JP2002526630A - Formulations containing particulate inorganic oxides - Google Patents

Abstract

  (57) [Summary] The invention relates to a) at least one oxide having an average primary particle size of 1 to 100 nm, preferably 1 to 50 nm; b) at least one dispersant having an average molecular weight Mw of more than 1000 g / mol; and c) A) formulations containing at least one solvent; The formulations according to the invention are particularly suitable for producing printing inks which are applied as a structured surface on a transparent, high-melting substrate using the ink-jet method. A transparent conductive layer is formed after sintering in a reducing atmosphere.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a formulation containing a particulate inorganic oxide, a method for its production, its use for producing printing inks, and a transparent, conductive, structured surface,
It relates to the use of printing inks for producing on transparent support materials.

The formation of transparent, conductive, structured surfaces (eg, for the display field), such as conductive paths on insulating transparent substrates, is performed in modern technology as follows. ing. After a continuous layer of a conductive material (eg, indium-tin oxide) is uniformly formed by evaporation, sputtering, spray pyrolysis, plasma evaporation, immersion, or CVD, it is common in semiconductor technology. The desired structure is formed using any lithographic method, for example, by etching or scoring. A disadvantage of this method is that extensive processing is required to produce structured surface bodies.

[0003] One object of the present invention is to produce a formulation that allows a transparent, structured surface, for example in the form of a conductive path, to be formed on a substrate with minimal processing. is there.

Another object of the present invention is to achieve conductivity inside a surface body having such a structure by sintering in a reducing atmosphere.

[0005] Printing inks for preparing formulations containing finely divided inorganic oxides, and using these formulations, in a structured manner, on transparent surfaces by ink-jet processes It became possible to prescribe. The structured surface body thus formed on the transparent substrate was then converted to a conductive, structured surface body by sintering in a reducing atmosphere. These conductive, structured surface structures (eg, conductive paths) are of particular interest to the electrical industry.

The present invention provides a composition comprising: a) at least one oxide having an average primary size of 1 to 100 nm; b) at least one dispersant having an average molecular weight Mw of more than 1000 g / mol; and c) at least one Formulations containing different solvents are provided.

Preferred formulations are: a) at least one oxide having an average primary size of 1 to 100 nm, preferably 1 to 50 nm, i) ABX [where A is Sn, In or B is Sb, Sn, F, P, Al or Cd; X is O, S, Se or Te, preferably O; and A forms a host lattice. B is doped in its host lattice, ie a part of A is replaced by B, the replacement of A by B is less than 20 at%, preferably less than 10 at%, Particularly preferred are tin oxides (A = In, B = Sn, X = O) and antimony stannic oxides (A = Sb, B = Sn, X = O), ii) tungsten bronze and molybdenum bronze. Here is the composition Re Z _x is a WO ₃ or Z _x MoO _3, 0 <a x <1, element Z is the first and / or the elements of the second main group of the periodic table of the elements, and / or iii An oxide of the type tungsten oxide and molybdenum oxide, wherein the composition is WO _3-x or MoO _3-x , respectively, where x <0.1; b) at least one of the compounds having an average molecular weight M w It contains more than 1000 g / mol, preferably more than 1000 g / mol and up to 500,000 g / mol of dispersant, and c) at least one solvent. a) Oxide The oxide a) contained in the composition of the present invention may be present in any form of primary particles, aggregates or aggregates of primary particles, or mixtures of the two. Aggregates or aggregates are particles formed by the interaction of multiple primary particles by Van der Waals forces, or the state in which primary particles adhere to each other during the manufacturing process as a result of a surface reaction or "sintering". These are the particles generated by

If the oxides a) contained in the formulations according to the invention are present in the form of primary particles, the average primary particle size of the oxides is generally between 1 and 100 nm, preferably between 1 and 50 n
m. The primary particles of the oxide are preferably spherical.

If the oxides a) contained in the formulations according to the invention are present in the form of aggregates or aggregates, the average particle size of these aggregates or aggregates is 500 nm
Less than 150 nm, preferably less than 150 nm.

The oxide a) contained in the inventive composition may be crystalline or amorphous, and is preferably crystalline.

The oxides a) can be obtained, for example, by the sol-gel method, chemical vapor reacti
on) (CVR), chemical vapor condensation or plasma desorption
).

The oxides a) contained in the formulations according to the invention preferably have a content of 0.05%, based on the formulation.
It is used in an amount of .about.80% by weight, in particular 0.1-30% by weight, particularly preferably 0.5-20% by weight.

A particularly preferred oxide is indium tin oxide (A = In, B = Sn, X = O)
And antimony tin oxide (A = Sb, B = Sn, X = O). b) Dispersant The dispersant has a molar mass greater than 1000 g / mol and up to 500,000 g / mol.
Preferably more than 1000 g / mol and up to 100,000 g / mol, especially 1000
A molecule that is in excess of g / mol and up to 10,000 g / mol. The dispersant can be a nonionic, anionic, cationic or amphoteric compound.

