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
2002-07-02
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...
Reexamination Certificate
active
06413924
ABSTRACT:
FIELD OF THE INVENTION
The present invention relates to hybrid metallocyanine photosensitizers and mixtures thereof useful in laundry detergent compositions as low hue photobleaches. The present invention also relates to compositions for cleaning and disinfecting hard surfaces. The present invention further relates to methods for photobleaching fabrics and to methods for disinfecting hard surfaces.
BACKGROUND OF THE INVENTION
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.
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. 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.
A major limitation to the use of phthalocyanine and naphthalocyanine compounds for fabric photobleaching is the fact that these molecules are highly colored materials. Phthalocyanines have Q-band absorption in the range of 600-700 nanometers, while naphthalocyanines have Q-band absorption in the 700-800 nanometer range.
Typically, cyanine rings are formed from four “monomer units” which are reacted together to form a macro cyclic cyanine ring. For example, four equivalents of ortho-dicyanobenzene react together to form the unsubstituted cyanine ring known as phthalocyanine. Cyanine rings comprised of four identical “monomer units” are, for the purposes of the present invention, defined as “homogeneous” cyanine rings. The properties of many substituted and homogeneous non-hybrid cyanines are well known in the art.
It has now surprisingly been found that “hybrid cyanines and hybrid metallocyanines” and mixtures of hybrid cyanines and metallocyanines produce singlet oxygen thereby having the capacity to act as photobleaches or photodisinfectants. These “hybrid cyanines and metallocyanines” have cyanine rings that are not entirely formed from the same four monomers. For example, the monomer units may comprise any combination of substituted or unsubstituted benzene, naphthalene, anthracene, or phenanthrene rings for A, B C, or D in the general formula below.
Conventional photobleach materials have a narrow, intense Q-band absorption. By contrast, the mixed cyanines and metallocyanines of the present invention have a broader, less intense Q-band absorption and this reduces the color of the photobleach.
The present invention also provides axially substituted hybrid metallocyanine and mixtures thereof having a high efficiency for singlet oxygen formation and desirable solubility and substantivity properties. The properties of these axially substituted metallocyanine rings can be varied independently of the axial groups. 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.
It is an object of the present invention to provide “substantive” and “non-substantive” hybrid metallocyanine photosensitizer mixtures. A “substantive” metallocyanine photosensitizer will be attracted to a surface and a “non-substantive” metallocyanine photosensitizer will repel a surface.
It is a further object of the present invention to provide substantive and non-substantive photobleaching laundry compositions for natural, synthetic or blended fabrics.
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.
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®, ceramic tile, glass, or for porous hard surfaces such as concrete or wood.
An object of the present invention is to provide a method for bleaching fabric with laundry compositions comprising hybrid metallocyanine photobleaches of the present invention.
An object of the present invention is to provide a method for cleaning hard surfaces with compositions comprising hybrid metallocyanine photobleaches of the present invention.
BACKGROUND ART
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. 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 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).
SUMMARY OF THE INVENTION
The present invention relates to hybrid metallocyanine photosensitizing mixtures, the mixtures comprise one or more hybrid photosensitizing compounds each of the compounds represented by the formula:
wherein each metallocyanine of the mixture comprises:
a) a photoactive metal or non-metal M wherein said photoactive metal or non-metal M is selected from the group consisting of silicon, germanium, tin, lead, aluminum, platinum, palladium, phosphorous, and mixtures thereof, provided said metal or non-metal has a valence of three or four;
b) aromatic rings A, B, C, and D wherein each ring is independently selected from the group consisting of substituted or unsubstituted benzene, 1,2-naphthalene, 2,3-naphthalene, a
Case Western Reserve University
Fay Sharpe Fagan Minnich & McKee LLP
Hardee John
LandOfFree
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