (III) phthalocyanine and
napthalocyanines having Q-band absorption maxima at wavelengths
greater than 660 nm and increased triplet state yields whereby
production of singlet oxygen is increased. Use of Sn.sup.4+, Ge
.sup.4+, Pt.sup.4+, Pd.sup.4+, Pb.sup.4+, P.sup.3+ pthalocyanine
and naphthalocyanines compounds in photobleaching compositions
allows for formulation of low hue laundry compositions, bleach
compositions, and hard surface cleaners.
Inventors: |
WILLEY, ALAN DAVID;
(CINCINNATI, OH) |
Correspondence
Address: |
Richard J. Minnich
FAY, SHARPE, FAGAN, MINNICH & McKEE, LLP
1100 Superior Avenue, Seventh Floor
Cleveland
OH
44114-2518
US
|
Assignee: |
Alan David Willey
|
Family ID: |
21885471 |
Appl. No.: |
09/355154 |
Filed: |
July 23, 1999 |
PCT Filed: |
January 22, 1998 |
PCT NO: |
PCT/US98/00225 |
Current U.S.
Class: |
510/372 |
Current CPC
Class: |
C11D 3/0063 20130101;
C11D 3/168 20130101; C07D 487/22 20130101 |
Class at
Publication: |
510/372 |
International
Class: |
C11D 003/00; C11D
007/18; C11D 007/54; C11D 009/42 |
Claims
What is claimed is:
1. A photochemical singlet oxygen generator having a Q-band maximum
absorption wavelength of 660 nanometers or greater, having the
formula: 36wherein M is a photoactive metal or non-metal, said
metal or non-metal selected from the group consisiting of Sn, Ge,
Pt, Pd, Pb, P and mixtures thereof; R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, and R.sup.6 units are each independently selected
from the group consisting of: a) hydrogen; b) halogen; c) hydroxy;
d) C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl, or
mixtures thereof; e) halogen substituted C.sub.1-C.sub.22 alkyl,
C.sub.3-C.sub.22 branched alkyl, C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl, or mixtures thereof; f)
polyhydroxyl substituted C.sub.3-C.sub.22 alkyl; g)
C.sub.1-C.sub.22 alkoxy; h) branched alkoxy having the formula:
37wherein Z is hydrogen, hydroxyl, C.sub.1-C.sub.30 alkyl,
C.sub.1-C.sub.30 alkoxy, --CO.sub.2H, --OCH.sub.2CO.sub.2H,
--SO.sub.3.sup.-M.sup.+, --OSO.sub.3.sup.-M.sup.+,
--PO.sub.3.sup.2-M, --OPO.sub.3.sup.2- M, or mixtures thereof; M is
a water soluble cation in sufficient amount to satisfy charge
balance; x is 0 or 1, each y independently has the value from 0 to
6, each z independently has the value from 0 to 100; i) substituted
aryl, unsubstituted aryl, or mixtures thereof; j) substituted
alkylenearyl, unsubstituted alkylenearyl, or mixtures thereof; k)
substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; l)
substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl, or
mixtures thereof; m) substituted alkyleneoxyaryl, unsubstituted
alkyleneoxyaryl, or mixtures thereof; n) C.sub.1-C.sub.22
thioalkyl, C.sub.3-C.sub.22 branched thioalkyl, or mixtures
thereof; o) an ester of the formula --CO.sub.2R.sup.9 wherein
R.sup.9 is i) C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched
alkyl, C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl,
or mixtures thereof; ii) halogen substituted C.sub.1-C.sub.22
alkyl, C.sub.3-C.sub.22 branched alkyl, C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl, or mixtures thereof; iii)
polyhydroxyl substituted C.sub.3-C.sub.22 alkylene; iv)
C.sub.3-C.sub.22 glycol, v) C.sub.1-C.sub.22 alkoxy; vi)
C.sub.3-C.sub.22 branched alkoxy; vii) substituted aryl,
unsubstituted aryl, or mixtures thereof; viii) substituted
alkylenearyl, unsubstituted alkylenearyl, or mixtures thereof; ix)
substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; x)
substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl, or
mixtures thereof; xi) substituted alkyleneoxyaryl, unsubstituted
alkyleneoxyaryl, or mixtures thereof: p) an alkyleneamino unit of
the formula: 38wherein R.sup.10 and R.sup.11 are C.sub.1-C.sub.22
alkyl, C.sub.3-C.sub.22 branched alkyl, C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl, or mixtures thereof; R.sup.12
is: i) hydrogen; ii) C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22
branched alkyl, C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched
alkenyl, or mixtures thereof; A is nitrogen or oxygen; X is
chlorine, bromine, iodine, or other water soluble anion, v is 0 or
1, u is from 0 to 22; q) an amino unit of the formula:
--NR.sup.17R.sup.18 wherein R.sup.17 and R.sup.18 are
C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl, or
mixtures thereof, r) an alkylethyleneoxy unit of the formula:
--(A).sub.v--(CH.sub.2).sub.y(OCH.s- ub.2CH.sub.2).sub.xZ wherein Z
is: i) hydrogen; ii) hydroxyl; iii) --CO.sub.2H; iv)
--SO.sub.3.sup.-M.sup.+; v) --OSO.sub.3.sup.-M.sup.+; vi)
C.sub.1-C.sub.6 alkoxy; vii) substituted aryl, unsubstituted aryl,
or mixtures thereof: viii) substituted aryloxy, unsubstituted
aryloxy, or mixtures thereof; ix) alkyleneamino; or mixtures
thereof; A is nitrogen or oxygen, M is a water soluble cation, v is
0 or 1, x is from 0 to 100, y is from 0 to 12; s) substituted
siloxy of the formula: --OSiR.sup.19R.sup.20R.sup.21 wherein each
R.sup.19, R.sup.20, and R.sup.21 is independently i)
C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl, or
mixtures thereof; ii) substituted aryl, unsubstituted aryl, or
mixtures thereof; iii) substituted aryloxy, unsubstituted aryloxy,
or mixtures thereof; iv) an alkylethyleneoxy unit of the formula:
--(A).sub.v--(CH.sub.2).sub.y(OCH.sub.2CH.sub.2).sub.xZ; wherein Z
is: a) hydrogen; b) hydroxyl; c) --CO.sub.2H; d)
--SO.sub.3.sup.-M.sup.+; e) --OSO.sub.3.sup.-M.sup.+; f)
C.sub.1-C.sub.6 alkoxy; g) substituted aryl, unsubstituted aryl, or
mixtures thereof; h) substituted aryloxy, unsubstituted aryloxy, or
mixtures thereof; i) alkyleneamino; or mixtures thereof; A is
nitrogen or oxygen, M is a water soluble cation, v is 0 or 1, x is
from 0 to 100, y is from 0 to 12; and mixtures thereof axial R
units wherein each R is independently selected from the group
consisting of: a) hydrogen; b) halogen; c) hydroxy; d)
C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl, or
mixtures thereof; e) halogen substituted C.sub.1-C.sub.22 alkyl,
C.sub.3-C.sub.22 branched alkyl C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl, or mixtures thereof; f)
polyhydroxyl substituted C.sub.3-C.sub.22 alkyl; g)
C.sub.1-C.sub.22 alkoxy; h) branched alkoxy having the formula:
39wherein Z is hydrogen, hydroxyl, C.sub.1-C.sub.30 alkyl,
C.sub.1-C.sub.30 alkoxy, --CO.sub.2H, --OCH.sub.2CO.sub.2H,
--SO.sub.3.sup.-M.sup.+, --OSO.sub.3.sup.-M.sup.+,
--PO.sub.3.sup.2-M, --OPO.sub.3.sup.2-M, or mixtures thereof; M is
a water soluble cation in sufficient amount to satisfy charge
balance; x is 0 or 1, each y independently has the value from 0 to
6, each z independently has the value from 0 to 100; i) substituted
aryl, unsubstituted aryl, or mixtures thereof; j) substituted
alkylenearyl, unsubstituted alkylenearyl, or mixtures thereof; k)
substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; l)
substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl, or
mixtures thereof; m) substituted alkyleneoxyaryl, unsubstituted
alkyleneoxyaryl, or mixtures thereof; n) C.sub.1-C.sub.22
thioalkyl, C.sub.3-C.sub.22 branched thioalkyl, or mixtures
thereof; o) a carboxylate of the formula: 40wherein R.sup.9 is: i)
C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl, or
mixtures thereof; ii) halogen substituted C.sub.1-C.sub.22 alkyl,
C.sub.3-C.sub.22 branched alkyl, C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl, or mixtures thereof; iii)
polyhydroxyl substituted C.sub.3-C.sub.22 alkylene; iv)
C.sub.3-C.sub.22 glycol; v) C.sub.1-C.sub.22 alkoxy; vi)
C.sub.3-C.sub.22 branched alkoxy; vii) substituted aryl,
unsubstituted aryl, or mixtures thereof; viii) substituted
alkylenearyl, unsubstituted alkylenearyl, or mixtures thereof; ix)
substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; x)
substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl, or
mixtures thereof; xi) substituted alkyleneoxyaryl, unsubstituted
alkyleneoxyaryl, or mixtures thereof; p) an alkyleneamino unit of
the formula: 41wherein R.sup.10 and R.sup.11 are C.sub.1-C.sub.22
alkyl, C.sub.3-C.sub.22 branched alkyl, C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl, or mixtures thereof; R.sup.12
is: i) hydrogen; ii) C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22
branched alkyl, C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched
alkenyl, or mixtures thereof; A is nitrogen or oxygen; X is
chlorine, bromine iodine, or other water soluble anion, v is 0 or
1, u is from 0 to 22; q) an amino unit of the formula:
--NR.sup.17R.sup.18 wherein R.sup.17 and R.sup.18 are
C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl, or
mixtures thereof; r) an alkylethyleneoxy unit of the formula:
--(A).sub.v--(CH.sub.2).sub.y(OCH.sub.2CH.sub.2).sub.xZ wherein Z
is: i) hydrogen; ii) hydroxyl; iii) --CO.sub.2H; iv)
--SO.sub.3.sup.-M.sup.+; v) --OSO.sub.3.sup.-M.sup.+; vi)
C.sub.1-C.sub.6 alkoxy; vii) substituted aryl, unsubstituted aryl,
or mixtures thereof; viii) substituted aryloxy, unsubstituted
aryloxy, or mixtures thereof; ix) alkyleneamino; or mixtures
thereof; A is nitrogen or oxygen. M is a water soluble cation, v is
0 or 1, x is from 0 to 100, y is from 0 to 12; s) substituted
siloxy of the formula: --OSiR.sup.19R.sup.20R.sup.21wherein each
R.sup.19, R.sup.20, and R.sup.21 is independently i)
C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl, or
mixtures thereof; ii) substituted aryl, unsubstituted aryl, or
mixtures thereof; iii) substituted aryloxy, unsubstituted aryloxy,
or mixtures thereof; iv) an alkylethyleneoxy unit of the formula:
--(A).sub.v--(CH.sub.2).sub.y(OCH.sub.2CH.sub.2).sub.xZ; wherein Z
is: a) hydrogen; b) hydroxyl; c) --CO.sub.2H; d)
--SO.sub.3.sup.-M.sup.+; e) --OSO.sub.3.sup.-M.sup.+; f)
C.sub.1-C.sub.6 alkoxy; g) substituted aryl, unsubstituted aryl, or
mixtures thereof; h) substituted aryloxy, unsubstituted aryloxy, or
mixtures thereof; i) alkyleneamino; or mixtures thereof; A is
nitrogen or oxygen, M is a water soluble cation, v is 0 or 1. x is
from 0 to 100, y is from 0 to 12, and mixtures thereof.
2. A laundry or cleaning composition comprising: A) at least 0.1%,
preferably from 0.1% to 30%, more preferably from 1% to 30%, most
preferably from 5% to 20% by weight, of a detersive surfactant,
said detersive surfactant is selected from the group consisting of
anionic, cationic, nonionic, zwitterionic, ampholytic surfactants,
and mixtures thereof; B) at least 0.001 ppm, preferably from 0.01
to 10000 ppm, more preferably from 0.1 to 5000 ppm, most preferably
form 10 to 1000 ppm, of a photosensitizing compound having a Q-band
maximum absorption wavelength of 660 nanometers or greater having
the formula: 42 43wherein M is Sn, Ge, Pt, Pd, Pb, P and mixtures
thereof; wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and
R.sup.6 units are each independently selected from the group
consisting of: wherein M is a photoactive metal or non-metal, said
metal or non-metal selected from the group consisiting of Sn, Ge,
Pt, Pd, Pb, P and mixtures thereof; R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, and R.sup.6 units are each independently selected
from the group consisting of: a) hydrogen; b) halogen; c) hydroxy;
d) C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl, or
mixtures thereof; e) halogen substituted C.sub.1-C.sub.22 alkyl,
C.sub.3-C.sub.22 branched alkyl, C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl, or mixtures thereof; f)
polyhydroxyl substituted C.sub.3-C.sub.22 alkyl; g)
C.sub.1-C.sub.22 alkoxy; h) branched alkoxy having the formula:
44wherein Z is hydrogen hydroxyl, C.sub.1-C.sub.30 alkyl,
C.sub.1-C.sub.30 alkoxy, --CO.sub.2H, --OCH.sub.2CO.sub.2H,
--SO.sub.3.sup.-M.sup.+, --OSO.sub.3.sup.-M.sup.+,
--PO.sub.3.sup.2-M, OPO.sub.3.sup.2- M, or mixtures thereof; M is a
water soluble cation in sufficient amount to satisfy charge
balance, x is 0 or 1, each y independently has the value from 0 to
6, each z independently has the value from 0 to 100; i) substituted
aryl, unsubstituted aryl, or mixtures thereof; j) substituted
alkylenearyl, unsubstituted alkylenearyl or mixtures thereof; k)
substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; l)
substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl, or
mixtures thereof; m) substituted alkyleneoxyaryl, unsubstituted
alkyleneoxyaryl, or mixtures thereof; n) C.sub.1-C.sub.22
thioalkyl, C.sub.3-C.sub.22 branched thioalkyl, or mixtures
thereof; o) an ester of the formula --CO.sub.2R.sup.9 wherein
R.sup.9 is i) C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched
alkyl, C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl,
or mixtures thereof; ii) halogen substituted C.sub.1-C.sub.22
alkyl, C.sub.3-C.sub.22 branched alkyl, C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl, or mixtures thereof; iii)
polyhydroxyl substituted C.sub.3-C.sub.22 alkylene; iv)
C.sub.3-C.sub.22 glycol; v) C.sub.1-C.sub.22 alkoxy; vi)
C.sub.3-C.sub.22 branched alkoxy; vii) substituted aryl,
unsubstituted aryl, or mixtures thereof; viii) substituted
alkylenearyl, unsubstituted alkylenearyl, or mixtures thereof; ix)
substituted aryloxy unsubstituted aryloxy, or mixtures thereof; x)
substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl, or
mixtures thereof; xi) substituted alkyleneoxyaryl, unsubstituted
alkyleneoxyaryl, or mixtures thereof; p) an alkyleneamino unit of
the formula: 45wherein R.sup.10 and R.sup.11 are C.sub.1-C.sub.22
alkyl, C.sub.3-C.sub.22 branched alkyl. C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl, or mixtures thereof; R.sup.12
is: i) hydrogen; ii) C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22
branched alkyl, C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched
alkenyl, or mixtures thereof; A is nitrogen or oxygen; X is
chlorine, bromine, iodine, or other water soluble anion, v is 0 or
1, u is from 0 to 22; q) an amino unit of the formula:
--NR.sup.17R.sup.18 wherein R.sup.17 and R.sup.18 are
C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl, or
mixtures thereof; r) an alkylethyleneoxy unit of the formula:
--(A).sub.v--(CH.sub.2).sub.y(OCH.s- ub.2CH.sub.2).sub.xZwherein Z
is: i) hydrogen; ii) hydroxyl; iii) --CO.sub.2H; iv)
--SO.sub.3.sup.-M.sup.+; v) --OSO.sub.3.sup.-M.sup.+; vi)
C.sub.1-C.sub.6 alkoxy; vii) substituted aryl, unsubstituted aryl,
or mixtures thereof; viii) substituted aryloxy, unsubstituted
aryloxy, or mixtures thereof; ix) alkyleneamino; or mixtures
thereof; A is nitrogen or oxygen. M is a water soluble cation. v is
0 or 1, x is from 0to 100, y is from 0 to 12; s) substituted siloxy
of the formula: --OSiR.sup.19R.sup.20R.sup.21 wherein each
R.sup.19, R.sup.20, and R.sup.21 is independently i)
C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl, or
mixtures thereof; ii) substituted aryl, unsubstituted aryl, or
mixtures thereof; iii) substituted aryloxy, unsubstituted aryloxy,
or mixtures thereof; iv) an alkylethyleneoxy unit of the formula:
--(A).sub.v--(CH.sub.2).sub.y(OCH.sub.2CH.sub.2).sub.xZ wherein Z
is: a) hydrogen; b) hydroxyl; c) --CO.sub.2H; d)
--SO.sub.3.sup.-M.sup.+; e) --OSO.sub.3.sup.-M.sup.+; f)
C.sub.1-C.sub.6 alkoxy; g) substituted aryl, unsubstituted aryl, or
mixtures thereof; h) substituted aryloxy, unsubstituted aryloxy, or
mixtures thereof; i) alkyleneamino; or mixtures thereof; A is
nitrogen or oxygen, M is a water soluble cation, v is 0 or 1, x is
from 0 to 100, y is from 0 to 12; and mixtures thereof axial R
units wherein each R is independently selected from the group
consisting of: a) hydrogen; b) halogen; c) hydroxy; d)
C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl, or
mixtures thereof; e) halogen substituted C.sub.1-C.sub.22 alkyl,
C.sub.3-C.sub.22 branched alkyl, C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl, or mixtures thereof; f)
polyhydroxyl substituted C.sub.3-C.sub.22 alkyl; g)
C.sub.1-C.sub.22 alkoxy; h) branched alkoxy having the formula:
46wherein Z is hydrogen, hydroxyl, C.sub.1-C.sub.30 alkyl,
C.sub.1-C.sub.30 alkoxy, --CO.sub.2H, --OCH.sub.2CO.sub.2H,
--SO.sub.3.sup.-M.sup.+, --OSO.sub.3.sup.-M.sup.+,
--PO.sub.3.sup.2-M, --OPO.sub.3.sup.2-M, or mixtures thereof; M is
a water soluble cation in sufficient amount to satisfy charge
balance; x is 0 or 1, each y independently has the value from 0 to
6, each z independently has the value from 0 to 100; i) substituted
aryl, unsubstituted aryl, or mixtures thereof; j) substituted
alkylenearyl, unsubstituted alkylenearyl, or mixtures thereof; k)
substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; l)
substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl, or
mixtures thereof; m) substituted alkyleneoxyaryl, unsubstituted
alkyleneoxyaryl, or mixtures thereof; n) C.sub.1-C.sub.22
thioalkyl, C.sub.3-C.sub.22 branched thioalkyl, or mixtures
thereof; o) a carboxylate of the formula: 47wherein R.sup.9 is: i)
C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl, or
mixtures thereof; ii) halogen substituted C.sub.1-C.sub.22 alkyl,
C.sub.3-C.sub.22 branched alkyl, C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl, or mixtures thereof; iii)
polyhydroxyl substituted C.sub.3-C.sub.22 alkylene; iv)
C.sub.3-C.sub.22 glycol; v) C.sub.1-C.sub.22 alkoxy; vi)
C.sub.3-C.sub.22 branched alkoxy; vii) substituted aryl,
unsubstituted aryl or mixtures thereof: viii) substituted
alkylenearyl, unsubstituted alkylenearyl, or mixtures thereof; ix)
substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; x)
substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl, or
mixtures thereof; xi) substituted alkyleneoxyaryl, unsubstituted
alkyleneoxyaryl, or mixtures thereof; p) an alkyleneamino unit of
the formula: 48wherein R.sup.10 and R.sup.11 are C.sub.1-C.sub.22
alkyl, C.sub.3-C.sub.22 branched alkyl, C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl, or mixtures thereof; R.sup.12
is: i) hydrogen; ii) C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22
branched alkyl, C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched
alkenyl, or mixtures thereof; A is nitrogen or oxygen; X is
chlorine, bromine, iodine, or other water soluble anion, v is 0 or
1, u is from 0 to 22; q) an amino unit of the formula:
--NR.sup.17R.sup.18wherein R.sup.17 and R.sup.18 are
C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl C.sub.3-C.sub.22 branched alkenyl, or
mixtures thereof; r) an alkylethyleneoxy unit of the formula:
--(A).sub.v--(CH.sub.2).sub.y(OCH.sub.2CH.sub.2).sub.xZ wherein Z
is: i) hydrogen; ii) hydroxyl; iii) --CO.sub.2H; iv)
--SO.sub.3.sup.-M.sup.+; v) --OSO.sub.3.sup.-M.sup.+; vi)
C.sub.1-C.sub.6 alkoxy; vii) substituted aryl, unsubstituted aryl,
or mixtures thereof; viii) substituted aryloxy, unsubstituted
aryloxy, or mixtures thereof; ix) alkyleneamino; or mixtures
thereof; A is nitrogen or oxygen, M is a water soluble cation, v is
0 or 1, x is from 0 to 100, y is from 0 to 12; s) substituted
siloxy of the formula: --OSiR.sup.19R.sup.20R.sup.21 wherein each
R.sup.19, R.sup.20, and R.sup.21 is independently i)
C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl, or
mixtures thereof; ii) substituted aryl, unsubstituted aryl, or
mixtures thereof; iii) substituted aryloxy, unsubstituted aryloxy,
or mixtures thereof; iv) an alkylethyleneoxy unit of the formula:
--(A).sub.v--(CH.sub.2).sub.y(OCH.sub.2CH.sub.2).sub.xZ; wherein Z
is: a) hydrogen; b) hydroxyl; c) --CO.sub.2H; d)
--SO.sub.3.sup.-M.sup.+; e) --OSO.sub.3.sup.-M.sup.+; f)
C.sub.1-C.sub.6 alkoxy; g) substituted aryl, unsubstituted aryl or
mixtures thereof: h) substituted aryloxy, unsubstituted aryloxy, or
mixtures thereof; i) alkyleneamino; or mixtures thereof; A is
nitrogen or oxygen, M is a water soluble cation v is 0 or 1. x is
from 0 to 100, y is from 0 to 12; and mixtures thereof; and C) the
balance carriers and adjunct ingredients.