[0014] Polymeric dispersants are particularly preferred.

As the polymer dispersant, for example, “Water-soluble Synth”
etic Polymers: Properties and Behavi
or "(Volume I + II, Philip Molyneux, CRCP
res., Florida 1983/84).

Polymeric dispersants can further include, for example, water-soluble and water-emulsifiable compounds, such as homo- and copolymers, graft polymers and copolymers and random block copolymers.

Particularly preferred polymeric dispersants include, for example, AB, BAB and ABC block copolymers. In AB or BAB block copolymers, the A segment is a hydrophobic homopolymer or copolymer that when used in the formulations of the present invention ensures that the block copolymer adheres to the oxide. The B block is a hydrophilic homopolymer or copolymer or a salt thereof, which when used in the formulation of the present invention, ensures that the oxide is dispersed in the solvent in the formulation of the present invention. Such polymeric dispersants and their synthesis are known, for example, from EP-A-518225 and EP-A-566649.

Useful polymeric dispersants include, for example, polyethylene oxide, polypropylene oxide, polyoxymethylene, polytrimethylene oxide, polyvinyl methyl ether, polyethylene imine, polyacrylic acid, polyacrylamide, polymethacrylic acid, polymethacrylamide. Poly-N, N-dimethylacrylamide, poly-N-isopropylacrylamide, poly-N-acryloylglycinamide, poly-N-methacryloylglycinamide, polyvinyl alcohol, polyvinyl acetal, a copolymer of polyvinyl alcohol and polyvinyl acetal,
Polyvinyl pyrrolidone, polyvinyl oxadridone and polyvinyl methyl oxadridone are mentioned.

Useful natural macromolecules include, for example, cellulose, starch, gelatin or derivatives thereof.

Useful nonionic dispersants include, for example, alkoxylates, alkylolamides, esters, amine oxides, silanes such as 3-glycidyloxypropyltrimethoxysilane, and alkyl polyglycosides.

Examples of useful nonionic dispersants further include compounds capable of alkoxylation with alkylene oxides, for example, aliphatic alcohols, aliphatic amines, fatty acids, phenols, alkylphenols, arylalkylphenols such as styrene-phenol condensates, Reaction products with carboxamides and resin acids.

The reaction products are ethylene oxide and 1) a saturated and / or unsaturated aliphatic alcohol having 6 to 20 carbon atoms or 2) an alkylphenol having 4 to 12 carbon atoms in an alkyl group or 3 A) a saturated and / or unsaturated aliphatic amine having 14 to 20 carbon atoms or 4) a saturated and / or unsaturated fatty acid having 14 to 20 carbon atoms or 5) a hydrogenated and / or non-hydrogenated resin acid. Is preferably an ethylene oxide adduct generated from the above reaction.

Useful ethylene oxide adducts include, in particular, the alkoxylatable compounds described in 1) to 5) above, in which 5 to 120, preferably 5 to 60,
Particularly, it is contained together with 5 to 30 ethylene oxide units.

For example, polyethylene oxide, polypropylene oxide, polyoxymethylene, polytrimethylene oxide, polyvinyl methyl ether, polyethylene imine, polyacrylic acid, polyacrylamide, polymethacrylic acid, polymethacrylamide, poly-N, N-dimethylacrylamide, Nonionic polymeric dispersants such as poly-N-isopropylacrylamide, poly-N-acryloylglycinamide, poly-N-methacryloylglycinamide, polyvinyl alcohol, polyvinylpyrrolidone and polyvinylmethyloxadridone are particularly preferred.

Useful anionic dispersants include, for example, alkyl sulfates, sulfate ethers, carboxylate ethers, phosphate esters, sulfosuccinate esters, sulfosuccinamides, paraffin sulfonates, olefin sulfonates, sarcosinates, isothionates, taurates, and And lignin compounds.

Anionic polymeric dispersants are particularly preferred.

Preferred anionic polymeric dispersants are the condensation products of aromatic sulfonic acids with formaldehyde, such as the condensation products of formaldehyde with alkylnaphthalenesulfonic acids, and the condensation products of formaldehyde with naphthalenesulfonic acid and / or benzenesulfonic acid. Condensation products or condensation products of substituted or unsubstituted phenols with formaldehyde and sodium bisulfite.

Similarly, reaction of naphthol with alkanol, addition of alkylene oxide,
Preference is given to the condensation products which can be obtained by conversion of at least some of the terminal hydroxyl groups to sulfo groups or monoesters of maleic acid, phthalic acid or succinic acid.

