KR20070023696A - Hydrophobic, salt-like structured silicate - Google Patents

Abstract

Silicates of salt-like hydrophobic structures are disclosed. The cations of the silicate of the salt-like structure are low molecular weight organic cations or combinations thereof and NH ₄ ⁺ , H ₃ O ⁺ , alkali metal ions, alkaline earth metal ions, earth metal and / or transition metal ions. The anions of the salt-like structures of the silicates are isolated, cyclic, grouped, chained, banded, layered or three-dimensional silicates or combinations thereof. The structured silicates comprise (a) their cations are NH ₄ ⁺ , H ₃ O ⁺ , alkali metals, alkaline earth metals, earth metal ions and / or transition metal ions or combinations thereof, the anions of which are isolated, cyclic, grouped, Reacting the structured silicates, which are chained, banded, layered or three-dimensional silicates or combinations thereof, with low molecular weight organic cations in an aqueous dispersion; (b) a hydrophobic compound selected from the group consisting of wax and metal soap in the aqueous structured silicate dispersion before, during and / or after performing step (a), a salt-like structure according to step (a) Adding vigorously mixing in an amount of 0.2 to 200% by weight of the silicate of; And (c) optionally removing the silicate of the salt-like hydrophobic structure formed in step (b), drying it and isolating it in powder form.

Description

HYDROPHOBIC, SALT-LIKE STRUCTURED SILICATE}

The present invention relates to a charge control agent which is the meaning of a component that selectively affects the electrostatic charge properties in the matrix.

In the electrophotographic recording method, a "potential charge phase" occurs on the photoconductor. This "potential charge phase" is developed by applying an electrostatically charged toner, and then transferred to, for example, paper, fabric, film or plastic, and fixed, for example, by the action of pressure, radiation, heat or solvent. . Common toners are one- or two-component powder toners (also called one- or two-component developer) and special toners (for example magnetic toners), and liquid toners or polymerized toners are also used. Polymerized toner is understood to mean a toner formed by, for example, suspension polymerization (condensation) or emulsion polymerization to induce improved particle properties of the toner. The term also means toner produced in a non-aqueous dispersion.

The specific charge (q / m, charge per unit weight) of the toner is a measure of its quality. In addition to the signs and levels of electrostatic charge, the rapid attainment of the desired charge level, the homeostasis of these charges over a relatively long activation period, and the climate influences, for example, the toner's insensitivity to temperature and atmospheric humidity, are important quality criteria. Depending on the type of method and apparatus, both positively and negatively chargeable toners are used in copiers and laser printers.

In order to achieve an electrophotographic toner or developer having a positive or negative charge, charge control agents are often added. Since charging of the toner binder often depends remarkably on the activation time, the charge control agent's task is to create the sign and level of the toner charging on the one hand, and on the other hand to hinder the charge drift of the toner binder and to maintain the homeostasis of the toner charging. To ensure. In addition, it is important for the charge control agent to have adequate thermal stability and good dispersibility in practice. The general temperature for introducing the charge control agent into the toner resin is 100 to 200 ° C if a kneader or an extruder is used. Thermal stability of 200 ° C. thus has a good advantage. It is also important that the thermal stability is ensured in various binder systems over a relatively long period of time (about 30 minutes).

For good dispersibility, it is advantageous if the charge control agent has no wax-like properties or tackiness and exhibits a melting point or softening point greater than 150 ° C, preferably greater than 200 ° C. Tackiness often causes problems when weighed into the toner formulation, and low melting or softening points can mean that no homogeneous distribution is achieved during dispersion, since the material fuses in droplet form into the carrier material.

Common toner binders are polymerization, polyaddition and polycondensation resins such as styrene, styrene acrylate, styrene-butadiene, acrylate, polyester and phenol-epoxy resins, as well as cycloolefin copolymers each or their Combinations and may also contain further constituents, for example colorants such as dyes and pigments, waxes or flow aids, or may be obtained later as additives (eg highly disperse silica).

Charge control agents can also be used to improve the electrostatic charging of powders and lacquers, especially in triboelectrically or electrokinetically sprayed powder coatings, for example metals, wood plastics, glass, ceramics, concrete, textile materials Used for surface coating of the object of paper, rubber or. Epoxy resins, carboxyl and hydroxyl group-containing polyester resins, polyurethane resins and acrylic resins are generally used as powder coating resins with conventional curing agents. Combinations of resins are also used. Thus, for example, epoxy resins are often used in combination with carboxyl and hydroxyl group-containing polyester resins.

It has also been found that charge control agents can significantly improve the charge and charge stability of electrostatic materials, especially in electrostatic fibers. Common electrostatic materials are based on polyolefins, halogenated polyolefins, polyacrylates, polyacrylonitriles, polystyrenes or fluorinated polymers such as polyethylene, polypropylene, polytetrafluoroethylene and perfluorinated ethylene and propylene, or Based on polyesters, polycarbonates, polyamides, polyimides or polyether-ketones, or based on polyarylene sulfides, in particular polyphenylene sulfides, polyacetals, cellulose esters, polyalkylene terephthalates and these Based on the mixture of In electrostatic fibers, in particular, the electrostatic material can be used for example for ultrafine dust filtration. The electrostatic material can be charged by corona discharge or triboelectric charging.

Charge control agents can also be used for electrostatic separation operations, in particular for polymer phase separation. Without charge control agents, low density polyethylene (LDPE) and high density polyethylene (HDPE) are triboelectrically charged in substantially the same manner. After addition of the charge control agent, the LDPE is highly positively charged and the HDPE is highly negatively charged, which can be easily separated. In addition to the external application of the charge control agent, its introduction into the polymer is also possible, for example to move the polymer into the triboelectric voltage series and to obtain a corresponding separation action. Other polymers such as polypropylene (PP) and / or polyethylene terephthalate (PET) and / or polyvinyl chloride (PVC) may also be separated from one another in this way. The salt material can also be separated if a reagent that enhances substrate-specific electrostatic charging is added beforehand (surface conditioning). Charge control agents are also used as electroconductivity providing reagents (ECPA) in inks and electronic inks or electronic paper of inkjet printers.

WO 01/40878 A1 discloses the use of salt-like structures of silicates as charge control agents. However, such charge control agents are typically sensitive to various atmospheric humidity conditions.

It is an object of the present invention to find active and ecotoxicologically acceptable charge control agents which have high and rapid charging and high charging stability and also exhibit only low sensitivity to various atmospheric humidity conditions, in particular high atmospheric humidity. They should also be very easily dispersible without decomposition in the various toner binders actually used (eg polyester, polystyrene acrylate or polystyrene butadiene / epoxy resins and cycloolefin copolymers). Their action should also have little to do with the resin / carrier combination to find a wide range of uses. They should also be readily dispersible without degradation in conventional powder coating binders and electrostatic materials such as polyesters (PES), epoxides, PES-epoxy hybrids, polyurethanes, acrylic systems and polypropylenes.

For electrostatic efficacy, the charge control agent should already be active at the lowest possible concentration (1% or less) and should not lose its efficacy when combined with carbon black or other colorants. It is known that colorants can in some cases have a lasting effect on triboelectric charging of the toner. Surprisingly, it was found here that the silicates of the hydrophobic salt-like structure described below satisfy this requirement.

