KR100265395B1 - Low hue photobleaches - Google Patents

Abstract

The present invention provides a low tone photobleaching composition comprising organosilicon (IV) phthalocyanine and naphthalocyanine, having a Q-band absorption maximum at a wavelength of at least 660 nm and having an increased triplet state yield resulting in increased production of singlet oxygen. It is about. The use of Si ⁴⁺ phthalocyanine and naphthalocyanine compounds in photobleaching compositions can produce low color wash compositions, bleaching compositions and hard surface cleaners.

Description

LOW HUE PHOTOBLEACHES

The present invention provides novel organosilicon photosensitive compounds having a Q-band maximum absorption wavelength of at least 660 nm, and photoactivators (photoresists) of the compounds, particularly in low hue photobleaching for removing contaminants from textile and hard surfaces. Or as a singlet oxygen generator. The invention also relates to laundry compositions and hard surface cleaners comprising the novel organosilicon photosensitive compounds of the invention. The invention also relates to a method for delivering a composition comprising a low color photobleach to stained and contaminated fabrics and hard surfaces.

It is known that various water soluble phthalocyanine and naphthalocyanine compounds, in particular phthalocyanine and naphthalocyanine compounds having a specific metal as a central atom, have a photosensitizing action and therefore can be used as photobleaching agents or antibacterial active compounds.

Phthalocyanine and naphthalocyanine, in particular when combined with suitable metals, can undergo a series of photochemical reactions with molecular oxygen to produce molecules of 'monotiary oxygen'. Excited 'monotiary oxygen' formed in this photosensitive reaction is an oxidative species that can cause so-called photochemical bleaching by reacting with contaminants and chemically bleaching them into a colorless and generally water soluble state.

There are many examples of photobleaching agents, including phthalocyanine and naphthalocyanine, the most common being zinc phthalocyanine and aluminum phthalocyanine. In the literature, the term 'photosensitive agent' is often used in place of the term 'photoactivator', and thus the term 'photosensitive agent' can be considered to mean 'photoactivator' throughout this specification.

Prior art teaches phthalocyanine and naphthalocyanine compounds having the general formula:

Where

Me is a transition metal or non-transition metal,

(Sens.) Is a phthalocyanine or naphthalocyanine ring that, when combined with a suitable Me unit, may experience photosensitization of molecular oxygen,

R unit is a substituent that binds to the photosensitive ring unit (Sens.) To increase the solubility or photochemical properties of the molecule,

The Y unit is a substituent that combines with a metal ion, such as an anion, to provide electrical neutrality.

The choice of specific substituent R units to be substituted into a molecule has been the focus of research for many years, and these units are typically chosen by the manufacturer to give the desired molecule the desired degree of water solubility without affecting the degree of photosensitivity.

The main limitation to the use of phthalocyanine and naphthalocyanine compounds in textile photobleaching is that these molecules have a Q-band maximum absorption wavelength (λ _max ) in the visible range. Thus, they are very colored materials. Phthalocyanine undergoes Q-band absorption at 600 to 700 nm, while naphthalocyanine undergoes Q-band absorption at 700 to 800 nm. This is not surprising given the fact that these molecules are structurally similar to dyes.

The second limitation is due to the fact that the parent phthalocyanine and naphthalocyanine compounds are not inherently water soluble when combined with transition or non-transition metals. This is especially true for naphthalocyanines. Therefore, the selection of polar or hydrophilic R unit residues to bind these (Sens.) Units to increase the water solubility of the molecule without adversely affecting the photochemical properties of the ring system may be desirable for phthalocyanine and naphthalocyanine photobleach manufacturers. It was a task.

Another challenge for manufacturers of phthalocyanine and naphthalocyanine is to modify the properties of the (Sens.) Units of the molecule in order to increase the 'photobleaching ability' (photophysical properties) of the molecule, in other words to increase the quantum efficiency. It was set as. In other words, the appropriate R units chosen to achieve this task should not adversely affect water solubility. Manufacturers must balance water solubility with improved photophysical properties, while ensuring that λ _max in the Q-band does not shift to wavelengths in the visible range. Although not having the more desirable 'low tint' properties of materials with Q-band λ _max of 700 nm or more, maintaining the Q-band λ _max at a wavelength of 660 nm or more provides molecules with the desired photobleaching properties of consumers.

Those skilled in the art are well aware that R units, which may increase one of the three properties as desired, may significantly reduce one or both of the other desirable properties. For example, a change that increases solubility may reduce the quantum efficiency of the molecule, making the final molecule lacking sufficient photobleaching properties. Exacerbating this problem is another factor, namely the selection of a suitable Y group. Many phthalocyanines and naphthalocyanines contain metal or nonmetal atoms that are hypervalent relative to the chelate ring system. Satisfying valence conditions of these atoms or providing electrical neutrality of the molecule may break the fragile balance of the properties once obtained.

Surprisingly, it has been found that the compounds of the present invention allow manufacturers to separately modify solubility, light efficiency, Q-band maximum wavelength and electrical conditions of the central silicon atom without adversely affecting other variables of the molecule. The ability to describe and selectively modify the major constituents that contribute to the object properties of the molecule allows manufacturers to proceed without resorting to risky strategies.

One factor of this ability to control the properties of the molecule can be seen by comparing the structure of known photobleaching agents, including phthalocyanine and naphthalocyanine, to the structure of the present invention. Examples of photobleaching agents previously described in the art are generally flat molecules due to their planar ring structure. This is essentially a form of molecular accumulation, stacking, and other aggregates that bring molecules together. Photobleaching molecules tend to overlap with other photobleaching molecules and quench each other, resulting in stopping the generation of singlet oxygen.

The organosilicon photosensitive compounds of the present invention contain axial substituents that act to disrupt this alignment result, effectively forming a single layer of photoresist evenly applied to a given substrate. Since each molecule of such a monolayer can contribute to bleaching, it is more cost effective for the manufacturer.

Surprisingly, it has been found that new uses of the compounds of the invention have been realized since the physical properties are divided into 'molecular zones' (eg R groups for solubility). Additives that provide unique solubility characteristics but deteriorate the mineral physical properties were once excluded from use in photobleach. However, by including these residues in the photobleach of the present invention, it was possible to formulate a photobleach for use in atypical applications such as dry cleaning applications. It is now possible to obtain the solvent-based or water-based solutions of the invention for the very reason that the control over solubility is evident by the choice of the axial R substituent.

By appropriate selection of the axial R units bound to the compounds of the invention, the manufacturer can balance the change in the light efficiency of the desired compound with the water solubility of the parent material. This modification of the axial R units also allows manufacturers to balance solubility, Q-band λ _max and quantum efficiencies in (Sens.) Units.

Various patent documents relate to photochemical bleaching of phthalocyanine and naphthalocyanine compounds or their combination and synthesis as well as their use. See, for example, US Patent No. 3,094,536, issued June 18, 1963; US Patent No. 3,927,967, issued December 23, 1975; US Patent No. 4,033,718, issued July 5, 1977; US Patent No. 4,166,718, issued September 4, 1979; US Patent No. 4,240,920, issued December 23, 1980; US Patent No. 4,255,273, issued March 10, 1981; US Patent No. 4,256,597, issued March 17, 1981; US Patent No. 4,318,883, issued March 9, 1982; US Patent No. 4,368,053, issued January 11, 1983; US Patent No. 4,497,741, issued February 5, 1985; US Patent No. 4,648,992, issued March 10, 1987; British Patent Application No. 1,372,035, published October 30, 1974; British Patent Application No. 1,408,144, published October 1, 1975; British Patent Application No. 2,159,516, published December 4, 1985; European Patent Application No. 484,027 A1, published May 6, 1992; See WO 91/18006, published November 28, 1991, and Japanese Patent Publication No. 94-73397, Derwent Abstract 94-128933, published March 15, 1994.

In addition to the patent publications cited above, other references describing the synthesis, preparation and properties of phthalocyanine and naphthalocyanine are also incorporated herein by reference: Phthalocyanines: Properties and Applications, Leznoff, CC and Lever ABP (Edit), VCH, 1989; Infrared Absorbing Dyes, Matsuoka, M. (edit), Plenum, 1990; Lowery, M. J. et al., Inorg. Chem., 4, p 128 (1965); Joyner R. D. et al., Inorg. Chem., 1, p 236 (1962); Croenke, W. E. et al., Inorg. Chem., 3, p696, 1964; Esposito, J. N. et al., Inorg. Chem. 5, p1979 (1966); Wheeler, B. L. et al., J. Am. Chem. Soc., 106, p7404 (1984); Ford, W. E. et al., Inorg. Chem., 31, p 3371 (1992); Witkiewicz, Z. et al., Material Science, 11, p39 (1978); Cook, M. J. et al., J. Chem. Soc. Perkin Trans. I, p 2453 (1988).

It is an object of the present invention to provide 'substantive' and 'non-substantive' organosilicon photosensitizers. The terms "direct" and "non-direct" as used herein and further defined below refer to the propensity of the compound to induce surface affinity, or otherwise to induce lack of surface affinity. In other words, the 'direct' organosilicon photosensitizer will be attracted to the surface and the 'direct' organosilicon photosensitizer will repel the surface.

It is another object of the present invention to provide compositions for photobleaching laundry directly and non-directly in natural, synthetic or blended fabrics.

It is another object of the present invention to provide a photobleaching composition comprising a photobleaching composition having a nonaqueous and low aqueous carrier, ie, a carrier in which water constitutes less than half of the carrier liquid.

Another object of the present invention is to provide a direct material for a non-porous hard surface (particularly Formica®, ceramic tile, glass) or a porous hard surface (eg concrete or wood). It provides a photobleaching composition and a cleaning composition comprising.

It is an object of the present invention to provide a method of bleaching a fabric with a laundry composition comprising the organosilicon photosensitive compound of the present invention.

It is an object of the present invention to provide a method for cleaning hard surfaces with a composition comprising the organosilicon photosensitive compound of the present invention.

It is an object of the present invention to provide a low tone organic organosilicon photosensitive compound having a Q-band maximum absorption wavelength of at least 660 nm.

The present invention

a) at least about 0.01% of a cationic, anionic, nonionic, amphoteric or dipolar surfactant;

b) an organosilicon (IV) photosensitive compound having a Q-band maximum absorption wavelength of at least 660 nm which is phthalocyanine of formula 2a or naphthalocyanine of formula 3a; And

c) residual amounts of additional components

It relates to laundry and other cleaning compositions comprising:

Where

R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ units

a) hydrogen;

b) halogen;

c) hydroxyl;

d) cyano;

e) nitrile;

f) oxymino;

g) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof;

h) halogen substituted C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof;

i) polyhydroxyl substituted C ₃ -C ₂₂ alkyl;

j) C ₁ -C ₂₂ alkoxy;

k) general formula

Branched alkoxy having the [wherein, B is hydrogen, hydroxyl, C ₁ -C ₃₀ alkyl, C ₁ -C _{30 alkoxy, -CO 2 H, -CH 2 CO} 2 H, -SO 3 - M +, -OSO 3 ^{_{- M +, -PO 3 2- M}} , -OPO 3 2- M, or mixtures thereof

High; M is a sufficient amount of water soluble cations to satisfy the charge balance;

x is 0 or 1; y each independently has a value from 0 to 6; z is each

Independently has a value of 0 to 100;

l) substituted aryl and unsubstituted aryl;

m) substituted alkylenearyl and unsubstituted alkylenearyl;

n) substituted aryloxy and unsubstituted aryloxy;

o) substituted oxyalkylenearyl and unsubstituted oxyalkylenearyl;

p) substituted alkyleneoxyaryl and unsubstituted alkyleneoxyaryl;

q) C ₁ -C ₂₂ thioalkyl, C ₄ -C ₂₂ branched thioalkyl and mixtures thereof;

r) an ester of the general formula -CO ₂ R ¹⁰ , wherein R ¹⁰ is

i) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof;

ii) halogen substituted C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof;

iii) polyhydroxyl substituted C ₃ -C ₂₂ alkyl;

iv) C ₃ -C ₂₂ glycol;

v) C ₁ -C ₂₂ alkoxy;

vi) C ₄ -C ₂₂ branched alkoxy;

vii) substituted aryl and unsubstituted aryl;

viii) substituted alkylaryl and unsubstituted alkylaryl;

ix) substituted aryloxy and unsubstituted aryloxy;

x) substituted alkoxyaryl and unsubstituted alkoxyaryl;

xi) substituted alkyleneoxyaryl and unsubstituted alkyleneoxyaryl; And mixtures thereof;

s) general formula

Alkyleneamino units wherein R ¹¹ and R ¹² represent C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof Including; R ¹⁶ is

i) hydrogen,

ii) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof

It includes; A unit comprises nitrogen or oxygen; X comprises chlorine, bromine, iodine or other water soluble anions; v is 0 or 1; u is 0 to 22;

t) amino units of —NR ¹¹ R ¹² , wherein R ¹¹ and R ¹² are C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl And mixtures thereof);

u) alkylethyleneoxy units of the general formula-(A) _v- (CH ₂ ) _y (OCH ₂ CH ₂ ) _x Z, wherein Z is

i) hydrogen,

ii) hydroxyl,

iii) -CO ₂ H,

Iii) -SO ₃ ^- M ⁺ ,

v) -OSO ₃ ^- M ⁺ ,

vi) C ₁ -C ₆ alkoxy,

vii) substituted aryl and unsubstituted aryl,

viii) substituted aryloxy and unsubstituted aryloxy,

ix) alkyleneamino, and mixtures thereof

It includes; A unit comprises nitrogen or oxygen; M is a water soluble cation; v is 0 or 1; x is 0 to 100; y is 0 to 12;

v) substituted siloxy of the formula -OSiR ⁷ R ⁸ R ⁹ , wherein R ⁷ , R ⁸ and R ⁹ are

i) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof;

ii) substituted aryl and unsubstituted aryl;

iii) substituted aryloxy and unsubstituted aryloxy;

iv) alkylethyleneoxy units of the formula-(A) _v- (CH ₂ ) _y (OCH ₂ CH ₂ ) _x Z, wherein Z is

a) hydrogen,

b) C ₁ -C ₃₀ alkyl,

c) hydroxyl,

d) -CO ₂ H,

e) -SO ₃ ^- M ⁺ ,

f) -OSO ₃ ^- M ⁺ ,

g) C ₁ -C ₆ alkoxy,

h) substituted aryl and unsubstituted aryl,

i) substituted aryloxy and unsubstituted aryloxy,

j) alkyleneamino, and mixtures thereof

It includes; A unit comprises nitrogen or oxygen; M is a water soluble cation; v is 0 or 1; x is 0 to 100; y is 0 to 12) and mixtures thereof

Independently selected from the group consisting of

Each independently selected from the group consisting of

In axial R units, R is each

a) hydrogen;

b) halogen;

c) hydroxyl;

d) cyano;

e) nitrile;

f) oxymino;

g) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof;

h) halogen substituted C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof;

i) polyhydroxyl substituted C ₃ -C ₂₂ alkyl;

j) C ₁ -C ₂₂ alkoxy;

k) general formula

Branched alkoxy having the [wherein, B is hydrogen, hydroxyl, C ₁ -C ₃₀ alkyl, C ₁ -C _{30 alkoxy, -CO 2 H, -CH 2 CO} 2 H, -SO 3 - M +, -OSO 3 ^{_{- M +, -PO 3 2- M}} , -OPO 3 2- M, or a mixture thereof; M is a sufficient amount of water soluble cations to satisfy the charge balance; x is 0 or 1; y each independently has a value from 0 to 6; z each independently has a value from 0 to 100;

l) substituted aryl and unsubstituted aryl;

m) substituted alkylenearyl and unsubstituted alkylenearyl;

n) substituted aryloxy and unsubstituted aryloxy;

o) substituted oxyalkylenearyl and unsubstituted oxyalkylenearyl;

p) substituted alkyleneoxyaryl and unsubstituted alkyleneoxyaryl;

q) C ₁ -C ₂₂ thioalkyl, C ₄ -C ₂₂ branched thioalkyl and mixtures thereof;

r) general formula

Alkyleneamino units wherein R ¹¹ and R ¹² represent C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof Including; R ¹⁶ is

i) hydrogen,

ii) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof

It includes; A unit comprises nitrogen or oxygen; X comprises chlorine, bromine, iodine or other water soluble anions; v is 0 or 1; u is 0 to 22;

s) amino units of —NR ¹¹ R ¹² wherein R ¹¹ and R ¹² are C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl And mixtures thereof);

t) alkyl ethyleneoxy units of the formula-(A) _v- (CH ₂ ) _y (OCH ₂ CH ₂ ) _x Z, wherein Z is

i) hydrogen,

ii) hydroxyl,

iii) -CO ₂ H,

iv) -SO ₃ ^- M ⁺ ,

v) -OSO ₃ ^- M ⁺ ,

vi) C ₁ -C ₆ alkoxy,

vii) substituted aryl and unsubstituted aryl,

viii) substituted aryloxy and unsubstituted aryloxy,

ix) alkyleneamino, and mixtures thereof

It includes; A unit comprises nitrogen or oxygen; M is a water soluble cation; v is 0 or 1; x is 0 to 100; y is 0 to 12;

u) general formula Of carboxylates, where R ¹⁰ is

i) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof;

ii) halogen substituted C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof;

iii) polyhydroxyl substituted C ₃ -C ₂₂ alkyl;

iv) C ₃ -C ₂₂ glycol;

v) C ₁ -C ₂₂ alkoxy;

vi) C ₄ -C ₂₂ branched alkoxy;

vii) substituted aryl and unsubstituted aryl;

viii) substituted alkylaryl and unsubstituted alkylaryl;

ix) substituted aryloxy and unsubstituted aryloxy;

x) substituted alkoxyaryl and unsubstituted alkoxyaryl;

xi) substituted alkyleneoxyaryl and unsubstituted alkyleneoxyaryl;

xii) alkyleneamino; And mixtures thereof;

v) substituted siloxy of the formula -OSiR ⁷ R ⁸ R ⁹ , wherein R ⁷ , R ⁸ and R ⁹ are each

i) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof;

ii) substituted aryl and unsubstituted aryl;

iii) substituted aryloxy and unsubstituted aryloxy;

iv) alkylethyleneoxy units of the formula-(A) _v- (CH ₂ ) _y (OCH ₂ CH ₂ ) _x Z, wherein Z is

a) hydrogen,

b) C ₁ -C ₃₀ alkyl,

c) hydroxyl,

d) -CO ₂ H,

e) -SO ₃ ^- M ⁺ ,

f) -OSO ₃ ^- M ⁺ ,

g) C ₁ -C ₆ alkoxy,

h) substituted aryl and unsubstituted aryl,

i) substituted aryloxy and unsubstituted aryloxy,

j) alkyleneamino, and mixtures thereof

It includes; A unit comprises nitrogen or oxygen; M is a water soluble cation; v is 0 or 1; x is 0 to 100; y is 0 to 12) and mixtures thereof

Independently selected from the group consisting of

Each independently selected from the group consisting of:

Unless stated otherwise, all percentages, ratios, and ratios herein are based on weight. Unless otherwise stated, all temperatures are in degrees Celsius (° C.). All cited references are cited in the relevant sections.