Preferred compounds for use as anionic dispersants include, in addition to those described above, compounds from the group of the sulfosuccinates, alkylbenzenesulfonates, sulfated alkoxylated fatty alcohols or salts thereof.
Alkoxylated fatty acid alcohols have in particular 5 to 120, preferably 5 to 60, particularly preferably 5 to 30 ethylene oxide units per molecule,
Saturated or unsaturated C ₆ -C ₂₂ fatty acid alcohols, especially stearyl alcohol. Particularly, an alkoxylated stearyl alcohol having 8 to 10 ethylene oxide units is preferable. Preferably, the sulfated alkoxylated fatty acid alcohol is present as a salt, especially an alkali metal salt or ammonium salt, more preferably as a diethyl ammonium salt.

Other examples of preferred anionic polymer dispersants include salts of polyacrylic acid, polyethylene sulfonic acid, polystyrene sulfonic acid, polymethacrylic acid, polyphosphoric acid and polyaspartic acid.

Similarly, anionic polymeric dispersants that are copolymers of acrylic acid monomers are preferred. These copolymers can be obtained, for example, by the following combinations of monomers, which form random or alternating copolymers or graft copolymers. Acrylamide, Acrylic acid; Acrylamide, Acrylonitrile; Acrylic acid, N-acryloylglycinamide; Acrylic acid, Ethyl acrylate; Acrylic acid, Methyl acrylate; Acrylic acid, Methylenebutyrolactam; N-Acryloylglycinamide, N-isopropylacrylamide Methacrylamide, Methacrylic acid; Methacrylic acid, Benzyl methacrylate; Methacrylic acid, Diphenylmethyl methacrylate; Methacrylic acid, Methyl methacrylate; Methacrylic acid, Styrene; Lignin sulfonate,
For example, sulphite or ligninsulfonate obtained by the kraft process (sulphite and kraft ligninsulphonate) are mentioned. They are partially hydrolyzed, oxidized, propoxylated, sulfonated, sulfomethylated or disulfonated,
And it is preferable that the product is fractionated by a known method based on, for example, the molecular weight or the degree of sulfonation. Mixtures of sulfites and kraft lignin sulfonates are also preferred. Particularly preferred lignin sulfonates are those having an average molecular weight of more than 1000 g / mol to 100,000 g / mol, an active lignin sulfonate content of at least 80%, and preferably a low polyvalent cation content. The degree of sulfonation may vary over a wide range.

Useful cationic dispersants include, for example, alkyl ammonium compounds and imidazole.

Particularly, a cationic polymer dispersant is preferable.

Examples of cationic polymer dispersants include polyethyleneimine, polyvinylamine, poly (2-vinylpyridine), poly (4-vinylpyridine), poly (diallyldimethylammonium) chloride, poly (4-vinylbenzyltrimethylammonium) ) Salts, salts of poly (2-vinylpyridine) and polylysine.

Useful amphoteric dispersants include, for example, betaines, glycinates, propionates and imidazolines.

Both anionic and cationic polymers are classified as polyelectrolytes and can be partially or completely dissociated in aqueous and / or organic phases.

The dispersant is preferably used in an amount of 0.1 to 200% by weight, in particular 0.5 to 100% by weight, particularly preferably 1 to 20% by weight, based on the amount of oxide used. Is done.