3. A composition according to either of claims 1 or 2 wherein the
photosensitizing compound comprises R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, and R.sup.6 units independently selected from the
group consisting of hydrogen, hydroxyl, halogen, C.sub.1-C.sub.22
thioalkyl, C.sub.3-C.sub.22 branched thioalkyl, C.sub.1-C.sub.22
alkoxy, C.sub.3-C.sub.22 branched alkoxy, aryloxy, an
alkylethyleneoxy unit of the formula
--(A).sub.v--(CH.sub.2).sub.y(OCH.sub.2CH.sub.2).sub.xZwherei- n Z
comprises hydrogen, hydroxyl, --CO.sub.2H, --SO.sub.3.sup.-M.sup.+,
--OSO.sub.3.sup.-M.sup.+, C.sub.1-C.sub.6 alkoxy, substituted and
unsubstituted aryl, substituted and unsubstituted aryloxy,
alkyleneamino; and mixtures thereof; A comprises nitrogen or
oxygen, M is a water soluble cation, v is 0 or 1, x is from 0 to
100, y is from 0 to 12.
4. A composition according to any of claims 1-3 wherein axial R
units comprise: a) alkylethyleneoxy units of the formula
--(A).sub.v--(CH.sub.2).sub.y(OCH.sub.2CH.sub.2).sub.xZwherein Z
comprises hydrogen, hydroxyl, --CO.sub.2H, --SO.sub.3.sup.-M.sup.+,
--OSO.sub.3.sup.-M.sup.+, C.sub.1-C.sub.6 alkoxy, substituted and
unsubstituted aryl, substituted and unsubstituted aryloxy,
alkyleneamino; A comprises nitrogen or oxygen, M is a water soluble
cation, v is 0 or 1, x is from 0 to 100, y is from 0 to 12; b)
branched alkoxy having the formula 49wherein B is hydrogen,
hydroxyl, C.sub.1-C.sub.30 alkyl, C.sub.1-C.sub.30 alkoxy,
--CO.sub.2H, --CH.sub.2CO.sub.2H, --SO.sub.3.sup.-M.sup.+,
--OSO.sub.3.sup.-M.sup.+, --PO.sub.3.sup.2-M, --OPO.sub.3.sup.2-M,
and mixtures thereof; M is a water soluble cation in sufficient
amount to satisfy charge balance; x is 0 or 1, each y independently
has the value from 0 to 6, each z independently has the value from
0 to 100; c) substituted siloxy of the formula
--OSiR.sup.7R.sup.8R.sup.9wherein each R.sup.7, R.sup.8, and
R.sup.9 is independently selected from the group consisting of
C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl,
substituted and unsubstituted aryl, substituted and unsubstituted
aryloxy, an alkylethyleneoxy unit of the formula
--(A).sub.v--(CH.sub.2).sub.y(OCH.sub.2CH.sub.2).sub.xZ wherein Z
comprises hydrogen, C.sub.1-C.sub.30 alkyl, hydroxyl, --CO.sub.2H,
SO.sub.3.sup.-M.sup.+, --OSO.sub.3.sup.-M.sup.+, C.sub.1-C.sub.6
alkoxy, substituted and unsubstituted aryl, substituted and
unsubstituted aryloxy, alkyleneamino, and mixtures thereof; A units
comprise nitrogen or oxygen, M is a water soluble cation, v is 0 or
1, x is from 0 to 100, y is from 0 to 12; preferably branched
alkoxy having the formula: 50wherein B is hydrogen, hydroxyl,
C.sub.1-C.sub.30 alkyl, C.sub.1-C.sub.30 alkoxy, --CO.sub.2H,
--CH.sub.2CO.sub.2H, --SO.sub.3.sup.-M.sup.+,
--OSO.sub.3.sup.-M.sup.+, --PO.sub.3.sup.2-M, --OPO.sub.3.sup.2-M,
and mixtures thereof; M is a water soluble cation in sufficient
amount to satisfy charge balance; x is 0 or 1, each y independently
has the value from 0 to 6, each z independently has the value from
0 to 100.
5. A composition according to any of claims 1-4 wherein the adjunct
ingredients are members selected from the group consisting of
buffers, builders, chelants, filler salts, soil release agents
dispersants, enzymes, enzyme boosters, perfumes, thickeners,
solvents, clays, bleaches, and mixtures thereof.
6. A laundry or cleaning composition comprising: A) at least 0.1%,
preferably from 0.1% to 30%, more preferably from 1% to 30%, most
preferably from 5% to 20% by weight, of a detersive surfactant,
said detersive surfactant is selected from the group consisting of
anionic, cationic, nonionic, zwitterionic, ampholytic surfactants,
and mixtures thereof; B) at least 0.001 ppm, preferably from 0.01
to 10000 ppm, more preferably from 0.1 to 5000 ppm, most preferably
form 10 to 1000 ppm, of a photosensitizing compound having a Q-band
maximum absorption wavelength of 660 nanometers or greater having
the formula: 51wherein M is a photoactive metal or non-metal
selected from the group consisting of Sn, Ge, Pt, Pd, Pb, P, and
mixtures thereof; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and
R.sup.6 units are moieties that provide a positive D.sub.triplet
yield of at least 1, preferably at least 10, more preferably at
least 30, when said moiety replaces hydrogen; wherein the R units
are axial units, said R units independently selected from the group
consisting of: a) hydrogen; b) halogen; c) hydroxy; i)
C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl, or
mixtures thereof; ii) halogen substituted C.sub.1-C.sub.22 alkyl,
C.sub.3-C.sub.22 branched alkyl, C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl, or mixtures thereof; iii)
polyhydroxyl substituted C.sub.3-C.sub.22 alkylene; iv)
C.sub.3-C.sub.22 glycol; v) C.sub.1-C.sub.22 alkoxy; vi)
C.sub.3-C.sub.22 branched alkoxy; vii) substituted aryl,
unsubstituted aryl, or mixtures thereof; viii) substituted
alkylenearyl, unsubstituted alkylenearyl, or mixtures thereof; ix)
substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; x)
substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl, or
mixtures thereof; xi) substituted alkyleneoxyaryl, unsubstituted
alkyleneoxyaryl, or mixtures thereof; p) an alkyleneamino unit of
the formula: 52wherein R.sup.10 and R.sup.11 are C.sub.1-C.sub.22
alkyl, C.sub.3-C.sub.22 branched alkyl, C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl, or mixtures thereof; R.sup.12
is: i) hydrogen; ii) C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22
branched alkyl, C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched
alkenyl, or mixtures thereof; A is nitrogen or oxygen; X is
chlorine, bromine, iodine, or other water soluble anion, v is 0 or
1, u is from 0 to 22; q) an amino unit of the formula:
--NR.sup.17R.sup.18wherein R.sup.17 and R.sup.18 are
C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl, or
mixtures thereof; r) an alkylethyleneoxy unit of the formula: d)
C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22branched alkenyl, or
mixtures thereof; e) halogen substituted C.sub.1-C.sub.22 alkyl,
C.sub.3-C.sub.22 branched alkyl, C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl, or mixtures thereof; f)
polyhydroxyl substituted C.sub.3-C.sub.22 alkyl; g)
C.sub.1-C.sub.22 alkoxy; h) branched alkoxy having the formula:
53wherein Z is hydrogen, hydroxyl, C.sub.1-C.sub.30 alkyl,
C.sub.1-C.sub.30 alkoxy, --CO.sub.2H. --OCH.sub.2CO.sub.2H,
--SO.sub.3.sup.-M.sup.+, --OSO.sub.3.sup.-M.sup.+,
--PO.sub.3.sup.2-M, --OPO.sub.3.sup.2-M, or mixtures thereof; M is
a water soluble cation in sufficient amount to satisfy charge
balance; x is 0 or 1, each y independently has the value from 0 to
6, each z independently has the value from 0 to 100; i) substituted
aryl, unsubstituted aryl, or mixtures thereof; j) substituted
alkylenearyl, unsubstituted alkylenearyl, or mixtures thereof; k)
substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; l)
substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl, or
mixtures thereof; m) substituted alkyleneoxyaryl, unsubstituted
alkyleneoxyaryl, or mixtures thereof; n) C.sub.1-C.sub.22
thioalkyl, C.sub.3-C.sub.22 branched thioalkyl, or mixtures
thereof; o) a carboxylate of the formula: 54wherein R.sup.9 is:
--(A).sub.v--(CH.sub.2).sub.y(OCH.sub.2CH.sub.2).sub.xZwherein Z
is: i) hydrogen; ii) hydroxyl; iii) --CO.sub.2H; iv)
--SO.sub.3.sup.-M.sup.+; v) --OSO.sub.3.sup.-M.sup.+; vi)
C.sub.1-C.sub.6 alkoxy; vii) substituted aryl, unsubstituted aryl,
or mixtures thereof; viii) substituted aryloxy, unsubstituted
aryloxy, or mixtures thereof; ix) alkyleneamino; or mixtures
thereof; A is nitrogen or oxygen, M is a water soluble cation, v is
0 or 1, x is from 0 to 100, y is from 0 to 12; s) substituted
siloxy of the formula: --OSiR.sup.19R.sup.20R.sup.21 wherein each
R.sup.19, R.sup.20 and R.sup.21 is independently i)
C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl, or
mixtures thereof; ii) substituted aryl, unsubstituted aryl, or
mixtures thereof; iii) substituted aryloxy, unsubstituted aryloxy,
or mixtures thereof; iv) an alkylethyleneoxy unit of the formula:
--(A).sub.v--(CH.sub.2).sub.y(OCH.sub.2CH.sub.2).sub.xZ wherein Z
is: a) hydrogen; b) hydroxyl; c) --CO.sub.2H; d)
--SO.sub.3.sup.-M.sup.+; e) --OSO.sub.3.sup.-M.sup.+; f)
C.sub.1-C.sub.6 alkoxy; g) substituted aryl, unsubstituted aryl, or
mixtures thereof; h) substituted aryloxy, unsubstituted aryloxy, or
mixtures thereof; i) alkyleneamino; or mixtures thereof; A is
nitrogen or oxygen M is a water soluble cation. v is 0 or 1, x is
from 0to 100. y is from 0 to 12; and mixtures thereof; and B) the
balance carriers and adjunct ingredients.
7. A laundry or cleaning composition comprising: A) at least 0.1%,
preferably from 0.1% to 30%, more preferably from 1% to 30%, most
preferably from 5% to 20% by weight, of a detersive surfactant,
said detersive surfactant is selected from the group consisting of
anionic, cationic, nonionic, zwitterionic, ampholytic surfactants,
and mixtures thereof; B) at least 0.001 ppm, preferably from 0.01
to 10000 ppm, more preferably from 0.1 to 5000 ppm, most preferably
form 10 to 1000 ppm, of a photosensitizing compound having a Q-band
maximum absorption wavelength of 660 nanometers or greater having
the formula: 55 56wherein M is a photoactive metal or non-metal
selected from the group consisting of Sn, Ge, Pt, Pd, Pb, P, and
mixtures thereof; R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and
R.sup.6 units are moieties that provide a positive red shift value
of at least 1, preferably a positive red shift value of at least
10, more preferrably a positive red shift value of at least 30,
when said moieties are substituted for hydrogen; R units are axial
units, said R units independently selected from the group
consisting of: a) hydrogen; b) halogen; c) hydroxy; d)
C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl, or
mixtures thereof; e) halogen substituted C.sub.1-C.sub.22 alkyl,
C.sub.3-C.sub.22 branched alkyl, C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl or mixtures thereof; f)
polyhydroxyl substituted C.sub.3-C.sub.22 alkyl; g)
C.sub.1-C.sub.22 alkoxy; h) branched alkoxy having the formula:
57wherein Z is hydrogen, hydroxyl C.sub.1-C.sub.30 alkyl,
C.sub.1-C.sub.30 alkoxy, --CO.sub.2H, --OCH.sub.2CO.sub.2H,
--SO.sub.3.sup.-M.sup.+, --OSO.sub.3.sup.-M.sup.+,
--PO.sub.3.sup.2-M, --OPO.sub.3.sup.2-M, or mixtures thereof; M is
a water soluble cation in sufficient amount to satisfy charge
balance; x is 0 or 1, each y independently has the value from 0 to
6, each z independently has the value from 0 to 100; i) substituted
aryl, unsubstituted aryl, or mixtures thereof; j) substituted
alkylenearyl, unsubstituted alkylenearyl, or mixtures thereof; k)
substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; l)
substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl, or
mixtures thereof; m) substituted alkyleneoxyaryl, unsubstituted
alkyleneoxyaryl, or mixtures thereof; n) C.sub.1-C.sub.22
thioalkyl, C.sub.3-C.sub.22 branched thioalkyl, or mixtures
thereof; o) a carboxylate of the formula: 58wherein R.sup.9 is: i)
C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl, or
mixtures thereof; ii) halogen substituted C.sub.1-C.sub.22 alkyl,
C.sub.3-C.sub.22 branched alkyl, C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl, or mixtures thereof; iii)
polyhydroxyl substituted C.sub.3-C.sub.22 alkylene; iv)
C.sub.3-C.sub.22 glycol; v) C.sub.1-C.sub.22 alkoxy; vi)
C.sub.3-C.sub.22 branched alkoxy; vii) substituted aryl,
unsubstituted aryl, or mixtures thereof; viii) substituted
alkylenearyl, unsubstituted alkylenearyl, or mixtures thereof; ix)
substituted aryloxy, unsubstituted aryloxy, or mixtures thereof; x)
substituted oxyalkylenearyl, unsubstituted oxyalkylenearyl, or
mixtures thereof; xi) substituted alkyleneoxyaryl, unsubstituted
alkyleneoxyaryl, or mixtures thereof; p) an alkyleneamino unit of
the formula: 59wherein R.sup.10 and R.sup.11 are C.sub.1-C.sub.22
alkyl C.sub.3-C.sub.22 branched alkyl, C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl, or mixtures thereof; R.sup.12
is: i) hydrogen; ii) C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22
branched alkyl, C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched
alkenyl, or mixtures thereof; A is nitrogen or oxygen; X is
chlorine, bromine, iodine, or other water soluble anion, v is 0 or
1, u is from 0 to 22; q) an amino unit of the formula:
--NR.sup.17R.sup.18 wherein R.sup.17 and R.sup.18 are
C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl, or
mixtures thereof; r) an alkylethyleneoxy unit of the formula:
--(A).sub.v--(CH.sub.2).sub.y(O CH.sub.2CH.sub.2).sub.xZ wherein Z
is: i) hydrogen; ii) hydroxyl; iii) --CO.sub.2H; iv)
--SO.sub.3.sup.-M.sup.+; v) --OSO.sub.3.sup.-M.sup.+; vi)
C.sub.1-C.sub.6 alkoxy; vii) substituted aryl, unsubstituted aryl,
or mixtures thereof; viii) substituted aryloxy, unsubstituted
aryloxy, or mixtures thereof; ix) alkyleneamino; or mixtures
thereof; A is nitrogen or oxygen, M is a water soluble cation, v is
0 or 1, x is from 0 to 100, y is from 0 to 12; s) substituted
siloxy of the formula: --OSiR.sup.19R.sup.20R.sup.21 wherein each
R.sup.19, R.sup.20, and R.sup.21 is independently i)
C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl, or
mixtures thereof; ii) substituted aryl, unsubstituted aryl, or
mixtures thereof; iii) substituted aryloxy, unsubstituted aryloxy,
or mixtures thereof; iv) an alkylethyleneoxy unit of the formula:
--(A).sub.v--(CH.sub.2).sub.y(OCH.sub.2CH.sub.2).sub.xZ wherein Z
is: a) hydrogen; b) hydroxyl; c) --CO.sub.2H; d)
--SO.sub.3.sup.-M.sup.+; e) --OSO.sub.3.sup.-M.sup.+; f)
C.sub.1-C.sub.6 alkoxy; g) substituted aryl, unsubstituted aryl, or
mixtures thereof; h) substituted aryloxy, unsubstituted aryloxy, or
mixtures thereof; i) alkyleneamino; or mixtures thereof; A is
nitrogen or oxygen, M is a water soluble cation, v is 0 or 1, x is
from 0to 100, y is from 0 to 12; and mixtures thereof; and B) the
balance carriers and adjunct ingredients.