Therefore, the present invention is a hydrophobic salt-like structure silicate, wherein the cation of the salt-like structure silicate is a low molecular weight organic cation or a combination thereof and NH ₄ ⁺ , H ₃ O ⁺ , alkali metal ion, alkaline earth metal ion, earth metal ion And / or transition metal ions, the anions of the salt-like structures of the silicates are isolated, cyclic, grouped, chained, banded, layered or three-dimensional silicates or combinations thereof,

(a) its cation is NH ₄ ⁺ , H ₃ O ⁺ , alkali metal ions, alkaline earth metal ions, earth metal ions and / or transition metal ions or combinations thereof, the anion of which is isolated, cyclic, grouped, chained Reacting the structured silicates, which are banded, layered or three-dimensional silicates or combinations thereof, with the low molecular weight organic cations in the aqueous dispersion;

(b) at least one hydrophobic compound selected from the group consisting of waxes and metal soaps in the aqueous dispersion of silicates of the structure before, during and / or after performing step (a) according to step (a) Based on salt-like silicates, mixing vigorously in amounts of 0.2 to 200% by weight, for example 1 to 200% by weight, preferably 0.5 to 150% by weight, particularly preferably 1 to 100% by weight. Adding; And

(c) optionally removing the hydrophobic salt-like structure silicate formed in step (b) from the liquid medium, drying it and isolating it as a powder

Silicates of hydrophobic salt-like structures obtainable by are provided.

A relatively large amount of wax, for example 3 to 5% by weight, based on the weight of the binder, is added to the binder of the electrophotographic toner, for example, toner is removed from the photoconductor (cold anti-offset) during the photocopy process. offset) or from a fixed roll (high temperature anti-offset) or it is known that the glass transition temperature of the polymer binder can be lowered. However, the object according to the invention is not achieved by externally adding wax. Only by the treatment according to the invention of the salt-like structure silicates the charge control agent is hydrophobized in such a way that the intended charge control properties are achieved and insensitive to environmental influences, in particular relatively high atmospheric humidity. Hydrophobic compounds, ie waxes or metal soaps, are believed to be embedded between the organic ions of the structured silicates and / or adsorbed onto the surface of the silicates of salt-like structure.

According to a common definition, the silicates of the mentioned structures are based on the following formula:

Isolated type silicate [SiO _{^4] 4} ^-, group type silicate _{^{[Si 2 O 7] 6 -}} , cyclic silicate [SiO _{3] n} ^2-, chain-like silicate [SiO _{3] m} ^2-, band-silicate [Si ₄ O ₁₁ ] _m ^6- , layered silicate [Si ₂ O ₅ ] _m ^2- , and three-dimensional silicate [Al _a Si _{1 - a} O ₂ ] _m ^a- , wherein n = 3, 4, 6 or 8, m is an integer and is 1 or more and 0 <a <1). Structured silicates are often added, for low molecular weight anions of, for example, ^{OH -, F -, Cl -} , Br -, J -, _{^{acetate, BO 3 3 -, BO 2}} (OH) 2-, BO (OH) 2 -, _{^{HCO 3 -, CO 3 2 -}} , NO 3 -, HS0 4 -, SO 4 2 -, H 2 PO 4 -, HPO 4 2 -, PO 4 3 -, HS - entails a ^-, S ^2. In addition, the individual Si atoms in the structured silicates may in some cases be substituted by other atoms, such as Al, B, P or Be (aluminosilicates, borosilicates, etc.). Structured silicates with naturally occurring or also synthesized by manufacturing also often easily exchangeable one or more different cations: and distinct in that it contains (such as Na ^+, K ^+, Mg ^{2 +,} Ca ^{2 +),} Example For example, they may be substituted by organic ions, thereby changing their chemical and physical properties. Preferred structured silicates in the context of the present invention are montmorillonite, bentonite, hectorite, kaolinite, serpentine, talc, pyrophyllite, mica, mica, biotite, dolomite, paragonite, vermiculite, baydelite, xanthophyll Lite, pearl mica, feldspar, zeolite, wollastonite, actinite, amosite, cyanite, wollastonite, nontronite, smectite, pulverite, saponite, pouersite, permutite and cecil. Examples of naturally occurring structured silicates are disclosed in WO 01/40878 A1. Silicates of ionic structure are, for example, of natural origin (eg bentonite or montmorillonite) contained in or by naturally occurring minerals or rocks, or synthetically prepared structured silicates (eg magnesium Hydrosilicate or synthetic hectorite or Na ₂ [Si ₂ O ₅ ]).

In the case of naturally occurring structured silicates, geographic precipitation can affect the chemical and physical properties of the material. Ionic structured silicates which inherently inherently involve other minerals or rocks (eg quartz) can be processed by mechanical or chemical processing steps, for example, very finely ground, purified or separated from other contaminants, It may be pH-treated, dehydrated, pressure-treated, heat-treated, oxidatively or reductively treated or treated with chemical auxiliaries.

In the context of the present invention, a low molecular weight organic cation is understood to mean a nonpolymeric organic cation selected from the group consisting of substituted ammonium, phosphonium, thionium, triphenylcarbonium ions or cationic metal complexes.

Preference is given to low molecular weight, ie nonpolymeric ammonium ions of the formulas a to j:

Where

또는

가 산 에스터 또는 산 아미드 결합으로 삽입될 수 있다); [(C₁-C₁₂)-알킬렌-O-]_1-100-H; 아릴, (C₁-C₁₈)-알킬렌아릴, -(O-SiR'₂)_1-32-O-SiR'₃(여기서, R'은 C₁-C₁₂-알킬, 페닐, 벤질 또는 C₁-C₁₂-알 콕시를 의미하는 것이다); 헤테로사이클릴, C₁-C₁₈-알킬렌-헤테로사이클릴이고;R ¹ to R ¹⁸ are the same or different and are hydrogen, CN, (CH ₂ ) _1-18 CN, halogen, eg F, Cl or Br, branched or unbranched C ₁ -C ₃₂ -alkyl, mono- Or polyunsaturated C ₂ -C ₃₂ -alkenyl, in particular C ₂ -C ₂₂ -alkenyl, for example tallow fatty alkyl; C ₁ -C ₂₂ -alkoxy, C ₁ -C ₂₂ -hydroxyalkyl, C ₁ -C ₂₂ -haloalkyl, C ₂ -C ₂₂ -haloalkenyl, C ₁ -C ₂₂ -aminoalkyl, (C _1- C ₁₂ ) -trialkyl-ammonium- (C ₁ -C ₂₂ ) -alkyl; (C ₁ -C ₂₂ ) -alkylene- (C═O) O— (C ₁ -C ₃₂ ) alkyl, (C ₁ -C ₂₂ ) -alkylene- (C═O) O-aryl, (C ₁ -C ₂₂ ) -alkylene- (C═O) NH— (C ₁ -C ₃₂ ) alkyl, (C ₁ -C ₂₂ ) -alkylene- (C═O) NH-aryl, (C ₁ -C ₂₂ ) -Alkylene-O (C═O)-(C ₁ -C ₃₂ ) alkyl, in particular (C ₁ -C ₁₈ ) -alkylene-O (CO)-(C ₁ -C ₃₂ ) alkyl, (C ₁ -C ₂₂ ) -alkylene-O (CO) aryl, (C ₁ -C ₂₂ ) -alkylene-NH (C═O)-(C ₁ -C ₃₂ ) alkyl, (C ₁ -C ₂₂ ) -alkyl Len-NHCO-aryl, wherein

or

Can be inserted into acid ester or acid amide bonds); [(C ₁ -C ₁₂₎ - alkylene -O-] _1-100 -H; Aryl, (C ₁ -C ₁₈ ) -alkylenearyl,-(O-SiR ' ₂ ) _1-32 -O-SiR' ₃ , wherein R 'is C ₁ -C ₁₂ -alkyl, phenyl, benzyl or C ₁ -C ₁₂ -alkoxy); Heterocyclyl, C ₁ -C ₁₈ -alkylene-heterocyclyl;

R ¹⁹ is C ₄ -C ₁₁ -alkylene,-(C ₂ H ₄ -0-) _l-17- (CH ₂ ) _l-2 -,-(C ₂ H ₄ -NR-) _1-17- ( CH _{2) 1-2} - provided that, where R is hydrogen or C ₁ -C ₁₂ - alkyl;