In the present invention, substituted aryl units are defined essentially as residues having the general formula:

Where

R ¹³ and R ¹⁴ are independently hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ branched alkoxy, halogen, morpholino, cyano, nitrile _{^{a, -CO 2 - M +, -SO}} 3 - M +, -OSO 3 - M +, -N (R 15) 2 , and _{^{-N + (R 15) 3 X}} - , and mixtures thereof Become;

Each R ¹⁵ is independently hydrogen or C ₁ -C ₄ alkyl;

M is a water soluble cation;

X is chlorine, bromine, iodine or other water soluble anions.

Examples of other water soluble anions include organic species such as fumarate, tartrate, oxalate and the like and inorganic species such as sulfate, hydrogen sulfide, phosphate and the like.

In the present invention, alkylenearyl units are defined essentially as residues having the general formula:

Where

R ¹³ and R ¹⁴ are as defined above;

p is from 1 to about 10.

In the present invention, aryloxy units are defined essentially as residues having the general formula:

Wherein R ¹³ and R ¹⁴ are as defined above.

In the present invention, alkyleneoxyaryl units are defined essentially as residues having the general formula:

Where

R ¹³ and R ¹⁴ are as defined above;

q is 0 to about 10.

In the present invention, oxyalkylenearyl units are defined essentially as residues having the general formula:

Where

R ¹³ and R ¹⁴ are as defined above;

w is 1 to about 10.

In the present invention, branched alkoxy units are defined essentially as residues having the general formula:

Where

B is hydrogen, hydroxyl, C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, -CO ₂ H, -CH ₂ CO ₂ H, -SO ₃ ^- M ⁺ , -OSO ₃ ^- M ⁺ , -PO ₃ ^2- M, -OPO ₃ ^2- M, or a mixture thereof, preferably C ₁ -C _{18 ^{alkyl, -CO 2 H, -SO 3 -}} M +, -OSO 3 - M +, -PO 3 2- M, -OPO ₃ ^2- M;

M is a sufficient amount of water soluble cations to satisfy the charge balance;

x is 0 or 1;

y are each independently 0-6;

z is 0-100 each independently.

In the present invention, substituted and unsubstituted aryl, alkylenearyl, aryloxy, oxyalkylenearyl and alkyleneoxyaryl all have the subscripts p, q and w as defined above, and aryl is substituted or unsubstituted Any aromatic moiety such as phenyl, naphthyl, thienyl, pyridinyl, and the like.

In the present invention, alkylethyleneoxy units are defined as residues having essentially the following general formula:

-(A) _v- (CH ₂ ) _y (OCH ₂ CH ₂ ) _x Z

Where

A is nitrogen or oxygen as a hetero atom, preferably oxygen;

The subscript v is 0 when no heteroatoms are present and 1 when heteroatoms are present;

Z is hydrogen, C ₁ -C ₆ alkoxy, aryl, substituted aryl, aryloxy, substituted aryloxy, alkyleneamino, -SO ₃ ^- M ⁺ , -OSO ₃ ^- M ⁺ , -CO ₂ H and their A mixture;

x is 1 to 100;

y is 1 to 12.

In the present invention, alkyleneamino units are defined essentially as residues having the general formula:

Where

R ¹¹ and R ¹² are each C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl;

R ¹⁶ is hydrogen, C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof;

A is nitrogen or oxygen as a hetero atom, preferably oxygen;

The subscript v is 0 when no heteroatoms are present and 1 when heteroatoms are present;

X is chloride, bromide, iodide or other water soluble anions,

u is from 0 to 22.

Examples of other water soluble anions include organic species such as fumarate, tartrate, oxalate and the like and inorganic species such as sulfate, hydrogen sulfide, phosphate and the like.

The present invention provides a photobleaching composition comprising an Si ⁴⁺ organosilicon photosensitive compound having essentially the following Formula 1, wherein the Q-band maximum absorption wavelength is at least 660 nm:

Where

(Sens.) Units are bidentate photosensitive units that form essentially planar chelates around the central silicon atom, and these (Sens.) Units are phthalocyanines of formula (2) or naphthalocyanines of formula (3), and Si ⁴⁺ is When combined with the aforementioned phthalocyanine or naphthalocyanine rings, they each form an organosilicon compound having essentially the following formulas (2a) and (3a), each aromatic ring of the phthalocyanine ring system having up to four units, for example R ¹ , R ² , R ³ and R ⁴ units may be substituted for up to 16 molecules per phthalocyanine, and each aromatic ring system of the naphthalocyanine ring system may be 6 or less units, for example, R ¹ , R ² , R ³ , R Substituted with ⁴ , R ⁵ and R ⁶ units, up to 24 per molecule of naphthalocyanine may be substituted:

Formula 2a

Formula 3a

Phthalocyanine and naphthalocyanine ring units

The hydrogen atoms of the phthalocyanine and naphthalocyanine bidentate chelate rings are substituted to change the photochemical properties of the molecule. Phthalocyanine has R ¹ , R ² , R ³ and R ⁴ units which may be substituted, and naphthalocyanine has R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ units which may be substituted. These units bind to the phthalocyanine or naphthalocyanine ring and are independently selected from the group consisting of the following a) to v):

a) hydrogen;

b) halogen;

c) hydroxyl;

d) cyano;

e) nitrile;

f) oxymino;

g) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl;

h) halogen substituted C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl;

i) polyhydroxyl substituted C ₃ -C ₂₂ alkyl;

j) C ₁ -C ₂₂ alkoxy, preferably C ₁ -C ₄ alkoxy, more preferably methoxy;

k) general formula

Branched alkoxy having the [wherein, B is hydrogen, hydroxyl, C ₁ -C ₃₀ alkyl, C ₁ -C _{30 alkoxy, -CO 2 H, -CH 2 CO} 2 H, -SO 3 - M +, -OSO 3 ^{_{- M +, -PO 3 2- M}} , -OPO 3 2- M , or a mixture thereof; M is a sufficient amount of water soluble cations to satisfy the charge balance; x is 0 or 1; y are each independently 0-6; z are each independently 0 to 100, preferably 0 to about 10, more preferably 0 to about 3;

l) essentially a general formula

Aryl and substituted aryl wherein R ¹³ and R ¹⁴ are hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ branched alkoxy, halogen, morpholino, cyano, _{^{nitrile, -CO 2 - M +, -SO}} 3 - M +, -OSO 3 - M +, -N (R 15) 2 , and _{^{-N + (R 15) 3 X}} - ( wherein, R ¹⁵ are each independently hydrogen or C ₁ -C ₄ alkyl) and is selected independently from the group consisting of and mixtures thereof, preferably hydrogen, C ₁ -C ₆ alkyl, -CO ₂ ^- M ^{+ _{, -SO 3 - M +, -OSO}} 3 - M + or a mixture thereof, more preferably a hydrogen moiety of R ¹³ and R ¹⁴ are, different moieties C ₁ -C ₆ alkyl; M is a water soluble cation; X is chlorine, bromine, iodine or other water soluble anions; At this time, examples of other water-soluble anions include organic species such as fumarate, tartrate and oxalate, and inorganic species such as sulfate, hydrogen sulfide, phosphate, and the like];

m) essentially a general formula

Alkylenearyl and substituted alkylenearyl, wherein R ¹³ and R ¹⁴ are hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ side chain Alkoxy, halogen, morpholino, cyano, nitrilo, -CO ₂ ^- M ⁺ , -SO ₃ ^- M ⁺ , -OSO ₃ ^- M ⁺ , -N (R ¹⁵ ) ₂ and -N ⁺ (R ¹⁵ ) ₃ X ^- (wherein, R ¹⁵ are each independently hydrogen or C ₁ -C ₄ alkyl) and is selected in the sub-emitter independently mixtures thereof, preferably hydrogen, C ₁ -C ₆ alkyl, - _{^{CO 2 - M +, -SO 3}} - M +, -OSO 3 - M + or a mixture thereof, more preferably a hydrogen moiety of R ¹³ and R ¹⁴ are, different moieties C ₁ -C ₆ alkyl ego; M is a water soluble cation; X is chlorine, bromine, iodine or other water soluble anions; Examples of other water-soluble anions at this time include organic species such as fumarate, tartrate, oxalate and the like and inorganic species such as sulfate, hydrogen sulfide, phosphate and the like; p is 1 to about 10, preferably 1 to about 3;

n) essentially a general formula

Aryloxy and substituted aryloxy wherein R ¹³ and R ¹⁴ are hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ branched alkoxy, Halogen, morpholino, cyano, nitrilo, -CO ₂ ^- M ⁺ , -SO ₃ ^- M ⁺ , -OSO ₃ ^- M ⁺ , -N (R ¹⁵ ) ₂ and -N ⁺ (R ¹⁵ ) ₃ X ^- (wherein, R ¹⁵ are each hydrogen or C ₁ -C ₄ alkyl independently) and are independently selected from the group consisting of and mixtures thereof, preferably hydrogen, C ₁ -C ₆ alkyl, -CO ₂ ^{- _{M +, -SO 3 - M +}} , -OSO 3 - M + or a mixture thereof, more preferably a hydrogen moiety of R ¹³ and R ¹⁴ are, different moieties C ₁ -C ₆ alkyl; M is a water soluble cation; X is chlorine, bromine, iodine or other water soluble anions; At this time, examples of other water-soluble anions include organic species such as fumarate, tartrate and oxalate, and inorganic species such as sulfate, hydrogen sulfide, phosphate, and the like];

o) essentially a general formula

Alkyleneoxyaryl and substituted alkyleneoxyaryl units defined as residues having R ¹³ and R ¹⁴ wherein hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl, C ₁ -C ₆ alkoxy , C ₁ -C ₆ branched alkoxy, halogen, morpholino, cyano, nitrilo, -CO ₂ ^- M ⁺ , -SO ₃ ^- M ⁺ , -OSO ₃ ^- M ⁺ , -N (R ¹⁵ ) ₂ and _{^{-N + (R 15) 3 X}} - ( wherein, R ¹⁵ are each independently hydrogen or C ₁ -C ₄ alkyl), and are independently selected from the group consisting of and mixtures thereof, preferably hydrogen, C ₁ - C _{6 ^{alkyl, -CO 2 - M +, -SO}} 3 - M +, -OSO 3 - M ⁺ and or a mixture thereof, and more preferably it is a hydrogen moiety of R ¹³ and R ¹⁴ are, other moieties C ₁ -C ₆ alkyl; M is a water soluble cation; X is chlorine, bromine, iodine or other water soluble anions; Examples of other water-soluble anions include organic species such as fumarate, tartrate, oxalate, and the like, and inorganic species such as sulfate, hydrogen sulfide, phosphate, and the like; q is 0 to about 10, preferably about 1 to about 3;

p) essentially a general formula

Oxyalkylenearyl and substituted oxyalkylenearyl, wherein R ¹³ and R ¹⁴ are hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ branched alkoxy, halogen, morpholino, cyano, nitrilo, -CO ₂ ^- M ⁺ , -SO ₃ ^- M ⁺ , -OSO ₃ ^- M ⁺ , -N (R ¹⁵ ) ₂ and -N ⁺ (R ¹⁵⁾ ₃ X ^- (wherein, R ¹⁵ are each independently hydrogen or C ₁ -C ₄ alkyl), and are independently selected from the group consisting of and mixtures thereof, preferably hydrogen, C ₁ -C ₆ alkyl, - _{^{CO 2 - M +, -SO 3}} - M +, -OSO 3 - M + or a mixture thereof, more preferably a hydrogen moiety of R ¹³ and R ¹⁴ are, different moieties C ₁ -C ₆ alkyl ego; M is a water soluble cation; X is chlorine, bromine, iodine or other water soluble anions; Examples of other water-soluble anions at this time include organic species such as fumarate, tartrate, oxalate and the like and inorganic species such as sulfate, hydrogen sulfide, phosphate and the like; w is 1 to about 10, preferably about 1 to about 3;

q) C ₁ -C ₂₂ thioalkyl, C ₄ -C ₂₂ substituted thioalkyl and mixtures thereof;

r) ester units of the general formula —CO ₂ R ¹⁰ wherein R ¹⁰ is alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl which may be substituted by halogen ; Polyhydroxyl substituted C ₃ -C ₂₂ alkyl, C ₃ -C ₂₂ glycol; C ₁ -C ₂₂ alkoxy, C ₄ -C ₂₂ branched alkoxy; Aryl, substituted aryl, alkylenearyl, aryloxy, alkyleneoxyaryl, alkyleneoxyaryl; Preferably C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl and mixtures thereof;

s) essentially a general formula

Alkyleneamino units wherein R ¹¹ and R ¹² are each C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl, and R ¹⁶ is hydrogen, C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; A is nitrogen or oxygen as a hetero atom, preferably oxygen; The subscript v is 0 when no heteroatoms are present, 1 when heteroatoms are present, preferably v is 0; X is chloride, bromide, iodide or other water soluble anions; u is 0 to 22, preferably 3 to about 10; Examples of other water-soluble anions include organic species such as fumarate, tartrate, oxalate and the like and inorganic species such as sulfate, hydrogen sulfide, phosphate, and the like];

t) amino units of the formula -NR ¹¹ R ¹² , wherein R ¹¹ and R ¹² are C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ side chain alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ side chain Alkenyl and mixtures thereof);

u) alkylethyleneoxy units having essentially the general formula — (A) _v — (CH ₂ ) _y (OCH ₂ CH ₂ ) _x Z, wherein A is nitrogen or oxygen as the heteroatom, preferably oxygen; The subscript v is 0 when no hetero atoms are present and 1 when heteroatoms are present; Z is hydrogen, C ₁ -C ₆ alkoxy, aryl, substituted aryl, aryloxy, substituted aryloxy, alkyleneamino, -SO ₃ ^- M ⁺ , -OSO ₃ ^- M ⁺ , -CO ₂ H or their Mixtures, preferably hydrogen or C ₁ -C ₆ alkoxy, more preferably methoxy; x is 1 to 100, preferably 0 to about 20, more preferably 3 to about 10; y is 1 to 12, preferably about 1 to about 5;

v) siloxy and substituted siloxy of the general formula —OSiR ⁷ R ⁸ R ⁹ wherein R ⁷ , R ⁸ and R ⁹ are C ₁ -C ₈ alkyl, C ₄ -C ₈ branched alkyl, C ₁ -C ₈ alkenyl, C ₄ -C ₈ branched alkenyl, substituted alkyl, aryl, alkylethyleneoxy units of the formula-(A) _v- (CH ₂ ) _y (OCH ₂ CH ₂ ) _x Z, wherein Z is hydrogen, C ₁ -C ₃₀ alkyl, ^{_{hydroxyl, -CO 2 H, -SO 3 -}} M +, -OSO 3 - M +, C 1 -C 6 alkoxy, aryl, substituted aryl, aryloxy, substituted aryl Oxy, alkyleneamino and mixtures thereof; A unit comprises nitrogen or oxygen; M is a water soluble cation; v is 0 or 1; x is 0 to 100; y is 0 to 12), and Independently from the group consisting of mixtures thereof.

Preferred R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ units are C ₁ -C ₂₂ alkoxy, branched alkoxy or halogen having the following general formula, more preferred R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ units are methoxy, branched alkoxy or halogen:

Where

B is hydrogen, hydroxyl, C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, -CO ₂ H, -CH ₂ CO ₂ H, -SO ₃ ^- M ⁺ , -OSO ₃ ^- M ⁺ , -PO ₃ ^2- M, -OPO ₃ ^2- M, or a mixture thereof, preferably C ₁ -C _{18 ^{alkyl, -CO 2 H, -SO 3 -}} M +, -OSO 3 - M +, -PO 3 2- M, -OPO ₃ ^2- M;

M is a sufficient amount of water soluble cations to satisfy the charge balance;

x is 0 or 1;

y are each independently 0-6;

z is each independently 0 to 100, preferably 0 to about 10, more preferably 0 to about 3.

More preferred R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ units are methoxy, branched alkoxy and halogen.

When the (Sens.) Unit is phthalocyanine, the most preferred R ¹ , R ² , R ³ and R ⁴ units are methoxy and branched alkoxy. When the (Sens.) Unit is naphthalocyanine, the most preferred R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ units are chlorine, bromine or iodine.

Axial R Unit

Compounds useful in the present invention also include axial R units bonded directly to a central silicon atom, wherein R is independently selected from the group consisting of the following a) to v):

a) hydrogen;

b) halogen;

c) hydroxyl;

d) cyano;

e) nitrile;

f) oxymino;

g) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl;

h) halogen substituted C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl;

i) polyhydroxyl substituted C ₃ -C ₂₂ alkyl;

j) C ₁ -C ₂₂ alkoxy, preferably C ₁ -C ₄ alkoxy, more preferably methoxy;

k) general formula

Branched alkoxy having the [wherein, B is hydrogen, hydroxyl, C ₁ -C ₃₀ alkyl, C ₁ -C _{30 alkoxy, -CO 2 H, -CH 2 CO} 2 H, -SO 3 - M +, -OSO 3 ^{_{- M +, -PO 3 2- M}} , -OPO 3 -2 M or a mixture thereof; M is a sufficient amount of water soluble cations to satisfy the charge balance; x is 0 or 1; y are each independently 0-6; z are each independently 0 to 100, preferably 0 to about 10, more preferably 0 to about 3;

l) essentially a general formula

Aryl and substituted aryl wherein R ¹³ and R ¹⁴ are hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ branched alkoxy, halogen, morpholino, cyano, _{^{nitrile, -CO 2 - M +, -SO}} 3 - M +, -OSO 3 - M +, -N (R 15) 2 , and _{^{-N + (R 15) 3 X}} - ( wherein, R ¹⁵ are each independently hydrogen or C ₁ -C ₄ alkyl), and are independently selected from the group consisting of and mixtures thereof, preferably hydrogen, C ₁ -C ₆ alkyl, -CO ₂ ^- M ^{+, _{-SO 3 - M +, -OSO 3}} - M + or a mixture thereof, more preferably a hydrogen moiety of R ¹³ and R ¹⁴ are, different moieties C ₁ -C ₆ alkyl; M is a water soluble cation; X is chlorine, bromine, iodine or other water soluble anions; At this time, examples of other water-soluble anions include organic species such as fumarate, tartrate and oxalate, and inorganic species such as sulfate, hydrogen sulfide, phosphate, and the like];

m) essentially a general formula

Alkylenearyl and substituted alkylenearyl, wherein R ¹³ and R ¹⁴ are hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ side chain Alkoxy, halogen, morpholino, cyano, nitrilo, -CO ₂ ^- M ⁺ , -SO ₃ ^- M ⁺ , -OSO ₃ ^- M ⁺ , -N (R ¹⁵ ) ₂ and -N ⁺ (R ¹⁵ ) ₃ X ^- (wherein, R ¹⁵ are each independently hydrogen or C ₁ -C ₄ alkyl) and is selected in the sub-emitter independently mixtures thereof, preferably hydrogen, C ₁ -C ₆ alkyl, - _{^{CO 2 - M +, -SO 3}} - M +, -OSO 3 - M + or a mixture thereof, more preferably a hydrogen moiety of R ¹³ and R ¹⁴ are, different moieties C ₁ -C ₆ alkyl ego; M is a water soluble cation; X is chlorine, bromine, iodine or other water soluble anions; Examples of other water-soluble anions at this time include organic species such as fumarate, tartrate, oxalate and the like and inorganic species such as sulfate, hydrogen sulfide, phosphate and the like; p is 1 to about 10, preferably 1 to about 3;