8. A method for cleaning a hard surface comprising contacting a
hard surface in need of cleaning with an aqueous cleaning
composition comprising at least 0.001 ppm photosensitizing compound
according to any of claims 1-6 and exposing the hard surface to a
source of light having a minimal wavelength range from 300 to 1200
nanometers.
9. A method for cleaning a stained fabric with a cleaning material
comprising a low aqueous cleaning composition comprising contacting
a stained fabric in need of stain removal with a low aqueous
cleaning solution comprising less than 50% water and at least 0.001
ppm of the photosensitizing compound according to any of claims 1-6
followed by exposing the surface of the treated fabric to a source
of light having a minimal wavelength range from 300 to 1200
nanometers.
10. A method for cleaning a hard surface with a low aqueous
cleaning composition comprising contacting a hard surface in need
of cleaning with a low aqueous cleaning composition comprising less
than 50% water and at least 0.001 ppm of the photosensitizing
compound according to any of claims 1-6 and exposing the hard
surface to a source of light having a minimal wavelength range from
300 to 1200 nanometers.
11. A bleaching composition comprising: a) at least 0.01% of a
non-hypohalite bleach; b) at least 0.001 ppm, preferably from 0.01
to 10000 ppm, more preferably from 0.1 to 5000 ppm, most preferably
form 10 to 1000 ppm, of a photosensitizing compound having a Q-band
maximum absorption wavelength of 660 nanometers or greater
according to claim 1; and c) the balance carriers and adjunct
ingredients, preferably bleach activators.
12. A composition according to claim 11 wherein the non-hypohalite
bleach is a selected from the group consisting of percarboxylic
acids, peroxides, percarbonates, perborates, and mixtures thereof.
Description
FIELD OF THE INVENTION
[0001] The present invention relates to novel organotin,
organogermanium, organoplatinum, organopalladium, organolead, or
organophosphorous photosensitizing compounds having a Q-band
maximum absorption wavelength of 660 nanometers or greater and
their use as photoactivators (photosensitizer) or singlet oxygen
producers, in particular for low hue photobleaching for removing
stains from textiles and hard surfaces. The present invention also
relates to laundry compositions and hard surface cleaners
comprising the novel organotin, organogermanium, organoplatinum,
organopalladium, organolead, or organophosphorous photosensitizing
compounds of the present invention. The present invention further
relates to a method of delivering compositions comprising low hue
photobleaches to soiled and stained fabrics and to hard
surfaces.
BACKGROUND OF THE INVENTION
[0002] It is known that certain water-soluble phthalocyanine,
naphthalocyanine, and metallocyanine compounds can be used as
photobleaching and anti-microbial agents. Phthalocyanines and
naphthalocyanines or their metal complexes can form "singlet
oxygen" an oxidative species capable of reacting with stains to
bleach them to a colorless and usually water-soluble state.
[0003] There are many examples of phthalocyanines and
naphthalocyanines photobleaches, the most common being the zinc and
aluminum phthalocyanines. In the literature the term
"photosensitizer" is often used instead of "photoactivator" and may
therefore be considered as standing equally well for the latter
term used throughout this specification
[0004] The prior art teaches phthalocyanine and naphthalocyanine
compounds having the general structure 1
[0005] where Me is a transition or non-transition metal, (Sens.) is
a phthalocyanine or naphthalocyanine ring which, when combined with
a suitable Me unit, is capable of undergoing photosensitization of
oxygen molecules, R units are substituent groups which are bonded
to the photosensitization ring units (Sens.) to enhance the
solubility or photochemical properties of the molecule, and Y units
are substituents associated with the metal atom, for example,
anions to provide electronic neutrality. The selection of a
particular substituent R unit for substitution into the molecule
has been the focus of many years of research and these units are
typically chosen by the formulator to impart into the target
molecule the desired level of water solubility.
[0006] A major limitation to the use of phthalocyanine and
naphthalocyanine compounds for fabric photobleaching is the fact
that these molecules are highly colored materials.
[0007] A second limitation is that the compounds are not inherently
water soluble. It has therefore been the task of phthalocyanine and
naphthalocyanine photobleach formulators to provide water soluble
photobleaches without adversely affecting their photochemical
properties.
[0008] A further task for the formulators of photobleaches has been
the need to modify the properties of the photosensitizer (Sens.)
unit of the molecule, in other words, to increase the quantum
efficiency without reducing the water solubility. While balancing
water solubility and enhanced photophysics, the formulator must
insure that the structural modifications do not increase the
color.
[0009] It is well known to formulators skilled in the art that an R
unit which may produce a desired increase in one of these three
properties may cause an equally large decrease in one or both of
the other desirable properties.
[0010] Surprisingly, it has been found that the compounds of the
present invention allow the formulators to modify the levels of
solubility, photoefficiency, Q-band wavelength maxima separately
without adversely affecting the other parameters of the molecule.
This ability to delineate and selectively modify the key structural
elements contributing to the target properties of the molecule
allows the formulator to proceed without having to rely upon a "hit
and miss" stratagem.
[0011] The photobleaches of the invention comprise two "elements".
The photo-sensitizing ring which is optimized for color (hue) and
generation of singlet oxygen, and axial groups which are optimized
to provide the desired level of solubility, substantivity, and
de-aggregation. These two elements will be described in more detail
herein below.
[0012] One key to this ability to control the molecular properties
is found when contrasting the structure of known photobleaches
comprising phthalocyanines and naphthalocyanines with those of the
present invention. The examples of photo-bleaches previously
described in the art are generally flat molecules due to their
planar ring structure. This planarity produces an propensity for
these molecules to aggretate wherein this aggregation tends to lead
to photochemical quenching, preventing efficient formation of
singlet oxygen.
[0013] The organotin, organogermanium, organoplatinum,
organopalladium, organolead, or organophosphorous photosensitizing
compounds of the present invention comprise axial substituents that
act to break up this ordering effect, hence providing an
efficiently formed mono-layer of photosensitizers evenly applied to
a given substrate. Because each molecule of this mono-layer can now
contribute to bleaching there is better cost efficiency to the
formulator.
[0014] It has been surprisingly found that because of the
separating out of physical properties into "molecular sectors",
e.g. R groups for solubility, new uses for the compounds of the
present invention have been realized. Adducts which provide unique
solubility profiles, but which detract from the photophysics, were
once excluded from use in photobleaches. However, the inclusion of
these moieties into the photobleaches of the present invention
results in the ability to formulate photobleaches for use in
non-classical applications, for example dry cleaning applications.
Solvent based or low aqueous solutions of the present invention are
now obtainable for the very reason that the present invention
provides control over solubility which is manifested in the choice
of the axial R substitutions.
[0015] The proper selection of axial R units attached to the
compounds of the present invention allow the formulator to balance
the changes in photoefficiency of the desired compound with the
water solubility of the parent material. In addition, these axial R
unit modifications provide the formulator with the ability to
balance solubility, Q-band .lambda..sub.max, and quantum efficiency
of the (Sens.) unit.
[0016] It is an object of the present invention to provide
"substantive" and " non-substantive" organotin, organogermanium,
organoplatinum, organopalladium, organolead, or organophosphorous
photosensitizers. A "substantive" organotin, organogermanium,
organoplatinum, organopalladium, organolead, or organophosphorous
photosensitizer will be attracted to a surface and a
"non-substantive" organotin, organogermaniumn, organoplatinum,
organopalladium, organolead, or organophosphorous photosensitizer
will repel a surface.
[0017] It is a further object of the present invention to provide
substantive and non-substantive photobleaching laundry compositions
for natural, synthetic or blended fabrics.
[0018] It is a further object of the present invention to provide
photobleaching compositions that comprise non-aqueous and low
aqueous carriers, that is, photobleaching compositions having
carriers wherein water constitutes less than half of the carrier
liquid.
[0019] It is a further object of the present invention to provide
substantive and non-substantive photobleaching hard surface
cleaning compositions for non-porous hard surfaces, inter alia,
Formica.RTM., ceramic tile, glass, or for porous hard surfaces such
as concrete or wood.
[0020] An object of the present invention is to provide a method
for bleaching fabric with laundry compositions comprising
organotin, organogermanium, organoplatinum, organopalladium,
organolead, or organophosphorous photobleaching compounds of the
present invention.
[0021] An object of the present invention is to provide a method
for cleaning hard surfaces with compositions comprising organotin,
organogermanium, organoplatinum, organopalladium, organolead, or
organophosphorous photobleaching compounds of the present
invention.
[0022] An object of the present invention is to provide for low hue
organotin, organogermanium, organoplatinum, organopalladium,
organolead, or organophosphorous photosensitizing compounds having
a Q-band maximum absorption wavelength of at least 660
nanometers.
BACKGROUND ART
[0023] Various patent documents relate to photochemical bleaching
or to the use of phthalocyanine and naphthalocyanine compounds as
well as their formulation and synthesis. See for example U.S. Pat.
No. 3,094,536 issued Jun. 18, 1963; U.S. Pat. No. 3,927,967 issued
Dec. 23, 1975; U.S. Pat. No. 4,033,718 issued Jul. 5, 1977; U.S.
Pat. No. 4,166,718 issued Sep. 4, 1979; U.S. Pat. No. 4,240,920
issued Dec. 23, 1980; U.S. Pat. No. 4,255,273 issued Mar. 10, 1981;
U.S. Pat. No. 4,256,597 issued Mar. 17, 1981; U.S. Pat. No.
4,318,883 issued Mar. 9, 1982; U.S. Pat. No. 4,368,053 issued Jan.
11, 1983; U.S. Pat. No. 4,497,741 issued Feb. 5, 1985; U.S. Pat.
No. 4,648,992 issued Mar. 10, 1987; and U.K. Pat. App. 1,372,035
published Oct. 30, 1974; U.K Pat. App. 1,408,144 published Oct. 1,
1975; U.K. Pat App. 2,159,516 published Dec. 4, 1985; E.P. 484,027
Al published May 6, 1992; WO 91/18006 published Nov. 28, 1991 and
Japanese Kokai 06-73397 Derwent Abst. No. (94-128933) published
Mar. 15, 1994.
[0024] In addition to the above cited patent publications, other
references describing the synthesis, preparation and properties of
phthalocyanines and naphthalocyanines, incorporated herein also by
reference; Phthalocyanines: Properties and Applications, Leznoff,
C. C. and Lever A. B. P. (Eds), VCH, 1989; Infrared Absorbing Dyes,
Matsuoka, M. (Ed), Plenum, 1990; Inorg. Chem., Lowery, M. J. et
al., 4, pg. 128, (1965); Inorg. Chem. Joyner R. D. et al., 1, pg.
236, (1962); Inorg. Chem., Kroenke, W. E. et al., 3, 696, 1964;
Inorg. Chem. Esposito, J. N. et al., 5, pg.1979, (1966); J. Am.
Chem. Soc. Wheeler, B. L. et al., 106, pg. 7404, (1984); Inorg.
Chem. Ford, W. E, et al., 31, pg. 3371, (1992); Material Science,
Witkiewicz, Z. et al., 11, pg. 39, (1978); J. Chem. Soc. Perkin
Trans. I, Cook, M. J., et al., pg. 2453, (1988); Acc. Chem. Res.,
Sayer, P., Gouterman, M., and Connell, C. R., 15, 73-79, (1982); J.
Am. Chem. Soc., Snow, A. W. and Jarvis, N. Lynn, 106, 4706-4711,
(1986); J. Am. Chem. Soc., Richter, B. D., Kenney, M. E., Ford, W.
E. and Rodgers, M. A. J., 112, 8064-8070, (1990); Cancer Letters,
Soncin M., Polo, L., Reddi, E., Jori, G., Kenny, M. E., Chang, G.,
and Rodgers, M. A. J., 89, 101-106, (1995); J. Inorg, Nucl. Chem.,
Rafaeloff, R., Kohl, F. J., Krueger, P. C., Kenney, M. E., 28,
899-902, (1966); J. Amer. Chem. Soc., Dirk, C. W., Inabe, T.,
Schoch, Jr., K. F., and Marks, T. J., 105, 1539-1550, (1985);
Polyhedron, Nyaokong, T., 2067-71, (1994); Angew. Chem., Int. Ed.
Engl., Kato, S., Noda, I., Mizuta, M. M., and Itoh, Y., 18, 82-3,
(1979); Photochemistry and Photobiology, Chan, W.-S., Marshall, J.
F., Svensen, R., Phillips, D., and Hart, I. R., 45, 757-61, (1987);
Inorganica Chemica Acta, Kraut, B., and Ferrandi, G., 149, 273-77,
(1988); Inorg. Chem., Kroenke, W. J., and Kenney, M. E., 3, 251-4,
(1964).
SUMMARY OF THE INVENTION
[0025] The present invention relates to a photochemical singlet
oxygen generator having a Q-band maximum absorption wavelength of
660 nanometers or greater, having the formula: 2
[0026] or the formula: 3
[0027] wherein M is a photoactive metal or non-metal, said metal or
non-metal selected from the group consisiting of Sn, Ge, Pt, Pd,
Pb, P and mixtures thereof;
[0028] R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.6
units are each independently selected from the group consisting
of:
[0029] a) hydrogen;
[0030] b) halogen;
[0031] c) hydroxy;
[0032] d) C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl, or
mixtures thereof;
[0033] e) halogen substituted C.sub.1-C.sub.22 alkyl,
C.sub.3-C.sub.22 branched alkyl, C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl, or mixtures thereof;
[0034] f) polyhydroxyl substituted C.sub.3-C.sub.22 alkyl;
[0035] g) C.sub.1-C.sub.22 alkoxy;
[0036] h) branched alkoxy having the formula: 4
[0037] wherein Z is hydrogen, hydroxyl, C.sub.1-C.sub.30 alkyl,
C.sub.1-C.sub.30 alkoxy, --CO.sub.2H, --OCH.sub.2CO.sub.2H,
--SO.sub.3.sup.-M.sup.+, --OSO.sub.3.sup.-M.sup.+,
--PO.sub.3.sup.2-M, OPO.sub.3.sup.2- M, or mixtures thereof; M is a
water soluble cation in sufficient amount to satisfy charge
balance; x is 0 or 1, each y independently has the value from 0 to
6, each z independently has the value from 0 to 100;
[0038] i) substituted aryl, unsubstituted aryl, or mixtures
thereof;
[0039] j) substituted alkylenearyl, unsubstituted alkylenearyl, or
mixtures thereof;
[0040] k) substituted aryloxy, unsubstituted aryloxy, or mixtures
thereof;
[0041] l) substituted oxyalkylenearyl, unsubstituted
oxyalkylenearyl, or mixtures thereof;
[0042] m) substituted alkyleneoxyaryl, unsubstituted
alkyleneoxyaryl, or mixtures thereof;
[0043] n) C.sub.1-C.sub.22 thioalkyl, C.sub.3-C.sub.22 branched
thioalkyl, or mixtures thereof;
[0044] o) an ester of the formula --CO.sub.2R.sup.9 wherein R.sup.9
is
[0045] i) C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl, or
mixtures thereof;
[0046] ii) halogen substituted C.sub.1-C.sub.22 alkyl,
C.sub.3-C.sub.22 branched alkyl, C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl, or mixtures thereof;
[0047] iii) polyhydroxyl substituted C.sub.3-C.sub.22 alkylene;
[0048] iv) C.sub.3-C.sub.22 glycol;
[0049] v) C.sub.1-C.sub.22 alkoxy;
[0050] vi) C.sub.3-C.sub.22 branched alkoxy;
[0051] vii) substituted aryl, unsubstituted aryl, or mixtures
thereof;
[0052] viii) substituted alkylenearyl, unsubstituted alkylenearyl,
or mixtures thereof;
[0053] ix) substituted aryloxy. unsubstituted aryloxy, or mixtures
thereof;
[0054] x) substituted oxyalkylenearyl, unsubstituted
oxyalkylenearyl, or mixtures thereof;
[0055] xi) substituted alkyleneoxyaryl, unsubstituted
alkyleneoxyaryl, or mixtures thereof.