Particularly preferred formulations are: a) at least one oxide having an average primary size of 1 to 100 nm, preferably 1 to 50 nm, i) ABX [where A is Sn, In Or Zn; B is Sb, Sn, F, P, Al or Cd; X is O, S, Se or Te, preferably O; and A forms a host lattice. And B is doped in its host lattice, ie a part of A is replaced by B, the replacement of A by B is less than 20 at%, preferably less than 10 at%, Particularly preferred are indium tin oxide (A = In, B = Sn, X = O) and antimony stannic oxide (A = Sb, B = Sn, X = O), ii) tungsten bronze and molybdenum bronze [Here, the composition is A respectively Z _x WO ₃ or Z _x MoO _3, 0 <a x <1, element Z is the element of the first and / or second main group of the periodic table of the elements, and / Or iii) an oxide of the type tungsten oxide and molybdenum oxide, where the composition is WO _3-x or MoO _3-x , respectively, where x <0.1; b) at least one average molecular weight Dispersants having a Mw of more than 1000 g / mol, preferably more than 1000 g / mol and up to 500,000 g / mol, comprising the following group of anionic dispersants: sulfosuccinates, alkylbenzenesulfonates, sulfated Alkoxylated fatty acid alcohols or salts thereof, sulfuric acid ethers, carboxylic acid ethers, phosphate esters, sulfosuccinamides, paraffin sulfonates, olefin sulfonates, monkeys Sinates, isothionates, taurates, lignin compounds, condensation products of aromatic sulfonic acids with formaldehyde, such as condensation products of formaldehyde and alkylnaphthalenesulfonic acids, condensation of formaldehyde with naphthalenesulfonic acid and / or benzenesulfonic acid Product, or condensation product of substituted or unsubstituted phenol with formaldehyde and sodium bisulfite, reaction of naphthol with alkanol, addition of alkylene oxide, and sulfo group or maleic acid at least a part of terminal hydroxyl group , Condensation products obtainable by the conversion of phthalic acid or succinic acid to monoesters, and polymers or amino acid units, in particular from polyaspartic acid, or from the group of the following cationic dispersants: quaternary alkyl ammonium compounds and From midazoles or from the following groups of amphoteric dispersants: glycinate, propionate and imidazoline or from the following groups of nonionic dispersants: alkoxylates, alkylolamides, esters, amine oxides, for example 3-glycidyloxypropyl tris Silanols such as methoxysilanes, alkyl polyglycosides, and compounds that can be alkoxylated with alkylene oxides, for example, aliphatic alcohols, aliphatic amines, fatty acids, phenols, alkylphenols, arylalkylphenols such as styrene-phenol condensates, carboxamides And a resin acid, preferably ethylene oxide, and 1) a saturated and / or unsaturated aliphatic alcohol having 6 to 20 carbon atoms or 2) a carbon atom having 4 to 12 carbon atoms in an alkyl group. Archi Phenol or 3) a saturated and / or unsaturated aliphatic amine having 14 to 20 carbon atoms or 4) a saturated and / or unsaturated fatty acid having 14 to 20 carbon atoms or 5) hydrogenated and / or non-hydrogenated Ethylene oxide adducts formed from the reaction with resin acids, particularly preferably the alkoxylatable compounds described in 1) to 5), are reacted with 5 to 120, preferably 5 to 60, In particular, it contains 5 to 30 ethylene oxide units together with a dispersant selected from the ethylene oxide adducts contained therein, and c) at least one solvent. c) Solvent The solvent c) used in the formulations according to the invention is preferably a C ₁ to C such as water, methanol, ethanol, isopropanol, n-propanol, n-butanol, isobutanol or tertiary butanol. aliphatic alcohol C _4, acetone, methyl ethyl ketone, aliphatic ketones such as methyl isobutyl ketone or diacetone alcohol, ethylene glycol, propylene glycol, butylene glycol, diethylene glycol, triethylene glycol, trimethylol propane, 4000 g average molecular weight 100 / Mol, preferably 400 to 1500 g /
Moles of polyethylene glycol, polyols such as glycerol, monohydroxy ethers, preferably monohydroxyalkyl ethers, especially ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether, propylene glycol monoethyl ether, thiodiglycol, triethylene glycol monomethyl ether or triethylene glycol monoethyl ether, monoalkyl glycol ethers of C ₁ -C _4, such as, 2-pyrrolidone, N- methyl-2-pyrrolidone, N
-Ethylpyrrolidone, N-vinylpyrrolidone, 1,3-dimethylimidazolidone, dimethylacetamide, and dimethylformamide are preferred.

It is preferred to use a mixture of solvents, particularly preferred is the use of a mixture of polyethylene glycol / 2-pyrrolidone / water or polyethylene glycol / 2-pyrrolidone / ethanol.

The amount of solvent used in the formulations according to the invention is preferably from 10 to 99% by weight, particularly preferably from 30 to 98% by weight, based on the solids content of the oxides in the formulations according to the invention. is there.

The formulations according to the invention furthermore comprise, in addition to the compounds a) to c) used,
Anionic, amphoteric, and / or nonionic surface active compounds, such as "Sulfact
Ants Europa, A Directory of Surface A
active Agents available in Europe "(Edite
d by Gordon L. Hollis, Royal Society of C
hemistry), Cambridge (1995).

If the dispersant b) used in the formulations according to the invention contains ionic groups,
The surface-active compound should preferably be a non-ionic or ionic compound identical to the dispersant b).

The formulations according to the invention can furthermore comprise additives in addition to the compounds a) to c) used.

Preferred additives are aromatic dicarboxylic acids and their esters.

Preferred aromatic dicarboxylic acids are phthalic acid, isophthalic acid and terephthalic acid. Preferred esters are structural formula _{RCOO-C 6 H 4 -COOR '} ( wherein, R
, R ′ are independently methyl, ethyl, propyl, isopropyl, butyl, isobutyl, pentyl, hexyl, phenyl or benzyl), diesters of phthalic, diester of phthalic and diesters of terephthalic acid.

[0046] Diethyl phthalate is particularly preferred. Mixtures of the abovementioned additives are also possible.

Other preferred additives are compounds from the group of the terpenes, terpenoids, fatty acids and fatty acid esters.