n) essentially a general formula

Aryloxy and substituted aryloxy wherein R ¹³ and R ¹⁴ are hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ branched alkoxy, Halogen, morpholino, cyano, nitrilo, -CO ₂ ^- M ⁺ , -SO ₃ ^- M ⁺ , -OSO ₃ ^- M ⁺ , -N (R ¹⁵ ) ₂ and -N ⁺ (R ¹⁵ ) ₃ X ^- (wherein, R ¹⁵ are each hydrogen or C ₁ -C ₄ alkyl independently) and are independently selected from the group consisting of and mixtures thereof, preferably hydrogen, C ₁ -C ₆ alkyl, -CO ₂ ^{- _{M +, -SO 3 - M +}} , -OSO 3 - M + or a mixture thereof, more preferably a hydrogen moiety of R ¹³ and R ¹⁴ are, different moieties C ₁ -C ₆ alkyl; M is a water soluble cation; X is chlorine, bromine, iodine or other water soluble anions; At this time, examples of other water-soluble anions include organic species such as fumarate, tartrate and oxalate, and inorganic species such as sulfate, hydrogen sulfide, phosphate, and the like];

o) essentially a general formula

Alkyleneoxyaryl and substituted alkyleneoxyaryl units defined as residues having R ¹³ and R ¹⁴ wherein hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl, C ₁ -C ₆ alkoxy , C ₁ -C ₆ branched alkoxy, halogen, morpholino, cyano, nitrilo, -CO ₂ ^- M ⁺ , -SO ₃ ^- M ⁺ , -OSO ₃ ^- M ⁺ , -N (R ¹⁵ ) ₂ and _{^{-N + (R 15) 3 X}} - ( wherein, R ¹⁵ are each independently hydrogen or C ₁ -C ₄ alkyl), and are independently selected from the group consisting of and mixtures thereof, preferably hydrogen, C ₁ - C _{6 ^{alkyl, -CO 2 - M +, -SO}} 3 - M +, -OSO 3 - M + or a mixture thereof, more preferably a hydrogen moiety of R ¹³ and R ¹⁴ are, the other moiety is C ₁ -C ₆ alkyl; M is a water soluble cation; X is chlorine, bromine, iodine or other water soluble anions; Examples of other water-soluble anions include organic species such as fumarate, tartrate, oxalate, and the like, and inorganic species such as sulfate, hydrogen sulfide, phosphate, and the like; q is 0 to about 10, preferably about 1 to about 3;

p) essentially a general formula

Oxyalkylenearyl and substituted oxyalkylenearyl, wherein R ¹³ and R ¹⁴ are hydrogen, C ₁ -C ₆ alkyl, C ₁ -C ₆ alkenyl, C ₁ -C ₆ alkoxy, C ₁ -C ₆ branched alkoxy, halogen, morpholino, cyano, nitrilo, -CO ₂ ^- M ⁺ , -SO ₃ ^- M ⁺ , -OSO ₃ ^- M ⁺ , -N (R ¹⁵ ) ₂ and -N ⁺ (R ¹⁵⁾ ₃ X ^- (wherein, R ¹⁵ are each independently hydrogen or C ₁ -C ₄ alkyl), and are independently selected from the group consisting of and mixtures thereof, preferably hydrogen, C ₁ -C ₆ alkyl, - _{^{CO 2 - M +, -SO 3}} - M +, -OSO 3 - M + or a mixture thereof, more preferably a hydrogen moiety of R ¹³ and R ¹⁴ are, different moieties C ₁ -C ₆ alkyl ego; M is a water soluble cation; X is chlorine, bromine, iodine or other water soluble anions; Examples of other water-soluble anions at this time include organic species such as fumarate, tartrate, oxalate and the like and inorganic species such as sulfate, hydrogen sulfide, phosphate and the like; w is 1 to about 10, preferably about 1 to about 3;

q) C ₁ -C ₂₂ thioalkyl, C ₄ -C ₂₂ substituted thioalkyl and mixtures thereof;

r) essentially a general formula

Alkyleneamino units wherein R ¹¹ and R ¹² are each C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl, and R ¹⁶ is hydrogen, C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; A is nitrogen or oxygen as a hetero atom, preferably oxygen; The subscript v is 0 when no heteroatoms are present, 1 when heteroatoms are present, preferably v is 0; X is chloride, bromide, iodide or other water soluble anions; u is 0 to 22, preferably 3 to about 10; Examples of other water-soluble anions include organic species such as fumarate, tartrate, oxalate and the like and inorganic species such as sulfate, hydrogen sulfide, phosphate, and the like];

s) amino units of the formula -NR ¹¹ R ¹² , wherein R ¹¹ and R ¹² are C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ side chain alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ side chain Alkenyl and mixtures thereof);

t) alkylethyleneoxy units having essentially the formula-(A) _v- (CH ₂ ) _y (OCH ₂ CH ₂ ) _x Z, wherein A is nitrogen or oxygen as the heteroatom, preferably oxygen; The subscript v is 0 when no heteroatoms are present and 1 when heteroatoms are present; Z is hydrogen, C ₁ -C ₆ alkoxy, aryl, substituted aryl, aryloxy, substituted aryloxy, alkylene amino, -SO ₃ ^- M ⁺ , -OSO ₃ ^- M ⁺ , -CO ₂ H or their Mixtures, preferably hydrogen or C ₁ -C ₆ alkoxy, more preferably methoxy; x is 1 to 100, preferably 0 to about 20, more preferably 3 to about 10; y is 1 to 12, preferably about 1 to about 5;

u) general formula Units of carboxylates wherein R ¹⁰ is C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl which may be halogen substituted; Polyhydroxyl substituted C ₃ -C ₂₂ alkyl; C ₃ -C ₂₂ glycol; C ₁ -C ₂₂ alkoxy; C ₄ -C ₂₂ branched alkoxy; Substituted aryl and unsubstituted aryl, substituted alkylenearyl and unsubstituted alkylenearyl, substituted aryloxy and unsubstituted aryloxy, substituted alkyleneoxyaryl and unsubstituted alkyleneoxyaryl; Preferably, C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, or mixtures thereof;

v) siloxy and substituted siloxy of the general formula —OSiR ⁷ R ⁸ R ⁹ wherein R ⁷ , R ⁸ and R ⁹ are C ₁ -C ₈ alkyl, C ₄ -C ₈ branched alkyl, C ₁ -C ₈ alkenyl, C ₄ -C ₈ branched alkenyl, substituted alkyl, aryl, alkylethyleneoxy units of the formula-(A) _v- (CH ₂ ) _y (OCH ₂ CH ₂ ) _x Z, wherein Z is hydrogen, C ₁ -C ₃₀ alkyl, ^{_{hydroxyl, -CO 2 H, -SO 3 -}} M +, -OSO 3 - M +, C 1 -C 6 alkoxy, aryl, substituted aryl, aryloxy, substituted aryl Oxy, alkyleneamino and mixtures thereof; A unit comprises nitrogen or oxygen; M is a water soluble cation; v is 0 or 1; x is 0 to 100; y is 0 to 12) and these Independently from the group consisting of a mixture of;

Preferred R units are polyhydroxy substituted C ₃ -C ₂₂ alkylene moieties which are essentially polyglycols of the general formula-(CHOH) _n CH ₂ OH where n is 2 to 21, and the preferred polyhydroxyl substitution Alkylene is essentially a polyhydroxy glycol of the general formula wherein the stereochemical structure of these polyhydroxyl residues corresponds to the object of the present invention:

Most preferred axial R units are branched alkoxys having the general formula:

Where

B is hydrogen, hydroxyl, C ₁ -C ₃₀ alkyl, C ₁ -C ₃₀ alkoxy, -CO ₂ H, -CH ₂ CO ₂ H, -SO ₃ ^- M ⁺ , -OSO ₃ ^- M ⁺ , -PO ₃ ^2- M, -OPO ₃ ^2- M or mixtures thereof;

M is a sufficient amount of water soluble cations to satisfy the charge balance;

x is 0 or 1;

y are each independently 0-6;

z is each independently 0 to 100, preferably 0 to about 10, more preferably 0 to about 3.

One or more substituents R, as in the case of phthalocyanines,^One, R², R³And R⁴With units or as in the case of naphthalocyanine^One, R², R³, R⁴, R⁵And R⁶In the case of units, the exact arrangement of the substituents may not be known exactly. However, in the compounds of the present invention, certain equivalent substitutions exist. For example the same R^OneThe two units of the following general formula containing substituents are the same in the present invention and choosing either of the two structures will not affect the desired properties of the molecules disclosed herein:

In addition, a compound containing a substituent represented by the following general formula containing the same R ¹ and R ² unit substituents is also the same in the present invention, and even if any of the two structures is selected, the properties of the molecules disclosed herein will be affected. Will not extend:

However, the above example is only representative of all the examples recognized by the person skilled in the art as the same structure.

One or more R as in the case of phthalocyanine^One, R², R³And R⁴R as in units substituted or as in the case of naphthalocyanine^One, R², R³, R⁴, R⁵And R⁶Compounds useful in the present invention wherein the units are substituted and the substituents are oriented essentially in the manner disclosed by the following general formula are not the same for the purposes of the present invention and R^OneAnd R²Regardless of whether the units are identical, we will construct separate compounds:

The above example is R recognized by those skilled in the art.^One, R², R³, R⁴, R⁵And R⁶Any combination of units is not used to exclude as many non-equivalent structures as possible.

Soluble axial R units are directly bonded to the central silicon atom, which is Si ⁴⁺ atom in the present invention and occupy an axial position with respect to planar (Sens.) Units. The utility of each R unit is primarily for the solubility of the compounds of the invention, and each R unit can be selected independently of one another. The R units can be selected by the 'direct' or 'non-direct' nature of the compound in addition to or instead of solubility requirements. R units are essentially nonionic, cationic or anionic units.

The following is the R of each aromatic residue^One, R², R³And R⁴One or more of the units Methoxy, and each R group is a general formula-(OCH₂CH₂)_xPreferred 'direct' of the invention comprising an phthalocyanine ring system in which the residue has an average ethoxy value of 7.2, including an ethyleneoxy unit of Z, where for each R unit Z is methoxy and x is 7.2 Examples of embodiments (having affinity for surfaces such as fabrics) are:

The following is the R of each aromatic residue^One, R², R³And R⁴More than one unit Methoxy, and each R group is a general formula-(OCH₂CH₂)_xMore preferred 'direct' of the present invention comprising a phthalocyanine ring system in which the residue has an average ethoxy value of 7.2, including an ethyleneoxy unit of Z (where Z is methoxy and x is 7.2 for each R unit). Affinity for surfaces such as fabrics)

The following is the R of each aromatic residue^One, R², R³, R⁴, R⁵And R⁶More than one unit Chlorine, and one R group is -OSiR⁷R⁸R⁹[Where R⁷And R⁸Unit is methyl and R⁹Is essentially a general formula-(CH₂)_yZ where Z is -SO₃ ^-M⁺And M is sodium and y is 6), and the "non-direct" (R with charge) of the present invention includes a naphthalocyanine ring system in which the second axial R unit is methoxy. Units reduce affinity for surfaces such as fabrics)

The following is the R of each aromatic residue^One, R², R³, R⁴, R⁵And R⁶One or more of the units Bromine and R is a general formula -OSiR⁷R⁸R⁹[Where R⁷And R⁸Unit is methyl and R⁹Is essentially a general formula-(CH₂)_yZ where Z is -SO₃ ^-M⁺And M is sodium and y is 6]. Decreases)

The compounds of the present invention can be modified to have a wide range of surface affinity. Molecules can be prepared 'directly' or 'directly' by selection of axial R units. The term 'directness' is defined herein as a property that allows the photobleach to successfully contact a particular object surface. For example, the axial R group, as defined herein below, may be selected such that the photobleach compound and durable surface, such as synthetic fabrics, ceramic tiles, or any fabric, article of manufacture, or location generally targeted for photobleaching, are compatible. .

For example, the R unit is consistent with the structural properties of either the material of interest (ie fabric) or the substrate of interest (ie contaminants). The option for tailoring the properties of the R units to materials such as the disposable paper product produced is due to the independent influence of the phthalocyanine or naphthalocyanine rings, thereby allowing selection of R units that do not affect the photophysical properties.

Another advantage of the photobleaching systems of the present invention is that they generally have higher fabric and color safety than conventional bleach (ie hypochlorite). While not wishing to be bound by theory, it is believed that the improved fabric safety and color safety is due to the quenching of singlet oxygen by the dye material used to make the colored product.

'Non-direct' molecules are preferred for applications where the photosensitive compound must remain in the liquid rather than attracted to a particular surface, ie used as a steeping agent. Without wishing to be limiting by way of example, by substituting a charge-bearing moiety in the R unit, the compound repels any surface having a similar charge.

As used herein and throughout the specification, the term 'low tint' refers to a photobleach that has a λ _max of Q-band of about 700 nm or greater and thus is perceived to be barely visible to the human eye. The term 'low color tone' photodisinfectant in the context of the present invention means a substance that is not recognized by most people even when present in concentrations greater than the operable range disclosed herein. This additional material of the present invention having a Q-band maximum wavelength in the 'visible' region (ie 660-700 nm) is the most suitable photo-disinfecting material if the recognition of the colored material is not a factor reducing the usefulness. 'Tint' is also relative to the surface and generally appears colorless in other uses (most notably when used as glass cleaners), which may have more of a unique color, eg slightly colored on white cotton fabrics. It seems to be a substance.

The term 'low color tone', as used herein and further defined below, is to be noted and, when compared to other conventional materials or standard surfaces, is visible when the organosilicon compounds of the present invention are used in solids with a white background. It means to be recognized. Compounds eliciting measurable 'hue' or 'cognition color' in standard optical measurements or 'white background' testing will not be recognized in most untrained eyes. However, some 'low color tone' organosilicon photosensitive compounds of the present invention will appear more visible than other embodiments depending on the type of surface used. Those skilled in the art of color perception will recognize that even colorless surfaces are 'hue' due to light scattering and other surface influences rather than due to inherent color. In addition, the amount or color recognized by the user of the compound of the present invention may be varied by the wavelength range of the light present or auxiliary components such as fluorescent bleaches, dyes, colorants.

While not wishing to be bound by theory, the mechanism by which photobleaching is performed is a process controlled by dispersion, and therefore the compounds of the present invention are well suited to produce high efficiency singlet oxygen by their unique structural properties. Effective photobleaching is anticipated by the production of singlet molecular oxygen and this theory is widely studied and well known to those skilled in the photobleaching arts. Since singlet oxygen species have a short lifespan and their photo-energy transfer is controlled by dispersion, that is, since singlet oxygen reacts rapidly with receptor molecules in the surrounding molecular environment, bacteria or similar objects that are 'attacked' It is most advantageous to have photosensitive molecules adjacent to the position of.

With the manufacturer's ability to obtain a convincing 'directness', the molecules of the invention can be directed to any desired surface. The additional ability to prevent the stacking or accumulation of photosensitive molecules due to the axial nature of the R units provides an efficient monolayer to be deposited at 'sites of action'. For example, an aspect of the present invention for removing contaminants from fabrics is that the organosilicon photosensitive compound will have affinity for the fabric surface (direct to the surface), and the photobleach compound will have the desired action for 'high molecular efficiency'. It is required to be located close to the site (obtained by one or more R unit manipulations). These presented requirements for depositing the 'monolayer' of the optical bleach would be clearly advantageous, requiring that the Q-band be at least 700 nm to prevent visual sensing of the optical bleach.

The invention also relates to a process for carrying out a photosensitive reaction or a reaction catalyzed by singlet oxygen, wherein at least one phthalocyanine or naphthalocyanine compound is introduced or brought into contact with the medium in which the reaction is carried out in the presence of oxygen. It mixes in and irradiates light.

Without wishing to be bound by theory, the photobleach of the present invention is more 'adjustable' in terms of efficiency of photophysics. Since the axial R residue has already been selected in view of solubility, there is no limit to the manufacturer's choice of substituents on the phthalocyanine or naphthalocyanine ring system, thus allowing full focus on optimizing the photophysical properties of the compound.

Certain large conjugated adducts such as phthalocyanine and naphthalocyanine rings can absorb light protons to form electrically excited species (single and triplet) and these species can be quenched by oxygen to produce 'excited oxygen species' Is well known. Particularly preferred 'excited oxygen species' are singlet oxygen which can be most easily formed by quenching the triplet state of a photosensitizer such as phthalocyanine by molecular oxygen. It is therefore the goal of photobleach manufacturers to produce compounds that prefer to form triplet states.

When irradiating light to the photosensitizer, the resulting singlet energy state undergoes various processes, namely re-emission (fluorescence) of light. The most important process for photobleaching with singlet oxygen is interstitial crossover (ISC). This is the mechanism by which singlet steps are converted to triplet steps in the molecule. In general, the efficiency of these processes is discussed in terms of quantum yield, i.e. the number of absorbed photons leading to the desired triplet excited state. The present invention increases photobleaching by varying the efficiency of the intersecting system from the singlet state to the triplet state. The molecules of the present invention can be modified by manufacturers to increase the quantum efficiency at which triplet states are formed. Surprisingly, manufacturers can further contribute to manipulating substituents in accordance with the present invention such that certain substituents have a 'heavy atom effect' which is a term familiar to those skilled in the art. Residues for the 'heavy atom effect' can be selected independently without excessive concern for other factors, such as solubility factors. This is because the selection of the axial R group for solubility is independent of the changes formed in the phthalocyanine or naphthalocyanine ring system.

As will be understood by those skilled in the art, the Q-band is a low energy absorption band associated with which electrons are excited in the first singlet step. For example, for the phthalocyanine and naphthalocyanine of the present invention, the wavelength associated with this absorption is typically between 600 and 800 nm. This range includes wavelengths in both the visible and near infrared spectra. For compounds of the invention, absorption bands weaker than Q-bands can be found at shorter wavelengths, including the UV and visible spectrum. This second absorption band is known as the B-band. Unlike the Q-band, the B-band indicates that the electron is excited to its second singlet state. The present invention relates to stronger Q-band absorption associated with strong colors such as phthalocyanine, naphthalocyanine and the like.

Determination of the Q-band wavelength value and variation at this wavelength occurs when certain residues (in units of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ ) replace hydrogen atoms of the phthalocyanine or naphthalocyanine cyclic Deciding whether to do it is simple. A solution of phthalocyanine or naphthalocyanine to be measured, typically having a concentration of about 1 × 10 ⁻⁶ M, is prepared using a suitable solvent (eg dimethylformamide) containing 1% by weight Triton X-100. Then obtain the UV / Visible spectrum and record the Q-band λ _max . This value is the substrate λ _s-max . The spectrum for the material before introducing the substituents is obtained in the same way. This value is the reference λ _r-max . The two spectra are compared and the measured results are introduced in Equation 1 below:

Here, if the number obtained is at least 1, the substituents produce at least 1 nm of positive red transitions and are suitable materials for use in embodiments of the present invention. Those skilled in the photochemistry field have a very small number of terms Δλ _max , and in the present invention, the Q-band of the modified photobleach is measured in nm and compared to the unmodified photobleach, Q of the modified photobleach. The band will recognize that the wavelength is increased by more than 1 nm. Other suitable solvents can be used if the material of interest is not soluble in dimethylformamide. Aggregation of phthalocyanine or naphthalocyanine compounds leading to false values for the Q-band wavelength can be avoided by the addition of Triton X-100.