[0056] an alkyleneamino unit of the formula: 5
[0057] wherein R.sup.10 and R.sup.11 are C.sub.1-C.sub.22 alkyl,
C.sub.3-C.sub.22 branched alkyl, C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl, or mixtures thereof;
[0058] R.sup.12 is:
[0059] i) hydrogen;
[0060] ii) C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl, or
mixtures thereof;
[0061] A is nitrogen or oxygen; X is chlorine, bromine, iodine,
or
[0062] other water soluble anion, v is 0 or 1, u is from 0 to
22;
[0063] q) an amino unit of the formula:
--NR.sup.17R.sup.18
[0064] wherein R.sup.17 and R.sup.18 are C.sub.1-C.sub.22 alkyl,
C.sub.3-C.sub.22 branched alkyl, C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl, or mixtures thereof;
[0065] r) an alkylethyleneoxy unit of the formula:
--(A).sub.v--(CH.sub.2).sub.y(OCH.sub.2CH.sub.2).sub.xZ
[0066] wherein Z is:
[0067] i) hydrogen;
[0068] ii) hydroxyl;
[0069] iii) --CO.sub.2H;
[0070] iv) --SO.sub.3.sup.-M.sup.+;
[0071] v) --OSO.sub.3.sup.-M.sup.+;
[0072] vi) C.sub.1-C.sub.6 alkoxy;
[0073] vii) substituted aryl, unsubstituted aryl, or mixtures
thereof;
[0074] viii) substituted aryloxy, unsubstituted aryloxy, or
mixtures thereof;
[0075] ix) alkyleneamino; or mixtures thereof;
[0076] A is nitrogen or oxygen, M is a water soluble cation, v is 0
or 1, x is from 0 to 100, y is from 0 to 12;
[0077] s) substituted siloxy of the formula:
--OSiR.sup.19R.sup.20R.sup.21
[0078] wherein each R.sup.19, R.sup.20, and R.sup.21 is
independently
[0079] i) C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl, or
mixtures thereof;
[0080] ii) substituted aryl, unsubstituted aryl, or mixtures
thereof;
[0081] iii) substituted aryloxy, unsubstituted aryloxy, or mixtures
thereof;
[0082] iv) an alkylethyleneoxy unit of the formula:
--(A).sub.v--(CH.sub.2).sub.y(OCH.sub.2CH.sub.2).sub.xZ;
[0083] wherein Z is:
[0084] a) hydrogen;
[0085] b) hydroxyl;
[0086] c) --CO.sub.2H;
[0087] d) --SO.sub.3.sup.-M.sup.+;
[0088] e) --OSO.sub.3.sup.-M.sup.+;
[0089] f) C.sub.1-C.sub.6 alkoxy;
[0090] g) substituted aryl, unsubstituted aryl, or mixtures
thereof;
[0091] h) substituted aryloxy, unsubstituted aryloxy, or mixtures
thereof;
[0092] i) alkyleneamino; or mixtures thereof;
[0093] A is nitrogen or oxygen, M is a water soluble cation, v is 0
or l, x is from 0 to 100, y is from 0 to 12;
[0094] and mixtures thereof
[0095] axial R units wherein each R is independently selected from
the group consisting of:
[0096] a) hydrogen;
[0097] b) halogen;
[0098] c) hydroxy;
[0099] d) C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl, or
mixtures thereof;
[0100] e) halogen substituted C.sub.1-C.sub.22 alkyl,
C.sub.3-C.sub.22 branched alkyl, C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl, or mixtures thereof;
[0101] f) polyhydroxyl substituted C.sub.3-C.sub.22 alkyl;
[0102] g) C.sub.1-C.sub.22 alkoxy;
[0103] h) branched alkoxy having the formula: 6
[0104] wherein Z is hydrogen, hydroxyl, C.sub.1-C.sub.30 alkyl,
C.sub.1-C.sub.30 alkoxy, --CO.sub.2H, --OCH.sub.2CO.sub.2H,
--SO.sub.3.sup.-M.sup.+, --OSO.sub.3.sup.-M.sup.+,
--PO.sub.3.sup.2-M, --OPO.sub.3.sup.2-M, or mixtures thereof; M is
a water soluble cation in sufficient amount to satisfy charge
balance; x is 0 or 1, each y independently has the value from 0 to
6, each z independently has the value from 0 to 100;
[0105] i) substituted aryl, unsubstituted aryl, or mixtures
thereof;
[0106] j) substituted alkylenearyl, unsubstituted alkylenearyl, or
mixtures thereof;
[0107] k) substituted aryloxy, unsubstituted aryloxy, or mixtures
thereof;
[0108] l) substituted oxyalkylenearyl, unsubstituted
oxyalkylenearyl, or mixtures thereof;
[0109] m) substituted alkyleneoxyaryl, unsubstituted
alkyleneoxyaryl, or mixtures thereof;
[0110] n) C.sub.1-C.sub.22 thioalkyl, C.sub.3-C.sub.22 branched
thioalkyl, or mixtures thereof;
[0111] o) a carboxylate of the formula: 7
[0112] wherein R.sup.9 is:
[0113] i) C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl, or
mixtures thereof;
[0114] ii) halogen substituted C.sub.1-C.sub.22 alkyl,
C.sub.3-C.sub.22 branched alkyl, C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl, or mixtures thereof;
[0115] iii) polyhydroxyl substituted C.sub.3-C.sub.22 alkylene;
[0116] iv) C.sub.3-C.sub.22 glycol;
[0117] v) C.sub.1-C.sub.22 alkoxy;
[0118] vi) C.sub.3-C.sub.22 branched alkoxy;
[0119] vii) substituted aryl, unsubstituted aryl, or mixtures
thereof;
[0120] viii) substituted alkylenearyl, unsubstituted alkylenearyl,
or mixtures thereof;
[0121] ix) substituted aryloxy, unsubstituted aryloxy, or mixtures
thereof;
[0122] x) substituted oxyalkylenearyl, unsubstituted
oxyalkylenearyl, or mixtures thereof;
[0123] xi) substituted alkyleneoxyaryl, unsubstituted
alkyleneoxyaryl, or mixtures thereof;
[0124] p) an alkyleneamino unit of the formula: 8
[0125] wherein R.sup.10 and R.sup.11 are C.sub.1-C.sub.22 alkyl,
C.sub.3-C.sub.22 branched alkyl, C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl, or mixtures thereof;
[0126] R.sup.12 is:
[0127] i) hydrogen;
[0128] ii) C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl, or
mixtures thereof;
[0129] A is nitrogen or oxygen; X is chlorine, bromine, iodine, or
other water soluble anion, v is 0 or 1, u is from 0 to 22;
[0130] q) an amino unit of the formula:
--NR.sup.17R.sup.18
[0131] wherein R.sup.17 and R.sup.18 are C.sub.1-C.sub.22 alkyl,
C.sub.3-C.sub.22 branched alkyl, C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl, or mixtures thereof;
[0132] r) an alkylethyleneoxy unit of the formula:
--(A).sub.v--(CH.sub.2).sub.y(OCH.sub.2CH.sub.2).sub.xZ
[0133] wherein Z is:
[0134] i) hydrogen;
[0135] ii) hydroxyl;
[0136] iii) --CO.sub.2H;
[0137] iv) --SO.sub.3.sup.-M.sup.+;
[0138] v) --OSO.sub.3.sup.-M.sup.+;
[0139] vi) C.sub.1-C.sub.6 alkoxy;
[0140] vii) substituted aryl, unsubstituted aryl, or mixtures
thereof;
[0141] viii) substituted aryloxy, unsubstituted aryloxy, or
mixtures thereof;
[0142] ix) alkyleneamino; or mixtures thereof;
[0143] A is nitrogen or oxygen, M is a water soluble cation, v is 0
or 1, x is from 0 to 100, y is from 0 to 12;
[0144] s) substituted siloxy of the formula:
--OSiR.sup.19R.sup.20R.sup.21
[0145] wherein each R.sup.19, R.sup.20, and R.sup.21 is
independently
[0146] i) C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl, or
mixtures thereof;
[0147] ii) substituted aryl, unsubstituted aryl, or mixtures
thereof;
[0148] iii) substituted aryloxy, unsubstituted aryloxy, or mixtures
thereof;
[0149] iv) an alkylethyleneoxy unit of the formula:
--(A).sub.v--(CH.sub.2).sub.y(OCH.sub.2CH.sub.2).sub.xZ;
[0150] wherein Z is:
[0151] a) hydrogen;
[0152] b) hydroxyl;
[0153] c) --CO.sub.2H;
[0154] d) --SO.sub.3.sup.-M.sup.+;
[0155] e) --OSO.sub.3.sup.-M.sup.+;
[0156] f) C.sub.1-C.sub.6 alkoxy;
[0157] g) substituted aryl, unsubstituted aryl, or mixtures
thereof;
[0158] h) substituted aryloxy, unsubstituted aryloxy, or mixtures
thereof;
[0159] i) alkyleneamino; or mixtures thereof;
[0160] A is nitrogen or oxygen. M is a water soluble cation, v is 0
or 1, x is from 0 to 100, y is from 0 to 12;
[0161] and mixtures thereof.
[0162] All percentages, ratios and proportions herein are by
weight, unless otherwise specified. All temperatures are in degrees
Celsius (.degree. C.) unless otherwise specified. All documents
cited are, in relevant part, incorporated herein by reference.
DETAILED DESCRIPTION OF THE INVENTION
[0163] The present invention relates to photobleaching compounds
and photobleaching compositions. The photobleaching compounds have
a Q-band maximum absorption wavelength of 660 nanometers or
greater. The photobleaching and photodisinfectants of the present
invention are phthalocyanies having the formula: 9
[0164] or naphthalocycanines having the formula: 10
[0165] wherein M is a photoactive metal or non-metal, said metal or
non-metal selected from the group consisiting of Sn, Ge, Pt, Pd,
Pb, P, and mixtures thereof. The phthalocyanine and
naphthalocyanine rings which comprise the photo sensitizers of the
present invention, can be substituted with hydrogen or other units
described further herein below. Surprisingly, selection of a
suitable R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, or R.sup.6
substituent is capable of providing the photobleach or
photodisinfectant with a positive .DELTA..sub.triplet yield of at
least 1, preferably at least 10, more preferably at least 30, when
said moiety replaces a hydrogen atom. In addition, the selection of
a suitable moiety for a R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, or R.sup.6 substitutent is also capable of providing a
positive red shift value of at least 1, preferably a positive red
shift value of at least 10, more preferrably a positive red shift
value of at least 30, when said moieties are substituted for
hydrogen.
[0166] Each R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and
R.sup.6 unit is independently:
[0167] a) hydrogen;
[0168] b) halogen;
[0169] c) hydroxyl;
[0170] d) C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl;
[0171] e) halogen substituted C.sub.1-C.sub.22 alkyl,
C.sub.3-C.sub.22 branched alkyl, C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl;
[0172] f) polyhydroxyl substituted C.sub.3-C.sub.22 alkyl;
[0173] g) C.sub.1-C.sub.22 alkoxy, preferably C.sub.1-C.sub.4
alkoxy, more preferred methoxy;
[0174] h) branched alkoxy having the formula 11
[0175] wherein Z is hydrogen, hydroxyl, C.sub.1-C.sub.30 linear
alkyl, C.sub.1-C.sub.30 branched alkyl, C.sub.1-C.sub.30 alkoxy,
--CO.sub.2H, --OCH.sub.2CO.sub.2H, --SO.sub.3.sup.-M.sup.+,
--OSO.sub.3.sup.-M.sup.+, --PO.sub.3.sup.2-M, --OPO.sub.3.sup.2-M,
and mixtures thereof; M is a water soluble cation in sufficient
amount to satisfy charge balance; x is 0 or 1, each y independently
has the value from 0 to 6, preferably from 0 to 6; each z
independently has the value from 0 to 100, preferably from 0 to
about 10, more preferably from 0 to about 3;
[0176] i) substituted aryl, and unsubstituted aryl having the
formula: 12
[0177] wherein R.sup.13 and R.sup.14 are independently selected
from the group consisting of hydrogen, C.sub.1-C.sub.6 alkyl,
C.sub.3-C.sub.6 alkenyl, C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.6
branched alkoxy, halogen, --CO.sub.2.sup.-M.sup.+,
--SO.sub.3.sup.-M.sup.+, --OSO.sub.3.sup.-M.sup.+,
--N(R.sup.15).sub.2, and --N.sup.+(R.sup.15).sub.3X-- wherein each
R.sup.15 is independently hydrogen or C.sub.1-C.sub.4 alkyl; and
mixtures thereof; preferably hydrogen C.sub.1-C.sub.6 alkyl,
--CO.sub.2.sup.-M.sup.+, --SO.sub.3.sup.-M.sup.+,
--OSO.sub.3.sup.-M.sup.+, and mixtures thereof, more preferably
R.sup.13 or R.sup.14 is hydrogen and the other moiety is
C.sub.1-C.sub.6 alkyl; wherein M is a water soluble cation and X is
a water soluble anion.
[0178] j) substituted alkylenearyl and unsubstituted alkylenearyl
having the formula: 13
[0179] wherein R.sup.13 and R.sup.14 are as defined above, p is
from 1 to about 10.
[0180] k) substituted aryloxy and unsubstituted aryloxy having the
formula: 14
[0181] wherein R.sup.13 and R.sup.14 are as defined above.
[0182] l) substituted alkyleneoxyaryl and unsubstituted
alkyleneoxyaryl units are defined as moieties having the formula:
15
[0183] wherein R.sup.13 and R.sup.14 are as defined above, q is
from 0 to about 10.
[0184] m) substituted oxyalkylenearyl and unsubstituted
oxyalkylenearyl having the formula: 16
[0185] wherein R.sup.13 and R.sup.14 are as defined above, w is
from about 1 to about 10.
[0186] n) C.sub.1-C.sub.22 linear, C.sub.3-C.sub.22 branched
thioalkyl, C.sub.1-C.sub.22 linear, C.sub.3-C.sub.22 branched
substituted thioalkyl, and mixtures thereof;
[0187] o) ester units of the formula --CO.sub.2R.sup.9 wherein
R.sup.9 is C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl, all of
which can be substituted with halogen; poly-hydroxyl substituted
C.sub.3-C.sub.22 alkyl, C.sub.3-C.sub.22 glycol; C.sub.1-C.sub.22
alkoxy, C.sub.3-C.sub.22 branched alkoxy; substituted and
unsubstituted aryl, alkylenearyl, aryloxy, oxyalkylenearyl,
alkyleneoxyaryl; preferably C.sub.1-C.sub.22 alkyl,
C.sub.3-C.sub.22 branched alkyl, and mixtures thereof;
[0188] p) alkyleneamino units having the formula: 17
[0189] wherein R.sup.10, and R.sup.11 are each a C.sub.1-C.sub.22
alkyl, C.sub.3-C.sub.22 branched alkyl, C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl, R.sup.12 is hydrogen,
C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl and
mixtures thereof, the index v is 0 or 1; X is a other water soluble
anion, u is from 0 to 22, preferably u is from 3 to about 10.
Examples of water soluble anions include organic species such as
fumarate, tartrate, oxalate and the like, inorganic species include
chloride, bromide, sulfate, hydrogen sulfate, phosphate and the
like;
[0190] q) an amino unit of the formula
--NR.sup.17R.sup.18
[0191] wherein R.sup.17 and R.sup.18 are each a C.sub.1-C.sub.22
alkyl, C.sub.3-C.sub.22 branched alkyl, C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl, or mixtures thereof;
[0192] r) alkylethyleneoxy units having the formula:
--(A).sub.v--(CH.sub.2).sub.y(OCH.sub.2CH.sub.2).sub.xZ
[0193] wherein Z is hydrogen, hydroxyl, --CO.sub.2H,
--SO.sub.3.sup.-M.sup.+, --OSO.sub.3.sup.-M.sup.+, C.sub.1-C.sub.6
alkoxy, substituted and unsubstituted aryl, substituted and
unsubstituted aryloxy; alkyleneamino as defined herein above; or
mixtures thereof; A units comprise nitrogen or oxygen, preferably
oxygen; M is a water soluble cation; v is 0 or 1; x is from 0 to
100, preferably from 0 to 20, more preferably from 0 to 5; y is
from 0 to 12, preferably from 1 to 4; however, no peroxide --O--O--
bonds are contained within the photobleaching compounds of the
present invention;
[0194] s) siloxy and substituted siloxy of the formula
--OSiR.sup.19R.sup.20R.sup.21 wherein each R.sup.19, R.sup.20, and
R.sup.21 is independently selected from the group consisting of
C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl, or
mixtures thereof, substituted or unsubstituted aryl, aryloxy;
alkylethyleneoxy units of the formula:
--(A).sub.v--(CH.sub.2).sub.y(OCH.sub.2CH.sub.2).sub.xZ
[0195] wherein Z is hydrogen, hydroxyl, C.sub.1-C.sub.30 alkyl,
--CO.sub.2H, --SO.sub.3.sup.-M.sup.+, --OSO.sub.3.sup.-M.sup.+,
C.sub.1-C.sub.6 alkoxy; substituted or unsubstituted aryl, and
aryloxy; alkyleneamino as defined herein above, and mixtures
thereof, preferably hydrogen or C.sub.1-C.sub.6 alkyl, more
preferably methyl; v is 0 or 1; x is from 1 to 100, preferably from
0 to about 20, more preferably from 3 to about 10; and y is from 0
to 12, preferably from about 0 to about 5.
[0196] Preferred R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and
R.sup.6 units are C.sub.1-C.sub.22 alkoxy and halogen, more
preferred R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5, and R.sup.6
units are C.sub.1-C.sub.4 alkoxy and halogen. When the (Sens.) unit
is phthalocyanine most preferred R.sup.1, R.sup.2, R.sup.3, and
R.sup.4 units are methoxy. When the (Sens.) unit is
naphthalocyanine most preferred R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, and R.sup.6 units are chlorine, bromine or iodine.