또는

의 의미를 갖고, X is Y and -CO-CH ₂ -CO-,

or

Has the meaning of

Y is

또는 o-, p-, m-(C₆-C₁₄)-아릴렌 또는 N, O 및/또는 S로 이루어진 군으로부터 선택된 1, 2, 3 또는 4개의 헤테로원자를 갖는(C₄-C₁₄)-헤테로아릴렌이고;

Or o-, p-, m- (C ₆ -C ₁₄ ) -arylene or having 1, 2, 3 or 4 heteroatoms selected from the group consisting of N, O and / or S (C ₄ -C ₁₄ ) -Heteroarylene;

R ⁶⁰ is C ₁ -C ₃₂ -acyl, C ₁ -C ₂₂ -alkyl, C ₂ -C ₂₂ -alkenyl, C ₁ -C ₁₈ -alkylene-C ₆ -C ₁₀ -aryl, C ₁ -C ₂₂ -Alkylene-heterocyclyl, C ₆ -C ₁₀ -aryl or (C ₄ -C ₁₄ ) -heteroaryl having 1, 2, 3 or 4 heteroatoms selected from the group consisting of N, 0 and / or S ego,

R ⁶¹ and R ⁶⁴ are — (CH ₂ ) _1-18- , C ₁ -C ₁₂ -alkylene-C ₆ -C _{10 -arylene} , C ₆ -C ₁₀ -arylene, C ₀ -C ₁₂ -alkyl Ren-heterocyclyl;

Z is -NH- or -0-;

A ₁ ^θ and A ₃ ^θ are -COO ^θ , -SO ₃ ^θ , -OS0 ₃ ^θ , -S0 ₂ ^θ , -COS ^θ or -CS ₂ ^θ ;

A ₂ is —S0 ₂ Na, —S0 ₃ Na, —S0 ₂ H, —S0 ₃ H or hydrogen;

또는

이고;R ⁶⁹ and R ⁷⁰ independently of one another are hydrogen, C ₁ -C ₃₂ -alkyl wherein the alkyl chain is one of the groups —NH—CO—, —CO—NH—, —CO—O— or —0-CO— Or more); C ₁ -C ₁₈ -alkylene-aryl, C ₀ -C ₁₈ -alkylene-heterocyclyl, C ₁ -C ₁₈ -hydroxyalkyl, C ₁ -C ₁₈ -halogenalkyl, aryl,-(CH ₂ ) ₃ -SO ₃ ^θ ,

or

ego;

R ⁷¹ and R ⁷² are — (CH ₂ ) _1-12 —;

R ⁷³ and R ⁷⁴ are hydrogen or C ₁ -C ₂₂ -alkyl.

Unless otherwise indicated, in the above and the following definitions, "aryl" is preferably C ₆ -C ₁₈ -aryl, in particular phenyl or naphthyl, and "heterocyclyl" is preferably N, O and / or S Saturated, unsaturated or aromatic, 5- to 7-membered rings having 1, 2, 3 or 4 heteroatoms selected from the group consisting of pyridyl, imidazolyl, triazinyl, pyridazyl , Pyrimidinyl, pyrazinyl, piperidinyl, popolinyl, furinyl, tetrazonyl, pyrrolyl. Aryl and heterocyclyl radicals are also on the carbon atom or heteroatom, C ₁ -C ₁₂ -alkyl, C ₁ -C ₄ -alkenyl, C ₁ -C ₄ -alkoxy, hydroxy- (C ₁ -C ₄ ) alkyl, amino, - (C ₁ -C ₄₎ alkyl, C ₁ -C ₄ - alkyl butylimino, carboxyl, hydroxyl, amino, nitro, cyano, halogen, C ₁ -C ₁₂ - acyl, C ₁ -C ₄ -halogen alkyl, C ₁ -C ₄ - alkylcarbonyl, C ₁ -C ₄ - alkyl-carbonyl-oxy, C ₁ -C ₄ - alkoxycarbonyl, C _l -C ₄ - alkyl, aminocarbonyl, C _l -C ₄ -alkylcarbonylimino, C ₆ -C _{10 -arylcarbonyl} , aminocarbonyl, aminosulfonyl, C ₁ -C ₄ -alkylaminosulfonyl, phenyl, naphthyl, heteroaryl, for example pyri It may be substituted once or several times, for example 2, 3, 4, 5 times, by dill, imidazolyl, triazinyl, pyrimidinyl.

또는

가 산 에스터 또는 산 아미드 결합으로 삽입될 수 있다); 니트로, 시아노, 할로겐, 폴리(C₁-C₁₂-알킬렌 옥사이드) 또는 C₁-C₂₂-아실, 특히 상기한 바와 같은 N- 또는 C-(C₁-C₂₂)-알킬레이트화 헤테로사이클릴, 예를 들면 N-(C₁-C₂₀)알킬-피리디늄 또는 1-메틸-1-스테아릴아미도에틸-2-스테아릴-이미다졸리늄이다.Preferred heterocyclic ammonium ions are also 5-12 membered heterocyclyls having aliphatic or aromatic, 1, 2, 3 or 4 N, O and / or S in the ring, wherein 2 to 8 rings may be fused In particular, pyridinium, pyridazinium, pyrimidinium, pyrazinium, furinium, tetraazaporpynium, piperidinium, morpholinium, tetrazonium. Suitable heterocyclyls also include, for example, pyrrolium, pyrazolium, imidazolium, benzimidazolium, imidazonium, benzimidazolonium, imidazolinium, benzimidazolinium, alkylpyrrolidino -Benzimidazolonium, indolium, isoindoleium, indolinium, pyrrolidinium, carbazolium, indazolium, quinolinium, isoquinolinium, pyrindenium, acridinium, phenantridinium, Ryllinium, Zulolinium, Natridinium, Cinolinium, Quinazolinium, Quinoxalinium, Perimidinium, Phenazonium, Phenazinium, 1,10-Phenanthronium, B-Carbolinium, Quin Norizinium, 1,8-naphthyldinium, teridinium, quinuclidinium, cornidinium, titanium hypophosphite, adenium, titanium xanthine, titanium isoxanthium, heterooxanthium, isoadenium, orb Annium, Epiguanium, Theophyllium, Titanium Paraxate, Theobromium, Caffeinium, Isocapium, Trihydroxyfurinium, Poppy Metal, complexed tetraazaporpyrinium (eg, Mg, Ca, Sr, Ba, Al, Mn, Fe, Co, Cu, Zr, Ti, Cr, Ni, Zn and ), Bis-tetrazonium, phenoxazinium, aminoxanthium, and derivatives of the mentioned cations mono- or multi-substituted on C or heteroatoms, said substituents being independently of one another carboxyl, hydroxyl, C _1- C ₂₂ -alkoxy, C ₁ -C ₃₂ -alkyl, in particular C ₁ -C ₂₂ -alkyl, C ₂ -C ₂₂ -alkenyl, hydroxy- (C ₁ -C ₂₂ ) -alkyl, amino, aminoalkyl, C _1- C ₁₈ -iminoalkyl, alkylamido, alkylcarbonyloxy, alkyloxycarbonyl, (C ₁ -C ₂₂ ) -alkylene- (C═O) O— (C ₁ -C ₃₂ ) alkyl, (C ₁ -C ₂₂ ) -alkylene- (C═O) O-aryl, (C ₁ -C ₂₂ ) alkylene- (C═O) NH— (C ₁ -C ₃₂ ) alkyl, (C _1- C ₂₂ ) -alkylene- (C═O) NH-aryl, (C ₁ -C ₂₂ ) -alkylene-O (C 0)-(C ₁ -C ₃₂ ) alkyl, (C ₁ -C ₂₂ ) alkylene -O (CO) - aryl, (C ₁ -C ₂₂₎ alkylene group -NH (C = 0) - ( C 1 -C 32) alkyl, (C ₁ -C ₂₂₎ - alkylene-aryl -NHCO- ( , Where,

or

Can be inserted into acid ester or acid amide bonds); Nitro, cyano, halogen, poly (C ₁ -C ₁₂ -alkylene oxide) or C ₁ -C ₂₂ -acyl, in particular the N- or C- (C ₁ -C ₂₂ ) -alkylated hetero as described above Cyclyl such as N- (C ₁ -C ₂₀ ) alkyl-pyridinium or 1-methyl-1-stearylamidoethyl-2-stearyl-imidazolinium.