Quantum yields and excitation state energies are well known to those skilled in the art and methods for measuring triplet quantum yields and similar photophysical parameters are all fully disclosed in the following references, which are incorporated herein by reference.

Bonnet, R, McGarvey, D.J., Harriman, A, Land, E.J., Truscott, T.G., Winfield, U. Photochem. Photobiol. 1988, 48 (3), p 271-6; Davidla, J., Harry Mann, Gulliya, K.S., J. Photochem. Photobiol. 1991, 53 (1), p 1-11; Davila, Harry Mann, J. Photochem. Photobiol. 1989, 50 (1), p 29-35; Charlesworth, P., Trusscourt, Brooks, R.C., Wilson, B.C., J. Photochem. Photobiol. part B, 1994, 26 (3), p 277-82; Zhang, X., Xu, H., J. Chem. Soc., Faraday Trans., 1993, 89 (18), p 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, p520-9; Phillips, D., Pure Appl. Chem., 1995, 67 (1), p 117-26; Wilkinson, F., Hellman, W.P., Ross, A.B., J. Phys. Chem. Ref. Data, 1993, 22 (1), p113-262; Lever, A.P.B., Licoccia, S., Magnell, K., Minor, P.C., Ramaswamy, B.S., Adv. Chem. Ser. 1982, 201, p237-52; West, M.A., Creat. Detect. Excited State, 1976, 4, p 217-307; Ford, W.E., Rihter, B.D., Kenney, M.E., Rogers, M.A., J. Photochem. Photobiol., 1989, 50 (3), p277-282; Firey, P.A., Ford, W.E., Sounik, J.R., Kenney, Rogers et al. Am. Chem. Soc., 1988, 110, p7626-7630; Piray, Rogers, J. Photochem. Photobiol., 1987, 45 (4), p535-8].

For the purposes of the present invention, the delta triplet yield is determined according to the following equation:

Wherein the value for the Φ _{triplet -based} —Φ _{triplet-reference} can be obtained by any of the methods disclosed herein by reference. When the ΔΦ _triplet value is at least 1, the substitution for the hydrogen atom in the (Sens.) Unit of the photosensitizer is suitable for use in the embodiments of the present invention.

In addition, modifications to 'hue', which are intrinsic colors or lack of color, can be manipulated without considering the properties possessed by the selection of the axial R groups.

In particular, the present invention relates to a process for removing stains from bleaching or textiles, removing contaminants on organic or inorganic substrates, and protecting the substrate against the attack of microorganisms, wherein the textile or substrate must be removed or protected against the microorganisms. Is treated with phthalocyanine or naphthalocyanine of the present invention in the presence of water, during which it is irradiated with light.

Another advantage of the present invention is that each R unit can have individual desirable properties, so that the molecules of the present invention can be considered 'sided'. For example, one axial R unit may be chosen to increase solubility and another axial R group to increase directivity for a given surface.

The ability to provide 'direct' to the molecules of the present invention is consistent with the manufacturer's purpose and ability to provide 'non-direct' to one example of the photodisinfectant of the present invention. The use of the direct embodiment of the present invention may be used when using the method of the present invention for the purpose of cleaning or disinfecting the toilet bowl using the photosensitizer of the present invention. Direct materials have more effect than non-direct materials that remain bound evenly in solution by binding or sticking to the sides of the toilet.

Irradiation may be performed using an artificial light source or sunlight. Good effects are obtained, for example, using light in the range between about 300 and 2500 nm, preferably between 600 and about 1500 nm. Thus, for example, it can be irradiated using a commercially available incandescent lamp. The intensity of the illumination can vary widely, depending on both the concentration of the active substrate and the nature of the light source relative to the photobleaching efficiency of any particular compound of the invention. Another variable that can be varied is the exposure time, i.e., to achieve the same effect, exposure at lower light intensities must be longer than at higher intensities. In general, depending on the field of use, exposure times of several minutes to several hours are possible.

If the process is carried out in an aqueous medium (for example, sterilization of textiles), light irradiation can be carried out directly in the treatment medium or subsequently wetted with the product using an artificial light source mounted inside or outside the medium. It may be performed by using an artificial light source or by exposure to sunlight. Excellent antimicrobial effects can be obtained even with very low concentrations, for example 0.001 ppm of active substance. Depending on the field of use and the phthalocyanine or naphthalocyanine derivative used, a concentration of 0.005 to 2000 ppm, preferably 0.01 to 1000 ppm is preferred.

The process of the invention can also be carried out in solvent-based carriers or low aqueous solutions. For the purposes of the present invention, the term low water content means that water is added to the carrier system to stabilize the substrate as well as to modify the properties of the carrier. For example, a solvent that can fix dissolved oxygen and form a system that can be mixed with water is preferred. Non-limiting examples of these solvents are butoxy propoxy propanol (BPP), which is approximately equal amounts of methoxy propoxy propanol (MPP), ethoxy propoxy propanol (EPP) and propoxy propoxy propanol (PPP). It is marketed in commercial quantities as a mixture of isomers. Embodiments of the present invention, including these atypical aqueous compositions, are most useful where a photobleach must be applied to a nonwoven fabric or surface containing reagents that repel water and moisture.

Sterilization of synthetic or natural raw textiles may be mentioned as an important use. Thus, the material to be washed at home or in the factory can be sterilized using the method of the present invention. The material to be washed can be treated for this purpose by the above-mentioned method with an aqueous solution of the phthalocyanine or naphthalocyanine of the present invention while being irradiated with light. Phthalocyanine and naphthalocyanine may advantageously be present in the treatment medium at a concentration of 0.01 to about 2000 mg, preferably 0.1 to 1000 mg, more preferably 1 to 500 mg per liter. Sterilization can advantageously be carried out in conjunction with the washing process. For this purpose, the material to be washed is treated with a washing medium which contains a conventional detergent material, at least one phthalocyanine or naphthalocyanine according to the invention, and optionally other auxiliary substances with inorganic salts and / or antibacterial properties. The washing process may for example be handwashed in a laundry tub or carried out in a washing machine. The necessary light exposure is carried out during the washing process using a suitable light source, or the moist material to be washed is also subsequently exposed to a suitable artificial light source, for example during drying, or simply exposed to sunlight during drying on a clothesline, for example. May be performed exposed.

Surface bleaching can be obtained, for example, by applying (eg spraying) an aqueous solution of a phthalocyanine or naphthalocyanine compound according to the invention to a suitable surface, which solution is preferably from about 0.001 to about 10% by weight of active substance It includes. The solution may also include other conventional additives such as wetting agents, dispersing agents or emulsifiers, detergent materials and optionally inorganic salts. After application of the solution, the surface may simply be exposed to sunlight or, if necessary, irradiated with an artificial light source, such as an incandescent lamp. It is desirable to maintain surface moisture during exposure to light.

The laundry compositions of the invention optionally include, for example, washable surfactants of anionic, cationic, nonionic, amphoteric and dipolar ions, but manufacturers should not be limited to these examples or combinations thereof. The surfactant is present at about 0 to about 95 weight percent of the composition, preferably about 5 to about 30 weight percent.

The cleaning compositions of the invention optionally include, for example, washable surfactants of anionic, cationic, nonionic, amphoteric and dipolar ions, but manufacturers should not be limited to these examples or combinations thereof. The surfactant is present at about 0% to about 50%, preferably about 5% to about 30% by weight of the composition.

The laundry compositions of the present invention optionally include builders such as silicates, carbonates and zeolites, but the user should not be limited to these examples or combinations thereof. The enhancer is present from about 0 to about 50 weight percent of the composition, preferably from about 5 to about 30 weight percent.

The cleaning compositions of the present invention optionally include enhancers such as silicates, carbonates and zeolites, but the user should not be limited to these examples or combinations thereof. The enhancer is present from about 0 to about 50 weight percent of the composition, preferably from about 5 to about 30 weight percent.

Hard surface cleaners of the present invention optionally include enhancers such as silicates, carbonates and zeolites, but the user should not be limited to these examples or combinations thereof. The enhancer is present from about 0 to about 50 weight percent of the composition, preferably from about 5 to about 30 weight percent.

The hard surface cleaner of the present invention optionally contains about 0.5 to about 85 weight percent of the composition, preferably about 10 to about 85 weight percent of the abrasive. Suitable abrasives are silicates, carbonates, pearlites, clays and ground ceramic clays, but the user should not be limited to these examples or combinations thereof.

The invention also relates to a process for carrying out a photosensitive reaction or a reaction catalyzed by singlet oxygen, wherein at least one phthalocyanine or naphthalocyanine compound in the presence of oxygen is brought into contact with or incorporated into the medium in which the reaction is carried out. Then light is irradiated.

If the method is carried out in an aqueous medium (eg sterilization of the fabric), light irradiation is subsequently carried out directly in the treatment medium or in a wet state using an artificial light source mounted inside or outside the medium. Again using an artificial light source or by exposure to sunlight. Excellent antibacterial effects can be obtained even with very low concentrations, for example 0.001 ppm of active substance. Depending on the field of use and the phthalocyanine or naphthalocyanine derivative used, a concentration of 0.005 to 100 ppm, preferably 0.01 to 50 ppm is preferred.

Materials which increase the activity can also be added to the process according to the invention, which in particular are electrolytes, for example inorganic salts such as sodium chloride, potassium chloride, sodium sulfate, potassium sulfate, sodium acetate, ammonium acetate, alkali metal phosphates and Alkali metal tripolyphosphates, especially sodium chloride and sodium sulfate. These salts are added to the reagents according to the invention, or directly in the application process so that they are present in the application solution at a concentration of preferably 0.1 to 10% by weight.

The term aqueous solution means a solution that is essentially water, but manufacturers may include surfactants and auxiliary materials to help remove 'treated' microorganisms during rinsing or subsequent cleaning. The presence of aqueous solutions facilitates the production of singlet oxygen because of the higher concentration of oxygen in water than in air.

Surfactants

The cleaning composition contains about 0.1 to about 60 weight percent of the surfactant selected from the group consisting of anionic, nonionic, amphoteric and bipolar ionic surfactants. In the case of liquids, the surfactant is preferably present in an amount from about 0.1 to 20% by weight of the composition. In the case of solids (ie granules) and viscous semisolids (ie gelatinous, pastes, etc.), the surfactant is preferably present in an amount of about 1.5 to 30% by weight of the weight of the composition.

Non-limiting examples of surfactants present from about 1 to about 55 weight percent, as used herein, typically include conventional C ₁₁ -C ₁₈ alkyl benzene sulfonates ('LAS') and primary side chains and random C ₁₀ -C ₂₀ alkyl sulfates ( 'AS'), the general formula _{CH 2 (CH 2) x (} CHOSO 3 - M +) CH 3 and _{CH 3 (CH 2) y (} CHOSO 3 - M +) CH 2 CH 3 ( where, x and (y + 1) is an integer of at least about 7, preferably at least about 9, M is a water-soluble cation, in particular sodium) unsaturated such as C ₁₀ -C ₁₈ secondary (2,3) alkyl sulfates, oleyl sulfates Sulfate, C ₁₀ -C ₁₈ alkyl alkoxy sulfate ('AE _x S'; in particular EO 1-7 ethoxy sulfate), C ₁₀ -C ₁₈ alkyl alkoxy carboxylate (particularly EO 1-5 ethoxycarboxylate), C ₁₀ -C ₁₈ glycerol ethers, C ₁₀ -C ₁₈ alkyl polyglycosides and their corresponding sulfated polyglycosides, and C ₁₂ -C ₁₈ alpha-sulfonated fatty acid esters. If desired, C ₁₂ -C ₁₈ alkyl ethoxylates ('AE') and C ₆ -C ₁₂ alkyl phenol alkoxylates, including so-called narrow peak alkyl ethoxylates (especially ethoxylates and mixed ethoxy / Conventional nonionic and amphoteric surfactants such as propoxy), C ₁₂ -C ₁₈ betaines and sulfobetaines ('sultaines), C ₁₀ -C ₁₈ amine oxides and the like can also be included in the overall composition. C ₁₀ -C ₁₈ N-alkyl polyhydroxy fatty acid amides may also be used. Typical examples include C ₁₂ -C ₁₈ N-methylglucamide. See WO 9,206,154. Other sugar-derived surfactants include N-alkoxy polyhydroxy fatty acid amides such as C ₁₀ -C ₁₈ N- (3-methoxypropyl) glucamide. N-propyl to N-hexyl C ₁₂ -C ₁₈ glucamide can be used to generate less foam. C ₁₀ -C ₂₀ conventional soaps can also be used. To generate a lot of foam, branched C ₁₀ -C ₁₆ soaps can be used. Mixtures of anionic and nonionic surfactants are particularly useful. Other conventional useful surfactants are also disclosed herein and listed in the standard literature.

Anionic surfactants can be broadly disclosed as water-soluble salts, especially alkali metal salts of organic sulfur reaction products having alkyl radicals of about 8 to about 22 carbon atoms and radicals selected from the group consisting of sulfonic acid and sulfuric acid ester radicals in their molecular structure. (The alkyl portion of the higher acyl radicals is included in the term alkyl.) An important example of an anionic synthetic detergent capable of forming the surfactant component of the composition of the present invention is sodium or potassium alkyl sulfates, especially glycerol of resins or coconut oil. Those obtained by sulphating the higher alcohols (C ₈ -C ₁₈ carbon atoms) produced by reducing the ride; Sodium or potassium alkyl benzene sulfonates having alkyl groups of about 9 to about 15 carbon atoms (alkyl radicals are straight or branched chain aliphatic); Sodium alkyl glyceryl ether sulfonates, especially ethers of higher alcohols derived from resins and coconut oil; Sodium coconut oil fatty acid monoglyceride sulfate and sulfonate; Sodium or potassium salts of sulfuric acid esters of the reaction product of one mole of higher fatty alcohols (eg resin or coconut alcohol) with about 1 to about 10 moles of ethylene oxide; Sodium or potassium salts of alkyl phenol ethylene oxide ether sulfates having about 1 to about 10 units of ethylene oxide per molecule and having 8 to 12 carbon atoms in the alkyl radical; Fatty acids derived from the sodium or potassium salts of fatty acid amides of methyl taude (fatty acids are derived from, for example, coconut oil) and sodium or potassium beta acetoxy- or beta-acetamido-alks having alkanes of 8 to 22 carbon atoms. Reaction product of sulfonate.

In addition, secondary alkyl sulfates may be used by the manufacturer alone or in combination with other surfactant materials, the following identifying and explaining the differences between sulfated surfactants and other conventional alkyl sulfate surfactants. Non-limiting examples of such components are as follows.

As described above, conventional primary alkyl sulfates (LAS) are of the general formula ROSO ₃ ^- M ⁺ , where R is generally a linear C ₈ -C ₂₂ hydrocarbyl group and M is a water soluble cation such as sodium LAS. Has Side chain primary alkyl sulfate surfactants having 8 to 20 carbon atoms (eg side chain 'PAS') are known (European Patent Application 439,316 to Smith et al., Filed Jan. 21, 1991).

Typical secondary alkyl sulfate surfactants are substances with sulfate residues randomly distributed along the hydrocarbyl 'backbone' of the molecule. These substances

_{CH 3 (CH 2) n (} CHOSO 3 - M +) (CH 2) m CH 3 ( wherein the total of m and n is an integer of 2 or more and m and n typically ranges from about 9 to 17, M is a water soluble cationic It is explained by the structure.

The aforementioned second alkyl sulfates are prepared by adding H ₂ SO ₄ to the olefins. General synthesis using α-olefins and sulfuric acid is described in US Pat. No. 3,234,258 to Morris on Feb. 8, 1966 or US Pat. No. 5,075,041 to Lutz on Dec. 24, 1991 Is disclosed. Synthesis is carried out in a solvent which can yield secondary (2,3) alkyl sulfates on cooling which product is purified which is purified to unreacted material, randomly sulfated material, unsulfated by-products ( Example: C10 or higher alcohols, secondary olefin sulfonates, etc.) are usually removed, resulting in a mixture of 2- and 3- sulphated materials (some sodium sulfate may be present) that is at least 90% pure, which is white, non-tacky It is a solid which is crystalline in appearance. Some 2,3-disulfate may also be present, but generally comprises no more than 5% of a mixture of secondary (2,3) alkyl mono sulfates. This material is commercially available under the name 'DAN' (eg DAN 200) from Shell Oil Company.

Bleach and bleach activator

The detergent compositions herein may optionally contain bleach, or bleach compositions containing bleach and one or more bleach activators. If present, the bleach will generally be from about 1% to about 30%, more generally from about 5% to about 20% of the detergent composition, especially for fabric washing. If present, the amount of bleach activator will generally be from about 0.1 to about 60%, more generally from about 0.5 to about 40% of the bleach composition comprising the bleach and bleach activator.

As used herein, the bleach may be any of the bleaches useful in detergent compositions that are now known or known in textile cleaning, hard surface cleaning, or other cleaning applications. This includes oxygen bleach in addition to hypohalite (eg hypochlorite) bleach. Perborate (eg mono- or tetra hydrate sodium salt) and percarbonate bleach can be used herein.

Another category of bleaches that can be used without limitation includes percarboxylic acid bleaches and salts thereof. Suitable examples of bleaches of this kind include magnesium monoperoxyphthalate hexahydrate, magnesium salts of metachloro perbenzoic acid, 4-nonylamino-4-oxopoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents include U.S. Patent No. 4,483,781 to Hartman on November 20, 1984, Burns et al., US Patent No. 740,446, filed on June 3,1985, and February 20, 1985. European Patent Application Nos. 0,133,354 to Banks et al., Published as date, and US Patent No. 4,412,934 to Chung et al. On November 1, 1983. Highly preferred bleaches also include 6-nonylamino-6-oxperoxycaproic acid, as disclosed in US Pat. No. 4,634,551 to Burns et al. On January 6, 1987.

Peroxygen bleach can also be used. Suitable peroxy bleach compounds include sodium carbonate peroxyhydrate and equivalent 'percarbonate' bleach, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide. Persulfate bleach (such as OXONE sold by DuPont) may also be used.

Preferred percarbonate bleaches comprise anhydrous particles having an average particle diameter of about 500 μm to about 1,000 μm, wherein up to about 10 wt% of the particles are less than about 200 μm and up to about 10 wt% of the particles are less than about 1,250 μm Big. Optionally, the percarbonate can be coated with a silicate, borate or water soluble surfactant. Percarbonate can be purchased from a variety of product sources such as FMC, Solvay and Tokai Denka.

It is also possible to use mixtures of bleaches.