[0197] The compounds useful for the present invention also comprise
axial R units, wherein R is independently selected from the group
consisting of:
[0198] a) hydrogen;
[0199] b) halogen;
[0200] c) hydroxyl;
[0201] d) C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl;
[0202] e) halogen substituted C.sub.1-C.sub.22 alkyl,
C.sub.3-C.sub.22 branched alkyl, C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl;
[0203] f) polyhydroxyl substituted C.sub.3-C.sub.22 alkyl,
[0204] g) C.sub.1-C.sub.22 alkoxy, preferably C.sub.1-C.sub.4
alkoxy, more preferred methoxy;
[0205] h) branched alkoxy having the formula 18
[0206] wherein Z is hydrogen, hydroxyl, C.sub.1-C.sub.30 linear
alkyl, C.sub.1-C.sub.30 branched alkyl, C.sub.1-C.sub.30 alkoxy,
--CO.sub.2H, --OCH.sub.2CO.sub.2H, --SO.sub.3.sup.-M.sup.+,
--OSO.sub.3.sup.-M.sup.+, --PO.sub.3.sup.2-M, --OPO.sub.3.sup.2-M,
and mixtures thereof; M is a water soluble cation in sufficient
amount to satisfy charge balance; x is 0 or 1, each y independently
has the value from 0 to 6, preferably from 0 to 6; each z
independently has the value from 0 to 100, preferably from 0 to
about 10, more preferably from 0 to about 3;
[0207] i) substituted aryl, and unsubstituted aryl having the
formula: 19
[0208] wherein R.sup.13 and R.sup.14 are independently selected
from the group consisting of hydrogen, C.sub.1-C.sub.6 alkyl,
C.sub.3-C.sub.6 alkenyl, C.sub.1-C.sub.6 alkoxy, C.sub.3-C.sub.6
branched alkoxy, halogen, --CO.sub.2.sup.-M.sup.+,
--SO.sub.3.sup.-M.sup.+, --OSO.sub.3.sup.-M.sup.+,
--N(R.sup.15).sub.2, and --N.sup.+(R.sup.15).sub.3X-- wherein each
R.sup.15 is independently hydrogen or C.sub.1-C.sub.4 alkyl; and
mixtures thereof, preferably hydrogen C.sub.1-C.sub.6 alkyl,
--CO.sub.2.sup.-M.sup.+, --SO.sub.3.sup.-M.sup.+,
--OSO.sub.3.sup.-M.sup.+, and mixtures thereof, more preferably
R.sup.13 or R.sup.14 is hydrogen and the other moiety is
C.sub.1-C.sub.6 alkyl; wherein M is a water soluble cation and X is
a water soluble anion.
[0209] j) substituted alkylenearyl and unsubstituted alkylenearyl
having the formula: 20
[0210] wherein R.sup.13 and R.sup.14 are as defined above, p is
from 1 to about 10.
[0211] k) substituted aryloxy and unsubstituted aryloxy having the
formula: 21
[0212] wherein R.sup.13 and R.sup.14 are as defined above.
[0213] l) substituted alkyleneoxyaryl and unsubstituted
alkyleneoxyaryl units are defined as moieties having the formula:
22
[0214] wherein R.sup.13 and R.sup.14 are as defined above, q is
from 0 to about 10.
[0215] m) substituted oxyalkylenearyl and unsubstituted
oxyalkylenearyl having the formula: 23
[0216] wherein R.sup.13 and R.sup.14 are as defined above, w is
from about 1 to about 10.
[0217] n) C.sub.1-C.sub.22 linear, C.sub.3-C.sub.22 branched
thioalkyl, C.sub.1-C.sub.22 linear, C.sub.3-C.sub.22 branched
substituted thioalkyl, and mixtures thereof;
[0218] o) carboxylate units of the formula 24
[0219] wherein R.sup.9 is C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22
branched alkyl, C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched
alkenyl, all of which can be substituted with halogen;
[0220] poly-hydroxyl substituted C.sub.3-C.sub.22 alkyl,
C.sub.3-C.sub.22 glycol; C.sub.1-C.sub.22 alkoxy, C.sub.3-C.sub.22
branched alkoxy; substituted and unsubstituted aryl, alkylenearyl,
aryloxy, oxyalkylenearyl, alkyleneoxyaryl; preferably
C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl, and
mixtures thereof;
[0221] p) alkyleneamino units having the formula: 25
[0222] wherein R.sup.10, and R.sup.11 are each a C.sub.1-C.sub.22
alkyl, C.sub.3-C.sub.22 branched alkyl, C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl, R.sup.12 is hydrogen,
C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl and
mixtures thereof, the index v is 0 or 1; X is a other water soluble
anion, u is from 0 to 22, preferably u is from 3 to about 10.
Examples of water soluble anions include organic species such as
fumarate, tartrate, oxalate and the like, inorganic species include
chloride, bromide, sulfate, hydrogen sulfate, phosphate and the
like;
[0223] q) an amino unit of the formula
--NR.sup.17R.sup.18
[0224] wherein R.sup.17 and R.sup.18 are each a C.sub.1-C.sub.22
alkyl, C.sub.3-C.sub.22 branched alkyl, C.sub.2-C.sub.22 alkenyl,
C.sub.3-C.sub.22 branched alkenyl, or mixtures thereof;
[0225] r) alkylethyleneoxy units having the formula:
--(A).sub.v--(CH.sub.2).sub.y(OCH.sub.2CH.sub.2).sub.xZ
[0226] wherein Z is hydrogen, hydroxyl, --CO.sub.2H,
--SO.sub.3.sup.-M.sup.+, --OSO.sub.3.sup.-M.sup.+, C.sub.1-C.sub.6
alkoxy, substituted and unsubstituted aryl, substituted and
unsubstituted aryloxy; alkyleneamino as defined herein above; or
mixtures thereof; A units comprise nitrogen or oxygen, preferably
oxygen; M is a water soluble cation; v is 0 or 1; x is from 0 to
100, preferably from 0 to 20, more preferably from 0 to 5; y is
from 0 to 12, preferably from 1 to 4; however, no peroxide --O--O--
bonds are contained within the photobleaching compounds of the
present invention;
[0227] s) siloxy and substituted siloxy of the formula
--OSiR.sup.19R.sup.20R.sup.21 wherein each R.sup.19, R.sup.20, and
R.sup.21 is independently selected from the group consisting of
C.sub.1-C.sub.22 alkyl, C.sub.3-C.sub.22 branched alkyl,
C.sub.2-C.sub.22 alkenyl, C.sub.3-C.sub.22 branched alkenyl, or
mixtures thereof, substituted or unsubstituted aryl, aryloxy;
alkylethyleneoxy units of the formula:
--(A).sub.v--(CH.sub.2).sub.y(OCH.sub.2CH.sub.2.sub.xZ
[0228] wherein Z is hydrogen, hydroxyl, C.sub.1-C.sub.30 alkyl,
--CO.sub.2H, --SO.sub.3.sup.-M.sup.+, --OSO.sub.3.sup.-M.sup.+,
C.sub.1-C.sub.6 alkoxy; substituted or unsubstituted aryl, and
aryloxy; alkyleneamino as defined herein above, and mixtures
thereof, preferably hydrogen or C.sub.1-C.sub.6 alkyl, more
preferably methyl; v is 0 or 1; x is from 1 to 100, preferably from
0 to about 20, more preferably from 3 to about 10; and y is from 0
to 12, preferably from about 0 to about 5.
[0229] According to the present invention the preferred axial R
units comprise moieties having the formula
--Y.sub.i--K.sub.j and --Y.sub.i--Q.sub.j
[0230] wherein Y is a linking moiety selected from the group
consisting of O, CR.sup.25R.sup.26, OSiR.sup.25R.sup.26,
OSnR.sup.25R.sup.26, and mixtures thereof; wherein R.sup.25 and
R.sup.26 are hydrogen, C.sub.1-C.sub.4 alkyl, halogen, and mixtures
thereof; i is 0 or 1, j is from 1 to 3;
[0231] K is a ligand selected from the group consisting of:
[0232] a) C.sub.1-C.sub.30 linear alkyl, C.sub.3-C.sub.30 branched
alkyl, C.sub.2-C.sub.30 linear alkenyl, C.sub.3-C.sub.30 branched
alkenyl, C.sub.6-C.sub.20 aryl, C.sub.7-C.sub.20 arylalkyl,
C.sub.7-C.sub.20 alkylaryl, and mixtures thereof;
[0233] b) an alkylethyleneoxy unit of the formula
--(R.sup.23).sub.y(OR.sup.22).sub.xOZ
[0234] wherein Z is selected from the group consisting of hydrogen,
C.sub.1-C.sub.20 alkyl, C.sub.3-C.sub.20 branched alkyl,
C.sub.2-C.sub.20 linear alkenyl, C.sub.3-C.sub.20 branched alkenyl,
C.sub.6-C.sub.20 aryl, C.sub.7-C.sub.30 arylalkyl, C.sub.6-C.sub.20
alkylaryl, and mixtures thereof; R.sup.22 is selected from the
group consisting of C.sub.1-C.sub.4 linear alkylene,
C.sub.3-C.sub.4 branched alkylene, C.sub.3-C.sub.6 hydroxyalkylene,
and mixtures thereof; R.sup.23 is selected from the group
consisting of C.sub.2-C.sub.20 alkylene, C.sub.3-C.sub.20 branched
alkylene, C.sub.6-C.sub.20 arylene, C.sub.7-C.sub.30 arylalkylene,
C.sub.7-C.sub.30 alkylarylene, and mixtures thereof; x is from 1 to
100; y is 0 or 1; and
[0235] Q is an ionic moiety having the formula:
--R.sup.24W
[0236] wherein R.sup.24 is selected from the group consisting of
C.sub.3-C.sub.30 linear alkylene, C.sub.3-C.sub.30 branched
alkylene, C.sub.2-C.sub.30 linear alkenylene, C.sub.3-C.sub.30
branched alkenylene, C.sub.6-C.sub.16 arylene, and mixtures
thereof; W is selected from the group consisting of
--CO.sub.2.sup.-M.sup.+, --SO.sub.3.sup.-M.sup.+,
--OSO.sub.3.sup.-M.sup.+; PO.sub.3.sup.2-M.sup.+,
--OPO.sub.3.sup.-M.sup.- +, --N.sup.+(R.sup.27).sub.3X--; wherein
R.sup.27 is independently hydrogen, C.sub.1-C.sub.6 alkyl,
--(CH.sub.2).sub.nOH, --(CH.sub.2CH.sub.2O).sub.nH, and mixtures
thereof; wherein n is from 1 to 4; M is a water soluble cation of
sufficient charge to provide electronic neutrality and X is a water
soluble anion as defined herein above.
[0237] Preferred axial R units are alkyl alkyleneoxy units of the
formula
--(R.sup.23).sub.y(OR.sup.22).sub.xOZ
[0238] wherein Z is selected from the group consisting of hydrogen,
C.sub.7-C.sub.20 linear alkyl, C.sub.3-C.sub.20 branched alkyl,
C.sub.2-C.sub.20 linear alkenyl, C.sub.3-C.sub.20 branched alkenyl,
C.sub.6-C.sub.10 aryl, C.sub.7-C.sub.20 arylalkyl, C.sub.7-C.sub.20
alkylaryl, and mixtures thereof; R.sup.22 is selected from the
group consisting of C.sub.1-C.sub.4 linear alkylene,
C.sub.3-C.sub.4 branched alkylene, and mixtures thereof; R.sup.23
is selected from the group consisting of C.sub.2-C.sub.6 alkylene,
C.sub.3-C.sub.6 branched alkylene, C.sub.6-C.sub.10 arylene, and
mixtures thereof; x is from 1 to 50; y is 0 or 1.
[0239] More preferred axial R units comprise y equal to 0, Z is
hydrogen, C.sub.1-C.sub.20 alkyl, C.sub.3-C.sub.20 branched alkyl,
C.sub.6-C.sub.10 aryl, and mixtures thereof, most preferred Z is
hydrogen or C.sub.6-C.sub.20 linear alkyl, C.sub.10-C.sub.20
branched alkyl; R.sup.22 is C.sub.1-C.sub.4 linear or
C.sub.3-C.sub.4 branched alkylene.
[0240] Also preferred R units having the formula:
--Y.sub.i--Q.sub.j
[0241] wherein Y is a linking moiety selected from the group
consisting of O, CR.sup.25R.sup.26 OSiR.sup.25R.sup.26,
OSnR.sup.25R.sup.26, and mixtures thereof; i is 0 or 1, j is from 1
to 3; Q is an ionic moiety having the formula:
--R.sup.24--W
[0242] wherein R.sup.24 is selected from the group consisting of
C.sub.2-C.sub.20 linear alkylene, C.sub.3-C.sub.20 branched
alkylene, C.sub.2-C.sub.20 linear alkenylene, C.sub.3-C.sub.20
branched alkenylene, C.sub.6-C.sub.10 arylene, and mixtures
thereof; W is selected from the group consisting of
--CO.sub.2.sup.-M.sup.+, --SO.sub.3.sup.-M.sup.+,
--OSO.sub.3.sup.-M.sup.+; PO.sub.3.sup.2-M.sup.+,
--OPO.sub.3.sup.-M.sup.- +, --N.sup.+(R.sup.27).sub.3X--; wherein
R.sup.27 is independently hydrogen, C.sub.1-C.sub.6 alkyl,
--(CH.sub.2).sub.nOH, --(CH.sub.2CH.sub.2O).sub.nH, and mixtures
thereof; wherein n is from 1 to 4; M is a water soluble cation of
sufficient charge to provide electronic neutrality and X is a water
soluble anion as defined herein above.
[0243] A preferred hydrophilic R has the index i equal to 1;
R.sup.24 is C.sub.3-C.sub.20 linear alkylene, C.sub.3-C.sub.20
branched alkylene; W is --CO.sub.2.sup.-M.sup.+,
--SO.sub.3.sup.-M.sup.+, --OSO.sub.3.sup.-M.sup.+; M is a water
soluble cation of sufficient charge to provide electronic
neutrality.
[0244] Examples of Y units suitable for use in R units having the
formula:
--Y.sub.i--K.sub.j
[0245] have the formula
--O--K.sup.1, --Sn--K.sup.1, --OSn--K.sup.1
[0246] wherein i is equal to 1 and j is equal to 1. Further
examples have the formula 26
[0247] wherein i is equal to 1 and j is equal to 3. The above
examples also apply to Y units when used with Q ionic moieties.
[0248] When compounds of the present invention have present one or
more substituent R.sup.1, R.sup.2, R.sup.3, and R.sup.4, units, as
in the case of phthalocyanine, or R.sup.1, R.sup.2, R.sup.3,
R.sup.4, R.sup.5, and R.sup.6 units, as in the case of
naphthalocyanines, the exact orientation of the substituents may
not be exactly known. However, for the purposes of the compounds of
the present invention, certain equivalencies of substitution exist.
For example, the two units of the following formula 27
[0249] which contain the same R.sup.1 substitution, are equivalent
for the purposes of the present invention and the selection of
either one structure over the other will not effect the desired
properties of the molecule described herein.
[0250] In addition, compounds containing the substitution
represented by the following formulas 28
[0251] which contain the same R.sup.1 and R.sup.2 unit
substitutions, are also equivalent for the purposes of the present
invention and the selection of either one structure over the other
will not effect the desired properties of the molecule described
herein. The above examples, however, are only representative of the
total number of equivalent structure examples that will be
recognized by those skilled in the art.
[0252] Compounds useful for the present invention having
substituted one or more R.sup.1, R.sup.2, R.sup.3, and R.sup.4
unit, as in the case of phthalocyanine, or R.sup.1, R.sup.2,
R.sup.3, R.sup.4, R.sup.5, and R.sup.6 unit, as in the case of
naphthalocyanines, which have their substitutions oriented in a
manner described by the following formula 29
[0253] are not equivalent for the purposes of the present invention
and would each constitute separate compounds regardless of the fact
that the R.sup.1 and R.sup.2 units are equivalent. The above
example does not exhaust the number of non-equivalent structures
that are possible using any combination of R.sup.1, R.sup.2,
R.sup.3, R.sup.4, R.sup.5, and R.sup.6 units recognized by those
skilled in the art.
[0254] Solublizing axial R units, are bonded directly to the
central tin, germanium, platinum or palladium atom. Each R unit can
be chosen independently of the other. The selection of an R unit is
made, for example, to provide solubility, non-solubility,
"substantivity", "non-substantivity" to the compound. These are a
few examples of the utility of the axial group and those skilled in
the art will recognize that other properties of the photobleaches
can be controlled via axial substitution. R units are nonionic,
cationic, or anionic units.
[0255] Below is an example of a preferred "substantive" embodiment
(has an affinity for surfaces, e.g. fabric) of the present
invention comprising a phthalocyanine ring system wherein at least
one of the R.sup.1, R.sup.2, R.sup.3, and R.sup.4 units of each
aromatic moiety is methoxy, each R group comprises an ethyleneoxy
unit of the formula
--(OCH.sub.2CH.sub.2).sub.xZ
[0256] wherein for each R unit Z is methoxy and x is 7.2 thereby
giving the moiety an average ethoxylation value of 7.2. 30
[0257] Below is an example of a "substantive" embodiment (has an
affinity for surfaces, e.g. fabric) of the present invention
comprising a phthalocyanine ring system wherein at least two of the
R.sup.1, R.sup.2, R.sup.3, and R.sup.4 units of each aromatic
moiety is methoxy, each R group comprises an ethyleneoxy unit of
the formula
--(OCH.sub.2CH.sub.2).sub.xZ
[0258] wherein for each R unit Z is methoxy and x is 7.2 thereby
giving the moiety an average ethoxylation value of 7.2. 31
[0259] Below is an example of a "non-substantive" embodiment
(charged R units reduces the affinity for surfaces, e.g. fabric) of
the present invention comprising a naphthalocyanine ring system
wherein at least two of the R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, and R.sup.6 units of each aromatic moiety are chlorine,
one R group comprises an siloxy unit the formula
--OSiR.sup.7R.sup.8R.sup.9 wherein R.sup.7 and R.sup.8 units are
methyl and R.sup.9 is of the formula
(CH.sub.2).sub.yZ
[0260] wherein Z is --SO.sub.3.sup.-M.sup.+, M is sodium and y is
equal to six; the second axial R unit is methoxy. 32
[0261] Below is an example of a "non-substantive" embodiment
(charged R units reduces the affinity for surfaces, e.g. fabric) of
the present invention comprising a naphthalocyanine ring system
wherein at least one of the R.sup.1, R.sup.2, R.sup.3, R.sup.4,
R.sup.5, and R.sup.6 units of each aromatic moiety is bromine, and
the R groups comprise an siloxy unit the formula
--OSiR.sup.7R.sup.8R.sup.9 wherein R.sup.7 and R.sup.8 units are
methyl and R.sup.9 is of the formula
--(CH.sub.2).sub.yZ
[0262] wherein Z is --SO.sub.3.sup.-M.sup.+, M is sodium and y is
equal to six. 33
[0263] The compounds of the present invention can be modified to
have a wide range of surface affinities. Molecules can be made
"substantive" or "non-substantive" by the choice of axial R units.