Preferred compounds are ocimene, myrcene, zeraniol, nerol, linalool, citronellol, geranial, citronellal, neral, limonene, menthol, such as (-)-menthol, mentone or bicyclic monoterpenes, such as stearic acid, olein 6 to 2 carbon atoms such as acid, linoleic acid and linolenic acid
2 saturated or unsaturated fatty acids. Mixtures of additives are also possible.

The preparation of the formulation according to the invention comprises a wet milling step and a dilution step.

[0050] Wet milling optionally comprises premilling, making a milling suspension, and milling.

In order to produce a milling suspension, the oxide a), optionally after premilling,
Usually in the form of a powder or wet presscake, with a portion of the dispersant and a polar organic solvent and / or water, preferably deionized water, crushed (ie, introduced and homogenized) to form a uniform grinding suspension. I do. In this step, the dispersant used is adsorbed on the surface of the oxide, and as a result, the oxide disaggregates and disperses. The production of this suspension for grinding can be carried out, for example, using a stirring vat, a dissolver and similar devices.

The suspension for milling may optionally also contain a low-boiling solvent (boiling point <150 ° C.) fraction which can be removed by evaporation in the course of the next micronization. On the other hand, the suspension can also contain high-boiling solvent fractions, the surface-active compounds mentioned above, or additional additives such as grinding aids, defoamers or wetting agents.

The solids content of the oxide a) in the milling suspension is preferably greater than or equal to the desired solids content in the final formulation. The desired solids content in the final formulation is preferably set after wet milling.

By milling, standardization to the desired particle refinement is achieved. Grinding is performed, for example, in a kneader, a roll mill, a kneading screw, a ball mill, a rotor-stator mill, a dissolver, a steel ball disk mill, or a vibration mill. The pulverization is preferably carried out in a continuous or discontinuous charged high-speed stirring media mill equipped with a pulverization medium having a diameter of 0.1 to 5 mm. The grinding media can be made of glass, ceramic, or metal such as steel. The grinding temperature is preferably from 0 to 250
It is preferably in the range of ° C, but usually at room temperature, particularly preferably below the cloud point of the dispersant b) used.

It is likewise preferred to carry out the milling in whole or in part in a high-pressure homogenizer or a so-called jet disperser (known from DE-A 195 36 845), whereby It is possible to minimize or completely avoid the level of grinding media abrasion in the suspension or the release of soluble substances (eg ions from the glass media) from the grinding media. In addition, the formation of bubbles can be suppressed and reagglomeration is avoided.

In the dilution step, the freshly milled suspension is mixed in a customary manner, optionally with the remaining dispersing agent and optionally further additives, into a solvent, preferably water, And adjusted to the desired solids content for the final formulation. In this step, if desired, additional dispersants can be added, for example to avoid reagglomeration of the microparticles in the final formulation.

[0057] The process for the preparation of the formulations according to the invention, in which sufficient dispersing agent is available for stabilization in the milling process for preparing the milled suspension, is particularly advantageous. Subsequent or after the dilution step, the dispersant and / or excess surfactant not adsorbed on the oxide a) used is removed from the solution and then the desired solids concentration in the final formulation is set. I do.

A method for removing the dispersant present in the solution is, for example, a method of centrifuging a ground suspension and then decanting the supernatant. A method using a membrane or a microfiltration method is also suitable.

The formulations of the present invention are structured, conductive and transparent surfaces (eg for display).
For example, it is preferably used to form a conductive path on an insulating and transparent substrate. The formulations of the present invention can be applied to substrates in the form of pastes or flowable compositions by knife-coating or casting, or in the form of printing inks by inkjet printing.

The composition of the present invention is preferably applied to a substrate in the form of a printing ink by an inkjet printing method.

The present invention further provides a printing ink comprising the formulation of the present invention.

The formulation of the present invention and the printing ink of the present invention include, for example, polyvinyl alcohol,
Viscosity modifiers for inks such as polyvinylpyrrolidone and methylcellulose and other additives known to those skilled in the art may be included as long as they do not adversely affect the stability of the printing ink, the printing function, and the drying function.

The printing ink of the present invention may further contain a preservative, a surfactant and a pH adjuster.

Preferred preservatives are methylisothiazolin-3-one, chloromethylisothiazolin-3-one, benzisothiazolin-3-one or mixtures thereof.

Preferred pH adjusters are NaOH, ammonia, aminomethylpropanol and N, N-dimethylaminoethanol.

The printing inks of the present invention can be prepared in a similar manner to the formulations of the present invention, and the standardization of the printing inks of the present invention to the desired viscosity, concentration, and surface tension is likely to be in accordance with the present invention. This can be performed in the process of standardizing the solid content of the printing ink.

The physical properties of the ink are preferably standardized for use in conventional ink jet printers, the surface tension is preferably 20-70 mN / m and the viscosity is
It is preferably less than 20 mPa · s, more preferably 0.5 to 10 mPa
-It is s.