Preference is given to using peroxygen bleach, perborate, percarbonate, etc. together with the bleach activator, which leads to the preparation of peroxy acid corresponding to the bleach activator in aqueous solution (during the washing process) in situ. Various non-limiting examples of active agents are disclosed in US Pat. No. 4,915,854, and US Pat. No. 4,412,934, issued to Mao et al. On April 10, 1990. Nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical and mixtures thereof may also be used. Other typical bleaches and activators useful herein are disclosed in US Pat. No. 4,634,551.

Highly preferred amido-derived bleaches are bleaches of the general formula R ¹ N (R ⁵ ) C (O) R ² C (O) L or R ¹ C (O) N (R ⁵ ) R ² C (O) L Wherein R ¹ is an alkyl group of about 6 to about 12 carbon atoms; R ² is an alkylene of 1 to about 6 carbon atoms; R ⁵ is H, or an alkyl, aryl, or alkaryl having about 1 to about 10 carbon atoms; L is any suitable leaving group. A leaving group is a group that is released from the bleaching activator as a result of the nucleophilic attack of the bleaching activator by the hydrolyzable anion. Preferred leaving group is phenyl sulfonate.

Preferred examples of the bleach activator of the general formula are (6-octaamido-caproyl) oxybenzenesulfonate, (6-nonanamidocapro), as described in US Pat. No. 4,634,551, which is incorporated herein by reference. 1) oxybenzenesulfonate, (6-decaneamido-caproyl) oxybenzenesulfonate and mixtures thereof.

Other types of bleach activators include benzoxazine-form activators disclosed in US Pat. No. 4,966,723 to Hodge et al., Filed October 30, 1990, which is incorporated herein by reference. Highly preferred benzoxazine-form active agents to be.

Another class of preferred bleach activators is acyl lactam activators, in particular general formula Are acyl camphoractam and acyl valerolactam, wherein R ⁶ is H or an alkyl, aryl, alkoxyaryl or alkaryl group having 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 caprolactam, benzoyl valerolactam, octa Noil valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. U.S. Patent 4,545,784, issued to Sanderson on October 8, 1985, which is incorporated herein by reference, discloses acyl caprolactam, including benzoyl caprolactam adsorbed on sodium perborate.

While not intending to be limiting thereby, in practice, the compositions and methods herein can be adjusted to at least 0.1 ppm of active bleach catalyst species in aqueous wash liquor, and the catalyst species in the wash liquor is preferably about 0.1 to about 700 ppm, more preferably Will be provided from about 1 to about 500 ppm.

Buffer

Buffers can be included for various purposes in the formulations herein. One of these aims is to adjust the pH of the cleaning surface to optimize the effect of the composition for hard surface cleaning on certain types of contaminants or stains. Buffers may also be used to stabilize ancillary products in terms of prolonging the storage period or for the purpose of maintaining compatibility with various aesthetic components. The hard surface cleaner of the present invention optionally contains a buffer to adjust the pH to about 7 to about 13, preferably about 8 to about 13, more preferably about 10 to about 11. Non-limiting examples of such suitable buffers include potassium carbonate, sodium carbonate and sodium bicarbonate, but manufacturers should not be limited to these examples or combinations thereof.

Adjunct

The compositions herein may optionally include one or more other detergent additives or other materials (eg, perfumes, colorants, dyes) that may aid or improve cleaning performance or treat surfaces to be cleaned or modify the aesthetics of the composition. And the like). The following examples of these additions are illustrative examples and are not intended to limit the scope.

Chelating agents

The detergent compositions herein may also optionally contain one or more iron and / or manganese chelating agents. Such chelating agents may be selected from the group consisting of amino carboxylates, amino phosphonates, multifunctional-substituted aromatic chelating agents, and mixtures thereof, all of which are as defined below. While not wishing to be bound by theory, the advantages of these materials are based in part on their particular ability to remove iron and manganese ions from the wash liquor by forming water soluble chelates.

Amino carboxylates useful as optional chelating agents include ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediamine tetrapropionate, triethylenetetraaminehexaacetate, diethylenetriaminepentaacetate , Ethanol diglycine, alkali metal, ammonium, substituted ammonium salts and mixtures thereof.

When at least a small amount of phosphorus is acceptable in the detergent composition, amino phosphonates are also suitable for use as chelating agents in the compositions herein, for example ethylenediaminetetrakis (methylenephosphonate) DEQUEST). Such amino phosphonates preferably do not contain alkyl or alkenyl groups having at least about 6 carbon atoms.

Multifunctional-substituted aromatic chelating agents are also useful in the compositions herein (US Pat. No. 3,812,044, issued to Connor et al. On May 21, 1974). Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

Preferred biodegradable chelating agents for use herein are ethylenediamine disuccinate ('EDDS'), specifically as disclosed in US Pat. No. 4,704,233 to Hartman and Perkins, dated Nov. 3, 1987. Same [S, S] isomer.

If such chelating agents are used, the chelating agents will generally comprise from about 0.1% to about 10% by weight of the detergent compositions herein. If such chelating agents are used, it is more preferred that the chelating agents contain from about 0.1% to about 3.0% by weight of such compositions.

Inert salts

The inert salts (filler salts) used in the compositions of the present invention may be any water soluble inorganic salts, organic salts or mixtures of such salts that do not destabilize the surfactant. In the present invention, the term 'water-soluble' means having a water solubility of 1 g or more per 100 g of water at 20 ° C. Examples of suitable salts include various alkali metal and / or alkaline earth metal sulfates, chlorides, borates, bromide, fluorides, phosphates, carbonates, bicarbonates, citrate, acetates, lactates and the like.

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 And magnesium lactate and sodium fluoride. Preferred salts are, as inorganic salts, sulfates and chlorides of alkali metals. Particularly preferred salts at low prices include sodium sulfate and sodium chloride. The amount of salt present in the composition is about 0 to 40%, preferably 10 to 20%.

abrasive

An essential component of many solids or viscous semisolid hard surface cleaning compositions is an abrasive material added to facilitate the scrubbing action. Abrasive Cleaning Detergents provide a convenient and useful way to disinfect porcelain and tile surfaces (specifically bathtubs, showers and toilets). Particulate abrasive materials in such compositions wipe off and loosen stains adhered to the hard surface and additionally create a closer contact between the contaminants on the hard surface and the surfactants and / or bleaches present in the cleaning composition.

Abrasive cleaners typically contain water-insoluble and relatively hard particulate minerals as abrasives. The most common of these abrasives is finely ground silica sand, having a particle diameter of about 1 to 300 μm and a specific gravity of at least about 2.1. Such materials are generally very effective at wiping off dirt and stains from the surface to be treated, but tend to be difficult to rinse this type of abrasive material from the toilet, shower or bath surface.

If medium or very high water soluble abrasive materials are required (eg sodium carbonate), imidodisulfate may be used either alone or in partially added form.

It has been found that certain forms of expanded pearlite abrasive, in combination with surfactants, filler materials, and other optional cleaning material components presented herein, can be used to make abrasive compositions of the desired form. Abrasive materials suitable for the present invention are those disclosed in US Pat. No. 4,051,056, issued to Hartman on September 27, 1977, which is incorporated herein by reference.

Spices

Perfume is an important component, especially in the aspect of the liquid composition. Perfume is generally used at 0% to 5%. U.S. Patent No. 4,246,129, issued herein to Kacher on January 20, 1981, incorporated herein by reference, discloses certain flavor substances that perform the additional function of reducing the solubility of anionic sulfonates and sulfate surfactants. Is disclosed.

dyes

Dyestuffs comprise about 0.5-12%, preferably 1.5-5%. Solids and viscous semisolids may comprise 1.5% of dye and no fragrances. Examples of suitable dyes include Alizarine Light Blue B (CI 63010), Carta Blue VP (CI 24401), Acid Green 2G (CI 42085), Astrogen Green D Astrogen Green D Z-RL) (CI Reactive Blue 18), Alizarin Light Blue H-RL (CI Acid Blue 182), FD & C Blue No. 1 and FD & C Green No. 3 (see US Pat. No. 4,248,827 to Kitko on Feb. 3, 1981 and US Pat. No. 4,200,606 to Apr. 29, 1980). C. I. refers to the color index.

Optional additional components

As a preferred embodiment, the conventional additional ingredients used herein may be selected from typical ingredients such as enzymes (which may use other additional ingredients together), in particular proteases, lipases, cellulases; Colored spots, sud booters, foam inhibitors, discoloration inhibitors and / or preservatives, contaminant-suspensions, fungicides, alkalinity sources, hydrotrope, antioxidants, enzyme stabilizers, solvents, clay contaminant chelating agents Will generally comprise from about 0.1% to about 10% by weight of the detergent compositions herein. When chelating agents are used, chelating agents can be used as re-deposit removers / preventers, polymeric dispersants, dye transfer inhibitors (e.g. polyvinylpyrrolidone and copolymers of N-vinyl imidazole with N-vinyl pyrrolidone, etc.). Polyamine N-oxide) preferably comprises from about 0.1% to about 3.0% by weight of the composition.

Example

Example 1

Preparation of 1,4-dimethoxy-2,3-dicyanobenzene

Dimethylsulfate (15 mL, 0.16 mol) and anhydrous potassium carbonate (24 g, 0.17 mol) were added to a solution of 2,3-dicyanohydroquinone (3.0 g, 0.019 mol) in 100 mL of 2-butanone. . The reaction mixture was refluxed for 18 h under an argon stream, cooled to room temperature and the resulting solid was collected by filtration. The residue was added to water (100 mL) to dissolve potassium carbonate and the resulting insoluble material was collected by filtration and dried in vacuo to give 3.10 g (88%) (m. P. 276-280 ° C).

¹ H NMR (DMSO-d ₆ , ppm); delta = 7.63 (s, 2H), 3.93 (s, 6H).

Example 2

Preparation of octamethoxy phthalocyanine di-lithium salt

Lithium methoxide (6.05 g, 0.16 mol) was added to a solution of 1,4-dimethoxy-2,3-dicyanobenzene (10 g, 0.05 mol) in 100 ml anhydrous methanol. The reaction mixture was pressurized with nitrogen gas to about 2000 to 2400 psi, heated to 120 ° C. for 6 hours, cooled to room temperature and then evacuated to atmospheric pressure. The resulting gray / green solid was collected by filtration and dried in vacuo to yield 7.08 g (70%). When using DMF as the solvent, the Q-band λ _max is 714 nm.

Example 3

Preparation of Octamethoxy Phthalocyanine

At 50 ° C. p-toluene sulfonic acid (15.73 g, 91 mmol) was added to a solution of octamethoxy phthalocyanine di-lithium salt (7.0 g, 9.1 mmol) in 100 mL anhydrous DMF. The reaction mixture was stirred for 8 hours at 50 ° C. under an argon stream and cooled to about 10 ° C. for 2 hours, the resulting purple solid was collected by filtration and dried in vacuo to give 4.91 g (71%). When using DMF as the solvent, the Q-band λ _max is 764 nm.

Example 4

Preparation of silicon (IV) octamethoxyphthalocyanine dichloride

Silicon tetrachloride (8 mL, 31.8 mmol) was added to a frozen mixture of octamethoxy phthalocyanine (1.0 g, 0.66 mmol) in 60 mL of anhydrous pyridine. The reaction mixture was pressurized with nitrogen gas to about 2000 to 2400 psi, heated to 180 ° C. for 24 hours, cooled to room temperature and then evacuated to atmospheric pressure. Water was added to precipitate the product and the resulting solid was collected by filtration. The filtrate was dissolved in methanol, precipitated by addition of 1N hydrochloric acid and collected by filtration. The product was purified by silica gel chromatography using methylene chloride as eluent. The yield of green product is 0.55 g (49%). When DMF is used as the solvent, the Q-band lambda _max is 730 nm.

Example 5

Preparation of Phthalocyanine Di-Lithium Salts

Phtharonitrile (6.4 g, 0.05 mol) was added to 100 mL of reflux anhydrous butanol containing lithium metal (1.11 g, 0.16 mol). The reaction mixture was refluxed for 2 hours under an argon stream, cooled to room temperature and the resulting solid was collected by filtration. The blue solid was dried under vacuum to give 4.26 g (65%).

Example 6

Preparation of Phthalocyanine

At 50 ° C. p-toluene sulfonic acid (13.14 g, 76 mmol) was added to a solution of phthalocyanine di-lithium salt (4.0 g, 7.6 mmol) in 100 mL of anhydrous DMF. The reaction mixture was stirred at 50 ° C. for 8 hours under an argon stream, cooled to about 10 ° C. and held at this temperature for 2 hours. The resulting blue solid was collected by filtration and dried to give 2.96 g (76%). When using DMF as the solvent, the Q-band λ _max is 659 and 690 nm.

Example 7

Preparation of Silicon (IV) Phthalocyanine Dichloride

Silicon tetrachloride (8 mL, 31.8 mmol) was added to the frozen mixture of phthalocyanine (0.68 g, 1.32 mmol) in 60 mL of anhydrous pyridine. The reaction mixture was pressurized with nitrogen gas to about 2000 to 2400 psi, heated to 180 ° C. for 24 hours, cooled to room temperature and then evacuated to atmospheric pressure. Water was added to precipitate the reaction product, which was then collected by filtration. The filtrate was dissolved in methanol, reprecipitated by adding 1N hydrochloric acid, and then collected by filtration. The product was purified by silica gel chromatography using methylene chloride as eluent. The yield of the blue product is 0.44 g (55%). When using DMF as the solvent, the Q-band λ _max is 670 nm.

Example 8

Preparation of tetrabromonaphthalocyanine di-lithium salt

Lithium methoxide (6.05 g, 0.16 mmol) was added to a solution of 6-bromo-naphthalene-2,3-dicarbonitrile (1 g, 4 mmol) in 100 mL anhydrous methanol. The reaction mixture was pressurized with nitrogen gas to about 2000 to 2400 psi, heated to 120 ° C. for 6 hours and then cooled to room temperature. The precipitate was collected by filtration and dried in vacuo to yield about 0.4 g (39%).

Example 9

Preparation of Tetrabromonaphthalocyanine

At 50 ° C. p-toluene sulfonic acid (15.73 g, 91 mmol) was added to a solution of tetrabromonaphthalocyanine di-lithium salt (0.3 g, 0.3 mmol) in 100 mL anhydrous DMF. The reaction mixture was stirred for 8 hours at 50 ° C. under an argon stream, cooled to about 10 ° C. and held for 2 hours, after which the precipitated solid was collected by filtration. The solid was dried under vacuum to yield 0.25 g (83%). When using DMF as the solvent, the Q-band λ _max is 782 nm.

Example 10

Preparation of tetra-t-butylphthalocyanine di-lithium salt

Lithium methoxide (6.05 g, 0.16 mmol) was added to a solution of 4-t-butylphthalonitrile (1 g, 5.4 mmol) in 100 mL anhydrous methanol. The reaction mixture was pressurized with nitrogen gas to about 2000 to 2400 psi, heated to 120 ° C. for 6 hours and then cooled to room temperature. The resulting precipitate was collected by filtration and dried in vacuo to yield about 0.8 g (79%).

Example 11

Preparation of Tetra-t-butylphthalocyanine

At 50 ° C. p-toluene sulfonic acid (15.73 g, 91 mmol) was added to a solution of tetra-t-butylphthalocyanine di-lithium salt (0.5 g, 0.6 mmol) in 100 mL anhydrous DMF. The reaction mixture was stirred at 50 ° C. for 8 hours under an argon stream, cooled to about 10 ° C. and held at this temperature for 2 hours, and then the precipitated solid was collected by filtration. The solid was dried under vacuum to yield 0.35 g (70%). When using DMF as the solvent, the Q-band λ _max is 680 nm.

Example 12

Preparation of 1,4-dipropoxy-2,3-dicyanobenzene

Propyl iodide (15 mL, 0.16 mmol) and anhydrous potassium carbonate (24 g, 0.17 mol) are combined with a solution of 2,3-dicyanohydroquinone (3.0 g, 0.019 mmol) in 100 mL 2-butanone. It was. The reaction mixture was refluxed for 18 hours under an argon stream, cooled to room temperature and the solid collected by filtration. The residue was then added to water (100 mL) to dissolve potassium carbonate and the resulting solid was collected by filtration and dried in vacuo to give 3.4 g (74%).

Example 13

Preparation of tetrapropoxyphthalocyanine di-lithium salt

Tetrapropoxy in the same manner as described in Example 2, using 1,4-dipropoxy-2,3-dicyanobenzene instead of 1,4-dimethoxy-2,3-dicyanobenzene as starting material Phthalocyanine di-lithium salts were prepared. Typically a yield of 52% was obtained.

Example 14

Preparation of Tetrapropoxyphthalocyanine

Tetrapropoxyphthalocyanine was prepared in the same manner as described in Example 3, using tetrapropoxyphthalocyanine di-lithium salt instead of tetramethoxyphthalocyanine as starting material. Typically a yield of 73% was obtained. The Q-band λ _max is 760 nm.

Example 15

Preparation of Silicon (IV) Phthalocyanine Di- (PEG 350 Mono-Methyl Ether)

Silicon (IV) phthalocyanine dichloride (2 g of 85% sample, 2.78 mmol) was added to a refluxing solution of 40 g PEG 350 mono-methyl ether in 100 ml anhydrous DMF. Reflow was continued while argon was applied for 48 hours, and then the reaction mixture was cooled to room temperature and then the DMF was removed under reduced pressure. The resulting 44.21 g of blue oil contains 7.78% of the desired material. When water is used as the solvent, the Q-band λ _max is 682 nm.

Example 16

Preparation of Silicon (IV) Phthalocyanine Di-Propoxide

Silicon (IV) phthalocyanine dichloride (0.20 g, 0.278 mmol of 85% active ingredient) was added to 25 mL of refluxing anhydrous n-propanol. Reflow was continued for an additional 48 hours while argon was applied, and then the reaction mixture was cooled to room temperature and then the solvent was removed to give 0.25 g of a blue solid. When using DMF as the solvent, the Q-band λ _max is 672 nm.

Example 17

Preparation of Silicon (IV) Phthalocyanine Di- (p-phenol Sulfonate Sodium Salt)

Silicon (IV) phthalocyanine dichloride (0.02 g, 0.278 mmol) of 85% active ingredient was added to a refluxing solution of anhydrous disodium phenol sulfonate (0.12 g, 0.56 mmol) in 100 mL anhydrous DMF. The reflux was continued while applying argon for 96 hours, and then the reaction was cooled to room temperature and then the DMF was removed under reduced pressure. The yield of blue oil is 0.31 g. When using DMF as the solvent, the Q-band λ _max is 674 nm.

Example 18

Preparation of Silicon (IV) Octanemethoxyphthalocyanine Di- (PEG 350 Mono-Methyl Ether)

The same method as described in Example 15 was used using 2.0 g of silicon (IV) octamethoxyphthalocyanine dichloride as starting material. The resulting green oil contains 6% of the desired product. When using DMF as the solvent, the Q-band λ _max is 736 nm.

Example 19

Preparation of 1,3-di-methoxy-3,6-di-iminoisoindolin from 1,4-di-methoxy-2,3-di-cyanobenzene

Anhydrous ammonia was brought into a solution consisting of 1,4-dimethoxy-2,3-di-cyanobenzene (10 g, 53.2 mmol), sodium methoxide (85 mg, 1.6 mmol) and anhydrous methanol (25 mL) at room temperature. The bubble was bubbled for 30 minutes at. The reaction mixture was then refluxed for 3.5 hours with continued addition of ammonia and then cooled to room temperature before the product was collected by filtration. The yield is 4.68 g (43%).