The term "substantivity" as defined herein is the property which
allows the photobleaching agent to successfully deposit on a
targeted surface. For example, the axial groups R, hereinafter
defined in the specification, may be selected to provide
compatibility of the photobleaching compound with a synthetic
fabric, a durable surface such as ceramic tile, or in general any
fabric, article of manufacture or situs that is to be a target of
photobleaching.
[0264] The present invention also relates to laundry detergent or
hard surface cleaning compositions comprising:
[0265] A) at least about 0.1%, preferably from about 0.1% to about
30%, more preferably from about 1% to about 30%, most preferably
from about 5% to about 20% by weight, of a detersive surfactant,
said detersive surfactant is selected from the group consisting of
anionic, cationic, nonionic, zwitterionic, ampholytic surfactants,
and mixtures thereof;
[0266] B) at least about 0.001 ppm, preferably from about 0.01 to
about 10000 ppm, more preferably from about 0.1 to about 5000 ppm,
most preferably form about 10 to about 1000 ppm, of a
photosensitizing compound having a Q-band maximum absorption
wavelength of 660 nanometers or greater according to the present
invention; and
[0267] C) the balance carriers and adjunct materials.
[0268] The present invention further relates to laundry detergent
or hard surface cleaning compositions comprising:
[0269] A) at least about 0.1%, preferably from about 0.1% to about
30%, more preferably from about 1% to about 30%, most preferably
from about 5% to about 20% by weight, of a detersive surfactant,
said detersive surfactant is selected from the group consisting of
anionic, cationic, nonionic, zwitterionic, ampholytic surfactants,
and mixtures thereof;
[0270] B) at least about 0.001 ppm, preferably from about 0.01 to
about 10000 ppm, more preferably from about 0.1 to about 5000 ppm,
most preferably form about 10 to about 1000 ppm, of a
photosensitizing compound having a Q-band maximum absorption
wavelength of 660 nanometers or greater according to the present
invention; wherein selection of a suitable moiety for a R.sup.1,
R.sup.2, R.sup.3, R.sup.4, R.sup.5, or R.sup.6 substituent is
capable of providing the photobleach or photodisinfectant with a
positive .DELTA..sub.triplet yield of at least 1, preferably at
least 10, more preferably at least 30, when said moiety replaces a
hydrogen atom; and
[0271] C) the balance carriers and adjunct materials.
[0272] The present invention yet further relates to laundry
detergent and hard surface cleaning compositions comprising:
[0273] A) at least about 0.1%, preferably from about 0.1% to about
30%, more preferably from about 1% to about 30%, most preferably
from about 5% to about 20% by weight, of a detersive surfactant,
said detersive surfactant is selected from the group consisting of
anionic, cationic, nonionic, zwitterionic, ampholytic surfactants,
and mixtures thereof;
[0274] B) at least about 0.001 ppm, preferably from about 0.01 to
about 10000 ppm, more preferably from about 0.1 to about 5000 ppm,
most preferably form about 10 to about 1000 ppm, of a
photosensitizing compound having a Q-band maximum absorption
wavelength of 660 nanometers or greater according to the present
invention; wherein selection of a suitable moiety for a R.sup.1,
R.sup.2, R.sup.3, R.sup.4, R.sup.5, or R.sup.6 substitutent is
capable of providing a positive red shift value of at least 1,
preferably a positive red shift value of at least 10, more
preferrably a positive red shift value of at least 30, when said
moieties are substituted for hydrogen; and
[0275] C) the balance carriers and adjunct materials
[0276] Selection of a specific R moiety is generally made for
adjustment of the solubility or substantivity of the molecule. For
example, the R unit is matched to the structural properties of
either the targeted material (i.e. fabric) or to the targeted
substrate (i.e. stain). The option to tailor the properties of the
R unit to the material, is due to the ability to select R units
independently of effecting the phthalocyanine or naphthalocyanine
ring.
[0277] An additional benefit of the photobleaching system of the
present invention is that they are generally more fabric and color
safe than conventional bleaches (i.e. hypochlorite).
"Non-substantive" molecules are desirable for applications where
the photosensitizing compound must remain in the liquor rather than
becoming attracted to a particular surface, i.e. water
sterilization.
[0278] The term "low hue" as used herein and throughout the
specification refers to photobleaches that have a .lambda..sub.max
of their Q-band above about 700 nm and are therefore only slightly
perceptible to the human eye. Those additional materials of the
present invention having Q-band maximum wavelengths in the
"visible" range, (i.e. 660-700 nanometers) are materials that are
most suitable when the perception of a colored material is not a
factor in deterring utility.
[0279] Effective photobleaching is predicated on the production of
a molecule of singlet oxygen, a theory which has been extensively
studied and is well understood by those skilled in the art of
photobleaching. Because the singlet oxygen species is short-lived,
having the photosensitizing molecule in proximity to the stain or
the microbe to be "attacked" is of primary advantage.
[0280] The molecules of the present invention because of the
ability of the formulator to control "substantivity", can be
directed to any desired surface. The additional ability to prevent
layering and stacking of photosensitizing molecules due to the
axial nature of the R units, provides for an efficient mono-layer.
For example, an embodiment of the present invention for removing
stains from a fabric will have the requirements that the organotin,
organogermanium, organoplatinum, organopalladium, organolead, or
organophosphorous photosensitizing compound have an affinity for
the fabric surface, and that the photobleaching compound be close
to the desired site of action. These requirements are achieved by
manipulation of one or more R units.
[0281] The present invention also relates to a process for carrying
out a photo-sensitized reaction or a reaction catalyzed by singlet
oxygen, wherein one or more phthalocyanine or naphthylocyanine
compounds in the presence of oxygen, are brought into contact with
the medium in which or on which the said reaction is to take place,
or are incorporated in this medium, and are irradiated with
light.
[0282] It has long been known that phthalocyanine and
naphthalocyanine rings, can absorb light quanta and form
electronically excited species (singlet and triplet) and that these
species can be quenched by oxygen to yield `excited oxygen
species`. A particularly preferred `excited oxygen species` is
singlet oxygen which is most reliably formed by the quenching of
the triplet state of a photosensitizer, such as a phthalocyanine,
by molecular oxygen. It is therefore an aim of the photobleach
formulator to produce compounds that favor the formation of the
triplet state.
[0283] When a photosensitizer is irradiated with light, the singlet
energy state that results undergoes a variety of processes i.e.
re-emission of light (fluorescence). The most important process
with regard to photobleaching via singlet oxygen is inter system
crossing (ISC). This is the mechanism by which the singlet state is
converted to the triplet state. In general, the efficiency of this
process is discussed in terms of quantum yield, i.e. the number of
photons absorbed that lead to the desired triplet excited state.
The present invention provides for increased photobleaching by
modifying the efficiency of inter system crossing from the singlet
state to the triplet state. The molecules of the present invention,
can be modified by the formulator to increase the quantum
efficiency of triplet formation via the "heavy atom effect". The
selection of a moiety for its "heavy atom effect" can be made
independently of other factors, for example, without undue concern
for solubility factors. This is because the choice of axial R
groups for solubility will have no bearing on the changes made to
the phthalocyanine or naphthalocyanine ring system.
[0284] The determination of the value of the Q-band wavelength and
whether a shift occurs in this wavelength when a particular moiety
(R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 or R.sup.6 unit)
replaces a hydrogen atom on the phthalocyanine or naphthalocyanine
ring is straight-forward. Typically, a solution having a
concentration of approximately 1.times.10.sup.-6 M of the
phthalocyanine or naphthalocyanine to be measured is prepared using
a suitable solvent (e.g. dimethylformamide) which contains 1 wt %
triton X-100. A UV/visible spectrum is then obtained and the Q-band
.lambda..sub.max is recorded. This value is the "substrate
.lambda..sub.s-max". A spectrum for the material prior to
introduction of the substituent group is obtained in the same
manner. This value is the "reference .lambda..sub.r-max". The two
spectra are compared and the resulting measured values are placed
into the following equation
wavelength red
shift=.DELTA..lambda..sub.max=.lambda..sub.s-max-.lambda..s-
ub.r-max
[0285] wherein if the number obtained is greater than or equal to
1, then the substituent group has produced a positive red shift of
at least one nanometer and the substituent is a preferred
embodiments of the present invention. If the material of interest
is not soluble in dimethylformamide another suitable solvent may be
used.
[0286] Quantum yields and excited state energies are well known to
those skilled in the art and the procedures for the determination
of triplet quantum yield and like photophysical parameters are
thoroughly described in the following references Bonnet, R.;
McGarvey, D. J.; Harriman, A.; Land, E. J.; Truscott, T. G.;
Winfield, U-J. Photochem. Photobiol. 1988, 48 (3), pg. 271-6;
Davila, J., Harriman, A., Gulliya, K. S., Photochem. Photobiol.,
1991, 53 (1), pg. 1-11; Davila, J., Harriman, A., Photochem.
Photobiol., 1989, 50 (1), pg. 29-35; Charlesworth, P., Truscottt,
T. G., Brooks, R. C., Wilson, B. C., J. Photochem, Photobiol., part
B 1994, 26 (3), pg. 277-82; Zhang, X., Xu, H., J. Chem. Soc.,
Faraday Trans., 1993, 89 (18), pg. 3347-51; Simpson, M. S. C.,
Beeby, A., Bishop, S. M., MacRobert, A. J., Parker, A. W.,
Phillips, D., Proc. SPIE-int. Soc. Opt. Eng., 1992, 1640, pg.
520-9; Phillips, D., Pure Appl. Chem., 1995, 67 (1), pg. 117-26;
Wilkinson, F., Helman, W. P., Ross, A. B., J. Phys. Chem. Ref.
Data, 1993, 22 (1), pg. 113-262; Lever, A. P. B., Licoccia, S.,
Magnell, K., Minor, P. C., Ramaswamy, B. S., Adv. Chem. Ser., 1982,
201, pg. 237-52; West, M. A., Creat. Detect. Excited State, 1976,
4, pg. 217-307; Ford, W E., Rihter, B. D., Kenney, M. E., Rodgers,
M. A. J., Photochem. Photobiol., 1989, 50 (3), pg. 277-282; Firey,
P. A., Ford, W. E., Sounik, J. R., Kenney, M. E., Rodgers, A. J.
R., J. Am. Chem. Soc., 1988, 110, pg. 7626-7630; Firey, P. A.,
Rodgers, M. A. J., Photochem. Photobiol., 1987, 45 (4), pg. 535-8;
all of which are incorporated by reference in their entirety.
[0287] For the purposes of the present invention the delta triplet
yield is determined by determining the % quantum yield of triplet
fro the phthalocyanine or naphthalocyanine of interest and this is
the term .PHI..sub.trip-substrate. The % quantum yield of triplet
for the phthalocyanine or naphthalocyanine prior to introduction of
the substituent is determine. This value is
.PHI..sub.trip-reference. The value are place in the following
equation
triplet state quantum yield
increase=.DELTA..PHI..sub.trip=.PHI..sub.trip--
substrate-.PHI..sub.trip-reference
[0288] When the value for .DELTA..PHI..sub.trip is a number greater
than or equal to 1, the substitution made therein for a hydrogen
atom on the (Sens.) unit of the photosensitizer is a preferred
embodiments of the present invention.
[0289] In particular, the present invention relates to process for
bleaching or removing stains from textiles, organic or inorganic
substrates. It is further an object of the present invention to
protect the latter against attack by microorganisms, wherein the
substrates are treated with phthalocyanines or naphthalocyanies of
the present invention, in the presence of water and while being
irradiated by light.
[0290] Another advantage of the present invention is the fact that
each R unit may be directed toward a separate desired property and
the molecules of the present invention can therefore be thought of
as being "sided". For example, one axial R unit may be direct
toward increased solubility while the other axial R group may be
chosen for its ability to provide increase substantivity.
[0291] The present invention also relates to a process for carrying
out a photo-sensitized reaction or a reaction catalyzed by singlet
oxygen, wherein one or more phthalocyanine or naphthylocyanine
compounds in the presence of oxygen, are brought into contact with
the medium in which or on which the said reaction is to take place,
or are incorporated in this medium, and are irradiated with
light.
[0292] If the method is carried out in an aqueous medium (for
example the sterilization of textiles), the irradiation with light
can either be carried out directly in the treatment medium by means
of an artificial source of light mounted inside or outside the
medium or the substrates, in a moist state, can subsequently either
be irradiated, again by means of an artificial source of light, or
can be exposed to sunlight. Good antimicrobial effects of the
present compounds can be achieved even with very low concentrations
of active substance, for example at 0.001 ppm. Depending on the
field of use and on the phthalocyanine or naphthylocyanine
derivative employed, a concentration between 0.005 and 100,
preferably 0.01 and 50 ppm is preferable. The irradiation can be
effected by means of an artificial source of light or by means of
sunlight. The intensity of the illumination can vary within wide
limits, and it depends both on the concentration of active as well
as the nature of the light source as to the photobleaching
efficiency of any particular compound of the present invention. A
further parameter which can be varied is the exposure time, i.e.
for the same effect exposure must be longer at a lower light
intensity than at a higher intensity. In general, depending on the
field of use, exposure time of a few minutes up to a few hours is
possible.
[0293] If the process is carried out in an aqueous medium (for
example the sterilization of textiles), the irradiation with light
can either be carried out directly in the treatment medium, by
means of an artificial source of light mounted inside or outside
the medium, or the articles, in a moist state, can subsequently
either be irradiated, again by means of an artificial source of
light, or can be exposed to sunlight. Good antimicrobial effects
con be achieved even with very low concentrations of active
substance, for example at 0.001 ppm. Depending on the field of use
and on the phthalocyanine or naphthylocyanine derivative employed,
a concentration between 0.005 and 2000, preferably 0.01 and 1000
ppm is preferable.
[0294] The methods of the present invention can also be
accomplished in solvent based carriers or in low aqueous solutions.
For the purpose of the present invention the term low aqueous means
that water is added to a carrier system to modify the properties of
the carrier and not solely for the purpose of solublizing the
substrate. For example, solvents that are capable of holding
solublized oxygen as well as forming a miscible system with water
are preferred. Non-limiting examples of these solvents are butoxy
propoxy propanol (BPP), methoxy propoxy propanol (MPP), ethoxy
propoxy propanol (EPP), and propoxy propoxy propanol (PPP).
Embodiments of the present invention which comprise these
non-classical aqueous compositions are most useful when the
photobleach must be applied to a woven fabric or surface that
contains agents which repel water and moisture.
[0295] The sterilization of textiles of synthetic or natural
original may be mentioned as an important application. Thus,
material to be washed in the household or in industry can be
disinfected by means of the methods of the present invention. The
material to be washed can be treated for this purpose in the manner
mentioned above with aqueous solutions of the phthalocyanines or
naphthalocyanines of the present invention while being irradiated
with light. The phthalocyanine and naphthalocyanines can
advantageously be present in the treatment medium in a
concentration of from 0.01 to about 2000 mg per liter, preferably
from 0.1 to 1000, more preferably from 1 to 500. The sterilization
can be carried out advantageously together with the washing
process. For this purpose, the material to be washed is treated
with a wash medium containing customary detergent substances, one
or more phthalocyanines or naphthalocyanines according to the
present invention and, if desired, inorganic salts and/or other
adjunct materials having antimicrobial properties. The washing
process con be carried out manually, for example in a tub, or can
be carried out in a washing machine. The necessary exposure to
light can be effected during the washing process by means of
suitable light sources, or the moist material being washed can
also, subsequently, for example during drying , either be exposed
to a suitable artificial source of light or simply exposed to
sunlight, for example line drying.
[0296] Surface bleaching can be achieved, for example by applying
to the appropriate surface, an aqueous solution of the
phthalocyanine or naphthalocyanine compound according to the
present invention, this solution preferably comprising from about
0.001 to about 10%, by weight of active substance. The solution can
also comprise, in addition, other customary additives, for example
wetting agents, dispersing agents or emulsifiers, detergent
substances and, if desired inorganic salts. After this solution has
been applied, the surface is simply exposed to sunlight or, if
required, it can in addition be irradiated by means of an
artificial source of light. It is advisable to keep the surface
moist during the exposure to light.
[0297] The laundry compositions of the present invention optionally
comprise detersive surfactants, examples of which are, anionic,
cationic, nonionic, amphoteric and zwitterionic, however the
formulator is not limited to these examples or combinations
thereof. The surfactants are present from about 0% to about 95%,
preferably from about 5% to about 30%, by weight of the
composition.
[0298] The cleaning compositions of the present invention
optionally comprise detersive surfactants, examples of which are,
anionic, cationic, nonionic, amphoteric and zwitterionic, however
the formulator is not limited to these examples or combinations
thereof. The surfactants are present from about 0% to about 50%,
preferably from about 5% to about 30%, by weight of the
composition.
[0299] The laundry compositions of the present invention optionally
contains builders, examples of which are, silicates, carbonates,
and zeolites, however the user is not limited to these examples or
combinations thereof. The builders are present from about 0% to
about 50%, preferably from about 5% to about 30%, by weight of the
composition.
