# US 7,611,812 B2 · Use of salts of layered double hydroxides as charge control agents

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- Number: US 7,611,812 B2
- Document ID: US7611812B2
- Status: Granted
- Kind: B2
- Application number: 10/523,536
- Filed: 2003-07-09
- Published: 2005-12-15
- Granted: 2009-11-03
- Earliest claimed: 2002-08-03
- Assignees: Clariant Produkte (Deutschland) GmbH
- Inventors: Eduard Michel; Ruediger Baur; Hans-Tobias Macholdt
- Web page: https://patentgrep.com/patent/US7611812B2

## CPC

- C08K 5/098: Metal salts of carboxylic acids
- C01F 7/785: Hydrotalcite
- C08K 5/0091: {Complexes with metal-heteroatom-bonds}
- C08K 5/41: Compounds containing sulfur bound to oxygen
- C09C 1/40: Compounds of aluminium {(C09C1/0009, C09C1/0015, C09C1/0078, C09C1/32 take precedence)}
- C09C 1/407: {Aluminium oxides or hydroxides}
- C09D 5/034: {Charge control agents (for toners G03G9/097)}
- G03G 9/09708: {Inorganic compounds}
- G03G 9/09716: {treated with organic compounds}
- C01P 2002/22: layered hydroxide-type, e.g. of the hydrotalcite-type
- C01P 2002/88: by thermal analysis data, e.g. TGA, DTA, DSC
- C01P 2004/51: Particles with a specific particle size distribution
- C01P 2004/61: Micrometer sized, i.e. from 1-100 micrometer
- C01P 2006/12: Surface area
- C01P 2006/40: Electric properties
- C08K: Use of inorganic or non-macromolecular organic substances as compounding ingredients (paints, inks, varnishes, dyes, polishes, adhesives C09)
- C01F: COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts of peroxyacids C01B15/00; sulfides or polysulfides of magnesium, calcium, strontium, or barium C01B17/42; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds other than ammonia or cyanogen containing nitrogen and non-metals and optionally metals C01B21/082; amides or imides of silicon C01B21/087}; metal {imides or} amides C01B21/092, {C01B21/0923}; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanic acid C01C3/14; salts of cyanamide C01C3/16; thiocyanates C01C3/20; {double sulfates of magnesium with sodium or potassium C01D5/12; with other alkali metals C01D15/00, C01D17/00})
- C09C: TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES (treatment of materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone C04B14/00, C04B18/00, C04B20/00); PREPARATION OF CARBON BLACK {; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS}
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- G03G: ELECTROGRAPHY; ELECTROPHOTOGRAPHY; MAGNETOGRAPHY
- C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS

## Abstract

Layered double hydroxide salts as charge control agents in electrophotographic toners and developers, in powder coating materials, electret materials and in electrostatic separation processes of chargeable materials, such as polymers, wherein the double hydroxide salt contains monovalent and/or divalent, and also trivalent, metal cations, and also contains one or more organic anions A of the formula (I) X—R—Y (1) wherein X is hydroxyl, carboxyl, sulfato or sulfo; Y is carboxyl, sulfato or sulfo, and R is an aliphatic, cycloaliphatic, heterocycloaliphatic, olefinic, cycloolefinic. heterocycloolefinic, aromatic, heteroaromatic, araliphatic or heteroaraliphatic radical having a total of at least 8 carbon atoms which can be substituted by one or several substituents from the group hydroxyl, amino, halogen, C1-C22-alkyl, C1-C22-alkoxy, —C1-C22-alkylene-(CO)—O—(CH2CH2O)0-50-alkyl,—C1-C22-alkylene-(CO)—O—(CH2H2O)0-50-haloalkyl, carboxy, sulfo, nitro or cyano.

## Claims

### Claim 1

A process for controlling the charge of an electrophotographic toner, electrophotographic developer, powder coating material, electret material or a chargeable material in an electrostatic separation process comprising the step of adding at least one charge control agent to the electrophotographic toner, electrophotographic developer, powder coating material electric material or chargeable material, wherein the at least one charge control agent is a layered double hydroxide salt comprising
a combination of trivalent and divalent and optionally monovalent metal cations having hydroxyl groups wherein the number of hydroxyl groups in the layered double hydroxide salt is from 1.8 to 2.2 times the sum of all the metal cations wherein the layered double hydroxide salt contains Mg2+ and Al3+, and one or more organic anions A selected from the group consisting of benzilic acid, naphthalenedisulfonic acid, naphthalenedicarboxylic acid, hydroxynaphthoic acid, octanedicarboxylic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, octadecanedicarboxylic acid, naphthalenetetracarboxylic acid, sulfosuccinic acid (C6-C20)-alkyl monoester, sulfosuccinic acid (C6-C22)-fluoroalkyl monoester, and an anion of a C12-C44 fatty acid.

