Bleach compositions containing metal bleach catalyst, and bleach activators and/or organic percarboxylic acids

• US 6,306,812 B1
• Filed: 09/07/1999
• Issued: 10/23/2001
• Est. Priority Date: 03/07/1997
• Status: Expired due to Term

• Current Assignee: The Procter & Gamble Company
• Original Assignee: The Procter & Gamble Company
• Inventors: Labeque, Regine, Kitko, David Johnathan, Williams, Barbara Kay, Burckett-St. Laurent, James Charles Theophile Roger, Johnston, James Pyott, Perkins, Christopher Mark, Burns, Michael Eugene
• Primary Examiner(s): DELCOTTO, GREGORY R
• Application Number:
  US09/380,673
• Time in Patent Office: 777 Days
• Field of Search: 510/302, 510/303, 510/304, 510/311, 510/310, 510/312, 510/313, 510/314, 510/220, 510/221, 510/224, 510/372, 510/376, 811/1, 813/7, 134/25.2, 134/42, 252/186.33
• US Class Current: 510/310
• CPC Class Codes: C11D 3/168 Organometallic compounds or orgometallic complexes
• CPC Class Codes: C11D 3/3907 Organic compounds
• CPC Class Codes: C11D 3/3932 Inorganic compounds or complexes
• CPC Class Codes: C11D 3/3945 Organic per-compounds C11D3/3902 takes precedence

Abstract

Laundry or cleaning composition comprising: a) an effective amount of a bleach activator and/or organic percarboxylic acid; b) a catalytically effective amount of a transition-metal bleach catalyst which is a complex of a transition-metal and a cross-bridged macropolycyclic ligand; and c) at least about 0.1% of one or more laundry or cleaning adjunct materials. Preferred compositions are laundry compositions and automatic dishwashing detergents which provide enhanced cleaning/bleaching benefits through the use of such catalysts in combination with bleach activators and/or organic perearboxylic acids.

Claims

1. A laundry or cleaning composition comprising:

(a) from 0.0001% to 99.9% of a bleach activator and/or organic percarboxylic acid;

(b) from 0.001 ppm to 49% of a transition-metal bleach catalyst, said catalyst comprising a complex of a transition metal and a cross-bridged macropolycyclic ligand, wherein;

(1) said transition metal is selected from the group consisting of Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV), Co(I), Co(II), Co(III), Ni(I), Ni(II), Ni(III), Cu(I), Cu(II), Cu(III), Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(III), V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II), Ru(III), and Ru(IV);

(2) said cross-bridged macropolycyclic ligand being coordinated by four or five donor atoms to the same transition metal and comprising;

(i) an organic macrocycle ring containing four or more donor atoms separated from each other by covalent linkages of 2 or 3 non-donor atoms, two to five of these donor atoms being coordinated to the same transition metal atom in the complex;

(ii) a cross-bridged chain which covalently connects at least 2 non-adjacent donor atoms of the organic macrocycle ring, said covalently connected non-adjacent donor atoms being bridgehead donor atoms which are coordinated to the same transition metal in the complex, and wherein said cross-bridged chain comprises from 2 to 10 atoms; and

(iii) optionally, one or more non-macropolycyclic ligands; and

(c) at least 0.1%, of one or more laundry or cleaning adjunct materials.

2. The composition according to claim 1 comprising a transition-metal bleach catalyst wherein the donor atoms in the organic macrocycle ring of the cross-bridged macropolycyclic ligand are selected from the group consisting of N, O, S, and P.

3. The composition according to claim 2 comprising a transition-metal bleach catalyst wherein all the donor atoms in the cross-bridged macropolycyclic ligand are selected from the group consisting of N and O.

4. The composition according to claim 3 comprising a transition-metal bleach catalyst wherein the cross-bridged macropolycyclic ligand comprises 4 or 5 donor atoms, all of which are coordinated with the same transition metal.

5. The composition according to claim 4 comprising a transition-metal bleach catalyst wherein the cross-bridged macropolycyclic ligand comprises 4 nitrogen donor atoms all coordinated to the same transition metal.