[0300] The cleaning compositions of the present invention
optionally contains builders, examples of which are, silicates,
carbonates, and zeolites, however the user is not limited to these
examples or combinations thereof. The builders are present from
about 0% to about 50%, preferably from about 5% to about 30%, by
weight of the composition.
[0301] The hard surface cleaner of the present invention optionally
contains builders, examples of which are, silicates, carbonates,
and zeolites, however the user is not limited to these examples or
combinations thereof. The builders are present from about 0% to
about 50%, preferably from about 5% to about 30%, by weight of the
composition.
[0302] The hard surface cleaner of the present invention optionally
contains abrasives from about 0.5% to about 85%, preferably from
about 10% to about 85%, by weight of the composition. Suitable
abrasives are silicates, carbonates, perlite, clay, and pulverized
ceramic clay, however, the user is not restricted to these examples
or combinations thereof.
[0303] Substances which increase the action can also be added in
the process according to the invention, inter alia electrolytes,
for example inorganic salts, for instance sodium chloride,
potassium chloride, sodium sulfate, potassium sulfate, sodium
acetate ammonium acetate, alkali metal phosphates and alkali metal
tri-polyphosphates, especially sodium chloride and sodium sulfate.
These salts can be added to the agents according to the invention
or can be added directly in the application method, so that they
are present in the application solution in a concentration of,
preferably 0.1 to 10%, by weight.
[0304] What is meant by the term aqueous solution is a solution
that is essentially water, however the formulator may include
adjunct materials as well as a surfactant to aid in removal of the
"treated" micro organisms during rinsing or subsequent cleaning.
The presence of an aqueous solution facilitates the production of
singlet oxygen due to the higher concentration of oxygen in water
than in air.
[0305] Surfactant--The instant cleaning compositions contain from
about 0.1% to about 60% by weight of a surfactant selected from the
group consisting of anionic, nonionic, ampholytic and zwitterinonic
surface active agents. For liquid systems, surfactant is preferably
present to the extent of from about 0.1% to 20% by weight of the
composition. For solid (i.e. granular) and viscous semi-solid (i.e.
gelatinous, pastes, etc.) systems, surfactant is preferably present
to the extent of from about 1.5% to 30% by weight of the
composition.
[0306] Nonlimiting examples of surfactants useful herein typically
at levels from about 1% to about 55%, by weight, include the
conventional C.sub.11-C.sub.18 alkyl benzene sulfonates ("LAS") and
primary, branched-chain and random C.sub.10-C.sub.20 alkyl sulfates
("AS"), the C.sub.10-C.sub.8 secondary (2,3) alkyl sulfates of the
formula CH.sub.3(CH.sub.2).sub.x(CHOSO.sub.3.sup.-M.sup.+) CH.sub.3
and CH.sub.3 (CH.sub.2).sub.y(CHOSO.sub.3.sup.-M.sup.+)
CH.sub.2CH.sub.3 where x and (y+1) are integers of at least about
7, preferably at least about 9, and M is a water-solubilizing
cation, especially sodium, unsaturated sulfates such as oleyl
sulfate, the C.sub.10-C.sub.18 alkyl alkoxy sulfates ("AE.sub.xS";
especially EO 1-7 ethoxy sulfates), C.sub.10-C.sub.18 alkyl alkoxy
carboxylates (especially the EO 1-5 ethoxycarboxylates), the
C.sub.10-C.sub.18 glycerol ethers, the C.sub.10-C.sub.18 alkyl
polyglycosides and their corresponding sulfated polyglycosides, and
C.sub.12-C.sub.18 alpha-sulfonated fatty acid esters. If desired,
the conventional nonionic and amphoteric surfactants such as the
C.sub.12-C.sub.18 alkyl ethoxylates ("AE") including the so-called
narrow peaked alkyl ethoxylates and C.sub.6-C.sub.12 alkyl phenol
alkoxylates (especially ethoxylates and mixed ethoxy/propoxy),
C.sub.12-C.sub.18 betaines and sulfobetaines ("sultaines"),
C.sub.10-C.sub.18 amine oxides, and the like, can also be included
in the overall compositions. The C.sub.10-C.sub.18 N-alkyl
polyhydroxy fatty acid amides can also be used. Typical exanples
include the C.sub.12-C.sub.18 N-methylglucamides. See WO 9,206,154.
Other sugar-derived surfactants include the N-alkoxy polyhydroxy
fatty acid amides, such as C.sub.10-C.sub.1.sub.18
N--(3-methoxypropyl) glucamide. The N-propyl through N-hexyl
C.sub.12-C.sub.18 glucamides can be used for low sudsing.
C.sub.10-C.sub.20 conventional soaps may also be used. If high
sudsing is desired, the branched-chain C.sub.10-C.sub.16 soaps may
be used. Mixtures of anionic and nonionic surfactants are
especially useful. Other conventional useful surfactants are
described further herein and are listed in standard texts.
[0307] Anionic surfactants can be broadly described as the
water-soluble salts, particularly the alkali metal salts, of
organic sulfuric reaction products having in their molecular
structure an alkyl radical containing from about 8 to about 22
carbon atoms and a radical selected from the group consisting of
sulfonic acid and sulfuric acid ester radicals. (Included in the
term alkyl is the alkyl portion of higher acyl radicals.) Important
examples of the anionic synthetic detergents which can form the
surfactant component of the compositions of the present invention
are the sodium or potassium alkyl sulfates, especially those
obtained by sulfating the higher alcohols (C.sub.8-18 carbon atoms)
produced by reducing the glycerides of tallow or coconut oil;
sodium or potassium alkyl benzene sulfonates, in which the alkyl
group contains from about 9 to about 15 carbon atoms, (the alkyl
radical can be a straight or branched aliphatic chain); sodium
alkyl glyceryl ether sulfonates, especially those ethers of the
higher alcohols derived from tallow and coconut oil; sodium coconut
oil fatty acid monoglyceride sulfates and sulfonates; sodium or
potassium salts of sulfuric acid ester of the reaction product of
one mole of a higher fatty alcohol (e.g. tallow or coconut
alcohols) and about 1 to about 10 moles of ethylene oxide; sodium
or potassium salts of alkyl phenol ethylene oxide ether sulfates
with about 1 to about 10 units of ethylene oxide per molecule and
in which the alkyl radicals contain from 8 to 12 carbon atoms; the
reaction products of fatty acids are derived from coconut oil
sodium or potassium salts of tatty acid amides of a methyl tauride
in which the fatty acids, for example, are derived from coconut oil
and sodium or potassium beta-acetoxy- or
beta-acetamido-alkanesulfonates where the alkane has from 8 to 22
carbon atoms.
[0308] Additionally, secondary alkyl sulfates may be used by the
formulator exclusively or in conjunction with other surfactant
materials and the following identifies and illustrates the
differences between sulfated surfactants and otherwise conventional
alkyl sulfate surfactants. Non-limiting examples of such
ingredients are as follows.
[0309] Conventional primary alkyl sulfates (LAS), such as those
illustrated above, have the general formula ROSO3-M+ wherein R is
typically a linear C8-22 hydrocarbyl group and M is a water
solublizing cation, for example sodium LAS. Branched chain primary
alkyl sulfate surfactants (i.e., branched-chain "PAS") having 8-20
carbon atoms are also know; see, for example, Eur. Pat. Appl.
439,316, Smith et al., filed Jan. 21, 1991.
[0310] Conventional secondary alkyl sulfate surfactants are those
materials which have the sulfate moiety distributed randomly along
the hydrocarbyl "backbone" of the molecule. Such materials may be
depicted by the structure
CH.sub.3(CH.sub.2).sub.n(CHOSO.sub.3.sup.-M.sup.+)(CH.sub.2).sub.mCH.sub.3
[0311] wherein m and n are integers of 2 of greater and the sum of
m+n is typically about 9 to 17, and M is a water-solublizing
cation.
[0312] The aforementioned secondary alkyl sulfates are those
prepared by the addition of H.sub.2SO.sub.4 to olefins. A typical
synthesis using alpha olefins and sulfuric acid is disclosed in
U.S. Pat. No. 3,234,258, Morris, issued Feb. 8, 1966 or in U.S.
Pat. No. 5,075,041, Lutz, issued Dec. 24, 1991. The synthesis
conducted in solvents which afford the secondary (2,3) alkyl
sulfates on cooling, yields products which, when purified to remove
the unreacted materials, randomly sulfated materials, unsulfated
by-products such as C10 and higher alcohols, secondary olefin
sulfonates, and the like, are typically 90+% pure mixtures of 2-
and 3- sulfated materials (some sodium sulfate may be present) and
are white, non tacky, apparently crystalline, solids. Some
2,3-disulfates may also be present, but generally comprise no more
than 5% of the mixture of secondary (2,3) alkyl mono-sulfates. Such
materials are available as under the name "DAN", e.g., "DAN 200"
from Shell Oil Company.
[0313] Bleaching Agents and Bleach Activators--The detergent
compositions herein may optionally contain bleaching agents or
bleaching compositions containing a bleaching agent and one or more
bleach activators. When present, bleaching agents will typically be
at levels of from about 1% to about 30%, more typically from about
5% to about 20%, of the detergent composition, especially for
fabric laundering. If present, the amount of bleach activators will
typically be from about 0.1% to about 60%, more typically from
about 0.5% to about 40% of the bleaching composition comprising the
bleaching agent-plus-bleach activator.
[0314] The bleaching agents used herein can be any of the bleaching
agents useful for detergent compositions in textile cleaning, hard
surface cleaning, or other cleaning purposes that are now known or
become known. These include oxygen bleaches other than the
hypohalite (e.g. hypochlorite) bleaches. Perborate (e.g., mono- or
tetra-hydrate sodium salts) and percarbonate bleaches can be used
herein.
[0315] Another category of bleaching agent that can be used without
restriction encompasses percarboxylic acid bleaching agents and
salts thereof. Suitable examples of this class of agents include
magnesium monoperoxyphthalate hexahydrate, the magnesium salt of
metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid
and diperoxydodecanedioic acid. Such bleaching agents are disclosed
in U.S. Pat. No. 4,483,781, Hartman, issued Nov. 20, 1984, U.S.
patent application Ser. No. 740,446, Burns et al, filed Jun. 3,
1985, European Patent Application 0,133,354, Banks et al, published
Feb. 20, 1985, and U.S. Pat. No. 4,412,934. Chung et al, issued
Nov. 1, 1983. Highly preferred bleaching agents also include
6nonylamino-6-oxoperoxycaproic acid as described in U.S. Pat. No.
4,634,551, issued Jan. 6, 1987 to Burns et al.
[0316] Peroxygen bleaching agents can also be used. Suitable
peroxygen bleaching compounds include sodium carbonate peroxn
hydrate and equivalent "percarbonate" bleaches, sodium
pyrophosphate peroxyhydrate. urea peroxyhydrate, and sodium
peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially
by DuPont) can also be used.
[0317] A preferred percarbonate bleach comprises dry particles
having an average particle size in the range from about 500
micrometers to about 1,000 micrometers, not more than about 10% by
weight of said particles being smaller than about 200 micrometers
and not more than about 10% by weight of said particles being
larger than about 1,250 micrometers. Optionally, the percarbonate
can be coated with silicate, borate or water-soluble surfactants.
Percarbonate is available from various commercial sources such as
FMC, Solvay and Tokai Denka.
[0318] Mixtures of bleaching agents can also be used.
[0319] Peroxygen bleaching agents, the perborates, the
percarbonates, etc., are preferably combined with bleach
activators, which lead to the in situ production in aqueous
solution (i.e., during the washing process) of the peroxy acid
corresponding to the bleach activator. Various nonlimiting examples
of activators are disclosed in U.S. Pat. No. 4,915,854, issued Apr.
10, 1990 to Mao et al, and U.S. Pat. No. 4,412,934. The
nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene
diamine (TAED) activators are typical, and mixtures thereof can
also be used. See also U.S. Pat. No. 4,634,551 for other typical
bleaches and activators useful herein.
[0320] Highly preferred amido-derived bleach activators are those
of the formulae:
R.sup.1N(R.sup.5)C(O)R.sup.2C(O)L or
R.sup.1C(O)N(R.sup.5)R.sup.2C(O)L
[0321] wherein R.sup.1 is an alkyl group containing from about 6 to
about 12 carbon atoms, R.sup.2 is an alkylene containing from 1 to
about 6 carbon atoms, R.sup.5 is H or alkyl, aryl, or alkaryl
containing from about 1 to about 10 carbon atoms, and L is any
suitable leaving group. A leaving group is any group that is
displaced from the bleach activator as a consequence of the
nucleophilic attack on the bleach activator by the perhydrolysis
anion. A preferred leaving group is phenyl sulfonate.
[0322] Preferred examples of bleach activators of the above
formulae include (6-octanamido-caproyl)oxybenzenesulfonate,
(6-nonanamidocaproyl)oxybenzenesulfonate,
(6-decanamido-caproyl)oxybenzen- esulfonate, and mixtures thereof
as described in U.S. Pat. No. 4,634,551, incorporated herein by
reference.
[0323] Another class of bleach activators comprises the
benzoxazin-type activators disclosed by Hodge et al in U.S. Pat.
No. 4,966,723, issued Oct. 30, 1990, incorporated herein by
reference. A highly preferred activator of the benzoxazin-type is:
34
[0324] Still another class of preferred bleach activators includes
the acyl lactam activators, especially acyl caprolactams and acyl
valerolactams of the formulae: 35
[0325] wherein R.sup.6 is H or an alkyl, aryl, alkoxyaryl, or
alkaryl group containing from 1 to about 12 carbon atoms. Highly
preferred lactam activators include benzoyl caprolactam, octanoyl
caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl
caprolactam, decanoyl caprolactam, undecenoyl caprolactarn, benzoyl
valerolactam, octanoyl valerolactam, decanoyl valerolactam,
undecenoyl valerolactarn, nonanoyl valerolactam,
3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also
U.S. Pat. No. 4,545,784, issued to Sanderson, Oct. 8, 1985,
incorporated herein by reference, which discloses acyl
caprolactams, including benzoyl caprolactam, adsorbed into sodium
perborate.
[0326] As a practical matter, and not by way of limitation, the
compositions and processes herein can be adjusted to provide on the
order of at least one part per ten million of the active bleach
catalyst species in the aqueous washing liquor, and will preferably
provide from about 0.1 ppm to about 700 ppm, more preferably from
about 1 ppm to about 500 ppm, of the catalyst species in the
laundry liquor.
[0327] Bleaching agents other than oxygen bleaching agents are also
known in the art and can be utilized herein. One type of non-oxygen
bleaching agent of particular interest includes photoactivated
bleaching agents such as the sulfonated zinc and/or aluminum
phthalocyanines. See U.S. Pat. No. 4,033,718, issued Jul. 5, 1977
to Holcombe et al. If used, detergent compositions will typically
contain from about 0.025% to about 1.25%, by weight, of such
bleaches, especially sulfonate zinc phthalocyanine.
[0328] Buffers--Buffers can be included in the formulations herein
for a variety of purposes. One such purpose is to adjust the
cleaning surface pH to optimize the hard surface cleaner
composition effectiveness relative to a particular type of soil or
stain. Buffers may be included to stabilize the adjunct ingredients
with respect to extended shelf life or for the purpose of
maintaining compatibility between various aesthetic ingredients.
The hard surface cleaner of the present invention optionally
contains buffers to adjust the pH in a range from about 7 to about
13, preferably from about 8 to about 13, more preferably from about
10 to about 11. Non-limiting examples of such suitable buffers are
potassium carbonate, sodium carbonate, and sodium bicarbonate,
however, the formulator is not restricted to these examples or
combinations thereof.
ADJUNCT MATERIALS
[0329] The compositions herein can optionally include one or more
other detergent adjunct materials or other materials for assisting
or enhancing cleaning performance, treatment of the surface to be
cleaned, or to modify the aesthetics of the composition (e.g.,
perfumes, colorants, dyes, etc.). The following are illustrative
examples of such adjunct materials but are not meant to be
exclusive or limiting in scope.
[0330] Chelating Agents--The detergent compositions herein may also
optionally contain one or more iron and/or manganese chelating
agents. Such chelating agents can be selected from the group
consisting of amino carboxylates, amino phosphonates,
polyfunctionally-substituted aromatic chelating agents and mixtures
therein, all as hereinafter defined. Without intending to be bound
by theory, it is believed that the benefit of these materials is
due in part to their exceptional ability to remove iron and
manganese ions from washing solutions by formation of soluble
chelates.
[0331] Amino carboxylates useful as optional chelating agents
include ethylenediaminetetracetates,
N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates,
ethylenediamine tetraproprionates,
triethylenetetraaminehexacetates, diethylenetriaminepentaacetates,
and ethanoldiglycines, alkali metal, ammonium, and substituted
ammonium salts therein and mixtures therein.
[0332] Amino phosphonates are also suitable for use as chelating
agents in the compositions of the invention when at lease low
levels of total phosphorus are permitted in detergent compositions,
and include ethylenediaminetetrakis (methylenephosphonates) as
DEQUEST. Preferred, these amino phosphonates to not contain alkyl
or alkenyl groups with more than about 6 carbon atoms.
[0333] Polyfunctionally-substituted aromatic chelating agents are
also useful in the compositions herein. See U.S. Pat. No.
3,812,044, issued May 21, 1974, to Connor et al. Preferred
compounds of this type in acid form are dihydroxydisulfobenzenes
such as 1,2-dihydroxy-3,5-disulfobenzen- e.
[0334] A preferred biodegradable chelator for use herein is
ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer
as described in U.S. Pat. No. 4,704,233, Nov. 3, 1987, to Hartman
and Perkins.
[0335] If utilized, these chelating agents will generally comprise
from about 0.1% to about 10% by weight of the detergent
compositions herein. More preferably, if utilized, the chelating
agents will comprise from about 0.1% to about 3.0% by weight of
such compositions
[0336] Inert Salts. The inert salts (filler salts) used in the
compositions of the present invention can be any water-soluble
inorganic or organic salt or mixtures of such salts which do not
destabilize the surfactant. For the purposed of the present
invention, "water-soluble" means having a solubility in water of at
least 1 gram per 100 grams of water at 20.degree. C. Examples of
suitable salts include various alkali metal and/or alkali earth
metal sulfate, chlorides, borates, bromides, fluorides, phosphates,
carbonates, bicarbonates, citrates, acetates, lactates, etc.