Of particular interest are the ions of formulas a to j wherein R ¹ to R ¹⁸ are hydrogen, CN, CH ₂ -CN, CF ₃ , C ₁ -C ₂₂ -alkyl, for example coconut alkyl, cetyl, stearyl or hydrodehydration Low fatty alkyl; C ₂ -C ₂₂ -alkenyl, especially C ₂ -C ₁₈ -alkenyl, C ₁ -C ₁₈ -alkoxy, C ₁ -C ₁₈ -hydroxy-alkyl, C ₁ -C ₁₈ -haloalkyl, C _2- C ₁₈ -haloalkenyl, where halo is preferably F or Cl, C ₁ -C ₁₈ -aminoalkyl, (C ₁ -C ₆ ) -trialkylammonium (C ₁ -C ₁₈ ) -alkyl, (C ₁ -C ₁₈ ) -alkylene-O (C═O)-(C ₁ -C ₂₂ ) alkyl, (C ₁ -C ₁₈ ) -alkylene-O (C═O) -phenyl, (C ₁ -C ₁₈ ) -alkylene-NHCO- (C ₁ -C ₂₂ ) alkyl, (C ₁ -C ₁₈ ) -alkylene-NHCO-phenyl, (C ₁ -C ₁₈ ) -alkylene- (C = O) O- (C ₁ -C ₂₂ ) alkyl, (C ₁ -C ₁₈ ) -alkylene- (C═O) O-phenyl, (C ₁ -C ₁₈ ) -alkylene- (C = O) NH- ( C ₁ -C ₂₂ ) alkyl, (C ₁ -C ₁₈ ) -alkylene-CONH-phenyl, benzyl, phenyl, naphthyl, C ₁ -C ₁₂ -alkylene-heterocyclyl;

R ¹⁹ is C ₄ -C ₅ -alkylene,-(C ₂ H ₄ -O) _1-9- (CH ₂ ) _1-2 -,-(C ₂ H ₄ -NH) _1-9- (CH ₂ ) _1-2- ;

R ⁶⁰ is C ₁ -C ₁₈ -acyl, C ₁ -C ₁₈ -alkyl, C ₂ -C ₁₈ -alkenyl, C ₁ -C ₁₂ -alkylene-phenyl, C ₁ -C ₁₈ -alkylene-pyridyl , Phenyl, pyridyl;

R ⁶¹ and R ⁶⁴ are — (CH ₂ ) _1-12 —, C ₁ -C ₈ -alkylene-phenylene, phenylene; C ₁ -C ₈ -alkylenepyridylene- or -piperidylene-;

R ⁷¹ and R ⁷² are — (CH ₂ ) _1-8 ;

R ⁷³ and R ⁷⁴ are hydrogen or (C ₁ -C ₁₈ ) -alkyl.

Preferred low molecular weight organic cations are also cationic metal complexes such as metal carboxylates, metal salicylates, metal sulfonates, 1: 1 metal-azo complexes or metal dithiocarbomates, wherein the metal is preferably Al , Mg, Ca, Sr, Ba, TiO, VO, Cr, V, Ti, Zr, Sc, Mn, Fe, Co, Ni, Cu, Zn and ZrO, and the metal complex optionally contains one or more additional ligands do.

Preferred metal carboxylates and salicylates are those having the formulas k and l:

Where

n is 2, 3 or 4;

m is 1, 2 or 3 but always less than n;

M ₁ ^{n +} and M ₂ ^{n −} are independently of each other metal cations from the main group or transition metal, for example B, Al, Mg, Ca, Sr, Ba, Sc, V, Ti, Zr, TiO, Cr , Mn, Fe, Co, Ni, Cu, Zn, ZrO;

R ₇₅ is C ₁ -C ₃₂ -alkyl (linear or branched), C ₁ -C ₂₂ -halogenalkyl, C ₁ -C ₁₈ -hydroxyalkyl, C ₁ -C ₁₈ -aminoalkyl, as defined above, C ₁ -C ₁₈ -ammoniumalkyl, C ₁ -C ₁₈ -alkylene-aryl, C ₁ -C ₁₈ -alkylene-heterocyclyl, aryl, heterocyclyl;

R ⁷⁶ to R ⁷⁸ independently of _one another, as defined above, are C ₁ -C ₁₂ -alkyl (linear or branched), C ₁ -C ₄ -alkoxy, hydroxy, carboxyl, C ₁ -C ₄ -alkenyl, Hydroxy- (C ₁ -C ₄ ) -alkyl, amino, (C ₁ -C ₄ ) -aminoalkyl, nitro, cyano, halogen, C ₁ -C ₁₂ -acyl, C ₁ -C ₄ -iminoal kill , C ₁ -C ₄ -haloalkyl, aryl or heterocyclyl.

The above-mentioned metals and ligands, for example α-hydroxyphenol, α-aminoaniline, α-hydroxyaniline, α-aminobenzoic acid, quinoline, 1,8-diaminophthalene, 1,4,5,8 Also suitable are -tetraaminonaphthalene, 1,8-dihydroxynaphthalene or analogous cation complexes or salts of 1,4,5,8-tetrahydroxynaphthalene.

The aforementioned metals and ligands or anions such as α, α-dipyridyl, ethylenediamine, diethylenetriamine, triethylenetetraamine, acetylacetonate, ortho-phenanthroline, benzoyl ketone, ethylenedi ( Bigguanidine), biguananidine or similar cationic complexes or salts of dimethylglyoxime are also more suitable.

의 트라이페닐메탄 양이온이 또한 적절하고 이때, R⁴³ 및 R⁴⁵는 동일하거나 상이하고 -NH₂, 모노- 및 다이알킬아미노 기(알킬기는 1 내지 4개, 바람직하게는 1 또는 2개의 탄소 원자를 가짐), 모노- 또는 다이-오메가-하이드록시알킬아미노 기(알킬기는 2 내지 4개, 바람직하게는 2개의 탄소 원자를 가짐), 선택적으로 N-(C₁-C₄)알킬-치환된 페닐 또는 펜알킬아미노 기(알킬기는 1 내지 4개, 바람직하게는 1 또는 2개의 탄소 원자를 갖고 그 페닐 핵은 라디칼 메틸, 에틸, 메톡시, 에톡시, 설포중 1 또는 2개를 수반할 수 있음)이고, R⁴⁴는 수소이거나 R⁴³ 및 R⁴⁵에 대해 언급한 의미중 하나를 갖고, R⁴⁶ 및 R⁴⁷은 수소, 할로겐, 바람직하게는 염소 또는 설폰산 기이거나, R⁴⁶은 R⁴⁷과 함께 융합된 페닐상 고리를 형성하고, R⁴⁸, R⁴⁹, R⁵¹ 및 R⁵²는 각각 수소 또는 탄소수 1 또는 2의 알킬 라디칼, 바람직하게는 메틸이고, R⁵⁰은 수소 또는 할로겐, 바람직하게는 염소이다.Chemical formula