6. The composition according to claim 4 comprising a transition-metal bleach catalyst wherein the cross-bridged macropolycyclic ligand comprises 5 nitrogen atoms all coordinated to the same transition metal.

7. The composition according to claim 6 wherein the transition-metal bleach catalyst is a monometallic, mononuclear complex.

8. The composition according to claim 7 comprising a transition-metal bleach catalyst wherein at least four of the donor atoms in the cross-bridged macropolycyclic ligand form an apical bond angle with the same transition metal of 180±

50° and

at least one equatorial bond angle of 90±

20°

.

9. The composition according to claim 8 comprising a transition-metal bleach catalyst having coordination geometry selected from the group consisting of distorted octahedral and distorted trigonal prismatic.

10. The composition according to claim 9 comprising a transition-metal bleach catalyst wherein two of the donor atoms in the cross-bridged macropolycyclic ligand occupy mutually trans positions of the coordination geometry, and at least two of the donor atoms in the cross-bridged macropolycyclic ligand occupy cis-equatorial positions of the coordination geometry.

11. The composition according to claim 10 comprising a transition-metal bleach catalyst which comprises one or two non-macropolycyclic ligands.

12. The composition according to claim 11 comprising a transition-metal bleach catalyst wherein the cross-bridged macropolycyclic ligand comprises an organic macrocycle ring containing at least 12 atoms.

13. The composition according to claim 12 comprising a transition-metal bleach catalyst wherein the transition metal is selected from manganese and iron.

14. The composition according to claim 13 further comprising an oxygen bleaching agent.

35. A method for cleaning fabrics or hard surfaces, said method comprising contacting a fabric or hard surface in need of cleaning with a composition according to claim 1 an oxygen bleaching agent.

36. The method according to claim 35 comprising a bleach activator selected from the group consisting quaternary carbamate-, quaternary carbonate-, quaternary ester- and quaternary amide cationic bleach activators, phenol sulfonate ester of alkanoyl aminoacids, acyl phenol sulfonates, acyl alkyl phenol sulfonates, acyl oxybenzenesulfonates, and bleach activators having the formulae:

or mixtures thereof, wherein R is a C₂-C₁₈ saturated or unsaturated alkyl, aryl, or alkylaryl moiety, R¹ is alkyl, aryl, or alkaryl containing from about 1 to about 14 carbon atoms, R² is alkylene, arylene or alkarylene containing from about 1 to about 14 carbon atoms, R⁵ is H, or an alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is a leaving group selected from the group consisting of;

and mixtures thereof, wherein R¹ is a linear or branched alkyl, aryl, or alkaryl group containing from about 1 to about 14 carbon atoms, R³ is an alkyl chain containing from 1 to about 8 carbon atoms, R⁴ is H or R³, and Y is H or a solubilizing group, selected from the group consisting of —

SO3⁻

M⁺, —

CO2⁻

M⁺, —

SO4⁻

M⁺, —

N⁺(R)4X⁻

and O←

N(R³)2, wherein R³ is an alkyl chain containing from about 1 to about 4 carbon atoms, M is a bleach-stable cation and X is a bleach-stable anion, and bleach activators having the formulae;

wherein R⁶ is H, alkyl, aryl, alkoxyaryl, an alkaryl group containing from 1 to about 12 carbon atoms, or substituted phenyl containing from about 6 to about 18 carbons.

37. The method according to claim 35 comprising a bleach activator selected from the group consisting of 2-(N,N,N-trimethyl ammonium) ethyl-4-sulphophenyl carbonate;

N-octyl,N,N-dimethyl-N 10-carbophenoxy decyl ammonium chloride;

3-(N,N,N-trimethyl ammonium) propyl sodium-4-sulphophenyl carboxylate;

N,N,N-trimethyl ammonium toluyloxy benzene sulfonate, N,N,N′

N′

-tetraacetyl ethylene diamine, sodium nonanoyloxybenzene sulfonate, sodium-4-benzoyloxy benzene sulfonate;

sodium-1-methyl-2-benzoyloxy benzene-4-sulphonate;

sodium-4-methyl-3-benzoyloxy benzoate;

trimethyl ammonium toluyloxy-benzene sulfonate;

sodium 3,5,5-trimethyl hexanoyloxybenzene sulfonate, (6-octanamidocaproyl)oxybenzene-sulfonate, (6-nonanamidocaproyl)oxybenzenesulfonate, (6-decanamidocaproyl)oxy-benzenesulfonate, and mixtures thereof.