The printing ink of the present invention is preferably filtered before use, for example using a 0.5 to 5 μm membrane or glass filter.

The printing ink of the present invention has excellent dispersibility and storage stability over a wide temperature range. When these are used in inkjet printers, no kogation or clogging occurs in the printhead. When printed on different transparent substrates, such as glass or heat resistant plastics, they show high water resistance and migration fastness.

The present invention is further directed to a method of making a conductive path in a conductive, structured transparent surface (eg, for display applications), for example, an insulating transparent substrate such as glass or a high melting point plastic. By applying the printing ink of the present invention in the form of a transparent surface body having a structure by inkjet printing, and then sintering the printed substrate in a reducing atmosphere, these structures were obtained. Provided is a manufacturing method by converting a transparent surface body into a conductive and structured transparent surface body.

Ink-jet printing by the ink-jet method itself is known. Generally, the printing ink is filled in a receiving container of the inkjet print head,
Sprayed in droplets on the substrate. The ejection of the ink in the form of droplets is preferably effected by piezoelectric crystals, heated cannula (bubble or thermal jet method) or by a mechanical pressure increase applied to the ink system to eject the ink droplets. Droplets are ejected onto the substrate by one or more small nozzles toward a target.

A method in which electrostatic deflection is used to cause a very small amount of ink jet to reach the substrate in droplet form can also be used.

By electronic control, the individual droplets are gathered together on a substrate and become a script character or a figure, for example a structured surface.

The method of the present invention comprises the steps of applying a printing ink and then applying the printed substrate in a reducing atmosphere (eg, an argon-hydrogen gas mixture), preferably with an active gas (= 5% hydrogen, 95% (Argon) under a temperature of 150 to 600 ° C.

Preferably, following this step, sintering is performed in air at a temperature of 400 to 600 ° C. to remove organic components without remaining.

The conductive, structured, transparent surface body produced according to the method of the present invention has a resistivity of 0.014-0.11 ohm * cm. EXAMPLES Example 1 2.5 g of polyaspartic acid (molar mass 3000 g / mol) were added to deionized water 24
Dissolved in 7.5 ml. To this solution, 50 g of solid indium tin oxide powder (prepared by a CVR method with a primary particle size of 2 to 30 nm as measured by TEM) was added with strong stirring (with a magnetic stirrer). The suspension was predispersed for 5 minutes using an ultrasonic finger (power, 200 watts).

Subsequently, this was heated under reflux for 5 hours (with a mantle heater). The cooled suspension is filtered with suction on a round filter made of glass frit (= HAWP® from Millipore) with a pore size of 0.22 μm and The residue was washed with water. Next, the residue was dried in a drying box at 70 ° C. for 12 hours.

5 g of the dried and modified indium tin oxide powder was collected and
(= Polyethylene glycol - le M _W = 1000 g / mol) was placed 16% and 2-pyrrolidone 8% in the solvent mixture 100ml comprising in water, and the pH adjusted to 6 with half-concentrated ammonia solution. This is then applied to an ultrasonic finger for 5 minutes.
Minutes.

To determine the powder properties of the formulation, a portion was diluted with the solvent mixture described above,
Then, the average particle diameter of the indium tin oxide particles was determined by a dynamic light scattering method (scattered light distribution). A particle size of 91 nm was measured. The following results were obtained when the mass distribution was determined using an ultracentrifuge.

[0080]

[Table 1]

(In the table, d ₁₀ indicates that 10% of all particles are 17 nm or less, and d ₅₀ indicates 5% of all particles.
0% is less than 43 nm, and d ₉₀ indicates that 90% of all particles are less than 87 nm). The particles mentioned here mean not only primary particles but also aggregates and aggregates. Example 2 2.5 g of polyaspartic acid (molar mass 3000 g / mol) in deionized water 24
Dissolved in 7.5 ml. To this solution, 50 g of solid indium tin oxide powder (prepared to have a primary particle size of 2 to 30 nm as measured by TEM by CVR method) was added with strong stirring (with a magnetic stirrer). The suspension was heated at reflux (mantle heater) for 5 hours. Cool the suspension to 0.22 μm
Round filter made of glass frit having a pore size of (= Mill)
Filtration over HAWP® from ipore) with suction, and the residue was washed with water. Next, the residue was dried in a drying box at 70 ° C. for 12 hours.

[0082] The dried, the denatured indium tin oxide powder 5 g, PEG 1000 (= polyethylene glycol - le _{M W = 1000g / mol) 10} %, 2- pyrrolidone 5%
And 100 ml of a solvent mixture comprising 35% of diethyl phthalate and ethanol in ethanol
(With a magnetic stirrer). This was then treated with an ultrasonic finger for 2 minutes.