Triphenylmethane cations of are also suitable, wherein R ⁴³ and R ⁴⁵ are the same or different and represent -NH ₂ , mono- and dialkylamino groups (alkyl groups having from 1 to 4, preferably 1 or 2 carbon atoms ), Mono- or di-omega-hydroxyalkylamino group (alkyl group having 2 to 4, preferably 2 carbon atoms), optionally N- (C ₁ -C ₄ ) alkyl-substituted phenyl Or phenalkylamino groups (alkyl groups have 1 to 4, preferably 1 or 2 carbon atoms and the phenyl nucleus may involve 1 or 2 of the radicals methyl, ethyl, methoxy, ethoxy, sulfo ) And R ⁴⁴ is hydrogen or has one of the meanings mentioned for R ⁴³ and R ⁴⁵ , R ⁴⁶ and R ⁴⁷ are hydrogen, halogen, preferably chlorine or sulfonic acid groups, or R ⁴⁶ together with R ⁴⁷ forming a fused phenyl ring, and R ^48, R ^49, R ⁵¹ and R ⁵² are each hydrogen or carbon Is the number 1 or 2 of the alkyl radical, preferably methyl, R ⁵⁰ is hydrogen or halogen, preferably chlorine.

In the context of the present invention, possible waxes are acid waxes, for example montanic acid waxes or partially esterified or partially saponified montanic acid waxes, ester waxes, for example hydroxystearic acid ester waxes, montanic acid ester waxes Or partially hydrolyzed montanic acid ester waxes, amide waxes such as C ₁₈ -C ₄₄ -fatty acid amide waxes, canova waxes, polyolefin waxes such as polyethylene or polypropylene waxes, polyolefin decomposed waxes, oxidized PE , PP or paraffin wax, PP wax, polyolefin-metallocene wax and paraffin wax grafted with additional monomers (eg silanes, acrylic acid derivatives, methacrylic acid derivatives, maleic anhydride or styrene). The wax is characterized by a relatively sharp melting point or dropping point of 40 to 200 ° C. (hardness of relatively low viscosity of 5 to 5,000 mPas above the dropping point), crystalline structure from coarse to fine, 250 to 20,000 g / mol Molecular weight (number average molecular weight, Mn), abrasiveness under mild pressure, relatively low acid value of 0 to 200 mg KOH / g, and very high water solubility, and at the same time above the drop point or melting point are also alkaline pH conditions.

Possible metal soaps are saturated or unsaturated C ₇ -C ₄₃ -carboxylic acid, C ₈ -C ₄₄ -sulfate, C ₈ -C ₄₄ -alkyl ether-sulfate, C ₈ -C ₄₄ -alkylamido ether-sulfate, C ₈ -C ₄₄ -alkylsulfonate, C ₈ -C ₄₄ -aralkylsulfonate, where aryl is C ₆ -C ₁₂ and alkyl is C ₁ -C ₃₂ , C ₈ -C ₄₄ -alkyl ether- sulfosuccinate, C ₈ -C ₄₄ - acyl glutamate, C ₈ -C ₄₄ - fatty acid isethionates, C ₈ -C ₄₄ - fatty acid methyl tau fluoride, C ₈ -C ₄₄ - fatty acid side Sako, C ₈ -C ₄₄ -phosphates, acid waxes, partially esterified acid waxes, partially hydrolyzed ester waxes or oxidized PE or paraffin waxes, in particular Li-, Na-, K-, Al-, Ba-, Sr-, Ca Fe-, Co-, Cu-, Mg-, Mn-, Ni-, Pb-, ZrO-, TiO- and Zn-stearate, behenate, erucate, palmitate, oleate, linoleate, Resinate, laurate, myristate, naphthenate, Talate, dodecyl sulfate, lauryl diglycol ether-sulfate, lauryl triglycol ether-sulfate, secondary C ₁₀ -C ₁₈ -alkylsulfonate, dodecylbenzenesulfonate, coconut alkylamido-polyglycol ether- 1, 2, 3 or 4 of a compound selected from the group consisting of sulfate, coconut alkyl polyglycol ether-sulfosuccinate, N-cocoylglutamate, coconut fatty acid isethionate, coconut fatty acid methyltauide and lauric acid sacoside Is a metal salt.

The present invention also provides a process for preparing silicates of hydrophobic salt-like structure, as described.

Salt-like silicates comprise (a) one or more natural or synthetic silicates with a salt containing a low molecular weight organic cation (e.g., the corresponding chloride, bromide, iodide, methyl-sulfate) and aqueous In a suspension (containing up to 30% by weight of organic solvent), the weight ratio of organic cation to silicate 1: 100 to 10: 1, preferably 1:20 to 3: 1, in one step at a temperature of 5 to 160 ° C or It can be prepared by reacting together in several steps. It is advantageous to disperse the structured silicates in water for 1/2 to 48 hours, preferably for 1 to 24 hours. It is also advantageous to adjust the aqueous suspension of salts and / or structured silicates of organic cations to a pH of 1-12, preferably 3-11, prior to the reaction in the aqueous medium.

The hydrophobic compound may already be added before starting the performance of step (a) and / or added during the performance of step (a) and / or after step (a) is terminated. Preferably, the hydrophobic compound is dissolved in an organic solvent and added as a solution at a temperature of 20 to 200 ° C., or the hydrophobic compound can be added at a temperature of 20 to 200 ° C. as an aqueous dispersion. The aqueous dispersion here can also contain an organic solvent, for example an alcohol (up to 40% by weight).

It is also possible to meter the hydrophobic compound as powder or in molten form, as appropriate, slowly at a temperature of 20 to 200 ° C., for example for at least 1 minute in a fine jet. The hydrophobic compound is added vigorously with an aqueous dispersion of the structured silicate, for example with vigorous stirring with a suitable stirring device (e.g., using Ultraturrax, a bead mill, or ultrasonic propeller stirrer). In the use of hydrophobic compounds in dispersions or solutions, one or more anionic, cationic, zwitterionic or nonionic low molecular weight or polymeric phase dispersion aids such as diethylaminoethanol (DEAE), alkylamines, alkyl-sulfates , Alkylsulfonates, alkyl phosphates, betaines, sulfobetaines, poly (vinyl alcohol-co-vinyl acetate-co-vinyl acetal) in the most varied monomer composition, poly (styrene-co-acrylic acid) Preferred are saturated or unsaturated fatty acids, alkyl or alkenyl poly (glycol ethers), fatty alcohol poly (glycol ethers) or fatty alcohol poly (glycol ether-block-propylene glycol ethers), nonionic and cationic dispersion aids. The content of the dispersion adjuvant or adjuvant in the dispersion or solution of the hydrophobic compound is 0.1 to 500% by weight, preferably 0.1 to 50% by weight, based on the amount of the hydrophobic compound. The average particle size (d ₅₀ value) in the dispersion of the hydrophobic compound is 500 µm or less, preferably 1 µm or less, particularly preferably 500 nm or less.

If divalent to tetravalent metal soaps are used, they are preferably produced by precipitation just prior to addition to the structured silicate or by precipitation only in the reaction mixture after addition to the structured silicate. In this process, the acid component, for example stearic acid, under the influence of heat in water, in a water-solvent mixture or in a reaction mixture, is optionally alkaline (eg, solid or aqueous sodium hydroxide) and optionally one above the melting point of these components. Is dissolved under the addition of one or more of the above-described dispersing aids, and the precipitate is divalent to tetravalent metal salts such as zinc sulfate, zinc chloride, zinc hydroxide, aluminum chloride, aluminum sulfate, aluminum hydroxide or zir By addition of an aqueous solution of the conyl chloride solution. In this context, the molar ratio of the charge of the higher valence metal cation to the acid value of the acid component of the metal soap is from 1: 100 to 10: 1, preferably from 1:50 to 5: 1, in particular from 1:10 to 3: May be one. When all the components are combined and suitably the pH is adjusted to a value of 2 to 11, preferably 2 to 10, the reaction mixture is properly separated from the liquid phase and still heated under selective pressure on the filter and desorbed. Impurities can be removed by washing with ionic water or a water-solvent mixture (e.g. water-alcohol mixture), the washing operation being controlled by conductivity and filtrate smaller than 10 mS / cm, preferably smaller than 1 mS / cm Conductivity is intended, the product is dried by, for example, circulating air drying, vacuum drying, spin flush drying, spray drying or fluidized bed drying and optionally ground to a powder.