38. The method according to claim 35 comprising a organic percarboxylic acid selected from the group consisting of organic percarboxylic acids of formula:

or mixtures thereof wherein R¹ is alkyl, aryl, or alkaryl containing from about 1 to about 14 carbon atoms, R² is alkylene, arylene or alkaryene containing from about 1 to about 14 carbon atoms, and R⁵ is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms.

39. The method according to claim 35 comprising a organic percarboxylic acid having formula HO—

O—

C(O)—

RO—

Y wherein R is an alkylene or substituted alkylene group containing from 1 to about 22 carbon atoms or a phenylene or substituted phenylene group, and Y is hydrogen, halogen, alkyl, alkyhalogen, aryl or —

C(O)—

OH or —

C(O)—

O—

OH.

40. The method according to claim 35 comprising a organic percarboxylic acid selected from the group consisting of magnesium monoperoxyphthalate hexahydrate, m-chloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid, 6-nonylamino-6-oxoperoxycaproic acid, peroxybenzoic acid and ring-substituted peroxybenzoic acids.

15. A laundry or cleaning composition comprising:

(a) from about 0.0001% to about 99.9% of a bleach activator and/or organic percarboxylic acid;

(b) from about 0.001 ppm to about 49% of a transition-metal bleach catalyst, said catalyst comprising a complex of a transition metal and a cross-bridged macropolycyclic ligand, wherein;

(1) said transition metal is selected from the group consisting of Mn(II), Mn(III), Mn(IV), Mn(V), Fe(II), Fe(III), Fe(IV), Co(I), Co(II), Co(III), Ni(I), Ni(II), Ni(III), Cu(I), Cu(II), Cu(III), Cr(II), Cr(III), Cr(IV), Cr(V), Cr(VI), V(III), V(IV), V(V), Mo(IV), Mo(V), Mo(VI), W(IV), W(V), W(VI), Pd(II), Ru(II), Ru(III), and Ru(IV), and;

(2) said cross-bridged macropolycyclic ligand is selected from the group consisting of;

(i) the cross-bridged macropolycyclic ligand of formula (I) having denticity of 4 or 5;

(ii) the cross-bridged macropolycyclic ligand of formula (II) having denticity of 5 or 6;

(iii) the cross-bridged macropolycyclic ligand of formula (III) having denticity of 6 or 7;

 

wherein in these formulas;

each “

E”

is the moiety (CR_n)_a—

X—

(CR_n)_a′

, wherein —

X—

is selected from the group consisting of O, S, NR and P, or is a covalent bond, and for each E the sum of a+a′

is independently selected from 1 to 5;

each “

G”

is the moiety (CR_n)_b;

each “

R”

is independently selected from H, alkyl, alkenyl, alkynyl, aryl, alkylaryl, and heteroaryl, or two or more R are covalently bonded to form an aromatic, heteroaromatic, cycloalkyl, or heterocycloalkyl ring;

each “

D”

is a donor atom independently selected from the group consisting of N, O, S, and P, and at least two D atoms are bridgehead donor atoms coordinated to the transition metal;

“

B”

is a carbon atom or “

D”

donor atom, or a cycloalkyl or heterocyclic ring;

each “

n”

is an integer independently selected from 1 and 2, completing the valence of the carbon atoms to which the R moieties are covalently bonded;

each “

n′

”

is an integer independently selected from 0 and 1, completing the valence of the D donor atoms to which the R moieties are covalently bonded;

each “

n″

”

is an integer independently selected from 0, 1, and 2 completing the valence of the B atoms to which the R moieties are covalently bonded;

each “

a” and

“

a′

”

is an integer independently selected from 0-5, wherein the sum of all “

a”

plus “

a′

”

in the ligand of formula (I) is within the range of from about 8 to about 12, the sum of all “

a”

plus “

a′

”