Example 20

Preparation of Octamethoxy Silicon (IV) Phthalocyanine Dichloride from 1,3-di-methoxy-3,6-di-iminoisoindolin

Silicon tetrachloride (3.59 g, 21.1 mmol) at room temperature was added to a solution of 1,3-di-methoxy-3,6-diiminoisoindolin (3 g, 14.6 mmol) in 25 mL anhydrous quinoline. The reaction mixture was then slowly refluxed for 1.5 hours, followed by continued reflux for an additional 30 minutes. The reaction mixture was subsequently cooled to 100 ° C. and the crude product was filtered off. The product was purified by silica gel chromatography using methylene chloride as eluent. The yield of green solid is 1.71 g (55%).

Example 21

Preparation of octamethoxy silicon (IV) phthalocyanine dichloride from octamethoxy phthalocyanine di-lithium salt

Silicon tetrachloride (2.22 g, 13.0 mmol) was added to a solution of octamethoxy phthalocyanine di-lithium salt (1 g, 1.3 mmol) in 50 mL anhydrous nitrobenzene. The reaction mixture was pressurized with nitrogen gas to about 2000 to 2400 psi and heated to 120 ° C. for 24 hours. The crude product was precipitated by addition of 400 mL anhydrous diethyl ether and the resulting solid was collected by filtration. Purification by silica gel chromatography using methylene chloride as eluent gave 0.57 g (51%) of a green solid.

Example 22

Preparation of Silicon (IV) Tetra-t-butylphthalocyanine Dichloride

The starting material was used in the same manner as described in Example 20 using 0.5 g of tetra-t-butylphthalocyanine di-lithium salt (prepared in Example 10). 50% yield of the desired product was obtained. When DMF is used as the solvent, the Q-band lambda _max is 700 nm.

Example 23

Preparation of Silicon (IV) Tetra-t-butylphthalocyanine Dipropoxide

The method as described in Example 16 was used using 0.2 g of silicon (IV) tetra-t-butylphthalocyanine (as in Example 22) as starting material. The desired product was obtained in 80% yield. When using propanol as a solvent, the Q-band λ _max is 690 nm.

Example 24

Preparation of 1,2-di-cyano-4,5-di-chloro-3,6-hydroquinone from 1,2-di-cyano-4,5-di-chloro-3,6-benzenequinone

Sodium bisulfite (34.4 g, 0.33 mol) is added to a solution of 1,2-di-cyano-4,5-di-chloro-3,6-benzenequinone (25 g, 0.11 mol) in 300 ml water It was. The reaction mixture was stirred for 3 hours at room temperature. The product was collected by filtration and dried to give 23.01 g (91.3%).

Example 25

1,2-di-cyano-4,5-di-chloro-3,6-di-methoxybenzene from 1,2-di-cyano-4,5-di-chloro-3,6-hydroquinone Manufacture

The desired material was obtained in 85% yield using the method as described above in Example 1.

Example 26

Preparation of octachloro-octamethoxyphthalocyanine di-lithium salt from 1,2-di-cyano-4,5-di-chloro-3,6-di-methoxybenzene

1,2-dicyano-4,5-dichloro-3,6-dimethoxybenzene (6.0 g, 23.3 mmol) was added to the refluxing solution of lithium metal (0.65 g, 93.4 mmol) in 75 mL anhydrous methanol. . The reaction mixture was refluxed for 24 hours with argon applied and then cooled to room temperature. The resulting green solid was collected by filtration to give 3.98 g (66%). When using DMF as the solvent, the Q-band λ _max is 692 nm.

Example 27

Preparation of silicon (IV) octachloro-octamethoxy phthalocyanine dichloride

The method as described above in Example 20 was used using 1 g of octachloro-octamethoxyphthalocyanine di-lithium salt as starting material. The desired product was obtained in 63% yield. When DMF is used as the solvent, the Q-band lambda _max is 730 nm.

Example 28

Bromination of Silicon (IV) Naphthalocyanine Chloride

To a solution of silicon (IV) naphthalocyanine dichloride (0.25 g, 0.26 mmol) in 100 mL anhydrous DMF, divided into 3 portions of N-bromosuccinimide (0.559 g, 3.1 mmol) at 70 ° C. Added. The reaction mixture was then stirred for 48 h at 70 ° C. under an argon stream, cooled to room temperature and the solvent was removed under reduced pressure. The residue obtained was stirred in 100 ml anhydrous methanol for 18 hours. The product was collected by filtration and dried to yield 0.189 g (77%). As a result of component analysis, it was confirmed that 1.2 equivalents of bromine were added.

Example 29

Preparation of Silicon (IV) Bromonaphthalocyanine Di- (PEG 2000 Monomethyl Ether)

The method as described in Example 15 was used using 0.1 g of silicon (IV) bromide naphthalocyanine dichloride (as in Example 27) and PEG 2000 mono methyl ether as starting material. The resulting green solids contained about 0.03% of the desired material. When using DMF as the solvent, the Q-band λ _max is 780 nm.

Example 30

Preparation of Silicon (IV) Tetrabromonaphthalocyanine Dichloride

The method as described in Example 20 was used using 0.2 g of tetrabromonaphthalocyanine di-lithium salt as starting material. The desired product was obtained in 40% yield. When using DMF as the solvent, the Q-band λ _max is 790 nm.

Example 31

Preparation of Silicon (IV) Tetrabromonaphthalocyanine Di- (PEG 2000 Monomethyl Ether)

Instead of PEG 350 in the previous example, the method as described in Example 15 was used using silicon (IV) tetrabromonaphthalocyanine dichloride (as in Example 28) and PEG 2000 monomethyl ether. The resulting green solids contain about 0.03% of the desired material. When using DMF as the solvent, the Q-band λ _max is 780 nm.

Example 32

Preparation of Octamethoxy Silicon (IV) Phthalocyanine Dihydroxide

Octamethoxy silicon (IV) phthalocyanine dichloride (0.2 g, 0.26 μmol) was added to a refluxing solution of sodium methoxide (0.8 g, 0.15 μmol) in 15 mL 95: 5 ethanol / water. The reaction mixture was refluxed for 4 hours and then cooled to room temperature. The resulting cyan precipitate was collected by filtration to give 0.174 g (92%). When using DMF as the solvent, the Q-band λ _max is 734 nm.

Example 33

Preparation of Glycerol-Di- (Triethylene Glycol Methyl Ether)

To a suspension of sodium hydride (20.4 g, 0.85 mol) in dioxane anhydride (500 mL) cooled to about 10 ° C. under an argon stream was added triethylene glycol mono-methyl ether (131.4 g, 0.80 mol) for about 1 hour. It was. The mixture was allowed to warm to room temperature and subsequently refluxed for 1 hour. After warming to room temperature, epichlorohydrin (37.0 g, 0.40 mol) was added. The solution was heated to reflux for 2 hours and then continued to reflux for an additional 48 hours. After cooling, the solvent was removed in vacuo. The resulting solid was slurried in ether (500 mL), cooled to about 10 ° C. and then 10% HCl (75 mL) was added for about 0.5 hours. The organic layer was extracted two more times with acid, following the aqueous layer. Three aqueous extracts were combined, saturated with NaCl and extracted four times with 50 ml of chloroform. The chloroform extracts were combined, dried over MgSO ₄ and concentrated to give 97.17 g of brown oil. The product was used without further purification.

Example 34

Preparation of Glycerol-Di- (Diethylene Glycol Methyl Ether)

To a suspension of sodium hydride (20.4 g, 0.85 mol) in dioxane anhydrous (500 mL) cooled to about 10 ° C. under an argon stream was added diethylene glycol mono-methyl ether (96.12 g, 0.80 mol) for about 1 hour. It was. The mixture was allowed to warm to room temperature and subsequently refluxed for 1 hour. After warming to room temperature, epichlorohydrin (37.0 g, 0.40 mol) was added. The solution was heated to reflux for 2 hours and then continued to reflux for an additional 48 hours. After cooling, the solvent was removed in vacuo. The resulting solid was slurried in ether (500 mL), cooled to about 10 ° C. and then 10% HCl (75 mL) was added for about 0.5 hours. The organic layer was extracted two more times with acid, following the aqueous layer. Three aqueous extracts were combined, saturated with NaCl and extracted four times with 50 mL of chloroform. The chloroform extracts were combined, dried over MgSO ₄ and concentrated to give 79.79 g of brown oil. The product was used without further purification.

Example 35

Preparation of Glycerol-Di- (Ethylene Glycol Methyl Ether)

Ethylene glycol mono-methyl ether (60.92 g, 0.80 mol) was added to a suspension of sodium hydride (20.4 g, 0.85 mol) in dioxane anhydrous (500 mL) cooled to about 10 ° C. under an argon stream. . The mixture was allowed to warm to room temperature and subsequently refluxed for 1 hour. After warming to room temperature, epichlorohydrin (37.0 g, 0.40 mol) was added. The solution was heated to reflux for 2 hours and then continued to reflux for an additional 48 hours. After cooling, the solvent was removed in vacuo. The resulting solid was slurried in ether (500 mL), cooled to about 10 ° C. and 10% HCl (75 mL) was added for about 0.5 hours. The organic layer was extracted two more times with acid, following the aqueous layer. Three aqueous extracts were combined, saturated with NaCl, and extracted four times with 50 ml of chloroform. The chloroform extracts were combined, dried over MgSO ₄ and concentrated to give 59.90 g of brown oil. The product was used without further purification.

Example 36

Preparation of Silicon (VI) Phthalocyanine-di-iso PEG 384

Silicon (VI) phthalocyanine di-hydroxide (1 g, 1.73 mmol), glycerol-di- (triethylene glycol methyl ether) (20 g, 52 mmol) (prepared according to Example 33) and xylene (175 mL) ) Was slowly heated to reflux for 2 hours. Once the reflux temperature was reached, the solution was continued to reflux with argon applied for an additional 48 hours to remove the produced water using azeotropy. The solution was cooled to room temperature and the solvent removed under reduced pressure to give 21.15 g of blue oil. When water is used as the solvent, the Q-band λ _max is 674 nm.

Example 37

Preparation of Silicon (VI) Naphthalocyanine-Di-Iso PEG 384

Silicon (VI) naphthalocyanine di-hydroxide (1 g, 1.29 mmol), glycerol-di- (triethylene glycol methyl ether) (15 g, 38.72 mmol) (prepared according to Example 33) and xylene (175 Ml) was slowly heated to reflux for 2 hours. Once the reflux temperature was reached, the solution was continuously refluxed while applying argon for an additional 48 hours to remove azeotropically the resulting water. The solution was cooled to room temperature and the solvent was removed under reduced pressure to yield 16.07 g of the resulting green oil. Using water, 1% Triton X-100 as the solvent, the Q-band lambda _max is 788 nm.

The cleaning composition obtained according to the present invention may be in the form of granules, liquids, bars or the like, and is typically formulated to have a pH of 9 to 11 in use, but in the case of a non-aqueous or low water composition May vary outside this range. Various carriers such as sodium sulfate, water, water-ethanol, BPP, MPP, EPP, PPP, sodium carbonate and the like may also be commonly used to prepare the final product. The granules were prepared by spray-drying or agglomeration using known methods to give products having a density of 350 to 950 g / l. The bar may be manufactured using conventional extrusion techniques. If necessary, the photobleach-chelating agent may be formed in advance. The composition may also contain conventional perfumes, fungicides, hydrotropes and the like. In the case of nonaqueous or low aqueous compositions, the cleaning compositions may be applied to articles used to convey the compositions of the present invention to fabrics or hard surfaces. Non-limiting examples according to the present invention are shown in Tables 1 to 5:

Example 45

The embodiment may be completely dry before exposure. After exposure, when reactivated with the solution, more desirable properties are exhibited.

Example 46

Example 47

Typically the fabric is washed using the above-described composition at a use concentration of about 10 to about 10,000 ppm. Improved photobleaching effects can be obtained when such fabrics are dried in the presence of light, preferably in natural light.

Since the organosilicon photosensitive compound according to the present invention has high solubility in solvents and is evenly applied to a substrate and exhibits direct or non-directivity depending on the substrate, the sterilization and disinfection effect is excellent, and its performance is better even when used in a small amount. Therefore, it is possible to provide excellent sterilizing and disinfecting compositions.

Claims (33)