The invention also relates to electrophotographic toners and developers, powder coatings, electrostatic materials, electronic inks (e-inks), electronic papers (e-papers) and electrostatic separation operations of hydrophobic salt-like structures in accordance with the invention. As a charge control agent, and as an additive to improve or control the flowability of toner powder, and as an anti-offset reagent.

Herein, the structured silicates-individually or in combination with each other or in combination with the further components mentioned below-are for example extruded or kneaded, by bead mills or using ultraturax (high-speed stirrers). Into a binder of a particular toner, developer, racker, powder coating, electrostatic material at a concentration of 0.01 to 50% by weight, preferably 0.05 to 20% by weight, particularly preferably 0.1 to 5.0% by weight, based on the total mixture, or It is introduced uniformly into the binder of the polymer to be electrostatically separated. Herein, the compounds used according to the invention are dried and ground powders, colloidal solutions, press-cakes, masterbatches, preparations, mixed pastes, on a suitable carrier as a compound absorbed from an aqueous or non-aqueous dispersion ( Silica gel), or may be mixed with such a carrier, ie TiO ₂ , Al ₂ O ₃ , carbon black. The compounds used according to the invention are likewise principally in principle during the preparation of certain binders, ie during the process of polymerization, polyaddition or polycondensation, and during the preparation of polymerized toners, for example during suspension, emulsion polymerization or assembly of polymer systems. Already added as toner particles. The charge control agent particles present after dispersion in the binder should be smaller than 1 μm, preferably smaller than 0.5 μm, with a narrow particle size distribution being advantageous.

The charge control agent according to the invention can also be used in finely divided aqueous, aqueous-organic or organic dispersions. The particle size (d ₅₀ -value) is 20 nm to 1 μm, preferably 50 to 500 nm. A concentration of a charge control agent of 0.01 to 50% by weight, preferably 0.1 to 30% by weight, based on the total weight of the dispersion is appropriate. In the case of an aqueous or aqueous-organic dispersion, water is preferably used in distilled or demineralized form. In the case of organic or aqueous-organic dispersions, at least one organic solvent is used as the organic medium, preferably selected from the group consisting of monohydric or polyhydric alcohols, ethers and esters thereof, for example alkanols, in particular having from 1 to 4 carbon atoms. Alkanols such as methanol, ethanol, propanol, isopropanol, butanol, isobutanol; Dihydric or trihydric alcohols, especially alcohols having 2 to 6 carbon atoms, for example ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1, 6-hexanediol, 1,2,6-hexanetriol, glycerol, diethylene glycol, dipropylene glycol, triethylene glycol, polyethylene glycol, tripropylene glycol, polypropylene glycol; Lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl or ethyl or butyl ether, triethylene glycol monomethyl or ethyl ether; Ketones and ketone alcohols such as acetone, methyl ethyl ketone, di-ethyl ketone, methyl isobutyl ketone, methyl pentyl ketone, cyclopentanone, cyclohexanone, diacetone alcohol; Amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone. Conventional ionic or nonionic low molecular weight or polymeric phase dispersing aids such as sulfates, sulfonates, phosphates, polyphosphates, carbonates, carboxylates, carboxylic acids, silicates, hydroxides, metal soaps, polymers such as acrylics Elates, fatty acid derivatives and glycoside compounds may additionally also be used for the preparation of stable dispersions. The dispersion may also contain metal-complex reagents such as EDTA or NTA. Dispersions may also contain polymers as conventional additives, such as preservatives, fungicides, antioxidants, degassers / defoamers and viscosity modifiers such as polyvinyl alcohol, cellulose derivatives or water soluble natural or synthetic resins and film-forming agents or binders. It may further contain to increase adhesive strength and frictional resistance. Organic or inorganic bases and acids are used as pH adjusters. Preferred organic bases are amines such as ethanolamine, diethanolamine, triethanolamine, diethylaminoethanol (DEAE), N, N-dimethyl-ethanolamine, diisopropylamine, aminomethylpropanol or dimethyl Iminomethylpropanol. Preferred inorganic bases are sodium hydroxide, potassium hydroxide, lithium hydroxide or ammonia. Further constituents can be used as combustible compounds, such as formamide, urea, tetramethylurea, E-caprolactam, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, butyl glycol, methylcellosobes, glycerol, Sugar, N-methylpyrrolidone, 1,3-diethyl-2-imidazolidinone, thiodiglycol, sodium benzenesulfonate, Na xylenesulfonate, Na toluenesulfonate, Na cumenesulfonate, Na benzoate , Na salicylate or Na butyl monoglycol-sulfate.

The charge control agent used in accordance with the present invention can also be combined with a known positive or negatively controlled charge control agent to achieve a particular charge and the total concentration of the charge control agent is suitably electrophotographic toner, developer, powder Or 0.01 to 50% by weight, preferably 0.05 to 20% by weight, particularly preferably 0.1 to 5% by weight, based on the total weight of the powder coating.

Possible further charge control agents are, for example, triphenylmethane; Ammonium and immonium compounds, iminium compounds; Ammonium fluoride and immonium fluoride compounds; Bis-cationic acid amides; Polymeric ammonium compounds; Diallyl ammonium compounds; Aryl sulfide derivatives, phenol derivatives; Phosphonium compounds and fluorinated phosphonium compounds; Carlix arene, cyclic oligosaccharides (cyclodextrins) and derivatives thereof; In particular boron ester derivatives, inter-polyelectrolyte complexes (IPEC); Polyester salts; Metal complex compounds, especially salicylate-metal complexes and salicylate-nonmetal complexes, hydroxycarboxylic acid-metal complexes and hydroxycarboxylic acid non-metal complexes, benzimidazolone; Azine, thiazine or oxazine (pigments, solvent dyes, basic dyes or acid dyes listed in the Color Index), and highly dispersible metal oxides such as SiO ₂ , TiO ₂ or Al ₂ O ₃ and may be surface-modified with carboxylate, amino, ammonium groups.

Examples of known charge control agents are listed in WO 01/40878 A1.

A set of two or more color toners of black, cyan, yellow, magenta, green, orange, red and blue, in order to produce an electrophotographic coloring toner, typically a colorant such as an organic colored pigment, an inorganic pigment or a dye , In the form of a dispersion, press-cake, solution or masterbatch.

The organic colored pigment may be selected from the group consisting of azo pigments or polycyclic pigments or mixed crystals of such pigments (solid solution).

Preferred blue and / or green pigments include copper phthalocyanine (eg color index blue pigment 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6), blue pigment 16 (metal-free phthalocyanine ), Or phthalocyanine with aluminum, nickel, iron or vanadium as the central atom, further triarylcarbonium pigments [eg blue pigments 1, 2, 9, 10, 14, 60, 62, 68, 80, green pigments 1, 4, 7, 45; Orange pigments such as P.O. 5, 62, 36, 34, 13, 43, 71; Yellow pigments such as P.Y. 12, 13, 14, 17, 74, 83, 93, 97, 111, 122, 139, 151, 155, 180, 174, 175, 185, 188, 191, 213, 214, red pigments such as P.R. 48, 57, 122, 146, 147, 149, 150, 184, 185, 186, 202, 207, 209, 238, 254, 255, 269, 270, 272, purple pigments such as P.V. 1, 19, carbon black, iron / manganese oxide; And a mixed crystal of color index purple pigment 19 and color index red pigment 122].