in the ligand of formula (II) is within the range of from about 10 to about 15, and the sum of all “

a”

plus “

a′

”

in the ligand of formula (III) is within the range of from about 12 to about 18;

each “

b”

is an integer independently selected from 0-9, or in any of the above formulas, one or more of the (CR_n)_b moieties covalently bonded from any D to the B atom is absent as long as at least two (CR_n)_b covalently bond two of the D donor atoms to the B atom in the formula, and the sum of all “

b”

is within the range of from about 1 to about 5; and

(iii) optionally, one or more non-macropolycyclic ligands; and

(c) at least about 0.1% of one or more laundry or cleaning adjunct materials.

16. The composition according to claim 15 comprising a transition-metal bleach catalyst wherein in the cross-bridged macropolycyclic ligand the D is selected from the group consisting of N and O.

17. The composition according to claim 16 comprising a transition-metal bleach catalyst wherein the transition metal is selected from manganese and iron.

18. The composition according to claim 17 comprising a transition-metal bleach catalyst wherein in the cross-bridged macropolycyclic ligand all “

a”

are independently selected from the integers 2 and 3, all X are selected from covalent bonds, all “

a′

”

are 0, and all “

b”

are independently selected from the integers 0, 1, and 2.

19. The composition according to claim 18 comprising a transition-metal bleach catalyst wherein the molar ratio of transition metal to cross-bridged macropolycyclic ligand is 1:

1.

20. The composition according to claim 19 wherein the transition-metal bleach catalyst comprises only one metal per catalyst complex.

21. The composition according to claim 20 comprising a transition-metal bleach catalyst wherein in the cross-bridged macropolycyclic ligand B is selected from carbon or nitrogen.

22. The composition according to claim 21 wherein the transition-metal bleach catalyst comprises a tetradentate or pentadentate cross-bridged macropolycyclic ligand.

23. The composition according to claim 22 comprising a transition-metal bleach catalyst wherein all the donor atoms in the cross-bridged macropolycyclic ligand are selected from the group consisting of N and O.

24. The composition according to claim 23 comprising a transition-metal bleach catalyst wherein the cross-bridged macropolycyclic ligand comprises 4 or 5 donor atoms, all of which are coordinated with the same transition metal.

25. The composition according to claim 24 comprising a transition-metal bleach catalyst wherein the cross-bridged macropolycyclic ligand comprises 4 nitrogen donor atoms all coordinated to the same transition metal.

26. The composition according to claim 24 comprising a transition-metal bleach catalyst wherein the cross-bridged macropolycyclic ligand comprises 5 nitrogen atoms all coordinated to the same transition metal.

27. The composition according to claim 26 wherein the transition-metal bleach catalyst is a monometallic, mononuclear complex.

28. The composition according to claim 27 comprising a transition-metal bleach catalyst containing at least four of the donor atoms in the cross-bridged macropolycyclic ligand, two of which form an apical bond angle with the same transition metal of 180±

50° and

two of which at least one equatorial bond angle of 90±

20°

.

29. The composition according to claim 28 comprising a transition-metal bleach catalyst having coordination geometry selected from the group consisting of distorted octahedral and distorted trigonal prismatic.

30. The composition according to claim 29 comprising a transition-metal bleach catalyst wherein two of the donor atoms in the cross-bridged macropolycyclic ligand occupy mutually trans positions of the coordination geometry, and at least two of the donor atoms in the cross-bridged macropolycyclic ligand occupy cis-equatorial positions of the coordination geometry.

31. The composition according to claim 30 comprising a transition-metal bleach catalyst which comprises one or two non-macropolycyclic ligands.

32. The composition according to claim 31 comprising a transition-metal bleach catalyst wherein the cross-bridged macropolycyclic ligand comprises an organic macrocycle ring containing at least 12 atoms.

33. The composition according to claim 32 further comprising an oxygen bleaching agent.

34. The composition according to claim 33 wherein the laundry or cleaning adjunct is selected from the group consisting of detersive surfactants, builders, enzymes, oxygen bleaching agents, and mixtures thereof, and wherein further said composition has a pH of from about 7 to about 9.5.