An organosilicon (IV) phthalocyanine photosensitive compound of formula 2a having a Q-band maximum absorption wavelength of at least 660 nm: Formula 2a Where R ¹ , R ² , R ³ and R ⁴ units are a) hydrogen; b) halogen; c) hydroxyl; d) cyano; e) nitrile; f) oxymino; g) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; h) halogen substituted C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; i) polyhydroxyl substituted C ₃ -C ₂₂ alkyl; j) C ₁ -C ₂₂ alkoxy; k) general formula Branched alkoxy having the [wherein, B is hydrogen, hydroxyl, C ₁ -C ₃₀ alkyl, C ₁ -C _{30 alkoxy, -CO 2 H, -CH 2 CO} 2 H, -SO 3 - M +, -OSO 3 _{^{- M +, -PO 3 2- M}} , -OPO 3 2- M, or a mixture thereof; M is a sufficient amount of water soluble cations to satisfy the charge balance; x is 0 or 1; y each independently has a value from 0 to 6; z each independently has a value from 0 to 100; l) substituted aryl and unsubstituted aryl; m) substituted alkylenearyl and unsubstituted alkylenearyl; n) substituted aryloxy and unsubstituted aryloxy; o) substituted oxyalkylenearyl and unsubstituted oxyalkylenearyl; p) substituted alkyleneoxyaryl and unsubstituted alkyleneoxyaryl; q) C ₁ -C ₂₂ thioalkyl, C ₄ -C ₂₂ branched thioalkyl and mixtures thereof; r) an ester of the general formula -CO ₂ R ¹⁰ , wherein R ¹⁰ is i) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; ii) halogen substituted C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; iii) polyhydroxyl substituted C ₃ -C ₂₂ alkyl; iv) C ₃ -C ₂₂ glycol; v) C ₁ -C ₂₂ alkoxy; vi) C ₄ -C ₂₂ branched alkoxy; vii) substituted aryl and unsubstituted aryl; viii) substituted alkylaryl and unsubstituted alkylaryl; ix) substituted aryloxy and unsubstituted aryloxy; x) substituted alkoxyaryl and unsubstituted alkoxyaryl; xi) substituted alkyleneoxyaryl and unsubstituted alkyleneoxyaryl; And mixtures thereof; s) general formula Alkyleneamino units wherein R ¹¹ and R ¹² represent C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof Including; R ¹⁶ is i) hydrogen, ii) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof It includes; A unit comprises nitrogen or oxygen; X comprises chlorine, bromine, iodine or other water soluble anions; v is 0 or 1; u is 0 to 22; t) amino units of —NR ¹¹ R ¹² , wherein R ¹¹ and R ¹² are C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl And mixtures thereof); u) alkylethyleneoxy units of the general formula-(A) _v- (CH ₂ ) _y (OCH ₂ CH ₂ ) _x Z, wherein Z is i) hydrogen, ii) hydroxyl, iii) -CO ₂ H, iv) -SO ₃ ^- M ⁺ , v) -OSO ₃ ^- M ⁺ , vi) C ₁ -C ₆ alkoxy, vii) substituted aryl and unsubstituted aryl, viii) substituted aryloxy and unsubstituted aryloxy, ix) alkyleneamino, and mixtures thereof It includes; A unit comprises nitrogen or oxygen; M is a water soluble cation; v is 0 or 1; x is 0 to 100; y is 0 to 12; v) substituted siloxy of the formula -OSiR ⁷ R ⁸ R ⁹ , wherein R ⁷ , R ⁸ and R ⁹ are i) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; ii) substituted aryl and unsubstituted aryl; iii) substituted aryloxy and unsubstituted aryloxy; iv) alkylethyleneoxy units of the formula-(A) _v- (CH ₂ ) _y (OCH ₂ CH ₂ ) _x Z, wherein Z is a) hydrogen, b) C ₁ -C ₃₀ alkyl, c) hydroxyl, d) -CO ₂ H, e) -SO ₃ ^- M ⁺ , f) -OSO ₃ ^- M ⁺ , g) C ₁ -C ₆ alkoxy, h) substituted aryl and unsubstituted aryl, i) substituted aryloxy and unsubstituted aryloxy, j) alkyleneamino, and mixtures thereof It includes; A unit comprises nitrogen or oxygen; M is a water soluble cation; v is 0 or 1; x is 0 to 100; y is 0 to 12) and mixtures thereof Independently selected from the group consisting of Each independently selected from the group consisting of In axial R units, R is each a) hydrogen; b) halogen; c) hydroxyl; d) cyano; e) nitrile; f) oxymino; g) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; h) halogen substituted C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; i) polyhydroxyl substituted C ₃ -C ₂₂ alkyl; j) C ₁ -C ₂₂ alkoxy; k) general formula Branched alkoxy having the [wherein, B is hydrogen, hydroxyl, C ₁ -C ₃₀ alkyl, C ₁ -C _{30 alkoxy, -CO 2 H, -CH 2 CO} 2 H, -SO 3 - M +, -OSO 3 _{^{- M +, -PO 3 2- M}} , -OPO 3 2- M, or a mixture thereof; M is a sufficient amount of water soluble cations to satisfy the charge balance; x is 0 or 1; y each independently has a value from 0 to 6; z each independently has a value from 0 to 100; l) substituted aryl and unsubstituted aryl; m) substituted alkylenearyl and unsubstituted alkylenearyl; n) substituted aryloxy and unsubstituted aryloxy; o) substituted oxyalkylenearyl and unsubstituted oxyalkylenearyl; p) substituted alkyleneoxyaryl and unsubstituted alkyleneoxyaryl; q) C ₁ -C ₂₂ thioalkyl, C ₄ -C ₂₂ branched thioalkyl and mixtures thereof; r) general formula Alkyleneamino units wherein R ¹¹ and R ¹² represent C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof Including; R ¹⁶ is i) hydrogen, ii) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof It includes; A unit comprises nitrogen or oxygen; X comprises chlorine, bromine, iodine or other water soluble anions; v is 0 or 1; u is 0 to 22; s) amino units of —NR ¹¹ R ¹² wherein R ¹¹ and R ¹² are C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl And mixtures thereof); t) alkyl ethyleneoxy units of the formula-(A) _v- (CH ₂ ) _y (OCH ₂ CH ₂ ) _x Z, wherein Z is i) hydrogen, ii) hydroxyl, iii) -CO ₂ H, iv) -SO ₃ ^- M ⁺ , v) -OSO ₃ ^- M ⁺ , vi) C ₁ -C ₆ alkoxy, vii) substituted aryl and unsubstituted aryl, viii) substituted aryloxy and unsubstituted aryloxy, ix) alkyleneamino, and mixtures thereof It includes; A unit comprises nitrogen or oxygen; M is a water soluble cation; v is 0 or 1; x is 0 to 100; y is 0 to 12; u) general formula Of carboxylates, where R ¹⁰ is i) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; ii) halogen substituted C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; iii) polyhydroxyl substituted C ₃ -C ₂₂ alkyl; iv) C ₃ -C ₂₂ glycol; v) C ₁ -C ₂₂ alkoxy; vi) C ₄ -C ₂₂ branched alkoxy; vii) substituted aryl and unsubstituted aryl; viii) substituted alkylaryl and unsubstituted alkylaryl; ix) substituted aryloxy and unsubstituted aryloxy; x) substituted alkoxyaryl and unsubstituted alkoxyaryl; xi) substituted alkyleneoxyaryl and unsubstituted alkyleneoxyaryl; xii) alkyleneamino; And mixtures thereof; v) substituted siloxy of the formula -OSiR ⁷ R ⁸ R ⁹ , wherein R ⁷ , R ⁸ and R ⁹ are i) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; ii) substituted aryl and unsubstituted aryl; iii) substituted aryloxy and unsubstituted aryloxy; iv) alkylethyleneoxy units of the formula-(A) _v- (CH ₂ ) _y (OCH ₂ CH ₂ ) _x Z, wherein Z is a) hydrogen, b) C ₁ -C ₃₀ alkyl, c) hydroxyl, d) -CO ₂ H, e) -SO ₃ ^- M ⁺ , f) -OSO ₃ ^- M ⁺ , g) C ₁ -C ₆ alkoxy, h) substituted aryl and unsubstituted aryl, i) substituted aryloxy and unsubstituted aryloxy, j) alkyleneamino, and mixtures thereof It includes; A unit comprises nitrogen or oxygen; M is a water soluble cation; v is 0 or 1; x is 0 to 100; y is 0 to 12) and mixtures thereof Independently selected from the group consisting of It is independently selected from the group consisting of. The method of claim 1, An organosilicon (IV) photosensitive compound comprising a phthalocyanine comprising at least one R ¹ , R ² , R ³ and R ⁴ unit wherein each unit is methoxy. The method of claim 1, An organosilicon (IV) photosensitive compound comprising a phthalocyanine wherein each unit comprises one or more R ¹ , R ² , R ³ and R ⁴ units selected from the group consisting of chlorine, bromine and iodine. a) at least about 0.01% of a nonionic, cationic, anionic, bipolar or amphoteric surfactant; b) an organosilicon (IV) phthalocyanine photosensitive compound of formula 2a having a Q-band maximum absorption wavelength of at least 660 nm; And c) residual amounts of additional components Laundry or cleaning composition comprising: Formula 2a Where R ¹ , R ² , R ³ and R ⁴ units are a) hydrogen; b) halogen; c) hydroxyl; d) cyano; e) nitrile; f) oxymino; g) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; h) halogen substituted C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; i) polyhydroxyl substituted C ₃ -C ₂₂ alkyl; j) C ₁ -C ₂₂ alkoxy; k) general formula Branched alkoxy having the [wherein, B is hydrogen, hydroxyl, C ₁ -C ₃₀ alkyl, C ₁ -C _{30 alkoxy, -CO 2 H, -CH 2 CO} 2 H, -SO 3 - M +, -OSO 3 _{^{- M +, -PO 3 2- M}} , -OPO 3 2- M, or a mixture thereof; M is a sufficient amount of water soluble cations to satisfy the charge balance; x is 0 or 1; y each independently has a value from 0 to 6; z each independently has a value from 0 to 100; l) substituted aryl and unsubstituted aryl; m) substituted alkylenearyl and unsubstituted alkylenearyl; n) substituted aryloxy and unsubstituted aryloxy; o) substituted oxyalkylenearyl and unsubstituted oxyalkylenearyl; p) substituted alkyleneoxyaryl and unsubstituted alkyleneoxyaryl; q) C ₁ -C ₂₂ thioalkyl, C ₄ -C ₂₂ branched thioalkyl and mixtures thereof; r) an ester of the general formula -CO ₂ R ¹⁰ , wherein R ¹⁰ is i) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; ii) halogen substituted C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; iii) polyhydroxyl substituted C ₃ -C ₂₂ alkyl; iv) C ₃ -C ₂₂ glycol; v) C ₁ -C ₂₂ alkoxy; vi) C ₄ -C ₂₂ branched alkoxy; vii) substituted aryl and unsubstituted aryl; viii) substituted alkylaryl and unsubstituted alkylaryl; ix) substituted aryloxy and unsubstituted aryloxy; x) substituted alkoxyaryl and unsubstituted alkoxyaryl; xi) substituted alkyleneoxyaryl and unsubstituted alkyleneoxyaryl; And mixtures thereof; s) general formula Alkyleneamino units wherein R ¹¹ and R ¹² represent C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof Including; R ¹⁶ is i) hydrogen, ii) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof It includes; A unit comprises nitrogen or oxygen; X comprises chlorine, bromine, iodine or other water soluble anions; v is 0 or 1; u is 0 to 22; t) amino units of —NR ¹¹ R ¹² wherein R ¹¹ and R ¹² units are C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ side chain alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ side chain eggs Kenyl and mixtures thereof); u) alkylethyleneoxy units of the general formula-(A) _v- (CH ₂ ) _y (OCH ₂ CH ₂ ) _x Z, wherein Z is i) hydrogen, ii) hydroxyl, iii) -CO ₂ H, iv) -SO ₃ ^- M ⁺ , v) -OSO ₃ ^- M ⁺ , vi) C ₁ -C ₆ alkoxy, vii) substituted aryl and unsubstituted aryl, viii) substituted aryloxy and unsubstituted aryloxy, ix) alkyleneamino, and mixtures thereof It includes; A unit comprises nitrogen or oxygen; M is a water soluble cation; v is 0 or 1; x is 0 to 100; y is 0 to 12; v) substituted siloxy of the formula -OSiR ⁷ R ⁸ R ⁹ , wherein R ⁷ , R ⁸ and R ⁹ are i) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; ii) substituted aryl and unsubstituted aryl; iii) substituted aryloxy and unsubstituted aryloxy; iv) alkylethyleneoxy units of the formula-(A) _v- (CH ₂ ) _y (OCH ₂ CH ₂ ) _x Z, wherein Z is a) hydrogen, b) C ₁ -C ₃₀ alkyl, c) hydroxyl, d) -CO ₂ H, e) -SO ₃ ^- M ⁺ , f) -OSO ₃ ^- M ⁺ , g) C ₁ -C ₆ alkoxy, h) substituted aryl and unsubstituted aryl, i) substituted aryloxy and unsubstituted aryloxy, j) alkyleneamino, and mixtures thereof It includes; A unit comprises nitrogen or oxygen; M is a water soluble cation; v is 0 or 1; x is 0 to 100; y is 0 to 12) and mixtures thereof Independently selected from the group consisting of Each independently selected from the group consisting of In axial R units, R is each a) hydrogen; b) halogen; c) hydroxyl; d) cyano; e) nitrile; f) oxymino; g) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; h) halogen substituted C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; i) polyhydroxyl substituted C ₃ -C ₂₂ alkyl; j) C ₁ -C ₂₂ alkoxy; k) general formula Branched alkoxy having the [wherein, B is hydrogen, hydroxyl, C ₁ -C ₃₀ alkyl, C ₁ -C _{30 alkoxy, -CO 2 H, -CH 2 CO} 2 H, -SO 3 - M +, -OSO 3 _{^{- M +, -PO 3 2- M}} , -OPO 3 2- M, or a mixture thereof; M is a sufficient amount of water soluble cations to satisfy the charge balance; x is 0 or 1; y each independently has a value from 0 to 6; z each independently has a value from 0 to 100; l) substituted aryl and unsubstituted aryl; m) substituted alkylenearyl and unsubstituted alkylenearyl; n) substituted aryloxy and unsubstituted aryloxy; o) substituted oxyalkylenearyl and unsubstituted oxyalkylenearyl; p) substituted alkyleneoxyaryl and unsubstituted alkyleneoxyaryl; q) C ₁ -C ₂₂ thioalkyl, C ₄ -C ₂₂ branched thioalkyl and mixtures thereof; r) general formula Alkyleneamino units wherein R ¹¹ and R ¹² represent C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof Including; R ¹⁶ is i) hydrogen, ii) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof It includes; A unit comprises nitrogen or oxygen; X comprises chlorine, bromine, iodine or other water soluble anions; v is 0 or 1; u is 0 to 22; s) amino units of —NR ¹¹ R ¹² , wherein R ¹¹ and R ¹² units are C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ side chain alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ side chain eggs Kenyl and mixtures thereof); t) alkyl ethyleneoxy units of the formula-(A) _v- (CH ₂ ) _y (OCH ₂ CH ₂ ) _x Z, wherein Z is i) hydrogen, ii) hydroxyl, iii) -CO ₂ H, iv) -SO ₃ ^- M ⁺ , v) -OSO ₃ ^- M ⁺ , vi) C ₁ -C ₆ alkoxy, vii) substituted aryl and unsubstituted aryl, viii) substituted aryloxy and unsubstituted aryloxy, ix) alkyleneamino, and mixtures thereof It includes; A unit comprises nitrogen or oxygen; M is a water soluble cation; v is 0 or 1; x is 0 to 100; y is 0 to 12; u) general formula Of carboxylates, where R ¹⁰ is i) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; ii) halogen substituted C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; iii) polyhydroxyl substituted C ₃ -C ₂₂ alkyl; iv) C ₃ -C ₂₂ glycol; v) C ₁ -C ₂₂ alkoxy; vi) C ₄ -C ₂₂ branched alkoxy; vii) substituted aryl and unsubstituted aryl; viii) substituted alkylaryl and unsubstituted alkylaryl; ix) substituted aryloxy and unsubstituted aryloxy; x) substituted alkoxyaryl and unsubstituted alkoxyaryl; xi) substituted alkyleneoxyaryl and unsubstituted alkyleneoxyaryl; xii) alkyleneamino; And mixtures thereof; v) substituted siloxy of the formula -OSiR ⁷ R ⁸ R ⁹ , wherein R ⁷ , R ⁸ and R ⁹ are i) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; ii) substituted aryl and unsubstituted aryl; iii) substituted aryloxy and unsubstituted aryloxy; iv) alkylethyleneoxy units of the formula-(A) _v- (CH ₂ ) _y (OCH ₂ CH ₂ ) _x Z, wherein Z is a) hydrogen, b) C ₁ -C ₃₀ alkyl, c) hydroxyl, d) -CO ₂ H, e) -SO ₃ ^- M ⁺ , f) -OSO ₃ ^- M ⁺ , g) C ₁ -C ₆ alkoxy, h) substituted aryl and unsubstituted aryl, i) substituted aryloxy and unsubstituted aryloxy, j) alkyleneamino, and mixtures thereof It includes; A unit comprises nitrogen or oxygen; M is a water soluble cation; v is 0 or 1; x is 0 to 100; y is 0 to 12) and mixtures thereof Independently selected from the group consisting of It is independently selected from the group consisting of. The method of claim 4, wherein Organosilicon photosensitive compounds are hydrogen, hydroxyl, halogen, C ₁ -C ₂₂ thioalkyl, C ₄ -C ₂₂ branched thioalkyl, C ₁ -C ₂₂ alkoxy, C ₁ -C ₂₂ branched alkoxy, aryloxy, general formula- _{(a) v - (CH 2} ) y (OCH 2 CH 2) x Z of alkyl ethylene oxide units [wherein, Z is hydrogen, ^{_{hydroxyl, -CO 2 H, -SO 3 -}} M +, -OSO 3 - M ⁺ , C ₁ -C ₆ alkoxy, substituted aryl and unsubstituted aryl, substituted aryloxy 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 0 to 100; y is 0 to 12]. A composition comprising R ¹ , R ² , R ^3, and R ⁴ units independently selected from the group consisting of: The method of claim 5, The axial R unit a) general formula _{- (A) v - (CH} 2) y (OCH 2 CH 2) x Z of alkyl ethylene oxide units [wherein, Z is hydrogen, ^{_{hydroxyl, -CO 2 H, -SO 3 -}} M +, -OSO ₃ ^- including M ^+, C ₁ -C ₆ alkoxy group, a substituted aryl, and unsubstituted aryl, a substituted aryloxy group and unsubstituted aryloxy group, and the alkylene and amino; A comprises nitrogen or oxygen; M is a water soluble cation; v is 0 or 1; x is 0 to 100; y is 0 to 12; b) general formula Branched alkoxy having the [wherein, B is hydrogen, hydroxyl, C ₁ -C ₃₀ alkyl, C ₁ -C _{30 alkoxy, -CO 2 H, -CH 2 CO} 2 H, -SO 3 - M +, -OSO 3 _{^{- M +, -PO 3 2- M}} , -OPO 3 2- M, or a mixture thereof; M is a sufficient amount of water soluble cations to satisfy the charge balance; x is 0 or 1; y each independently has a value from 0 to 6; z each independently has a value from 0 to 100; c) substituted siloxy of the formula -OSiR ⁷ R ⁸ R ⁹ wherein R ⁷ , R ⁸ and R ⁹ are C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl , C ₄ -C ₂₂ branched alkenyl, substituted aryl and unsubstituted aryl, substituted aryloxy and unsubstituted aryloxy, general formula-(A) _v- (CH ₂ ) _y (OCH ₂ CH ₂ ) _x of Z-alkyl ethyleneoxy units (wherein, Z is hydrogen, C ₁ -C ₃₀ alkyl, ^{_{hydroxyl, -CO 2 H, -SO 3 -}} M +, -OSO 3 - M +, C 1 -C 6 alkoxy, substituted Aryl and unsubstituted aryl, substituted aryloxy and unsubstituted aryloxy, alkyleneamino and mixtures thereof; A unit comprises nitrogen or oxygen; M is a water soluble cation; v is 0 or 1, x is 0 to 100 and y is 0 to 12); And d) mixtures thereof Composition comprising a. The method of claim 6, Axial R unit is general formula Branched alkoxy having the [wherein, B is hydrogen, hydroxyl, C ₁ -C ₃₀ alkyl, C ₁ -C _{30 alkoxy, -CO 2 H, -CH 2 CO} 2 H, -SO 3 - M +, -OSO 3 ^- the _{^{M +, -PO 3 2- M,}} -OPO 3 2- M, or mixtures thereof and; M is a sufficient amount of water soluble cations to satisfy the charge balance; x is 0 or 1; y each independently has a value from 0 to 6; z each independently have a value of 0 to 100]. The method of claim 7, wherein The organosilicon photosensitive compound is selected from the group consisting of halogen, C ₁ -C ₂₂ thioalkyl, C ₄ -C ₂₂ branched thioalkyl, C ₁ -C ₂₂ alkoxy, C ₁ -C ₂₂ branched alkoxy and mixtures thereof. A composition comprising a phthalocyanine comprising at least one R ¹ , R ² , R ³ and R ⁴ unit independently selected. The method of claim 8, The organosilicon photosensitive compound comprises at least one R ¹ , R ² , R ³ and R ⁴ unit wherein each unit is independently halogen or C ₁ -C ₆ alkoxy. The method of claim 9, The organosilicon photosensitive compound comprises one or more R ¹ , R ² , R ³ and R ⁴ units, wherein each unit is methoxy. The method of claim 4, wherein The washable surfactant is a kind selected from the group consisting of nonionic, cationic, anionic, dipolar and zwitterionic surfactants and mixtures thereof. The method of claim 11, The additional component is selected from the group consisting of buffers, builders, chelating agents, filler salts, contaminant release agents, dispersants, enzymes, enzyme boosters, perfumes, thickeners, abrasives, solvents, clays, bleaches and mixtures thereof A kind of composition. The method of claim 12, An organosilicon photosensitive compound comprising about 0.005 to about 2000 ppm. The method of claim 13, An organosilicon photosensitive compound comprising about 0.1 to about 1000 ppm. The method of claim 4, wherein A composition comprising about 0.1 