Mixtures with organic dyes are particularly suitable for adjusting the color intensity as well as increasing the brightness. Such dyes to be mentioned are preferably water-soluble dyes such as direct, reactive acid dyes, and solvent soluble dyes such as solvent dyes, disperse dyes and vat salt dyes. Examples that may be mentioned are color index reactive yellow 37, acid yellow 23, reactive red 23, 180, acid red 52, reactive blue 19,21, acid blue 9, direct blue 199, solvent yellow 14, 16, 25, 56, 62, 64, 79, 81, 82, 83, 83: 1, 93, 98, 133, 162, 174, solvent red 8, 19, 24, 49, 89, 90, 91, 92, 109, 118, 119, 122, 124, 127, 135, 160, 195, 212, 215, solvent blue 44, 45, solvent orange 41,60, 63, dispersed yellow 64, Vat red 41, solvent black 45 and 27.

The electrophotographic toner and powder coating according to the invention, of course also further comprise a wax added as anti-offset reagent, as mentioned above. The compounds according to the invention are added to the finished powder toner, again as external additives, either individually or in combination with free flowing reagents such as highly disperse silica, metal oxides or metal soaps to improve fluidity, improve adhesion properties and electrostatic Fine tuning can be improved. The present invention also provides in each case 30 to 99.99% by weight, preferably 40 to 99.5% by weight, for example styrene, styrene acrylate, styrene-, based on the total weight of the electrophotographic toner, powder or powder coating. Butadiene, acrylate, urethane, acrylic, polyester or epoxy resins or the last two combinations; 0.01 to 50% by weight, preferably 0.05 to 20% by weight, particularly preferably 0.1 to 5% by weight of one or more hydrophobic salt-like structures; And optionally 0.001 to 50% by weight of colorant, preferably 0.05 to 20% by weight of the electrophotographic toner, powder or powder coating.

In the following examples,% is by weight.

Production Example  One

25 g of bentonite (pH 7-12) are dispersed by stirring in 500 mL of deionized water at 20 ° C. for 12 h. The suspension is then adjusted with dilute sulfuric acid to a pH of 4 to 10 and then 10 g of 77% strength aqueous distearyldimethylammonium chloride solution (DSDMAC) is added to the bentonite suspension and the reaction mixture is stirred at 60 ° C. for 1 hour. do. After 1 hour reaction time, a mixture of 7 g of 77% aqueous DSDMAC solution and 50 g of 10% aqueous montanic acid ester wax dispersion (which is a molten montanic acid ester wax (Licowax® F, Clariant) , Acid value 6-10 mg KOH / g, dropping point 75-81 ° C.) 10 g 21% concentration KOH-ethylene glycol solution 0.7g, 10% concentration polyvinyl alcohol solution (Mowiol (registered trademark) 4 to 88, Prepared by addition to a hot aqueous solution at about 95 ° C. comprising 3 g of Kuraray, Germany, and 86.3 g of deionized water. The reaction mixture is then stirred again at 60 ° C. for 1 hour, the solid is suction filtered off, washed several times with deionized water and then dried at 60 ° C. in vacuo.

Yield: 39.8g off-white powder

Production Example  2

25 g of bentonite (pH 7-12) are dispersed by stirring in 500 mL of deionized water at 20 ° C. for 12 h. The suspension was then adjusted with dilute sulfuric acid to a pH of 4 to 10, followed by adding 17 g of 77% strength aqueous distearyldimethylammonium chloride solution (DSDMAC) in two portions to the bentonite suspension and the reaction mixture at 80 ° C. for 1 hour. Stir while. After 1 hour reaction time, 50 g of a 10% strength isopropanolic wax solution containing a wax mixture of 75% erucic acid amide wax and 25% canova wax is added. The reaction mixture is then stirred again at 80 ° C. for 1 hour, the solids are filtered off with suction, washed several times with deionized water and dried at 60 ° C. in vacuo.

Yield: 38.9 g of ivory powder

Production Example  3

25 g of bentonite (pH 7-12) are dispersed by stirring in 500 mL of deionized water at 20 ° C. for 12 h. The suspension was then adjusted with dilute sulfuric acid to a pH of 4 to 10, followed by adding 17 g of 77% strength aqueous distearyldimethylammonium chloride solution (DSDMAC) in two portions to the bentonite suspension and the reaction mixture at 80 ° C. for 1 hour. Stir while. After 1 hour reaction time, 5 g of stearic acid, 95 g of deionized water, 1.8 g of purified sodium hydroxide, 8 g of iso-propanol and 0.5 g of coconut fatty alcohol polyglycol ether (Genapol® C 050, German Clariant) 80 dissolved in ℃, and the prepared subsequent to Al ₂ (SO ₄₎ 50g of deionized water at the same temperature, precipitated with a solution of ₃ 18H ₂ O 2.3g, adjust the suspension to settle for 3 to 12 pH aqueous aluminum Stearate dispersion is added. The reaction mixture is then adjusted to a pH of 3 to 10, stirred again at 80 ° C. for 1 hour, the solids are removed by suction filtration, washed several times with deionized water and dried at 60 ° C. in vacuo.

Yield: 41.1g off-white powder

Production Example  4

25 g of bentonite (pH 7-12) are dispersed by stirring in 500 mL of deionized water at 20 ° C. for 12 h. The suspension was then adjusted with dilute sulfuric acid to a pH of 4 to 10, followed by adding 17 g of 77% strength aqueous distearyldimethylammonium chloride solution (DSDMAC) in two portions to the bentonite suspension and the reaction mixture at 60 ° C. for 1 hour. Stir while. After 1 hour reaction time, 2.5 g of sodium dodecyl sulfate are added as a powder or as an aqueous solution and the reaction mixture is stirred at 60 ° C. for an additional time. The reaction mixture is then adjusted to a pH of 3 to 10, the solid is suction filtered off, washed several times with deionized water and then dried at 60 ° C. in vacuo.

Yield: 37.1 g of off-white powder

Production Example  5 to 14

Example  1a

One part of the compound from Production Example 1 is uniformly introduced into 99 parts of the polyester resin on the basis of bisphenol A (Fine Tone® 382-ES) by a kneader over 30 minutes. The mixture is subsequently ground on an industrial general purpose mill and graded on a centrifugal sifter. The intended particle fraction (4-25 μm) is activated with a carrier comprising silicon-coated ferrite particles of 50-200 μm size at 25 ° C./40-60% relative atmospheric humidity.

Example  1b

The procedure is the same as in use example 1a and is activated 24 hours after the toner is stored as a carrier and the toner-carrier mixture is stored at 25 ° C./90% relative atmospheric humidity. The measurement is carried out on a conventional q / m measuring station. A sieve having a mesh width of 45 μm is used so that the carrier is not accompanied at all when the toner flies away. The following q / m values [μC / g] were measured according to the activation period:

Example  2 to 19

The procedure is the same as in Use Example 1a or 1b, and the compounds listed below were used in place of the compounds from Preparation Example 1.

Example  20 to 23

The procedure is the same as in Example 1a, using 2 or 3 parts of the corresponding compound instead of 1 part.

Example  24 to 26

The procedure is the same as in use example 1a, with organic pigments (Carbon Black Mogul® L, Cabot; Toner Magenta® E02, Clariant (Color Index Pigment Red 122); Toner To 5 parts yellow (Toner Yellow® HG, Clariant (color index pigment yellow 180)) additionally are also introduced.