[0337] Specific examples of suitable salts include sodium sulfate,
sodium chloride, potassium chloride, sodium carbonate, potassium
sulfate, lithium chloride, lithium sulfate, tripotassium phosphate,
sodium borate, potassium bromide, potassium fluoride, sodium
bicarbonate, magnesium sulfate, magnesium chloride, sodium citrate,
sodium acetate, magnesium lactate, sodium fluoride. The preferred
salts are inorganic salts preferably the alkali metal sulfates and
chlorides . Particularly preferred salts, because of their low cost
are sodium sulfate and sodium chloride. The salts are present in
the compositions at levels of from 0% to 40%, preferably 10% to
20%.
[0338] Abrasives. An essential component of many solid or viscous
semi-solid hard surface cleaning compositions is the abrasive
material added to facilitate the action of scouring. Abrasive
scouring cleansers provide a convenient and useful means for
carrying out the sanitizing of porcelain and tile surfaces,
especially tubs, showers and toilet bowls. The particulate abrasive
material within such compositions serves to abrade and loosen soil
adhering to hard surfaces and further serves to create more
intimate contact between hard surface stain and the surfactant
and/or bleaching agents also present in the cleansing
compositions.
[0339] Abrasive cleaners have traditionally contained
water-insoluble, relatively hard, particulate mineral material as
the abrasive agent. The most common such abrasive agent is finely
divided silica sand having particle size varying between about 1
and 300 microns and specific gravity of about 2.1 or higher. While
such material is generally very effective in scouring soil and
stains from the surfaces being treated, abrasive material of this
type tends to be difficult to rinse away from the toilet bowl,
shower or bathtub surface.
[0340] In the case where moderate or highly water soluble abrasive
material is required (i.e. sodium carbonate) imidodisulfate can be
used as the sole abrasive or otherwise added in part.
[0341] It has been discovered that abrasive compositions of this
desired type can be realized by utilizing a particular type of
expanded perlite abrasive in combination with the surfactants,
filler material, and other optional scouring material ingredients
listed herein. The abrasive materials suitable to the present
invention are those contained in U.S. Pat. No. 4,051,056, Hartman,
issued Sep. 27, 1977 and included herein by reference.
[0342] Perfumes. Perfumes are an important ingredient especially
for the liquid composition embodiment. Perfume is usually used at
levels of from 0% to 5%. In U.S. Pat. No. 4,246,129, Kacher, issued
Jan. 20, 1981 (incorporated herein by reference), certain perfume
materials are disclosed which perform the added function reducing
the solubility of anionic sulfonate and sulfate surfactants.
[0343] Dyes. Dyes may be include at levels of from abut 0.5% to
12%, preferably 1.5% to 5%. Solids and viscous semi-solids can be
made with 1.5% dye and no perfume. Examples of suitable dyes are
Alizarine Light Blue B (C.I. 63010), Carta Blue VP (C.I. 24401),
Acid Green 2G (C.I. 42085), Astrogen Green D (C.I. 42040), Supranol
Cyanine 7B (C.I. 42675, Maxilon Blue 3RL (C.I. Basic Blue 80),
Drimarine Blue Z-RL (C.I. Reactive Blue 18), Alizarine Light Blue
H-RL (C.I. Acid Blue 182), FD&C Blue No. 1 and FD&C Green
No. 3. (See the patents of Kitko, U.S. Pat. No. 4,248,827 issued
Feb. 3, 1981 and U.S. Pat. No. 4,200,606, issued Apr. 29, 1980,
both incorporated herein by reference.) C.I. refers to Color
Index.
[0344] Optional Adjuncts Ingredients. As a preferred embodiment,
the conventional adjunct ingredients employed herein can be
selected from typical components such as enzymes (compatible with
the applicable with other adjunct ingredients), especially
proteases, lipases, cellulases, color speckles, suds boosters, suds
supressors, anti-tarnish and/or anti-corrosion agents,
soil-suspending agents, germicides, alkalinity sources,
hydrotropes, anti-oxidants, enzyme stabilizing agents, solvents,
clay soil chelating agents will generally comprise from about 0.1%
to about 10% by weight of the detergent compositions herein. More
preferably, if utilized, the chelating agents will comprise from
about 0.1% to about 3.0% by weight of such composition
removal/anti-redepositio- n agents, polymeric dispersing agents,
dye transfer inhibiting agents, including polyamine N-oxides such
as polyvinylpyrrolidone and copolymers of N-vinyl imidazole and
N-vinyl pyrrolidone, etc.
EXAMPLE 1
Preparation of dilithium naphthalocyanine
[0345] To a refluxing solution of 2,3-dicyanonaphthalene (10 g,
56.1 mmole) in anhydrous 1-butanol (300 mL) is added lithium shot
(1.56 g, 224.5 mmole). The solution is refluxed 6 hours under
argon, diluted with 500 mL methanol and allowed to crystallize in
the cold at about 0.degree. C. for 18 hours. The resulting green
solid is recovered by filtration, dried in vacuo at 80.degree. C.
and used without further purification.
[0346] The above procedure is suitable for preparing
1,4,8,11,15,18,22,25-octabutoxy-29,31 -dilithium phthalocyanine
from 3,6-dibutoxyphthalonitrile;
2,3,9,10,16,17,23,24-octachloro-29,31 -dilithium phthalocyanine
from 4,5-dichlorophthalonitrile; and tetrabutoxy-29,31 -dilithium
phthalcyanine from 3 -butoxyphthalonitrile.
EXAMPLE 2
Preparation of naphthalocyanine
[0347] To a solution of dilithium naphthalocyanine (2 g, 2.75
mmole) in DMF (200 ml) is added 1N HCl (10 mL). The solution is
stirred at room temperature of approximately 1 hour. The solution
is then diluted with 200 mL of water over a period of about 30
minutes. The green solid which results is collected by filtration
and dried in vacuo at 100.degree. C. and used without further
purification.
[0348] The above procedure is suitable for preparing
1,4,8,11,15,18,22,25-octabutoxy-29H,31H-phthalocyanine;
2,3,9,10,16,17,23,24-octachloro-29H,31H-phthalocanine; and
tetrabutoxy-29H,31H-phthalcyanine.
EXAMPLE 3
Preparation of tin(IV) naphthalocyanine dichloride
[0349] A mixture of naphthalocyanine (0.2 g, 0.28 mmole), tin
tetrachloride pentahydrate (0.456 g, 1.3 mmole) in DMF is refluxed
for one hour under argon then allowed to cool. The green solid that
results is filtered off, dired in vacuo, and used without further
purification.
[0350] The above procedure is suitable for preparing
1,4,8,11,15,18,22,25-octabutoxy tin(IV) phthalocyanine dichloride;
2,3,9,10,16,17,23,24-octachloro tin(IV) phthalocanine dichloride;
and tetrabutoxy tin(IV) phthalcyanine dichloride.
EXAMPLE 4
Preparation of germanium(IV) naphthalocyanine dichloride
[0351] To a refluxing solution of naphthalocyanine (0.20 g, 0.28
mmole), germanium tetrachloride (0.15 mL) in anhydrous DMF (20 mL)
under argon, is added in portions over a period of 5 hours
additional germanium tetrachloride (0.25 mL). The solution is
cooled, diluted with dichloromethane 940 mL), extracted twice with
30 mL portions of 10% hydrochloric acid, then three times with 30
mL portions of distilled water, died over MgSO.sub.4, filtered and
concentrated to yield a green solid that is used without further
purification.
[0352] The above procedure is auitable for preparing
1,4,8,11,15,18,22,25-octabutoxy germanium(IV) phthalocyanine
dichloride; 2,3,9,10,16,17,23,24-octachloro germanium(IV)
phthalocyanine dichloride; and tetrabutoxy germanium(IV)
phthalcyanine dichloride.
EXAMPLE 5
Preparation of 1,4,8,11,15,18,22,25-octabutoxy platinum(IV)
dichloride
[0353] To a refluxing solution of
1,4,8,11,15,18,22,25-Octabutoxyphthalocy- anine (0.20 g, 0.18
mmole), Platinum Tetrachloride (0.15 ml) in 20 ml anhydrous
N,N-Dimethylformamide under argon over a five hour period is added
in five portions Platinum Tetrachloride (0.25 ml). The solution is
cooled, diluted with 40 ml Dichloromethane, extracted 2.times.30 ml
10% hydrochloric acid, 3.times.30 ml distilled water, dried over
anhydrous Magnesium Sulfate and stripped of solvent yielding a
green solid which is used without further purification.
EXAMPLE 6
Preparation of 1,4,8,11,15,18,22,25-octabutoxy germanium(IV)
phthalocyaninedi-(poly(ethylene glycol 350) methyl ether)
[0354] A mixture of 1,4,8,11,15,18,22,25-octabutoxy germanium(IV)
phthalocyanine dihydroxide (1.0 g, 0.81 mmole), poly(ethylene
glycol 350) methyl ether (22.68 g, 64.8 mmole) and xylene (175 mL)
is slowly heated to reflux under argon over a period of 3 hours.
The reaction flask is fitted with a Dean-Stark trap and the water
is removed by azeotropic distillation. After 48 hours the reaction
is cooled, the solvent removed in vacuo and the crude product is
used without further pruification.
[0355] The above procedure is suitable for use in preparing
1,4,8,11,15,18,22,25-octabutoxy germanium(IV)
phthalocyanine-di-(glycerol- -di-(diethylene glycol methyl ether));
1,4,8,11,15,18,22,25-octabutoxy germanium(IV)
phthalocyanine-di-(Neodol 23-6.5); tetrabutoxy tin(IV)
phthalcyanine-di-(poly(ethylene glycol 350) methyl ether);
tetrabutoxy tin(IV) phthalcyanine-di-(glycerol-di-(diethylene
glycol methyl ether)); and tetrabutoxy tin(IV)
phthalcyanine-di-(Neodol 23-6.5).
EXAMPLE 7
Preparation of 1,4,8,11,15,18,22,25-octabutoxy germanium(IV)
phthalocyanine-di-(triethanol amine dimethyl sulfate quat.)
[0356] A mixture of 1,4,8,11,15,18,22,25-octabutoxy germanium(IV)
phthalocyanine dihydroxide (0.5 g, 0.405 mmole), anhydrous
triethanolamine (10 g, 67.04 mmole) and xylene (175 mL) is slowly
heated to reflux over a period of 1.5 hours. The reaction flask is
fitted with a Dean-Stark trap and the water is removed by
azeotropic distillation. After 2 hours the solution is cooled, and
the solvent is removed in vacuo. The resulting oil is dissolved in
50 mL DMF and slowly added to 800 mL of water over 0.5 hour. The
blue solid which results is collected by filtration and dried under
vacuum at 80.degree. C. This solid product is added to a dioxane
(100 mL) which contains dimethylsulfate (0.15 g, 1.215 mmole). The
resulting blue solid is collected by filtration, dried and used
without further purification.
[0357] The above procedure is suitable for use in preparing
tetrabutoxy tin(IV) phthalcyanine-di-(triethanolamine dimethyl
sulfate quat).
[0358] The cleaning compositions provided in accordance with this
invention may be in the form of granules, liquids, bars, and the
like, and typically are formulated to provide an in-use pH in the
range of 9 to 11, however in the case of non-aqueous or low aqueous
compositions the pH ranges may vary outside this range. Various
carriers such as sodium sulfate, water, water-ethanol, BPP, MPP,
EPP, PPP, sodium carbonate, and the like, may be used routinely to
formulate the finished products. Granules may be produced by
spray-drying or by agglomeration, using known techniques, to
provide products in the density range of 350-950 g/l. Bars may be
formulated using conventional extrusion techniques. The
photobleach-chelant may be pre-formed, if desired. The compositions
may also contain conventional perfumes, bactericides, hydrotropes
and the like. In the case of non-aqueous or low aqueous
compositions, the cleaning compositions may be applied to an
article which is used to deliver the compositions of the present
invention to a fabric or to a hard surface. Non-limiting examples
of compositions according to this invention are as follows:
1 Examples 8-11 Weight % Ingredients 8 9 10 11 Sodium linear
alkylbenzene 15 30 20 25 sulfonate NEODOL 1 1 1 1 Alkyl dimethyl
ammonium 0.5 1 0.5 0.7 chloride Sodium tripolyphosphate 15 35 22 28
Sodium carbonate 10 10 15 15 SOKALAN 2 2 2 2 Carboxymethylcellulose
1 1 1 1 Tinopal CBS-X 0.1 0.1 0.1 0.1 Soil release agent.sup.1 0.2
0.2 0.3 0.3 Savinase 6.0T 0.3 0.6 0.5 0.6 Ban 300T 0.2 0.5 0.5 0.6
Lipolase 100T 0.1 0.2 0.2 0.3 CAREZYME 5T 0.1 0.2 0.2 0.3 Sodium
perborate -- -- 3 5 Nonanoyloxybenzenesulfonate -- -- 2 3
Photobleach.sup.2 (ppm) 0.005 0.01 -- -- Photobleach.sup.3 (ppm) --
-- 0.008 0.01 Minors/fillers balance balance balance balance
.sup.1Soil release polymer according to U.S. Pat. No. 4,968,451
Scheibel et al. .sup.2Photobleach
germanium(IV)octabutoxyphthalocyanine poly(ethylene glycol 350)
according to Example 6 .sup.3Photobleach
tin(IV)octabutoxyphthalocyanine poly(ethylene glycol 350) according
to Example 6
[0359]
2 Examples 12-15 Weight% Ingredients 12 13 14 15 C.sub.12-C.sub.14
alkyl sulfate 6 6 8 7 C.sub.12-C.sub.14 alkyl ethoxylate (EO 4.2)
11 12 10 5 Zeolite 38 35 30 10 Trisodium citrate -- -- -- 2 SKS-6
silicate builder -- -- -- 10 Acrylate/maleate copolymer -- -- -- 4
Sodium carbonate 9 10 4 5 EDTMP.sup.1 0.2 -- 0.3 -- Ethylenediamine
disuccinate -- -- -- 0.4 Sodium percarbonate 8 -- 10 25
Nonanolyoxybenzene sulfonate -- -- 3 -- Tetraacetylethylenediamine
7 -- -- -- Savinase (4.0 KNPU/g) 2 1.5 2 1.5 Lipolase (100,000
LU/g) 0.2 0.5 0.5 -- Soap 1 -- -- -- Suds suppressor 2 2 2 2 Soil
release agent.sup.2 0.5 -- 0.5 -- Soil release agent.sup.3 0.5 0.5
-- 0.5 Dispersent.sup.4 -- 2.5 -- -- Photobleach.sup.5 (ppm) 0.005
0.01 -- -- Photobleach.sup.6 (ppm) -- -- 0.008 0.01 Minors/fillers
balance balance balance balance .sup.1Ethylenediamine
tetramethylenephosphonate .sup.2Soil release polymer according to
U.S. Pat. 5,415,807, Gosselink et al. issued May 16, 1995.
.sup.3Soil release polymer according to U.S. Pat. 4,702,857,
Gosselink issued October 27, 1987. .sup.4Hydrophobic soil
dispersent according to U.S. Pat. 5,565,145, Watson et al. issued
October 15, 1996. .sup.5Photobleach germanium(IV)
octabutoxyphthalocyanine according to Example 7. .sup.6Photobleach
tin(IV) tetrabutoxyphthalocyanine according to Example 7.
[0360]
3 Example 16 Ingredients Weight % C.sub.12 Linear alkyl benzene
sulphonate 30 Phosphate (as sodium tripolyphosphate) 7 Sodium
carbonate 15 Sodium pyrophosphate 7 Coconut monoethanolamide 2
Zeolite A 5 Carboxymethylcellulose 0.2 Polyacrylate (m.w. 1400) 0.2
Sodium percarbonate 15 Protease 0.3 CaSO.sub.4 1 MgSO.sub.4 1
Photobleach.sup.1 (ppm) 0.01 Minors/fillers balance
.sup.1Photobleach germanium(IV) octabutoxyphthalocyanine-di-(Neodol
23-6.5).
Low Aqueous Cleaning Composition
[0361]
4 Example 17 Ingredients Weight % Photobleach.sup.1 0.005-1.5
BPP.sup.2 5-25 1,2-octanediol 0.1-70 Magnesium alkylethoxy (E1)
sulfate 0.01-0.8 Magnesium alkylethoxy (E6.5) sulfate 0.01-0.8
C.sub.12 dimethylamine oxide 0.01-0.8 PEMULEN.sup.3 0.05-0.2
Perfume 0.01-1.5 Water balance .sup.1Photobleach germanium(IV)
octabutoxyphthalocyanine di[glycerol-di-(diethylene glycol methyl
ether)]. .sup.2Other co-solvents which can be used herein together
with the BPP, MPP, EPP and PPP primary solvents include various
glycol ethers, including materials marketed under trademarks such
as Carbitol, methyl Carbitol, butyl Carbitol, propyl Carbitol,
hexyl Cellosolve, and the like. If desired, and having due regard
for safety and odor for in-home use, various conventional
chlorinated and hydrocarbon dry cleaning solvents may also be used.
Included among these are 1,2-dichloroethane, #trichloroethylene,
isoparaffins, and mixtures thereof. .sup.3As disclosed in U.S. Pat.
Nos. 4,758,641 and 5,004,557, such polyacrylates include
homopolymers which may be crosslinked to varying degrees, as well
as non-crosslinked. Preferred herein are homopolymers having a
molecular weight in the range of from about 100,000 to about
10,000,000, preferably 2000,000 to 5,000,000.
[0362] For the materials disclosed in Example 29, excellent
cleaning performance is secured using any non-immersion processes
and articles to provide from about 5 g to about 50 g of the
cleaning compositions per kilogram of fabric being cleaned. Use of
the polyacrylate emulsifier at the indicated low levels minimizes
residues on the fabrics.
[0363] Fabrics are laundered using the foregoing compositions,
typically at usage concentrations of from about 10 ppm to about
10,000 ppm. The fabrics are dried in the presence of light,
preferably natural sunlight, to achieve improved photobleaching
benefits.
* * * * *