### Claim 2 (depends on 1)

The process as claimed in claim 1, wherein the layered double hydroxide salt comprises monovalent metal cations selected from the group consisting of Li+, Na+ and K+.

### Claim 3 (depends on 1)

The process as claimed in claim 1, wherein the layered double hydroxide salt has a molar ratio Mg2+: Al3+ of from 3.1:1 to 1:2.

### Claim 4 (depends on 1)

The process as claimed in claim 1, wherein the layered double hydroxide salt is a calcined hydrotalcite.

### Claim 5 (depends on 1)

The process as claimed in claim 1, wherein the adding step further comprises adding at least one charge control agent selected from the group consisting of triphenylmethanes; ammonium compounds; immonium compounds, iminium compounds; fluorinated ammonium compounds; fluorinated immonium compounds; biscationic acid amides; polymeric ammonium compounds; diallylammonium compounds; aryl sulfide derivatives, phenol derivatives; phosphonium compounds; fluorinated phosphonium compounds; calix[n]arenes, cyclically linked oligosaccharides, interpolyelectrolyte complexes; polyester salts; metal complex compounds, salts of ionic structured silicates, hydroxycarboxylic acid-metal complexes; hydroxycarboxylic acid-nonmetal complexes, benzimidazolones; azines, thiazines and oxazines.

### Claim 6 (depends on 1)

The process as claimed in claim 1, wherein the at least one charge control agent is present from 0.01% to 50% by weight, based on the total weight of the electrophotographic toner, electrophotographic developer, coating material, powdercoating material, electret material or chargeable material.

### Claim 7 (depends on 1)

The process as claimed in claim 1, wherein divalent metal cations are selected from the group consisting of Mg2+, Ca2+, Zn2+, Co2+, Ni2+, Fe2+, Cu2+ and Mn2+.

### Claim 8 (depends on 1)

The process as claimed in claim 1, wherein the trivalent metal cations present are selected from the group consisting of Al3+,Fe3+, Co3+, Mn3+, Ni3+, Cr3+ and B3+.

### Claim 9 (depends on 1)

The process as claimed in claim 1, wherein the C12-C44 fatty acid is stearic acid.

### Claim 10 (depends on 1)

A charge controlled electrophotographic toner, electrophotographic developer, powder coating material, electret material or chargeable material for use in an and in electrostatic separation process made in accordance with the process of claim 1.

### Claim 11 (depends on 1)

The process according to claim 1, wherein the electrophotographic toner, electrophotographic developer, powder coating material, electret material or a chargeable material further comprises a binder and the adding step further comprises incorporating the at least one charge control agent into the binder.

### Claim 12 (depends on 1)

The process as recited in claim 1, wherein the at least one charge control agent is present as an aqueous, aqueous-organic or organic dispersion.

### Claim 13

An electrophotographic toner, powder or powdercoating material, comprising from 30% to 99.99% by weight of a binder, from 0.01% to 50% by weight of at least one layered double hydroxide salt comprising
a calcined hydrotalcite or an uncalcined hydrotalcite, and one or more organic anions A selected from the group consisting of benzilic acid, naphthalenedisulfonic acid, naphthalenedicarboxylic acid, hydroxynaphthoic acid, octanedicarboxylic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, octadecanedicarboxylic acid, naphthalenetetracarboxylic acid, sulfosuccinic acid (C6-C20)-alkyl monoester, sulfosuccinic acid (C6-C22)-fluoroalkyl monoester, and an anion of a C12-C44 fatty acid, wherein the weight percentages are based on the total weight of the electrophotographic toner, powder or powdercoating material.

### Claim 14 (depends on 13)

The electrophotographic toner, powder or powdercoating material as claimed in claim 13, further comprising from 0.001% to 50% by weight of a colorant.