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
2001-10-02
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...
C540S128000, C540S139000, C540S140000
Reexamination Certificate
active
06297207
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to photochemical singlet oxygen generators having a photon harvester moiety which enhances the singlet oxygen yield of the generator without adversely affecting the remaining properties of the molecule. The photochemical singlet oxygen generators described herein are useful in laundry detergent compositions or hard surface cleaning compositions as bleaching agents or anti-microbial agents. The present invention also relates to methods for bleaching fabrics and cleaning hard surfaces with the photochemical singlet oxygen generators.
BACKGROUND OF THE INVENTION
It is known that certain water soluble phthalocyanine and naphtalocyanine, mixed cyanine and metallocyanine compounds can be used as photobleaching and anti-microbial agents. Phthalocyanines and naphthalocyanines or their metal complexes 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 tnansition 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 and/or the water solubility. Typically this has been accomplished by substitution on the photochemical (Sens.) ring. However, substituents that improve one property may have a negative effect on the other. Consequently it has proven difficult to provide photobleaches which are water soluble and efficient.
Surprisingly, it has been found that the compounds of the present invention allow formulators to increase the photoefficiency of the singlet oxygen generators while being able to maintain the other parameters of the molecule. In addition, the solubility of the photochemical singlet oxygen generator can be modified without producing an undesired effect in the photophysics 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.
The present invention provides a means by which an effective photosensitizer can have its efficiency increased without risking a concomitant loss of other desired properties inter alia solubility or color. This task is achieved by attaching a photon “harvester” moiety to the singlet oxygen generator. This harvester absorbs ultra violet light and transfers the energy to the photosensitizer portion of the molecule via a process known to those of skill in the art as “Foster Energy Transfer”. This harvester group must be within a critical distance to facilitate this energy transfer. This energy transfer acts to increase the effective number of photons absorbed by the photosensitizer unit and, as photons are “consumed” in producing singlet oxygen, an increase therefore in singlet oxygen generation.
It is therefore an object of the present invention to provide photochemical singlet oxygen generators which serve as photobleaches and photodisinfectants and which have a higher efficiency in producing singlet oxygen. 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. (94128933) 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 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);
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 or disinfectant in laundry detergent compositions and hard surface cleaning compositions, said singlet oxygen generators having the formula:
wherein P is a photosensitizer unit; R is an axial moiety which mediates the solubility or substantivity of the singlet oxygen generator, and D is a unit which increases the efficiency of singlet oxygen production, said unit having the formula
—L
1
—E
or
—L
1
—B—[L
2
—E]
m
wherein E is an aromatic unit, provided said E aromatic unit:
a) absorbs ultra violet radiation at a wavelength of from about 200 nm to about 400 nm;
b) has an extinction coefficient of at least about 100; and
c) has a fluorescence spectrum which overlaps an absorption band of said photosensitizer unit;
B is a branching unit; 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 20 continuous covalent bonds from said P unit to said E units; m is from 2 to 4.
All percentages, ratios and proportions herein are by weight, unless otherwise specified.
Harriman Anthony
Ingram David William
Jeffreys Brian
Willey Alan David
Case Western Reserve University
Fay Sharpe Fagan Minnich & McKee LLP
Hardee John
LandOfFree
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