Example  27 and 28

The procedure is the same as in use examples 1a and 3a, and 2 parts of a colorant (color index solvent blue 125) having an electrostatically positive intrinsic effect are also introduced into 1 part of the compound from preparations 1 or 3.

Comparative example  A

The procedure is the same as in Examples 1a and 1b, and instead of the compound from Preparation Example 1 the corresponding compound was used without the hydrophobicization step according to the invention:

Under high atmospheric humidity conditions the triboelectric charge turns out to be significantly less than that of the product according to the invention.

Comparative example  B

The procedure is the same as in use examples 1a and 1b, and instead of the compound from preparation example 1, the corresponding compound is used without the hydrophobization step according to the invention, but based on the total weight of the toner, powdered wax (Ricowax F, Clariant) 2 Add% by weight to the binder system:

Under high atmospheric humidity conditions the triboelectric charge turns out to be significantly less than that of the product according to the invention. This means that a separate addition of powdered wax shows no hydrophobic effect in relation to the frictional charge, even if used in much larger amounts than in Preparation Example 1.

Claims (14)

As a hydrophobic salt-like structure silicate, the cation of the salt-like structure silicate is combined with a low molecular weight organic cation or a combination thereof with NH ₄ ⁺ , H ₃ O ⁺ , alkali metal ions, alkaline earth metal ions, earth metal ions and / or transition metals. Ions, the anions of the salt-like structured silicates are isolated, cyclic, grouped, chained, banded, layered or three-dimensional silicates or combinations thereof, (a) its cation is NH ₄ ⁺ , H ₃ O ⁺ , an alkali metal ion, an alkaline earth metal ion, an earth metal ion, a transition metal ion or a combination thereof, the anion of which is an isolated, cyclic, group, chain, band Reacting the structured silicates, which are type, layered or three-dimensional silicates or combinations thereof, with the low molecular weight organic cations in the aqueous dispersion; (b) adding at least one hydrophobic compound selected from the group consisting of waxes and metal soaps to the aqueous dispersion of the structured silicate before, during and / or after performing step (a), the salt- according to step (a). Adding with vigorous mixing in an amount of 0.2 to 200 weight percent based on silicates of similar structure; And (c) optionally removing the hydrophobic salt-like structure silicate formed in step (b) from the liquid medium, drying it and isolating it as a powder Silicates of hydrophobic salt-like structures obtainable by. The method of claim 1, The silicates are montmorillonite, bentonite, hectorite, kaolinite, serpentine, talc, pyrophyllite, mica, gold mica, biotite, dolomite, paragonite, vermiculite, baydelite, xanthophyllite, pearl mica, feldspar, Silicate of hydrophobic salt-like structure, which is an anion selected from the group consisting of zeolite, wollastonite, actinite, amosite, cyanite, wollastonite, nontronite, smectite, calcite, saponite, pouersite, permutite and cecil. The method according to claim 1 or 2, Silicate of a hydrophobic salt-like structure wherein the low molecular weight organic cation is substituted ammonium, phosphonium, thionium, triphenylcarbonium ions or cationic metal complexes. The method according to any one of claims 1 to 3, The wax is acid wax, ester wax, amide wax, canova wax, polyolefin wax, polyolefin decomposition wax, oxidized PE, PP or paraffin wax, PP wax grafted with monomers, polyolefin-metallocene wax and paraffin wax Or a hydrophobic salt-like structure, which is a compound selected from the group consisting of mixtures thereof. The method according to any one of claims 1 to 3, C ₇ -C ₄₃ -carboxylic acid, C ₈ -C ₄₄ -sulfate, C ₈ -C ₄₄ -alkyl ether-sulfate, C ₈ -C ₄₄ -alkylamido ether-sulfate, C ₈ -C ₄₄ -alkylsulfonate, C ₈ -C ₄₄ -aralkylsulfonate, where aryl is C ₆ -C ₁₂ and alkyl is C ₁ -C ₃₂ , C ₈ -C ₄₄ -alkyl ether-sul when pitching carbonate, C ₈ -C ₄₄ - acyl glutamate, C ₈ -C ₄₄ - fatty acid isethionates, C ₈ -C ₄₄ - fatty acid methyl tau fluoride, C ₈ -C ₄₄ - fatty acid side Sako, C ₈ -C ₄₄ Hydrophobic salt-like compounds which are compounds selected from the group consisting of phosphates, acid waxes, partially esterified acid waxes, partially hydrolyzed ester waxes or oxidized PE or paraffin waxes Silicate of the structure. The method according to any one of claims 1 to 3, C ₇ -C ₄₃ -carboxylic acid, C ₈ -C ₄₄ -sulfate, C ₈ -C ₄₄ -alkyl ether-sulfate, C ₈ -C ₄₄ -alkylamido ether-sulfate, C ₈ -C ₄₄ -alkylsulfonate, C ₈ -C ₄₄ -aralkylsulfonate, where aryl is C ₆ -C ₁₂ and alkyl is C ₁ -C ₃₂ , C ₈ -C ₄₄ -alkyl ether-sul when pitching carbonate, C ₈ -C ₄₄ - acyl glutamate, C ₈ -C ₄₄ - fatty acid isethionates, C ₈ -C ₄₄ - fatty acid methyl tau fluoride, C ₈ -C ₄₄ - fatty acid side Sako, C ₈ -C ₄₄ Silicates of hydrophobic salt-like structure which are compounds selected from the group consisting of phosphates, acid waxes, partially esterified acid waxes, partially hydrolyzed ester waxes or monovalent metal salts of oxidized PE or paraffin wax. The method according to any one of claims 1 to 6, Silicate of hydrophobic salt-like structure in which the hydrophobic compound is present in an amount of 1 to 100% by weight based on the silicate of the salt-like structure according to step (a). The method according to any one of claims 1 to 7, Silicate of hydrophobic salt-like structure wherein hydrophobic compound is added as a solution or an aqueous dispersion at a temperature of 20 to 200 ° C. The method according to any one of claims 1 to 7, Silicate of hydrophobic salt-like structure, wherein the hydrophobic compound is added for at least 1 minute as a melt in the fine jet at a temperature of 20 to 200 ° C. (a) its cation is NH ₄ ⁺ , H ₃ O ⁺ , an alkali metal ion, an alkaline earth metal ion, an earth metal ion, a transition metal ion or a combination thereof, the anion of which is an isolated, cyclic, group, chain, band Reacting the structured silicates, which are type, layered or three-dimensional silicates or combinations thereof, with the low molecular weight organic cations in the aqueous dispersion; (b) a hydrophobic compound selected from the group consisting of waxes and metal soaps in an aqueous dispersion of the structured silicate prior to, during and / or after performing step (a), salt-like according to step (a) Adding with vigorous mixing in an amount of 0.2 to 200 weight percent based on the silicates in the structure; And (c) optionally removing the hydrophobic salt-like structure silicate formed in step (b) from the liquid medium, drying it and isolating it as a powder A method for preparing silicates of hydrophobic salt-like structure as claimed in any one of claims 1 to 9 comprising a. The method of claim 10, Process (b) is carried out in the presence of a dispersing aid. The method of claim 10, In step (b), when a divalent to tetravalent metal soap is used as the hydrophobic compound, the structured silicate is precipitated by precipitating the corresponding acid component having the divalent to tetravalent metal salt and optionally adjusting the pH to 2-11. A process for producing only in the reaction mixture after addition to. Claims 1 to 3, used as charge control agents in electrophotographic toners and developers, powder coatings, electrostatic materials, electronic inks, electronic paper and in electrostatic separation operations, and as anti-offset reagents in toners. Use of silicates of hydrophobic salt-like structure as claimed in claim 9. Use of a hydrophobic salt-like structure as claimed in any of claims 1 to 9 as an external additive to powder toners for controlling fluidity and charge, and as an anti-offset reagent.