IP Library Granted Patent US 12680052
Granted Patent B2
US 12680052 · App. 18/144,980 · Granted Jul 14, 2026

Metal complexes-containing dishwashing detergents

Inventors: Christian Kropf (Hilden, DE); Christian Umbreit (Neuss, DE)
Assignee: Henkel AG & Co. KGaA
C11D3/168C11D1/72C11D1/722C11D3/20C11D3/2041C11D3/2075C11D3/2079C11D3/26C11D7/261C11D7/262C11D7/266C11D7/3254C11D2111/14
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Quick Facts
Patent No.
US 12680052
App. No.
18/144,980
Granted
Jul 14, 2026
Kind
B2
Abstract

Dishwashing detergents containing a metal complex of the general formula (I) (A q+ ) p [M s+ L m− ](X o− ) r (I) and related methods.

Claims (83)

1 . A dishwashing detergent comprising:

a metal complex of the general formula (I),

(

A

q

+

)

p

[

M

s

+

L

m

-

]

(

X

o

-

)

r

(

I

)

wherein:

q is 1 or 2,

A q+ represents a cation selected from the group consisting of alkali metal cations where q=1, ½ alkaline earth cations where q=2, and ammonium ions where q=1,

M s+ represents an aluminum ion, a transition metal ion, or a lanthanide metal ion,

s is a number from 1 to 5,

L represents a ligand of the formula (II),

wherein:

each R 1 and R 2 independently of each other is selected from the group consisting of H, unsubstituted or substituted, linear or branched C 1-20 alkyl, unsubstituted or substituted, linear or branched C 1-20 heteroalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted, linear or branched C 2-20 alkenyl, unsubstituted or substituted, linear or branched C 2-20 heteroalkenyl, unsubstituted or substituted, linear or branched C 2-20 alkinyl, unsubstituted or substituted, linear or branched alkylaryl, and unsubstituted or substituted, linear or branched alkylheteroaryl, and

each R 3 independently of each other represents CH 2 COOH or CH 2 COO − ,

n is 0 or 1,

X o− represents an anion selected from the group consisting of F − , Cl − , Br − , I − , OH − , HSO 3 − , SO 3 2− , SO 4 2− , HSO 4 − , NO 2 − , NO 3 − , PO 4 3− , HPO 4 2− , H 2 PO 4 − , BF 4 − , PF 6 − , ClO 4 − , acetate, citrate, formate, glutarate, lactate, malate, malonate, oxalate, pyruvate, tartrate, methane sulfonate, methyl sulfate, p-toluene sulfate, and succinate,

m is a number from 0 to 5,

is a number from 1 to 3, and

p and r are independently of each other a number from greater than 0 to 6, such that the sum of s and the product of p and q is equal to the sum of m and the product of r and o, and further such that the charge of formula (II) resulting from the radicals R 1 , R 2 and R 3 is neutral or negative.

2 . The detergent of claim 1 , wherein M s+ is selected from the group consisting of Al 3+ , Ti 4+ , Y 3+ , Zr 4+ , Ce 3+ , Ce 4+ , Sc 3+ , Yb 3+ , and any mixture thereof.

3 . The detergent of claim 1 , wherein each R 1 and R 2 is independently selected from the group consisting of —COOH, —COO, —SH, —SO 3 H, —SO 3 − , —C(O)R 4 , —OR 4 , and —(NR 5 R 6 R 7 R 8 ) + , wherein:

R 4 represents H or linear or branched C 1-6 alkyl, and

R 5 to R 8 independently of each other represent linear or branched C 1-6 alkyl groups.

4 . The detergent of claim 1 , wherein n is 0 in the ligand of the general formula (II).

5 . The detergent of claim 1 , wherein the detergent comprises from 0.001 wt. % to 10 wt. % of the metal complex of the general formula (I), based on the total weight of the detergent.

6 . The detergent of claim 5 , wherein the detergent comprises from 0.01 wt. % to 3 wt. % of the metal complex of the general formula (I), based on the total weight of the detergent.