to about 95 weight percent of a washable surfactant. The method of claim 15, A composition comprising about 0.1 to about 30 weight percent of a washable surfactant. a) silicon (IV) phthalocyanine of formula (2a); And b) residual amounts of additional components; Silicon (IV) phthalocyanine photobleaching composition comprising: Formula 2a Where R ¹ , R ² , R ³ and R ⁴ units are residues that provide one or more positive red shift values in place of hydrogen; In axial R units, R is each a) hydrogen; b) halogen; c) hydroxyl; d) cyano; e) nitrile; f) oxymino; g) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; h) halogen substituted C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; i) polyhydroxyl substituted C ₃ -C ₂₂ alkyl; j) C ₁ -C ₂₂ alkoxy; k) general formula Branched alkoxy having the [wherein, B is hydrogen, hydroxyl, C ₁ -C ₃₀ alkyl, C ₁ -C _{30 alkoxy, -CO 2 H, -CH 2 CO} 2 H, -SO 3 - M +, -OSO 3 _{^{- M +, -PO 3 2- M}} , -OPO 3 2- M, or a mixture thereof; M is a sufficient amount of water soluble cations to satisfy the charge balance; x is 0 or 1; y each independently has a value from 0 to 6; z each independently has a value from 0 to 100; l) substituted aryl and unsubstituted aryl; m) substituted alkylenearyl and unsubstituted alkylenearyl; n) substituted aryloxy and unsubstituted aryloxy; o) substituted oxyalkylenearyl and unsubstituted oxyalkylenearyl; p) substituted alkyleneoxyaryl and unsubstituted alkyleneoxyaryl; q) C ₁ -C ₂₂ thioalkyl, C ₄ -C ₂₂ branched thioalkyl and mixtures thereof; r) general formula Alkyleneamino units wherein R ¹¹ and R ¹² represent C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof Including; R ¹⁶ is i) hydrogen, ii) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof It includes; A unit comprises nitrogen or oxygen; X comprises chlorine, bromine, iodine or other water soluble anions; v is 0 or 1; u is 0 to 22; s) amino units of the formula -NR ¹¹ R ¹² , wherein R ¹¹ and R ¹² units are C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ Side chain alkenyl and mixtures thereof); t) alkyl ethyleneoxy units of the formula-(A) _v- (CH ₂ ) _y (OCH ₂ CH ₂ ) _x Z, wherein Z is i) hydrogen, ii) hydroxyl, iii) -CO ₂ H, iv) -SO ₃ ^- M ⁺ , v) -OSO ₃ ^- M ⁺ , vi) C ₁ -C ₆ alkoxy, vii) substituted aryl and unsubstituted aryl, viii) substituted aryloxy and unsubstituted aryloxy, ix) alkyleneamino, and mixtures thereof It includes; A unit comprises nitrogen or oxygen; M is a water soluble cation; v is 0 or 1; x is 0 to 100; y is 0 to 12; u) general formula Of carboxylates, where R ¹⁰ is i) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; ii) halogen substituted C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; iii) polyhydroxyl substituted C ₃ -C ₂₂ alkyl; iv) C ₃ -C ₂₂ glycol; v) C ₁ -C ₂₂ alkoxy; vi) C ₄ -C ₂₂ branched alkoxy; vii) substituted aryl and unsubstituted aryl; viii) substituted alkylaryl and unsubstituted alkylaryl; ix) substituted aryloxy and unsubstituted aryloxy; x) substituted alkoxyaryl and unsubstituted alkoxyaryl; xi) substituted alkyleneoxyaryl and unsubstituted alkyleneoxyaryl; xii) alkyleneamino; And mixtures thereof; v) substituted siloxy of the formula -OSiR ⁷ R ⁸ R ⁹ , wherein R ⁷ , R ⁸ and R ⁹ are i) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; ii) substituted aryl and unsubstituted aryl; iii) substituted aryloxy and unsubstituted aryloxy; iv) alkylethyleneoxy units of the formula-(A) _v- (CH ₂ ) _y (OCH ₂ CH ₂ ) _x Z, wherein Z is a) hydrogen, b) C ₁ -C ₃₀ alkyl, c) hydroxyl, d) -CO ₂ H, e) -SO ₃ ^- M ⁺ , f) -OSO ₃ ^- M ⁺ , g) C ₁ -C ₆ alkoxy, h) substituted aryl and unsubstituted aryl, i) substituted aryloxy and unsubstituted aryloxy, j) alkyleneamino, and mixtures thereof It includes; A unit comprises nitrogen or oxygen; M is a water soluble cation; v is 0 or 1; x is 0 to 100; y is 0 to 12) and mixtures thereof Independently selected from the group consisting of It is independently selected from the group consisting of. The method of claim 17, R ¹ , R ² , R ³ and R ⁴ are hydrogen, hydroxyl, halogen, C ₁ -C ₂₂ thioalkyl, C ₄ -C ₂₂ branched thioalkyl, C ₁ -C ₂₂ alkoxy, C ₁ -C ₂₂ branched alkoxy , aryloxy, the formula _{- (a) v - (CH} 2) y (OCH 2 CH 2) x Z of alkyl ethylene oxide units [wherein, Z is hydrogen, ^{_{hydroxyl, -CO 2 H, -SO 3 -}} M _{^{+, -OSO 3 - M +,}} C 1 -C 6 alkoxy, and including substituted aryl and unsubstituted aryl, a substituted aryloxy group and unsubstituted aryloxy, amino-alkylene, and mixtures thereof; A comprises nitrogen or oxygen; M is a water soluble cation; v is 0 or 1; x is 0 to 100; y is 0 to 12]. The method of claim 18, The axial R unit a) general formula _{- (A) v - (CH} 2) y (OCH 2 CH 2) x Z of alkyl ethylene oxide units [wherein, Z is hydrogen, ^{_{hydroxyl, -CO 2 H, -SO 3 -}} M +, -OSO ₃ ^- including M ^+, C ₁ -C ₆ alkoxy group, a substituted aryl, and unsubstituted aryl, a substituted aryloxy group and unsubstituted aryloxy group, and the alkylene and amino; A comprises nitrogen or oxygen; M is a water soluble cation; v is 0 or 1; x is 0 to 100; y is 0 to 12; b) general formula Branched alkoxy having the [wherein, B is hydrogen, hydroxyl, C ₁ -C ₃₀ alkyl, C ₁ -C _{30 alkoxy, -CO 2 H, -CH 2 CO} 2 H, -SO 3 - M +, -OSO 3 _{^{- M +, -PO 3 2- M}} , -OPO 3 2- M, or a mixture thereof; M is a sufficient amount of water soluble cations to satisfy the charge balance; x is 0 or 1; y each independently has a value from 0 to 6; z each independently has a value from 0 to 100; c) substituted siloxy of the formula -OSiR ⁷ R ⁸ R ⁹ wherein R ⁷ , R ⁸ and R ⁹ are C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl , C ₄ -C ₂₂ branched alkenyl, substituted aryl and unsubstituted aryl, substituted aryloxy and unsubstituted aryloxy, general formula-(A) _v- (CH ₂ ) _y (OCH ₂ CH ₂ ) _x of Z-alkyl ethyleneoxy units (wherein, Z is hydrogen, C ₁ -C ₃₀ alkyl, ^{_{hydroxyl, -CO 2 H, -SO 3 -}} M +, -OSO 3 - M +, C 1 -C 6 alkoxy, substituted Aryl and unsubstituted aryl, substituted aryloxy and unsubstituted aryloxy, alkyleneamino and mixtures thereof; A unit comprises nitrogen or oxygen; M is a water soluble cation; v is 0 or 1, x is 0 to 100 and y is 0 to 12); And d) mixtures thereof Composition comprising a. The method of claim 19, R ¹ , R ² , R ³ and R ⁴ are independently from the group consisting of halogen, C ₁ -C ₂₂ thioalkyl, C ₄ -C ₂₂ branched thioalkyl, C ₁ -C ₂₂ alkoxy, aryloxy and mixtures thereof Selected composition. The method of claim 20, R ¹ , R ² , R ³ and R ⁴ are independently selected from the group consisting of halogen, C ₁ -C ₂₂ alkoxy and mixtures thereof. The method of claim 21, R ¹ , R ² , R ³ and R ⁴ are independently selected from the group consisting of halogen, C ₁ -C ₆ alkoxy and mixtures thereof. The method of claim 22, R ¹ , R ² , R ³ and R ⁴ are methoxy. The method of claim 17, Wherein the additional component is selected from the group consisting of washable surfactants, buffers, enhancers, chelating agents, filler salts, contaminant release agents, dispersants, enzymes, enzyme boosters, perfumes, thickeners, clays, bleaches, solvents, and mixtures thereof. The method of claim 24, And wherein the washable surfactant is selected from the group consisting of nonionic, cationic, anionic, bipolar and amphoteric surfactants, and mixtures thereof. The method of claim 17, The composition whose red mutation value is 10 or more. The method of claim 17, A composition having a red shift value of 30 or more. a) silicon (IV) phthalocyanine of formula (2a); And b) residual amounts of additional components; Silicon phthalocyanine photobleaching composition comprising: Formula 2a Where R ¹ , R ² , R ³ and R ⁴ units are residues which, when substituted for hydrogen, give a positive Δ _triplet yield; In axial R units, R is each a) hydrogen; b) halogen; c) hydroxyl; d) cyano; e) nitrile; f) oxymino; g) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; h) halogen substituted C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; i) polyhydroxyl substituted C ₃ -C ₂₂ alkyl; j) C ₁ -C ₂₂ alkoxy; k) general formula Branched alkoxy having the [wherein, B is hydrogen, hydroxyl, C ₁ -C ₃₀ alkyl, C ₁ -C _{30 alkoxy, -CO 2 H, -CH 2 CO} 2 H, -SO 3 - M +, -OSO 3 _{^{- M +, -PO 3 2- M}} , -OPO 3 2- M, or a mixture thereof; M is a sufficient amount of water soluble cations to satisfy the charge balance; x is 0 or 1; y each independently has a value from 0 to 6; z each independently has a value from 0 to 100; l) substituted aryl and unsubstituted aryl; m) substituted alkylenearyl and unsubstituted alkylenearyl; n) substituted aryloxy and unsubstituted aryloxy; o) substituted oxyalkylenearyl and unsubstituted oxyalkylenearyl; p) substituted alkyleneoxyaryl and unsubstituted alkyleneoxyaryl; q) C ₁ -C ₂₂ thioalkyl, C ₄ -C ₂₂ branched thioalkyl and mixtures thereof; r) general formula Alkyleneamino units wherein R ¹¹ and R ¹² represent C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof Including; R ¹⁶ is i) hydrogen, ii) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof It includes; A unit comprises nitrogen or oxygen; X comprises chlorine, bromine, iodine or other water soluble anions; v is 0 or 1; u is 0 to 22; s) amino units of —NR ¹¹ R ¹² wherein R ¹¹ and R ¹² are C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl And mixtures thereof); t) alkyl ethyleneoxy units of the formula-(A) _v- (CH ₂ ) _y (OCH ₂ CH ₂ ) _x Z, wherein Z is i) hydrogen, ii) hydroxyl, iii) -CO ₂ H, iv) -SO ₃ ^- M ⁺ , v) -OSO ₃ ^- M ⁺ , vi) C ₁ -C ₆ alkoxy, vii) substituted aryl and unsubstituted aryl, viii) substituted aryloxy and unsubstituted aryloxy, ix) alkyleneamino, and mixtures thereof It includes; A comprises nitrogen or oxygen; M is a water soluble cation; v is 0 or 1; x is 0 to 100; y is 0 to 12; u) general formula Of carboxylates, where R ¹⁰ is i) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; ii) halogen substituted C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; iii) polyhydroxyl substituted C ₃ -C ₂₂ alkyl; iv) C ₃ -C ₂₂ glycol; v) C ₁ -C ₂₂ alkoxy; vi) C ₄ -C ₂₂ branched alkoxy; vii) substituted aryl and unsubstituted aryl; viii) substituted alkylaryl and unsubstituted alkylaryl; ix) substituted aryloxy and unsubstituted aryloxy; x) substituted alkoxyaryl and unsubstituted alkoxyaryl; xi) substituted alkyleneoxyaryl and unsubstituted alkyleneoxyaryl; xii) alkyleneamino; And mixtures thereof; v) substituted siloxy of the formula -OSiR ⁷ R ⁸ R ⁹ , wherein R ⁷ , R ⁸ and R ⁹ are i) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; ii) substituted aryl and unsubstituted aryl; iii) substituted aryloxy and unsubstituted aryloxy; iv) alkylethyleneoxy units of the formula-(A) _v- (CH ₂ ) _y (OCH ₂ CH ₂ ) _x Z, wherein Z is a) hydrogen, b) C ₁ -C ₃₀ alkyl, c) hydroxyl, d) -CO ₂ H, e) -SO ₃ ^- M ⁺ , f) -OSO ₃ ^- M ⁺ , g) C ₁ -C ₆ alkoxy, h) substituted aryl and unsubstituted aryl, i) substituted aryloxy and unsubstituted aryloxy, j) alkyleneamino, and mixtures thereof It includes; A unit comprises nitrogen or oxygen; M is a water soluble cation; v is 0 or 1; x is 0 to 100; y is 0 to 12) and mixtures thereof Independently selected from the group consisting of It is independently selected from the group consisting of. The method of claim 28, A composition wherein the triplet state yield increase is at least 10. The method of claim 28, Wherein the triplet state yield increase is at least 30. a) at least about 0.01% non-hypohalite bleach; b) at least 0.001 ppm of an organosilicon (IV) phthalocyanine photosensitive compound of formula 2a having a Q-band maximum absorption wavelength of at least 660 nm; And c) residual amounts of additional components and carriers Bleaching composition comprising: Formula 2a Where R ¹ , R ² , R ³ and R ⁴ units are a) hydrogen; b) halogen; c) hydroxyl; d) cyano; e) nitrile; f) oxymino; g) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; h) halogen substituted C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; i) polyhydroxyl substituted C ₃ -C ₂₂ alkyl; j) C ₁ -C ₂₂ alkoxy; k) general formula Branched alkoxy having the [wherein, B is hydrogen, hydroxyl, C ₁ -C ₃₀ alkyl, C ₁ -C _{30 alkoxy, -CO 2 H, -CH 2 CO} 2 H, -SO 3 - M +, -OSO 3 _{^{- M +, -PO 3 2- M}} , -OPO 3 2- M, or a mixture thereof; M is a sufficient amount of water soluble cations to satisfy the charge balance; x is 0 or 1; y each independently has a value from 0 to 6; z each independently has a value from 0 to 100; l) substituted aryl and unsubstituted aryl; m) substituted alkylenearyl and unsubstituted alkylenearyl; n) substituted aryloxy and unsubstituted aryloxy; o) substituted oxyalkylenearyl and unsubstituted oxyalkylenearyl; p) substituted alkyleneoxyaryl and unsubstituted alkyleneoxyaryl; q) C ₁ -C ₂₂ thioalkyl, C ₄ -C ₂₂ branched thioalkyl and mixtures thereof; r) an ester of the general formula -CO ₂ R ¹⁰ , wherein R ¹⁰ is i) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; ii) halogen substituted C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; iii) polyhydroxyl substituted C ₃ -C ₂₂ alkyl; iv) C ₃ -C ₂₂ glycol; v) C ₁ -C ₂₂ alkoxy; vi) C ₄ -C ₂₂ branched alkoxy; vii) substituted aryl and unsubstituted aryl; viii) substituted alkylaryl and unsubstituted alkylaryl; ix) substituted aryloxy and unsubstituted aryloxy; x) substituted alkoxyaryl and unsubstituted alkoxyaryl; xi) substituted alkyleneoxyaryl and unsubstituted alkyleneoxyaryl; And mixtures thereof; s) general formula Alkyleneamino units wherein R ¹¹ and R ¹² represent C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof Including; R ¹⁶ is i) hydrogen, ii) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof It includes; A unit comprises nitrogen or oxygen; X comprises chlorine, bromine, iodine or other water soluble anions; v is 0 or 1; u is 0 to 22; t) amino units of —NR ¹¹ R ¹² wherein R ¹¹ and R ¹² units are C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ side chain alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ side chain eggs Kenyl and mixtures thereof); u) alkylethyleneoxy units of the general formula-(A) _v- (CH ₂ ) _y (OCH ₂ CH ₂ ) _x Z, wherein Z is i) hydrogen, ii) hydroxyl, iii) -CO ₂ H, iv) -SO ₃ ^- M ⁺ , v) -OSO ₃ ^- M ⁺ , vi) C ₁ -C ₆ alkoxy, vii) substituted aryl and unsubstituted aryl, viii) substituted aryloxy and unsubstituted aryloxy, ix) alkyleneamino, and mixtures thereof It includes; A comprises nitrogen or oxygen; M is a water soluble cation; v is 0 or 1; x is 0 to 100; y is 0 to 12; v) substituted siloxy of the formula -OSiR ⁷ R ⁸ R ⁹ , wherein R ⁷ , R ⁸ and R ⁹ are i) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; ii) substituted aryl and unsubstituted aryl; iii) substituted aryloxy and unsubstituted aryloxy; iv) alkylethyleneoxy units of the formula-(A) _v- (CH ₂ ) _y (OCH ₂ CH ₂ ) _x Z, wherein Z is a) hydrogen, b) C ₁ -C ₃₀ alkyl, c) hydroxyl, d) -CO ₂ H, e) -SO ₃ ^- M ⁺ , f) -OSO ₃ ^- M ⁺ , g) C ₁ -C ₆ alkoxy, h) substituted aryl and unsubstituted aryl, i) substituted aryloxy and unsubstituted aryloxy, j) alkyleneamino, and mixtures thereof It includes; A unit comprises nitrogen or oxygen; M is a water soluble cation; v is 0 or 1; x is 0 to 100; y is 0 to 12) and mixtures thereof Independently selected from the group consisting of Independently selected from the group consisting of In axial R, R is each a) hydrogen; b) halogen; c) hydroxyl; d) cyano; e) nitrile; f) oxymino; g) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; h) halogen substituted C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; i) polyhydroxyl substituted C ₃ -C ₂₂ alkyl; j) C ₁ -C ₂₂ alkoxy; k) general formula Branched alkoxy having the [wherein, B is hydrogen, hydroxyl, C ₁ -C ₃₀ alkyl, C ₁ -C _{30 alkoxy, -CO 2 H, -CH 2 CO} 2 H, -SO 3 - M +, -OSO 3 _{^{- M +, -PO 3 2- M}} , -OPO 3 2- M, or a mixture thereof; M is a sufficient amount of water soluble cations to satisfy the charge balance; x is 0 or 1; y each independently has a value from 0 to 6; z each independently has a value from 0 to 100; l) substituted aryl and unsubstituted aryl; m) substituted alkylenearyl and unsubstituted alkylenearyl; n) substituted aryloxy and unsubstituted aryloxy; o) substituted oxyalkylenearyl and unsubstituted oxyalkylenearyl; p) substituted alkyleneoxyaryl and unsubstituted alkyleneoxyaryl; q) C ₁ -C ₂₂ thioalkyl, C ₄ -C ₂₂ branched thioalkyl and mixtures thereof; r) general formula Alkyleneamino units wherein R ¹¹ and R ¹² represent C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof Including; R ¹⁶ is i) hydrogen, ii) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof It includes; A unit comprises nitrogen or oxygen; X comprises chlorine, bromine, iodine or other water soluble anions; v is 0 or 1; u is 0 to 22; s) amino units of —NR ¹¹ R ¹² , wherein R ¹¹ and R ¹² units are C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ side chain alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ side chain eggs Kenyl and mixtures thereof); t) alkyl ethyleneoxy units of the formula-(A) _v- (CH ₂ ) _y (OCH ₂ CH ₂ ) _x Z, wherein Z is i) hydrogen, ii) hydroxyl, iii) -CO ₂ H, iv) -SO ₃ ^- M ⁺ , v) -OSO ₃ ^- M ⁺ , vi) C ₁ -C ₆ alkoxy, vii) substituted aryl and unsubstituted aryl, viii) substituted aryloxy and unsubstituted aryloxy, ix) alkyleneamino, and mixtures thereof It includes; A unit comprises nitrogen or oxygen; M is a water soluble cation; v is 0 or 1; x is 0 to 100; y is 0 to 12; u) general formula Of carboxylates, where R ¹⁰ is i) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; ii) halogen substituted C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; iii) polyhydroxyl substituted C ₃ -C ₂₂ alkyl; iv) C ₃ -C ₂₂ glycol; v) C ₁ -C ₂₂ alkoxy; vi) C ₄ -C ₂₂ branched alkoxy; vii) substituted aryl and unsubstituted aryl; viii) substituted alkylaryl and unsubstituted alkylaryl; ix) substituted aryloxy and unsubstituted aryloxy; x) substituted alkoxyaryl and unsubstituted alkoxyaryl; xi) substituted alkyleneoxyaryl and unsubstituted alkyleneoxyaryl; xii) alkyleneamino; And mixtures thereof; v) substituted siloxy of the formula -OSiR ⁷ R ⁸ R ⁹ , wherein R ⁷ , R ⁸ and R ⁹ are i) C ₁ -C ₂₂ alkyl, C ₄ -C ₂₂ branched alkyl, C ₁ -C ₂₂ alkenyl, C ₄ -C ₂₂ branched alkenyl and mixtures thereof; ii) substituted aryl and unsubstituted aryl; iii) substituted aryloxy and unsubstituted aryloxy; iv) alkylethyleneoxy units of the formula-(A) _v- (CH ₂ ) _y (OCH ₂ CH ₂ ) _x Z, wherein Z is a) hydrogen, b) C ₁ -C ₃₀ alkyl, c) hydroxyl, d) -CO ₂ H, e) -SO ₃ ^- M ⁺ , f) -OSO ₃ ^- M ⁺ , g) C ₁ -C ₆ alkoxy, h) substituted aryl and unsubstituted aryl, i) substituted aryloxy and unsubstituted aryloxy, j) alkyleneamino, and mixtures thereof It includes; A unit comprises nitrogen or oxygen; M is a water soluble cation; v is 0 or 1; x is 0 to 100; y is 0 to 12) and mixtures thereof Independently selected from the group consisting of It is independently selected from the group consisting of. The method of claim 31, wherein And wherein the non-hypohalite bleach is selected from the group consisting of percarboxylic acids, peroxides, percarbonates, perborates, and mixtures thereof. The method of claim 32, Composition wherein the additional component comprises a bleach activator.