To determine the powder properties of the formulation, a portion was diluted with the solvent mixture described above,
Then, the average particle diameter of the indium tin oxide particles was determined by a dynamic light scattering method (scattered light distribution). A particle size of 91 nm was measured. The following results were obtained when the mass distribution was determined using an ultracentrifuge.

[0084]

[Table 2]

(In the table, d ₁₀ indicates that 10% of all particles are 34 nm or less, and d ₅₀ indicates 5% of all particles.
0% is less than 79 nm and d ₉₀ indicates that 90% of all particles are less than 107 nm). The particles mentioned here mean not only primary particles but also aggregates and aggregates. Example 3 2.5 g of polyacrylic acid (molar mass 2500 g / mol) in 247.
Dissolved in 5 ml. To this solution, 50 g of solid indium tin oxide powder (prepared to have a primary particle size of 2 to 30 nm as measured by TEM by CVR method) was added with strong stirring (with a magnetic stirrer). This suspension was pre-dispersed for 5 minutes using an ultrasonic probe (power: 220 w). Subsequently, it was heated under reflux for 5 hours (with a mantle heater). Cool the suspension to 0.22μ
Round filter made of glass frit having a pore size of m (= Millip
Filtration over HAWP® from ore) with suction and washing the residue with water. Next, the residue was dried in a drying box at 70 ° C. for 12 hours.

[0086] The dried, the denatured indium tin oxide powder 5 g PEG 1000 - a (= polyethylene glycol le M _W = 1000 g / mol) 16% and 2-pyrrolidone 8% solvent mixture comprising in water 100ml And the pH was adjusted to 6 with a semi-concentrated ammonia solution. This was then treated with an ultrasonic finger for 5 minutes.

To determine the powder properties of the formulation, a portion was diluted with the solvent mixture described above and the average particle size of the indium tin oxide particles was determined by dynamic light scattering (scattered light distribution).
I asked for it. A particle size of 91 nm was measured. The following results were obtained when the mass distribution was determined using an ultracentrifuge.

[0088]

[Table 3]

(In the table, d ₁₀ indicates that 10% of all particles are 23 nm or less, and d ₅₀ indicates ₅₀ % of all particles.
% Is below 60 nm, and d ₉₀ indicates that 90% of all particles are below 92 nm). The particles mentioned here mean not only primary particles but also aggregates and aggregates. Example 4 2.5 g of polyacrylic acid (molar mass 2500 g / mol) in 247.
Dissolved in 5 ml. To this solution, 50 g of solid indium tin oxide powder (prepared to have a primary particle size of 2 to 30 nm as measured by TEM according to the CVR method) was added with strong stirring (with a magnetic stirrer). The suspension is refluxed for 5 minutes.
Heated (with mantle heater) for hours. The cooled suspension is filtered with suction on a round filter made of glass frit with a pore size of 0.22 μm (= HAWP® from Millipore) and the residue is filtered off. Washed with water. Next, the residue was dried in a drying box at 70 ° C. for 12 hours.

5 g of the dried and modified indium tin oxide powder was mixed with 10% of PEG1000 (= polyethylene glycol MW = 1000 g / mol), 5% of 2-pyrrolidone and 35% of diethyl phthalate in ethanol. 100 m solvent mixture contained therein
1 with strong stirring (with a magnetic stirrer). This was then treated with an ultrasonic finger for 2 minutes.

To determine the powder properties of the formulation, a portion was diluted with the solvent mixture described above,
Then, the average particle diameter of the indium tin oxide particles was determined by a dynamic light scattering method (scattered light distribution). A particle size of 91 nm was measured. The following results were obtained when the mass distribution was determined using an ultracentrifuge.

[0092]

[Table 4]

(In the table, d ₁₀ indicates that 10% of all particles are 34 nm or less, and d ₅₀ indicates ₅₀ % of all particles.
% Is below 67 nm, and d ₉₀ indicates that 90% of all particles are below 110 nm). The particles mentioned here mean not only primary particles but also aggregates and aggregates. Example 5 2.5 g of 3-glycidyloxypropyltrimethoxysilane was added to ethanol 49.
Dissolved in 7.5 g. 50 g of solid indium tin oxide powder (prepared to have a primary particle size of 2 to 30 nm as measured by TEM by CVR method) and 3 m
One liter of 1 molar hydrochloric acid was added with vigorous stirring (with a magnetic stirrer). The suspension was heated at reflux (mantle heater) for 5 hours. The cooled suspension is filtered with suction on a round filter made of glass frit (= HAWP® from Millipore) with a pore size of 0.22 μm and The residue was washed with ethanol. Next, the residue was dried in a drying box at 70 ° C. for 12 hours.