7 . A method of washing dishes in an automatic dishwasher, the method comprising introducing the detergent of claim 1 into an interior of the automatic dishwasher.

8 . The detergent of claim 1 , further comprising a surfactant.

9 . The detergent of claim 8 , wherein the surfactant is a non-ionic surfactant.

10 . The detergent of claim 9 , wherein the non-ionic surfactant is present in an amount of at least 2 wt %, based on the total weight of the detergent.

11 . The detergent of claim 9 , wherein the non-ionic surfactant is an alkyl glycoside of general formula RO(G) x ,

wherein:

R represents a primary straight-chain or methyl-branched aliphatic radical,

G represents a glycose unit having 5 or 6 carbon atoms, and

x, which indicates the distribution of monoglycosides and oligoglycosides, is from 1 to 10.

12 . The detergent of claim 11 , wherein G is glucose.

13 . The detergent of claim 11 , wherein x is from 1.2 to 1.4.

14 . The detergent of claim 8 , wherein the surfactant is an anionic surfactant.

15 . The detergent of claim 1 , further comprising at least one of a builder, an enzyme, a thickener, a sequestering agent, an electrolyte, a corrosion inhibitor, a foam inhibitor, a dye, a fragrance, a bitter substance, an antimicrobial agent, or a disintegration aid.

16 . The detergent of claim 15 , wherein the corrosion inhibitor is a silver protectant or a glass corrosion inhibitor.

17 . A dishwashing unit comprising:

a water-soluble wrapping; and

the detergent of claim 1 contained within the water-soluble wrapping.

18 . A dishwashing detergent comprising:

a non-ionic surfactant comprising an alkyl glycoside of general formula RO(G) x ,

wherein: R represents a primary straight-chain or methyl-branched aliphatic radical, G represents a glycose unit having 5 or 6 carbon atoms, and

X, which indicates the distribution of monoglycosides and oligoglycosides, is from 1 to 10; and a metal complex of the general formula (I), (A q+ ) p [M s+ L m− ](X o− ) r (I)

wherein:

q is 1 or 2,

A q+ represents a cation selected from the group consisting of alkali metal cations where q=1, ½ alkaline earth cations where q=2, and ammonium ions where q=1,

M s+ represents an aluminum ion, a transition metal ion, or a lanthanide metal ion,

s is a number from 1 to 5,

L represents a ligand of the formula (II),

wherein:

each R 1 and R 2 independently of each other is selected from the group consisting of H, unsubstituted or substituted, linear or branched C 1-20 alkyl, unsubstituted or substituted, linear or branched C 1-20 heteroalkyl, unsubstituted or substituted aryl, unsubstituted or substituted heteroaryl, unsubstituted or substituted, linear or branched C 2-20 alkenyl, unsubstituted or substituted, linear or branched C 2-20 heteroalkenyl, unsubstituted or substituted, linear or branched C 2-20 alkinyl, unsubstituted or substituted, linear or branched alkylaryl, and unsubstituted or substituted, linear or branched alkylheteroaryl, and

each R 3 independently of each other represents CH 2 COOH or CH 2 COO − ,

n is 0 or 1,

X o− represents an anion selected from the group consisting of F − , Cl − , Br − , I − , OH − , HSO 3 − , SO 3 2− , SO 4 2− , HSO 4 − , NO 2 − , NO 3 − , PO 4 3− , HPO 4 2− , H 2 PO 4 − , BF 4 − , PF 6 − , ClO 4 − , acetate, citrate, formate, glutarate, lactate, malate, malonate, oxalate, pyruvate, tartrate, methane sulfonate, methyl sulfate, p-toluene sulfate, and succinate,

m is a number from 0 to 5,

is a number from 1 to 3, and

p and r are independently of each other a number from 0 to 6, such that the sum of s and the product of p and q is equal to the sum of m and the product of r and o, and further such that the charge of formula (II) resulting from the radicals R 1 , R 2 and R 3 is neutral or negative.