Cleaning compositions for solid surfaces – auxiliary compositions – Cleaning compositions or processes of preparing – For cleaning a specific substrate or removing a specific...
Reexamination Certificate
1999-07-23
2002-06-18
Hardee, John (Department: 1751)
Cleaning compositions for solid surfaces, auxiliary compositions
Cleaning compositions or processes of preparing
For cleaning a specific substrate or removing a specific...
Reexamination Certificate
active
06407049
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to photochemical singlet oxygen generators having a cationic axial substituent which enhances the substantivity of said singlet oxygen generators for fabric surfaces. The photochemical singlet oxygen generators described herein are useful in laundry detergent compositions as bleaching agents. The present invention also relates to methods for bleaching fabrics with the photochemical singlet oxygen generators.
BACKGROUND OF THE INVENTION
It is known that certain water soluble phthalocyanine, naphthalocyanine, mixed cyanine and metallocyanine compounds can be used as photobleaching and anti-microbial agents. Phthalocyanines, naphthalocyanine, mixed cyanine and metallocyanines can form “singlet oxygen”.
Singlet oxygen can be formed by chemical as well as photochemical processes. Singlet oxygen is a highly oxidative species capable of reacting with substances, for example, with stains on a fabric to bleach them to a colorless and usually water-soluble state. 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.
The prior art teaches phthalocyanine and naphthalocyanine compounds having the general structure
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.
It has been a task of formulators of photobleaches to modify the properties of the (Sens.) unit of the molecule to increase the quantum efficiency without reducing the water solubility. Typically this has been accomplished by substitution on the photochemical (Sens.) ring. However, substitution on the macrocyclic ring is frequently difficult and can adversely affect other photobleach properties such as color, substantivity and photoefficiency.
Surprisingly, it has been found that the compounds of the present invention allow formulators to increase the photoefficiency of the singlet oxygen generators without adversely affecting the other parameters of the molecule. In addition, the substantivity of the photochemical singlet oxygen generator for fabric surface can be modified without producing an undesired effect in the photophysics of the molecule. This ability to delineate and selectively modify these 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.
The present invention provides a means by which an effective photosensitizer can be made to have an enhanced affinity for the surface of fabric, especially cotton fabric. This task is achieved by attaching an axial cationic moiety to the singlet oxygen generator. This axial cationic moiety is capable of interacting with various surfaces, especially fabric surfaces which can contain a negative charge. By this interaction, the cationic group draws the photoactive singlet oxygen producing portion of the molecule into proximity with the surface of the fabric where the bleaching action of the photosensitizer can take place on stains.
It is therefore an object of the present invention to provide photochemical singlet oxygen generators which serve as photobleaches and which have a higher efficiency for cleaning stains on fabric. It is a further object of the present invention to provide photobleaching compositions suitable for use as laundry detergent bleaching compositions.
It is a yet further object of the present invention to provide enhanced photobleaching hard surface cleaning compositions for non-porous hard surfaces, inter alia, Formica®, ceramic tile, glass, or for porous hard surfaces such as concrete or wood.
It is a still further object of the present invention is to provide a method for bleaching fabric with laundry compositions comprising the photobleaching compounds of the present invention.
It is yet still a further object of the present invention is to provide a method for cleaning hard surfaces with the photobleaching compounds of the present invention.
BACKGROUND ART
Various patent documents relate, to photochemical bleaching or to the use of cyanine 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. 285,965 A2; E.P. 381,211 A2 published Aug. 8, 1990; E.P. 484,027 A1 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.
In addition to the above cited patent publications, other references describing the synthesis, preparation and properties of cyanines, 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 at., 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);
J. Chin Chem. Soc
., 40, pg. 141, (1993);
J. Inorg. Nucl. Chem
., 28, pg. 899, (1966);
Polymer Preps
, 25, pg. 234, (1986);
Chem. Lett
., 2137, (1990);
J. Med. Chem
., 37, pg. 415, (1994).
SUMMARY OF THE INVENTION
The present invention relates to singlet oxygen generators useful as a bleaching agent in laundry detergent compositions, said singlet oxygen generators having the formula:
wherein P is a photosensitizer unit; R is an axial moiety which mediates the solubility of the singlet oxygen generator; and D is a unit which increases the fabric substantivity of the singlet oxygen generator, said unit having the formula:
—L
1
—E or —L
1
—B—[L
2
—E]
m
wherein E is a unit which comprises a tetravalent nitrogen having the formula:
wherein each R
30
-R
35
is linear and branched C
1
-C
22
alkyl, linear and branched C
1
-C
22
alkenyl, substituted and unsubstituted aryl, substituted and unsubstituted alkylenearyl, substituted and unsubstituted aryloxy, substituted and unsubstituted alkyleneoxyaryl, substituted and unsubstituted oxyalkylenearyl, alkyleneoxyalkyl, or any R
30
-R
35
can be taken together to form a nitrogen-containing ring, and mixtures thereof; X is a water soluble anion; B is a branching unit having the formula:
wherein B is selected from the group consisting of boron, aluminum, nitrogen, phosphorous, carbon, silicon, tin, germanium, and mixtures thereof, preferably carbon or silicon; and L
1
and L
2
are linking units, provided said linking units when taken together with said B unit comprise a total of at least 2 continuous covalent bonds from said P unit to said E units; m is from 2 to
Ingram David William
Jeffreys Brian
Willey Alan David
Case Western Reserve University
Fay Sharpe Fagan Minnich & McKee LLP
Hardee John
LandOfFree
Photochemical singlet oxygen generators having cationic... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Photochemical singlet oxygen generators having cationic..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Photochemical singlet oxygen generators having cationic... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2958172