[0094] drying, the modified indium tin oxide powder 5 g PEG 1000 (= polyethylene glycol - le _{M W = 1000g / mol) 10} %, 2- pyrrolidone 5% and 35% dimethyl phthalate ethanol - in Le The resulting solvent mixture (100 ml) was placed under vigorous stirring (with a magnetic stirrer).

To determine the powder properties of the formulation, a portion was diluted with the above solvent mixture and the average particle size of the indium tin oxide particles was determined by dynamic light scattering (scattered light distribution).
I asked for it. A particle size of 91 nm was measured. The following results were obtained when the mass distribution was determined using an ultracentrifuge.

[0096]

[Table 5]

(In the table, d ₁₀ is that 10% of all particles are 31 nm or less, and d ₅₀ is ₅₀ % of all particles.
% Is less than 64 nm and d ₉₀ indicates that 90% of all particles are less than 117 nm). The particles mentioned here mean not only primary particles but also aggregates and aggregates. Example 6 The formulations prepared in Examples 1 to 5 were used as printing inks. These were used in an ink jet printer to print a structured surface and conductive paths on a glass plate having a thickness of 1 to 2 mm.

The printed glass plate was sintered at 400 ° C. under an active gas (5% hydrogen, 95% argon) for 6 hours and then in a furnace at 400 ° C. in air for 6 hours. The conductive, structured surface produced in this way is transparent and has a resistivity of 0.014 to 0.11 ohm * cm.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C09D 17/00 C09D 17/00 (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, TZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU) , TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CR, CU, CZ, DE, DK, D M, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS , LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, TZ, UA, UG, US, UZ, VN, YU, ZA, ZW (71) Applicant D-51368 Leverkusen, Germany F term (reference) AA12 AA24 AA28 CB30 DD24 4J039 AB01 AB02 AB07 AD06 AD07 AD09 AD12 AD23 AE07 BA13 BA18 BA19 BA31 BA33 BA36 BE12 BE22 BE30 EA24 EA33 GA24

Claims (13)

[Claims] 1. a) at least one oxide having an average primary particle size of 1 to 100 nm; b) at least one dispersant having an average molecular weight Mw of more than 1000 g / mol; c) at least one solvent A formulation containing 2. A) at least one oxide having an average primary particle size of 1 to 100 nm, i) ABX (where A is Sn, In or Zn, B is Sb, X is O, S, Se or Te, preferably O, and A forms a host lattice, and B is doped in the host lattice. Ie, part of A is replaced by B, and the amount of A replaced by B is less than 20 at%, preferably less than 10 at%), and / or ii) tungsten bronze and molybdenum bronze (wherein The composition is Z _x WO ₃ or Z _x MoO ₃ , respectively, where 0 <x <1, and Z is an element of the first and / or second main group of the periodic table of the elements), and / Or iii) tungsten oxide and Oxides of the type molybdenum oxide and molybdenum oxide, wherein the composition is WO _3-x or MoO _3-x , respectively, where x <0.1; b) at least one having an average molecular weight Mw of 1000 g / mol A formulation according to claim 1, comprising more than one dispersant; c) at least one solvent. 3. The method according to claim 1, wherein the oxide is indium tin oxide (A = In, B = Sn, X =
O) or antimony tin oxide (A = Sb, B = Sn, X = O). 4. The at least one oxide a), based on the formulation, from 0.05 to 80% by weight, and from 0.1 to 200% by weight, based on the amount of oxide used, of at least one oxide. 4. The formulation according to claim 1, wherein the formulation comprises a dispersant b) and from 10 to 98% by weight, based on the formulation, of at least one solvent c). 5. The oxide a) is present as primary particles, agglomerates, aggregates and / or mixtures thereof, the aggregates and aggregates having an average particle size of 500 nm.
Formulation according to any of the preceding claims, characterized in that it is less than 150 nm. 6. A formulation according to claim 1, wherein the dispersant b) is a polymeric dispersant. 7. The composition according to claim 1, further comprising a cationic, anionic, amphoteric and / or nonionic surface active compound, particularly an aromatic dicarboxylic acid or a dister thereof. object. 8. A method for producing a blend according to any one of claims 1 to 7, comprising a step of producing a suspension for grinding, a grinding step, and a dilution step. A method in which pre-milling is performed or not performed before producing a suspension. 9. Use of a formulation according to claim 1 for producing printing inks. 10. A printing ink containing the composition according to claim 1. 11. The printing ink according to claim 9, comprising a pH adjuster and / or a surfactant and / or a preservative. 12. A method for producing a conductive, structured surface on a substrate, comprising applying the printing ink according to claim 9 to the structured surface by inkjet printing. Coated into a shape, then sintering the printed substrate at a temperature of 150-600 ° C. in a reducing atmosphere to convert the structured surface into a conductive structured surface. A method comprising: 13. A substrate printed with the printing ink according to claim 9. Description: