DE102009014378A1 - Electrically conductive ink composition, useful e.g. in mass printing method, comprises electrically non-conductive polymer, polymerizable material, siccative, carbon component comprising graphite and/or carbon black and optionally solvent - Google Patents

Abstract

Electrically conductive ink composition comprises (a) an electrically non-conductive polymer, (b) an oxidatively polymerizable material which is different from (a), (c) a siccatives, (d) at least an electrically conductive carbon component comprising (d1) electrically conductive graphite and/or (d2) structured electrically conductive carbon black, and (e) optionally at least a non-aqueous solvent in the form of drying or non-drying oil. Independent claims are included for: (1) producing the ink composition, comprising (i) producing a binder from (a)-(c) and optionally (e) by heating and mixing these components, (ii) mixing (d) with the obtained composition optionally under the addition of solvent, (iii) mixing the obtained composition using a dissolver and (iv) subsequently mixing in a three-roll mill, high shear mixer or extruder; (2) a layered, electrically conductive structure, obtained using the ink composition; (3) an article comprising a solid or flexible carrier and the layered, electrically conductive structure; and (4) producing the article, comprising providing the ink composition, and carrier, where optionally at least a portion of the surface on which the ink composition is applied, is pretreated, applying the ink composition by a mass-printing method in the form of one or more electrically conductive, functional structures and optionally drying the applied ink composition.

Description

The The present invention relates to an electrically conductive, carbonaceous ink composition for offset printing as well as flexo printing. In particular, the present invention relates a solvent-containing carbonaceous ink composition for the generation of electrically conductive, functional structures, a layered, electrically conductive, functional Structure obtained by applying the invention Printing ink composition by means of a mass printing method a carrier material is obtained, as well as a method for Preparation of the printing ink composition according to the invention.

In The electronics industry is increasingly demanding production processes which allow a very high production speed. Especially In the field of low-cost electronics is increasingly relying on mass printing. So far, however, these processes are mainly Printing ink formulations based on electrically conductive Polymers available in the market. These formulations However, some have significant disadvantages, such as Wetting problems on substrates, as they are preferably on Water base are produced, or especially in the offset process a problematic separation behavior. Furthermore, the show so far used electrically conductive polymers an unfavorable Aging behavior, which can lead to it resulting applications continuously lose their electrical function and thus have a limited life, as well a strong dependence on external influences, the too strong fluctuations in their electrical properties leads and thus a big problem with their applications represents. Likewise, these materials are at low-cost applications the price-determining factor, as they are still very expensive. A problem of electrically conductive ink formulations metal-based is also due to the high price of materials, which should continue to increase in the future. Therefore, the use of electrically conductive ink formulations is likely based on metallic components on special applications of printed Restrict electronic components. Therefore, there is a need for electrically conductive components that are reasonably priced and be made available to the market as a bulk commodity can, a stable behavior towards outer Possess influences as well as an environmentally sound problem-free Allow disposal. The biggest progress with electrically conductive printing inks, it was probably well in the field of inkjet printing. There can also be very precise circuits are built. The for However, the product quantities required for the low-cost range are most likely to be above conventional ones To realize mass printing process.

EP 1 826 247 A1 describes an aqueous dispersion of carbon black for use as ink for ink-jet printing. For the aqueous compositions, applications are described for ink jet printing only, but not for conventional mass printing processes. The document does not contain a description of an electrically conductive composition. Also, compositions containing a siccative or oil as an essential ingredient are not described. In this context, it should be pointed out that an indication of carbon black is not synonymous with electrically conductive structured carbon black, since the electrical conductivity of the carbon black in a polymer composite is largely determined by its structure and not by its electrical conductivity.

In the patent DE 693 21 366 T2 describes an aqueous, electrically conductive ink containing as an electrically conductive component of metal particles, carbon black or graphite, with metal particles, in particular silver flakes, are preferred. The applications described for printing processes are limited to screen printing, with screen printing in particular being the focus. A concrete application for mass printing, z. As the offset printing, missing in this specification and seems hardly possible due to the composition. In the above-identified patent no compositions with a siccative or an oil as an essential component are described. Further, neither the usable carbon black nor the usable graphite is further characterized.

DE 10 2007 013 276 A1 discloses an aqueous printing ink composition containing an electroconductive polymer in aqueous dispersion, carbon black and graphite. In this composition, the electrically conductive polymer forms an essential part of the electrical conductivity. The comparatively high price of electrically conductive polymers and their difficult processability in conventional mass printing methods allow the use of today's mass printing techniques only to a limited extent, especially in view of the special requirements of offset printing. In the above-mentioned composition, an electrically conductive polymer is contained, which is expensive on the one hand and, on the other hand, can have problems such as aging problems, difficult processability, etc. In the above-identified application no compositions with a siccative or an oxidatively polymerisable material are described as essential constituents.

Of the possesses elemental carbon in its various modifications a huge potential as a functional electronic Low-cost applications, if successful, this material the mass printing process in an easy-to-use form provide. An object of the present invention is Therefore, one over the prior art equivalent and preferably improved ink composition with lighter Processability for conventional mass pressure for To make available. Another object is printing ink compositions reasonably priced and applicable to mass-produced goods Market to provide a stable behavior against external influences own as well as an environmentally friendly problem-free disposal permit.

Even though Carbon black is used as the black pigment in printing inks it has not succeeded in the electrically conductive properties to take full advantage of this material. That is mainly Remember that the focus of the properties is on the coloring properties and flowability targeted. Therefore have been so far finely divided and low-structured carbon blacks in printing inks used. The low structured carbon blacks are, though an electrical intrinsic conductivity is present, difficult or unable to have a sufficient network in the electrical not form conductive binder solids. The electric Conductivity of the carbon black in a polymer composite is largely determined by its structure and not by its electrical conductivity. For Applications in the electronics sector, however, it comes less to the Color properties of the printed structure, but rather on their electronic structure and mechanical resilience. Consequently is it possible to use substances that are suitable for the previous optical requirements of a printing ink untypical and appeared disadvantageous. By using these components resulting disadvantages of their flow properties can on the one hand by variation of the binder mixture and on the other by little change of process parameters of the Be balanced printing process.

• a) ein elektrisch nicht leitfähiges Polymer,
• b) ein oxidativ polymerisierbares Material, welches sich vom elektrisch nicht leitfähigen Polymer a) unterscheidet,
• c) ein Sikkativ,
• d) mindestens eine elektrisch leitfähige Kohlenstoffkomponente, ausgewählt aus elektrisch leitfähigem Graphit d1), strukturiertem, elektrisch leitfähigen Ruß d2) und Gemischen davon, und
• e) gegebenenfalls mindestens ein nicht wässriges Lösungsmittel in Form eines trocknenden oder nicht trocknenden Öls.

The present invention relates to an electrically conductive ink composition for the production of electrically conductive, functional structures, the ink composition comprising:

• a) an electrically nonconductive polymer,
• b) an oxidatively polymerizable material which differs from the electrically non-conductive polymer a),
• c) a siccative,
• d) at least one electrically conductive carbon component selected from electrically conductive graphite d1), structured, electrically conductive carbon black d2) and mixtures thereof, and
• e) optionally at least one nonaqueous solvent in the form of a drying or non-drying oil.

In an embodiment of the present invention is the electrically non-conductive polymer a) not electrically conductive polymer resin. The electrically non-conductive Polymer resin is preferably selected from a modified Rosin resin such as a phenol-modified rosin resin or a maleinate-modified rosin resin, a modified Hydrocarbon resin and mixtures thereof.

In an embodiment of the present invention, in particular Of all the above embodiments, this is oxidative polymerizable material b) selected from an alkyd resin based on linseed oil, a soya oil-based alkyd resin, a linseed oil varnish, drying vegetable oils and mixtures thereof.

In another embodiment of the present invention, in particular, all of the above embodiments, is the siccative c) selected from a manganese salt, a Cobalt salt and mixtures thereof.

In another embodiment of the present invention, in particular, all of the above embodiments, is the electrically conductive carbon component d) electrically conductive graphite d1) selected from a synthetic graphite and mixtures of several synthetic Graphite.

In another embodiment of the present invention, in particular, all of the above embodiments, is the electrically conductive carbon component d) is selected from a structured electrically conductive carbon black d2) or a mixture of a plurality of structured electrically conductive Russen d2).

In another embodiment of the present invention, in particular, all of the above embodiments, has the electrically conductive graphite d1) has an average particle size from 0.1 to 100 microns.

In a further embodiment of the present invention, in particular of all the abovementioned embodiments, component d) is selected from a structured electrically conductive carbon black d2) and mixtures of a plurality of structured electrically conductive carbon blacks d2) with an oil requirement number of 100-700 ml / 100 g, more preferably with an oil requirement of 100-550 ml / 100 g, measured after Standard ASTM D 2414 ,

In another embodiment of the present invention, in particular, all of the above embodiments, is the non-aqueous solvent e) is selected from a mineral oil, a vegetable oil or Mixtures thereof.

• a) 10–40 Gew.-% eines elektrisch nicht leitfähigen Polymerharzes,
• b) 20–50 Gew.-% eines oxidativ polymerisierbaren Materials, welches sich vom elektrisch nicht leitfähigen Polymer a) unterscheidet,
• c) 0,01–2 Gew.-% eines Sikkativs,
• d) 10–50 Gew.-% einer elektrisch leitfähigen Kohlenstoffkomponente, ausgewählt aus elektrisch leitfähigem Graphit d1), strukturiertem elektrisch leitfähigen Ruß d2) und Gemischen davon, und
• e) gegebenenfalls 10–50 Gew.-% mindestens eines nicht wässrigen Lösungsmittels in Form eines trocknenden oder nicht trocknenden Öls,

jeweils bezogen auf das Gesamtgewicht der Druckfarbenzusammensetzung.In a preferred embodiment of the present invention, in particular of all the abovementioned embodiments, the printing ink composition comprises:

• a) 10-40% by weight of an electrically non-conductive polymer resin,
• b) 20-50 wt .-% of an oxidatively polymerizable material which is different from the electrically non-conductive polymer a),
• c) 0.01-2% by weight of a siccative,
• d) 10-50 wt .-% of an electrically conductive carbon component selected from electrically conductive graphite d1), structured electrically conductive carbon black d2) and mixtures thereof, and
• e) optionally 10-50% by weight of at least one non-aqueous solvent in the form of a drying or non-drying oil,

each based on the total weight of the ink composition.

In another embodiment of the present invention, in particular of all the above-mentioned embodiments the ink composition is preferably less than 5.0% by weight, more preferably less than 3.0% by weight, even more preferably less than 2.0% by weight, more preferably less than 1.0% by weight, less than 0.5% by weight or less than 0.25% by weight, and in particular no water, based on the total weight of Ink composition.

In a further embodiment of the present invention, in particular of all the above-mentioned embodiments, the ink composition preferably contains less than 2.0% by weight, more preferably less than 1.0% by weight, even more preferably less than 0.7% by weight. -% or less than 0.5 wt .-%, more preferably less than 0.4 wt .-%, less than 0.25 wt .-% or less than 0.1 wt .-% of electrically conductive polymers with an electrical Conductivity of 10 ^-1 S / m and greater (measured according to DIN IEC 60093 (measured as resistance)), based on the total weight of the electrically conductive carbon component.

In a further embodiment of the present invention, in particular of all the above-mentioned embodiments, the ink composition preferably contains less than 2.0% by weight, more preferably less than 1.0% by weight, even more preferably less than 0.7% by weight. -% or less than 0.5 wt .-%, more preferably less than 0.4 wt .-%, less than 0.25 wt .-% or less than 0.1 wt .-% of electrically conductive polymers with an electrical Conductivity greater than 10 ^-3 S / m (measured according to DIN IEC 60093 (measured as resistance)), based on the total weight of the electrically conductive carbon component.

In a further embodiment of the present invention, in particular of all the above-mentioned embodiments, the ink composition preferably contains less than 2.0% by weight, more preferably less than 1.0% by weight, even more preferably less than 0.7% by weight. -% or less than 0.5 wt .-%, more preferably less than 0.4 wt .-%, less than 0.25 wt .-% or less than 0.1 wt .-% of electrically conductive polymers with an electrical Conductivity greater than 10 ^-6 S / m (measured according to DIN IEC 60093 (measured as resistance)), based on the total weight of the electrically conductive carbon component.

In a further embodiment of the present invention, in particular of all the above-mentioned embodiments, the ink composition preferably contains less than 2.0% by weight, more preferably less than 1.0% by weight, even more preferably less than 0.7% by weight. -% or less than 0.5 wt .-%, more preferably less than 0.4 wt .-%, less than 0.25 wt .-% or less than 0.1 wt .-% of electrically conductive polymers with an electrical Conductivity greater than 10 ^-8 S / m (measured according to DIN IEC 60093 (measured as resistance)), based on the total weight of the electrically conductive carbon component.

In a further embodiment of the present invention, in particular of all the abovementioned embodiments, the ink composition preferably contains no electrically conductive polymer having an electrical conductivity of 10 ^-1 S / m and greater, more preferably no electrically conductive polymer having an electrical conductivity greater than 10 ^{, 3} S / m, even more preferably no electrically conductive polymer having an electrical conductivity greater than 10 ^-6 S / m, and more preferably no electrically conductive polymer having an electrical conductivity greater than 10 ^-8 S / m, measured according to DIN IEC 60093 (measured as resistance).

The The present invention further relates to a layered, electrically conductive structure, which by mass pressure and optionally subsequent drying of one of the above said ink composition is obtained. The present The invention further relates to an article comprising a solid or flexible carrier and a layered, electrically conductive structure, which preferably by Mass pressure and optionally subsequent drying one of the above-mentioned ink composition has been. The carrier of the invention Article is preferably selected from paper, cardboard, Textiles, wood, polymers, polymer resins, glass and composites. In the above materials, which is a recording of the liquid components b) and e) and optionally of liquid dissolved components of the ink composition allow, for. B. by suction, infiltration, porosity etc., the amount consumed is not more than 90, 80, 70, 60, 50, 40, 30, 20 or 10 wt .-% of the liquid Component of the ink composition, wherein the liquid Component of the total proportion of all components of the ink composition which is in liquid at room temperature (20 ° C) Form (i.e., not as a solid) is present. In a preferred Embodiment of the invention Object has the layered, electrically conductive Structure the shape of a printed circuit.

• A) Herstellen eines Bindemittels aus einem elektrisch nicht leitfähigen Polymer a), einem oxidativ polymerisierbaren Material b), das sich vom Polymer a) unterscheidet, einem Sikkativ c) und gegebenenfalls mindestens einem nicht wässrigen Lösungsmittel in Form eines trocknenden oder nicht trocknenden Öls e) durch Erwärmen und Vermischen dieser Komponenten,
• B) Vermischen der in Schritt A) erhaltenen Zusammensetzung mit mindestens einer elektrisch leitfähigen Kohlenstoffkomponente d), ausgewählt aus elektrisch leitfähigem Graphit d1), strukturiertem elektrisch leitfähigen Ruß d2) und Gemischen davon, gegebenenfalls unter (weiterer) Zugabe von nicht wässrigem Lösungsmittel in Form eines trocknenden oder nicht trocknenden Öls e),
• C) Vermischen der im Schritt B) erhaltenen Zusammensetzung mittels eines Dissolvers und anschließend
• D) Vermischen der im Schritt C) erhaltenen Zusammensetzung in einem Dreiwalzenstuhl, Hochschermischer oder Extruder.

Das Vermischen im Schritt B) kann mittels eines Rührers, Knetrührers, Ankerrührers oder Butterflymischers erfolgen.The present invention further relates to a process for the preparation of a printing ink composition according to the invention, comprising the following steps:

• A) producing a binder from an electrically nonconductive polymer a), an oxidatively polymerizable material b) which differs from the polymer a), a siccative c) and optionally at least one nonaqueous solvent in the form of a drying or non-drying oil e) by heating and mixing these components,
• B) mixing the composition obtained in step A) with at least one electrically conductive carbon component d) selected from electrically conductive graphite d1), structured electrically conductive carbon black d2) and mixtures thereof, optionally with (further) addition of nonaqueous solvent in the form of a drying or non-drying oil e),
• C) mixing the composition obtained in step B) by means of a dissolver and then
• D) mixing the composition obtained in step C) in a three-roll mill, high shear mixer or extruder.

The mixing in step B) can be effected by means of a stirrer, paddle stirrer, anchor stirrer or butterfly mixer.

The The present invention further relates to the use of any of the above said ink compositions for producing an electrical conductive, functional structure on a substrate. The present invention further relates to the use of one of aforesaid printing ink compositions in a mass printing process, selected from offset printing, flexo printing and gravure printing, for To Print. The present invention further relates to the use one of the abovementioned printing ink compositions in one Mass printing process, selected from offset printing, flexo printing and Gravure printing, for the production of an electrically conductive, functional structure on a carrier material.

Of the Expression "mass printing" means here a printing process selected from offset printing, flexo printing and gravure. Offset printing methods close usual Wet offset and dry offset processes as well as older ones Procedures, such as Dilitho method and driography, a.

The term "electrically non-conductive" here means an electrical conductivity of 10 ^-6 S / m and lower, determined according to DIN IEC 60093 (measured as resistance). The term "electrically conductive" here means an electrical conductivity of 10 ^-1 S / m and greater, determined according to DIN IEC 60093 (measured as resistance). The electrical conductivity (of the printed structures) is determined by measuring the sheet resistance. Sheet resistance in this invention is understood to be the ohmic resistance obtained on a structure having a uniform thickness when contacting a square area of any size at two opposite edges and the current as a function of the voltage (DC voltage) is measured. The sheet resistance is measured in Ω. By electrical conductivity is meant the value obtained by multiplying the reciprocal of the sheet resistance with the average thickness of a structure deposited on an electrically nonconductive support, the structure being that of the undried, the dried, the uncured or the cured invention Composition is formed. The conductivity is given in S / m unless stated otherwise.

The Electrically non-conductive used in the present invention Polymer a) is preferably one in organic solvents soluble polymer or a polymer resin. examples for organic solvent-soluble polymers are polystyrenes, polymethyl methacrylate (PMMA), cellulose nitrate and acetate, polycarbonates, polyurethanes, polyvinyl chloride, etc.

Examples for usable polymer resins are dammar resin, shellac, Rosin, chemically modified rosin, chemically modified Natural resin, modified hydrocarbon resin, terpene resin, gilsonite, Coumarone, indene, cyclopentadiene resins, tall resin and ketone resins. In a preferred embodiment, the polymer is a) a polymer resin, preferably selected from a chemical modified rosin resin and a modified hydrocarbon resin. Examples of a chemically modified rosin resin are a phenol-modified rosin resin and a maleinate-modified Koloponiumharz. Such modified rosins are commercially available available, such. B. phenol-modified rosin resin the company Robert Kraemer GmbH & Co. KG with a melting point of 140 ° C-155 ° C or a phenol-modified rosin from Worlée-Chemie GmbH with a melting point of 135-155 ° C.

Preferably contains the printing ink composition according to the invention 10-40 wt .-% of an electrically non-conductive Polymer resin, more preferably 15-35 wt .-%, especially preferably 25-30 wt .-%, based on the total weight of Ink composition. The weight always refers to the pure basic substance used (eg solid) without solution or dispersants, etc. It can be both one and several types of component a) are used.

Of the Means "oxidatively polymerizable material" here one by chemical reactions with oxygen, preferably Atmospheric oxygen, polymerizable or crosslinkable or polymerizing and crosslinkable material. Preferably, this is oxidatively polymerizable Material a chemically with oxygen, z. B. atmospheric oxygen, curable Material. Here, a polymerization, a crosslinking or both by chemical reactions of functional groups of the Materials with oxygen (atmospheric oxygen). One speaks also here of chemical drying or chemical hardening of the material. The chemical types of curing include, for. B. the oxidative crosslinking, wherein under atmospheric oxygen influence linkages of aliphatic double bonds of a material, partly below Formation of oxygen bridges, entry, and crosslinking by polymerization. Chemical hardening (chemical Drying) can be accelerated with the help of siccatives. By Chemical hardening (chemical drying) is the viscosity the composition comprising the oxidatively polymerizable material contains, due to the crosslinking and / or polymerization of the significantly increased oxidatively polymerizable material, so that preferably z. B. very tough, elastic films be formed.

The oxidatively polymerizable material b) used in the present invention is different from the particular material used for the component a). The oxidatively polymerizable material b) is selected, for example, from air-drying alkyd resins, urethane alkyds, epoxy esters with unsaturated fatty acids and oil-modified phenolic resins. Preferred examples are fatty acid-modified alkyd resins. More preferred examples of the oxidatively polymerizable material b) are linseed oil-based alkyd resins, soybean oil-based alkyd resins, linseed oil varnish, and mixtures thereof. Further examples of alkyd resins are polycondensation resins having a viscosity according to DIN 53015 respectively. DIN 53214 of 8-10 Pa · s, a hydroxyl number according to DIN EN ISO 4629 of 15-25, which contain as polyol pentaerythritol / glycerol and as acid isophthalic acid, and are based on linseed oil or soybean oil. Commercially available linseed oil or linseed oil, commercial alkyd resin based on linseed oil or soybean oil can also be used.

Further examples of a usable oxidatively polymerizable material b) are partially polymerized, dehydrated, semi-drying and drying oils. Preferred semi-drying and drying oils contain unsaturated fatty acids, dry or harden oxidatively under the action of atmospheric oxygen, and preferably form tough, elastic or solid films. The term "drying," unless otherwise specified, in this invention includes the term "semi-dry". The degree of dryness is determined by the proportion of unsaturated fatty acids in the oil and by the number and position of the double bonds in the molecule. The double bonds in turn can be expressed by the iodine number. The death toll (IZ, unit g / 100 g) indicates how many grams of iodine are added and is a measure of the double bonds in the molecule (eg, unsaturated fatty acid). Good and quick-drying oils generally have an IZ of> 170, semi-drying oils an IZ of 100-170. Oils with smaller IZ are among the non-drying oils. Usable semi-drying oils are z. Soybean oil, safflower oil, tall oil, sunflower oil and rapeseed oil. The drying oils are usually natural products such as flax, wood, poppy, walnut, perilla, oiticica oil, safflower oil and fish oils, such as whale and herring oil. Other semi-drying or drying oils are cottonseed oil, rapeseed oil, ricinole oil, nut oil, hemp oil, corn oil, beech oil, sesame oil, peanut oil, castor oil, coconut oil, olive oil, palm and palm kernel oil and animal tallow and lard. Iodine numbers for some oils, depending on their source, are for example: linseed oil IZ 160-190, soybean oil IZ 114-138, wood oil IZ 170, poppy oil IZ 133-150, walnut oil IZ> 130, perilla oil IZ> 130, oiticica oil IZ> 130, Safflower oil IZ> 100, tall oil IZ> 100, sunflower oil IZ 118-140, rapeseed oil IZ 95-115, hemp oil IZ 140-160, almond oil IZ 105, sesame oil IZ 110. Iodine is determined by Wijs DIN 53241-1 , The above-mentioned oils may be used singly or in any combination with each other as component b). Component b) can also be used for additional pigment wetting.

The oxidatively polymerizable material b) is preferably at room temperature (20 ° C) liquid and is preferably in liquid Used, it being optionally a solvent, such as monohydric and polyhydric alcohols having 2 or more carbon atoms, z. As propanol, isopropanol, 1- or 2-butanol, ethylene glycol, propylene glycol and glycerol, higher esters or ketones having 3 or more carbon atoms may contain. Preferably, the inventive Printing ink composition 20-50 wt .-% of an oxidative polymerizable material b), more preferably 25-50 or 35-50% by weight, and even more preferably 40-46 Wt .-%, based on the total weight of the ink composition. It can be both one and several types of component b) are used.

The Desiccant c) useful in the present invention is preferred an oil-soluble metal salt of a fatty acid or rosin acid. Under the term "siccative" understands usually a dry matter, for example a (soluble in organic solvents and binders) Metal salt of organic acids. One or more siccatives become oxidatively polymerisable (chemically curing) binders added to the polymerization, crosslinking or both, d. H. the curing process, and thus speed up the drying process. Siccatives support and accelerate the drying process, by being catalytically active in the formation of radicals. Often if siccatives are compounds with a metal, this easily between two oxidation states separated by one can change. Examples are cobalt (II / III), Fe (II / III) or Mn (II / III). The siccative usable in the present invention serves as a catalyst to accelerate oxidative curing (oxidative drying) of the oxidatively polymerizable material b).

Preferred examples of fatty acids in the metal salts are saturated and unsaturated C ₆ -C ₂₀ fatty acids, such as octanoic acid and linolenic acid. Preferred examples of resin acids are abietic acid, neoabietic acid, pimaric acid, levopimaric acid and palustric acid. Further examples of salts are naphthenates and tallates. Examples of metals which form metal salts which can be used in particular with the abovementioned examples of the fatty acids and resin acids as component c) are cobalt, manganese, iron, cerium, calcium, lithium, zinc, zirconium and potassium. The metals in the metal salts may have all the usual oxidation states for salts. Preference is given to a manganese ²⁺ - or cobalt ²⁺ salt of a C ₆ -C ₂₀ fatty acid, dissolved in a white spirit with max. 1% aromatics content. Particularly preferred oil-soluble metal soaps are cobalt and manganese octanoates. The metal salts are used in the form of solutions. The solvents used are, for example, white spirits, such as refined gasolines having boiling points in the ranges of 130-185 ° C, 140-200 ° C, 150-190 ° C, 180-220 ° C, 130-220 °. The solutions preferably contain 20-50% by weight, more preferably 30-45% by weight of the salt, e.g. B. 38 wt .-%, in a white spirit.

Preferably contains the printing ink composition according to the invention 0.01-2% by weight of a siccative, more preferably 0.05-1.5 wt%, more preferably 0.05-1 Wt .-% and particularly preferably 0.1-0.5 wt .-% of the pure Component c) based on the total weight of the ink composition. It can be both one and several types of component c) are used.

The term "drying" is understood in the printing technique, the transition of the printed, flowable or liquid ink film into a solid elastic layer with good binding to the carrier used (film-forming phases). The drying process can be done physically or chemically as well as in combination of both processes. The ink is generally considered to be dry if it is touch-proof, ie it is no longer spread or sticky, and if it is in contact with the same substrate (eg placing the same substrate on the printed structure) no imprint or fabric excess leave more on this. In this state, with partial chemical drying, the curing process must not yet be completed, since in a first phase only a surface hardening can take place and only in the second phase after removal or evaporation of the solvent chemical crosslinking (curing) use (eg Two-component paints) can (through hardening). By varying the component c), the drying properties of the printing ink composition can be adapted to the respectively required process specification and the carrier material to be used. By varying the proportion of component c) or by using different metal salts, the drying of the printing ink composition can be accelerated or slowed down. When using absorbent carrier materials, the drying takes place partly by knocking the oils into the substrate and only in part oxidatively. In the case of an absorbent carrier, all the solvents present in the composition penetrate into the carrier. Thus, the proportion of the still chemically to be dried amount is (substantially) less than when using a non-absorbent carrier. Therefore, the proportion of component c) can be kept lower.

The Composition according to the invention further comprises at least one electrically conductive carbon component d) selected from electrically conductive graphite d1), structured electrically conductive carbon black d2) and mixtures thereof. Preferably, the inventive Ink composition, the electrically conductive carbon component d) in a range of 10-50% by weight, stronger preferably 15-45% by weight, more preferably 20-40 Wt .-% and most preferably 25-30 wt .-%, based on the total weight of the ink composition. It can both one and several types of component d) can be used.

The graphite d1) usable in the present invention is electrically conductive. The graphite d1) is preferably selected from a synthetic or natural graphite. The graphite may have a flake-like, platelet-like or spherical particle shape or a mixture of these particle shapes. The graphite may contain individual graphite particles or aggregates or agglomerations of graphite particles. Preferably, the particles, aggregates or agglomerations have an average particle size of 0.1-100 microns, more preferably 0.5-50 microns, even more preferably an average particle size of 1-25 microns, more preferably 1-10 microns and all more preferably 4-6 μm. In another embodiment, the graphite d1) has an ashing residue of less than 0.5% as measured ASTM D 1506 , In a further embodiment, the graphite d1) has a moisture content of less than 0.5%, measured according to ASTM D 1509-95 , The graphite is produced by means of a well-known graphitization process. The graphite is used as a solid. Commercially available graphite for printing applications can be used, as it is available, for example, from TIMCAL AG, CH-6743 Bodio, Switzerland, preferably under the name TIMREX KS4 or TIMREX KS6.

The structured electrically conductive carbon black d2) usable in the present invention may be selected, for example, from Furnace Black, Lamp Black, Channel Black, Acetylene Black and Thermal Black. A preferred carbon black d2) is furnace carbon black, preferably in a bubbled form, for example prepared from gaseous or liquid hydrocarbons with the highest possible aromatic content. Further, carbon blacks having a primary particle size of 10-500 nm, more preferably 10-100 nm, and an oil demand number of 50-1000 ml / 100 g ( ASTM D-2414 ), prefers. Furthermore, carbon blacks with a carbon content> 95% are preferred. Furthermore, carbon blacks with an ashing residue <1% ( ASTM D-1506 ), an H content <2% (elemental analysis), an O content <1% (elemental analysis) and a content of toluene-extractable substances <1% ( DIN 53553 ) prefers. Both one and several types of component d2) can be used.

Under The term "structured" is understood to mean the extent of Linking of carbon black primary particles to branched, chain-shaped, intergrown, larger Aggregates and agglomerates by mechanical action only can be partially broken up again. Thus, "low structured" carbon blacks only a small and "highly structured" carbon black a high level of aggregate formation. Under "Structure" of Soot is the concatenation or fusion of Carbon black particles to aggregates or agglomerates, by even the most thorough dispersion or mechanical Processing can only be partially reduced. A measure of the structure is the oil demand number. The higher the oil requirement a soot, the higher its structure.

The higher the structure, ie the aggregate or network formation of a carbon black, the higher the expected electrical conductivity in a polymer composite containing the carbon black. However, the high structure causes a very high binder requirement and a high yield strength of the printing ink. This is probably the reason why these carbon blacks have not previously been used for printing inks. In this invention, carbon blacks which are used as filler carbon black or additives for common plastics or rubber blends may be used be used. Manufacturers or distributors also frequently point out that the carbon blacks offered are only useful as additives for the above purposes and that suitability for printing inks is not considered possible. Thus, it is not obvious to those skilled in the art to use these materials for printing inks. All the more, the results of this invention are surprising in that useful ink compositions can be provided for mass printing processes which include, among others, patterned carbon black as electrically conductive component d) and enable the production of excellent and inexpensive bulk printed electroconductive structures.

at When used as carbon blacks, the carbon blacks are preferred still oxidatively aftertreated, d. H. it will be additional Oxide groups generated on the surface. This is achieved a reduced binder requirement. For electrically conductive Carbon blacks are disturbing to these surface oxides for the conductivity. In a preferred embodiment In the present invention, structured carbon blacks are used d2), which were not oxidatively treated.

usable structured carbon blacks d2) may optionally be surface-modified be provided that the surface modification by the electrical Conductivity of the untreated carbon black not essential is worsened, d. H. not more than 20%, 10% or 5% in the Compared to the untreated carbon black is reduced.

at The manufacturing process is the furnace carbon black process the one with which one purposefully the structure of the soot in wide limits may vary. For all other procedures a certain structure is due to the process. gas blacks, Acetylene blacks and flame blacks have a high Structure, while thermal blacks have a low.

An important parameter for the carbon blacks d2) is the oil demand, which is also related to the conductivity of the material. The oil demand number is a common characteristic for characterizing the oil requirement of pigments and fillers, expressed as the unit ml / 100 g. The specified oil requirement is below Standard ASTM 2414 measured. In a preferred embodiment, the patterned electrically conductive carbon black d2) has an oil demand number of 50-1000 ml / 100 g, more preferably 100-700 ml / 100 g, and even more preferably 100-550 ml / 100 g.

The average particle size of the carbon black particles can vary in a wide range. In a further embodiment can be the mean primary particle size of carbon black preferably 10-100 nm, stronger preferably 15-40 nm, and more preferably 18-30 nm, measured by scanning electron microscope.

It can also be commercially available, structured electrically conductive carbon blacks used for the printing industry such as the conductivity carbon black Printex 16 with an oil requirement of 119 ml / 100 g from Evonik or the Conductivity Soot Ensaco 250 G with an oil requirement 192 ml / 100 g Timcal. Very particularly preferred are the Commercially available high conductivity carbon black Printex XE2 with an oil requirement of 380 ml / 100 g from Evonik, the high conductivity black Pearls 2000 with an oil requirement 330 ml / 100 g Cabot or the High conductivity soot Ensaco 350 G with an oil requirement 329 ml / 100 g from Timcal. Printex XE2 and Printex 16 are in the Color Index listed as Black 7-77266. Another one Example is Ketjenblack EC-600 JD with an oil requirement of 480-510 ml / 100 g from Akzo Nobel.

The Composition according to the invention can be considered as electrically conductive carbon component d) also a mixture of one or more electrically conductive graphites d1) and one or more structured, electrically conductive Carbon black d2). A preferred range for a ratio of graphite: soot is 10: 1 to 1:10, more preferably 5: 1 to 1: 5 and more preferably 2: 1 to 1: 2, for example, 1: 1.

It may be advantageous when using carbon blacks with a Lower oil consumption of less than 100 ml / 100 g and at Use of graphite amounts of more than 50 wt .-% of electrical conductive component d), based on the inventive Ink composition. The low structured Carbon blacks are, although an electrical Eigenfähigkeit is present, with the use of small amounts may be difficult or unable to have a sufficient network in the electrical form non-conductive binder solids. These Low structured carbon blacks should therefore be in a higher Salary used to similar conductivities such as To achieve Printex XE2.

The at least one not usable in the present invention aqueous solvent in the form of a drying or non-drying oil e) is preferably a mineral oil, a vegetable oil or a mixture thereof. Under the term "drying" is here a chemical drying ability (chemical Hardening) to understand how they related to above component b) has been defined. Under the expression "not drying "is to be understood that the oil e) not the possibility of chemical drying (chemical hardening) and drying by knocking (infiltration, sucking etc.) into the carrier material or by evaporation (i.e. H. a physical drying) takes place. The component e) can for example, to set the desired viscosity the composition can be used before use.

preferred Examples of a drying oil are all the in the description of component b) drying oils, especially linseed oil and linseed oil varnish. It deals This is predominantly complex mixtures of glycerol esters unsaturated fatty acids. These count to the non-conjugated oils.

Examples of non-drying oils are mineral oils. Preferred examples of mineral oils are mineral oils from refined petroleum distillates, such as a C ₁₂ -C ₁₆ fraction. Preferred mineral oils have a boiling range of 240-300 ° C. (for example commercially available pressure oil). Further usable are mineral oils having a boiling range of 190-240 ° C, 240-270 ° C, 260-290 ° C, 260-310 ° C, 280-310 ° C, 310-390 ° C, 270-280 ° C, 280-340 ° C, 320-360 ° C.

Preferably contains the printing ink composition according to the invention 10-50% by weight of at least one non-aqueous Solvent in the form of a drying or non-drying oil e), more preferably 25-50% by weight, especially preferably 35-47% by weight and most preferably 40-45 Wt .-%, based on the total weight of the ink composition. It can be both one and several types of component e) are used.

In another embodiment of the present invention, In particular, all of the above embodiments, can at least a portion or the entire amount of the oxidatively polymerizable Materials b) also the non-aqueous solvent in the form of a drying oil e). In the invention Composition must contain an oxidizable material in each case but this is also the function of the solvent in the form of a drying oil e) take over can. If z. B. the oxidatively polymerizable material b) in the form linseed oil, which can be oxidized by oxidation, is present, this can also be used as solvent e) become.

By varying the components a) and b) and e), the viscosity of the binder to the respective oil requirement number of the electrically conductive components while maintaining the for the mass pressure, z. As the offset printing, necessary separation behavior can be adjusted. The viscosity range for the offset printing is usually 40-300 Pa · s, for the gravure printing 0.01-1 Pa · s and for the flexographic printing 0.01-2 Pa · s, determined after DIN 53214 (measured with Physica MCR 301 (Anton Paar GmbH, Austria) at 23 ° C). In the case of variation of component a), the viscosity generally increases with increasing amount of a), although the increase may also be dependent on the nature of the material used. As the amount of component b) increases, a decreasing viscosity of the printing ink composition is generally achieved, which, however, also depends on the type of component b) used. As the amount of solvent e) increases, a decreasing viscosity is generally observed. Furthermore, in general: an increasing oil requirement number of the soot d2) results in an increase in viscosity, as well as in its higher amount used. Graphite shows increasing viscosity with increasing input.

By Variation of the type and amount of electrically conductive Material can reduce the electrical conductivity of the resulting electrically conductive, functional structure in a wide range while maintaining the necessary process parameters of the printing process be set. By using high conductivity soot, such as B. Printex XE2, one achieves a good electrical conductivity, low carbon blacks or graphite are used in the General structures with lower electrical conductivity receive. Depending on what the application requires, the controller can the electrical conductivity over the way and the amount of electrically conductive material, increasing the amount to increase the electrical conductivity leads.

By varying the electrically conductive component d) and the component e), in addition to the electrical conductivity of the resulting electrically conductive functional structure, further physical properties such as electron work function and surface structure can be adapted to the necessary application. Since soot and graphite have different values in their electron exit work, it is it is possible to produce appropriately adjusted ink compositions based on carbon black as well as on graphite. Furthermore, the two modifications have different particle morphologies that also affect their roughness on the printed surface. This is particularly interesting for more complex circuits with multilayer construction, transistors, etc.

The The present invention is characterized in that at least an electrically conductive component consisting of carbon in the form of electrically conductive graphite or in the form a structured electrically conductive carbon black preferably having an oil demand of 50-1000 ml / 100 g as electrically conductive main component in the ink composition of the invention is. The present invention is based inter alia on the use just this electrically conductive graphite and structured Soot, which is actually called filler soot or conductivity additives used for plastics be, with the highest possible oil consumption Use of customary for offset printing binder components. The printing ink compositions of the invention can advantageously be easily in common Mass printing methods such as offset, flexo and gravure integrated without more complicated changes Process parameters needed. By using inexpensive graphites and Carbon blacks instead of expensive conductive polymers is also a cost effective pressure of electrically conductive Structures possible because in the inventive Ink composition usually not electrically conductive Polymers are included.

Furthermore, it may be advantageous to adjust the viscosity of the printing ink composition by adding an organic solvent depending on the type of process to be used. Preferred solvents for gravure printing are toluene, ethanol, denatured with methyl ethyl ketone (MEK) or cyclohexane, ethyl acetate, 1-propanol, 2-propanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, acetone, benzene including cycloaliphatic , Dipropylene glycol monomethyl ether, ethoxypropyl acetate, isopropyl acetate, methoxypropyl acetate, methyl ethyl ketone (2-butanone), methoxypropyl ketone, propyl acetate, propylene glycol and diacetone alcohol, with a preferred viscosity of 0.01-1 Pa.s (measured after DIN 53214 measured with Physica MCR 301 (Anton Paar GmbH, Austria) at 23 ° C). Preferred solvents for flexographic printing are customary liquid alcohols, preferably isopropanol, the preferred viscosity being 0.01-2 Pa · s (measured according to DIN 53214 , measured with Physica MCR 301 (Anton Paar GmbH, Austria) at 23 ° C).

In the ink composition of the invention may also optionally conventional additives and adjuvants are used. examples for this are Natural waxes, synthetic waxes (polypropylene waxes, polytetrafluoroethylene waxes), Paraffins, waxy fatty acids such as stearic acid for increasing lubricity and abrasion resistance, wherein these additives are used in the range of 0.1-2 wt% become. Additions of alcohols like tridecanol can in the range of 0.1-2% by weight. Strength, Silica, kaolin, powdered hydrocarbon resins can be used in the range of 0.1-2 wt .-%. additions of inorganic dispersants, such as calcium or zinc sulfonates, or polymeric dispersing agents are optionally in the range of 0.1-1 wt .-% possible. Anti-skinning agents such as butylhydroxytoluene may optionally be used. Furthermore, can optionally also be added silicone oil.

• A) Herstellen eines Bindemittels aus einem elektrisch nicht leitfähigen Polymer a), einem oxidativ polymerisierbaren Material b), welches sich vom Polymer a) unterscheidet, einem Sikkativ c) und gegebenenfalls mindestens einem nicht wässrigen Lösungsmittel in Form eines trocknenden oder nicht trocknenden Öls e) durch Erwärmen und Vermischen dieser Komponenten, wobei das Erwärmen des Gemisches im Allgemeinen bis über den Schmelzpunkt des Polymers (Polymerharzes) a) erfolgt (ca. 140–200°C, je nach Polymerart).
• B) Vermischen der in Schritt A) erhaltenen Zusammensetzung mit mindestens einer elektrisch leitfähigen Kohlenstoffkomponente d), ausgewählt aus elektrisch leitfähigem Graphit d1), strukturiertem elektrisch leitfähigen Ruß d2) und Gemischen davon, gegebenenfalls unter weiterer Zugabe von nicht wässrigem Lösungsmittel in Form eines trocknenden oder nicht trocknenden Öls e),
• C) Vermischen der im Schritt B) erhaltenen Zusammensetzung mittels eines Dissolvers und anschließend
• D) Vermischen der im Schritt C) erhaltenen Zusammensetzung in einem Dreiwalzenstuhl, einem Hochschermischer, z. B. Ultra-Thurrax, oder Extruder.

The present invention also provides a process for the preparation of the printing ink composition according to the invention. The method preferably comprises the following steps:

• A) producing a binder from an electrically non-conductive polymer a), an oxidatively polymerizable material b), which differs from the polymer a), a siccative c) and optionally at least one non-aqueous solvent in the form of a drying or non-drying oil e) by heating and mixing these components, the heating of the mixture generally taking place above the melting point of the polymer (polymer resin) a) (about 140-200 ° C, depending on the type of polymer).
• B) mixing the composition obtained in step A) with at least one electrically conductive carbon component d) selected from electrically conductive graphite d1), structured electrically conductive carbon black d2) and mixtures thereof, optionally with further addition of nonaqueous solvent in the form of a drying or non-drying oil e),
• C) mixing the composition obtained in step B) by means of a dissolver and then
• D) mixing the composition obtained in step C) in a three-roll mill, a high shear mixer, z. B. Ultra-Thurrax, or extruder.

Production methods of ink composition for mass printing are known to a person skilled in the art. In the present invention, any commonly used methods can be used. As an example, in step A) of the above process, the polymer a) with the drying oil or mineral oil e) to a temperature of 140-200 ° C, depending on the melting point of the polymer used, to Formation of a homogeneous solution or dispersion heated as possible in the absence of air. Then, the addition of component b), z. B. the alkyd resin, and then the addition of the siccative c) in dissolved form with vigorous mixing by means of a stirrer. After the formation of a homogeneous mixture, the mixture is removed from the reaction vessel and then optionally cooled. By step A), a binder is provided. Component b) can also be added immediately in step A), the same applies to siccative c), ie all substances can be heated simultaneously. Alternatively, the siccative c) can be added before adding b).

The Preparation of the binder system is done in a manner such as the person skilled in the art is aware of by boiling a polymer resin a) with component b) and e). The proportion by weight of the polymer resin in the binder may preferably 30-60 wt .-%, based on the binder amount. The proportion of component b) may be preferred 20-70 wt .-%, based on the binder, each after, in which way the component b) is used. there it is possible to use component b) both as a low-viscosity drying oil as well as prepolymerized or modified material, for example as alkyd resin or as a mixture. It continues possible, in a manner known to those skilled in the binder by a boiling of the polymer resin a) in a preferred Content of 30-50 wt .-%, based on the binder, with a mineral oil with a preferred content of 30-50 Wt .-%, based on the binder, with the addition of a modified drying oil in the form of an alkyd resin with a preferred Content of 20-40 wt .-%, based on the binder to produce.

The Mixing in step B) may preferably be carried out by means of a stirrer, Knürührers or Ankerrührers done. The im Step A) obtained binder is in a mixing vessel submitted. If necessary, the material must be filled be heated in advance of the mixing container, depending on its Viscosity. Then, the addition of component d) and optionally a further amount of component e). The components are slowly mixed continuously until no dust is more visible (complete wetting of the component d) or e). The addition of any additives is after the step B), but also after step C) possible.

in the Step C) is the mixture obtained in step B), optionally with renewed addition of a solvent e), at 1000-4000 RPM with a dissolver, usually strong heat development occurs, but beneficial affects the overall process. A dissolver is a disk stirrer, mainly in the paint and varnish industry, chemical industry and plastic industry is used for dispersing and high Shearing action. When a homogeneous mixture has formed, the process is ended and cooled.

in the Step D) takes place intimately mixing the obtained in step C) Composition in a three-roll chair, a high shear mixer, z. B. Ultra Thurrax, or extruder. Preferably, the resulting composition from step C) for fine dispersion and removal of entrapped Grind air bubbles in the three-roll mill (three-roll mill).

The present invention is also a layered, electrically conductive, functional structure by applying the ink composition of the invention by conventional mass printing methods, such as. B. offset printing, flexographic printing and gravure printing, on a support and optionally subsequent drying is obtained. Depending on how fast the drying of the printing ink takes place (also depending on the substrate), the drying temperature as well as the residence time in the dryer (controllable via printing speed) must be set accordingly. Preferred viscosity settings for the respective printing process are: offset 40-300 Pa · s, gravure 0.01-1 Pa · s, flexographic pressure 0.01-2 Pa · s, measured after DIN 53214 (measured with Physica MCR 301 (Anton Paar GmbH, Austria) at 23 ° C).

The present invention provides versatile applications ready. The compositions of the invention can be used to produce electrically conductive, functional structures, such as interconnects, electrically conductive Surfaces, contacts resistors, switches, printed electrical circuits, etc., but also of fine structural units with widths and / or thicknesses in the range of 0.5-500 microns or 1-100 μm (for eg transistors) be used. The electrically conductive, functional Structures are preferably fixed or flexible Carrier materials produced. Non-limiting examples for electrically conductive, functional structures are surfaces, bars, lines, electrodes or finger structures with a surface resistance of 0.1-100 kΩ / square (kΩ / □) preferably with a sheet resistance from 0.1-50 kΩ / □, more preferably 0.1-30 kΩ / □ particularly preferably 1-10 kΩ / □, with a mean layer thickness of 0.5-100 μm, preferably with an average layer thickness of 1-50 μm, more preferably with an average layer thickness of 1-25 μm, particularly preferred with a mean layer thickness 2-5 microns.

The Drying of the printing ink composition according to the invention can be done by conventional means, such as by means of a known to the expert hot air drying at 150-200 ° C in the form of a printing process downstream dryer.

The The ink composition of the present invention can to all commonly used, fixed or flexible, applied electrically non-conductive substrates become. Preferably, the carrier material of paper, Cardboard, wood, polymers (plastics), polymer resins, glass, textiles or composite materials. Particularly preferred are paper, Cardboard and polymers. In the aforementioned materials, the a recording of the liquid components b) and e) and optionally of liquid dissolved components of the ink composition allow, for. B. by suction, infiltration, porosity etc., the amount consumed is not more than 90, 80, 70, 60, 50, 40, 30, 20 or 10 wt .-% of the liquid Component of the ink composition, wherein the liquid Component of the total proportion of all components of the ink composition which is in liquid at room temperature (20 ° C) Form (i.e., not as a solid) is present. Preferred polymers are Polyolefins, polyesters, polyamides, polyimides, poly (meth) acrylates and the same. Examples are polystyrene, polymethyl (meth) acrylate, Polyethyl (meth) acrylate, polyethylene, polypropylene, polyethylene terephthalate, Polyamide 12, polyimide, polyetheretherketone etc. It is also possible the means of the ink composition of the invention electrically conductive, functional structures on one To create temporary support and the finished structures then transfer to the desired carrier and to laminate. For example, first on one Foil or paper with low adhesion printed Transfer structures on another carrier and applied, with the film or paper subsequently Will get removed.

The Support materials may optionally be pretreated be to apply the ink composition of the invention to facilitate or stick to the carrier to increase. Examples of a pretreatment are the pretreatment of at least part of the surface the carrier to increase the surface roughness by conventional mechanical means such as grinding, at Plastics and plastic films Corona pretreatment, application a primer or adhesive and the like.

The manufactured, electrically conductive, functional structure can after application (imprinting) on a support or provisional carrier before or after drying, preferably after drying (hardening), with. a protective layer provided become. Close examples of a protective layer continuous or discontinuous layers of materials selected from varnishes, adhesives, polymers, paper, Textile materials and combinations thereof. The protective layer can transparent, not transparent or colored. The protective layer can by applying and drying a solution, dispersion or emulsion of the desired material or by application (eg, laminating) a film or sheet of the desired material getting produced. Layer thicknesses for such protective layers are preferably 0.1-10 μm, more preferably 0.1-5 μm, and more preferably 1-5 μm.

One Another aspect of the present invention is an article comprising a carrier and a layered, electric conductive, functional structure by applying the ink composition of the invention by conventional mass printing on the carrier and optionally subsequent drying was obtained. The article according to the invention can all be described above said embodiments of the invention in any combination.

The The present invention includes all possible Combinations of all the above-mentioned embodiments one, especially those combinations that are not explicit above as far as the combination in question is technical makes sense for a professional.

following For example, the present invention will be described by way of example without the invention whose scope is from the claims results, limited to these embodiments should be. All% figures are based on weight, as far as do not state otherwise. The weight always refers to the pure basic substance used (eg solid) without solvent or dispersants etc.

Examples

• ¹⁾ siehe Tabelle 2;
• ²⁾ phenolmodifiziertes Kolophoniumharz (Schmelzbereich 135–155°C);
• ³⁾ Leinöl, Viskosität 0,05–0,1 Pa·s (Haake Rotovisko, C35/1, D = 250 s^–1);
• ⁴⁾ leinölbasiertes Alkydharz, Viskosität bei 20°C 8–10 Pa·s (Haake Rotovisko, C35/1, D = 250 s^–1), Hydroxyzahl ( DIN EN ISO 4629 ) 15–25, Polyol Pentaerythrit/Glycerin, Gehalt an Isophthalsäure 18%;
• ⁵⁾ Octa Soligen Mangan 6 (Borchers GmbH), 39 Gew.-% in Testbenzin mit max. 1% Aromatengehalt, Mangansalze von Fettsäuren (verzweigt) C₆-C₁₉;
• ⁶⁾ PKWF 28/31, Halterman Produkts, Siedebereich 280–310°C.

The preparation of the examples listed below in Table 1 was carried out according to the general procedure described above. Table 1 Example no. Carbon component ¹⁾ [% by weight] Polymer resin ²⁾ [% by weight] Drying oil ³⁾ [% by weight] Alkyd resin ⁴⁾ [% by weight] Siccative ⁵⁾ [% by weight] Mineral oil ⁶⁾ [% by weight] 1. 27.5 26 26 17 0.5 3 Second 25 23 23 16 1 12 Third 20 25 25 16 1 13 4th 13 27 27 18 1 14 5th 12 26 26 17.5 1 17.5 6th 14 30 30 20 1 5 7th 13 24 24 16 1 22 8th. 13 25 25 16 1 20

• ¹⁾ see Table 2;
• ²⁾ phenol-modified rosin resin (melting range 135-155 ° C);
• ³⁾ linseed oil, viscosity 0.05-0.1 Pa.s (Haake Rotovisko, C35 / 1, D = 250 s ^-1 );
• ⁴⁾ oil-based alkyd resin, viscosity at 20 ° C 8-10 Pa.s (Haake Rotovisko, C35 / 1, D = 250 s ^-1 ), hydroxyl number ( DIN EN ISO 4629 ) 15-25, polyol pentaerythritol / glycerin, content of isophthalic acid 18%;
• ⁵⁾ octa Soligen manganese 6 (Borchers GmbH), 39 wt .-% in white spirit with max. 1% aromatic content, manganese salts of fatty acids (branched) C ₆ -C ₁₉ ;
• ⁶⁾ PKWF 28/31, Halterman product, boiling range 280-310 ° C.

Mit der Vierpunktmethode kann der Widerstand ortsaufgelöst gemessen werden, wobei der Abstand der Stromkontakte ein Maß für die Grenze der Auflösung ist.The measurement of the surface resistance was carried out according to the four-point method. Four measuring tips are brought to the surface in a row, whereby a known current flows over the two outer ones and with the two inner ones the potential difference, ie the electric voltage between these tips, is measured. Since the method is based on the principle of four-wire measurement, it is largely independent of the contact resistance between the measuring tips and the surface. If adjacent measuring tips each have the same distance, one obtains the sheet resistance RF from the measured voltage U and the current I by means of the formula

With the four-point method, the resistance can be measured spatially resolved, wherein the distance of the current contacts is a measure of the limit of the resolution.

• Graphit: Timrex KS6 (Firma Timcal): Partikelgröße D₉₀ 5,8–7,1 μm, Veraschungsrückstand < 0,1%, BET Oberfläche 20 m²/g;
• Printex 16 (Firma Evonik): Ölbedarfszahl ( ASTM 2414 ) 119 ml/100 g, Veraschungsrückstand max. 0,05%, Iodadsorbtion ( ASTM D 1510 ) 300 mg/g;
• Printex XE2 (Firma Evonik): Ölbedarfszahl ( ASTM 2414 ) 380 ml/100 g, Veraschungsrückstand max. 1%, Iodadsorbtion ( ASTM D 1510 ) 1075 mg/g;
• Black Pearls 2000 (Firma Cabot): Ölbedarfszahl ( ASTM 2414 ) 330 ml/100 g;
• Ensaco 250 G (Firma Timcal): Ölbedarfszahl ( ASTM 2414 ) 192 ml/100 g, Veraschungsrückstand max. 0,05%, BET Oberfläche 66,8 m²/g;
• Ensaco 350 G (Firma Timcal): Ölbedarfszahl ( ASTM 2414 ) 329 ml/100 g, Veraschungsrückstand max. 0,15%, BET Oberfläche 780 m²/g.

The proportions of the total binder including solvent e), of the respectively used electrically conductive material and the respectively measured sheet resistance values of the ink composition of the invention applied in offset printing (examples from Table 1) are summarized in the following table. Table 2 Example no. Total binder content incl. Solvent [% by weight] Electrically conductive material Content of conductive material [% by weight] Sheet resistance [kΩ] 1. 72.5 graphite 27.5 28 Second 75 Printex L6 25 20 Third 80 Ensaco 250 G 20 11 4th 87 Printex XE2 13 4 5th 88 Printex XE2 12 4.5 6th 86 Ensaco 250 G 14 22 7th 87 Ensaco 350G 13 15 8th. 87 Black Pearls 2000 13 22

• Graphite: Timrex KS6 (Timcal): particle size D ₉₀ 5.8-7.1 μm, ashing residue <0.1%, BET surface area 20 m ² / g;
• Printex 16 (Evonik): oil demand ( ASTM 2414 ) 119 ml / 100 g, ashing residue max. 0.05%, iodine adsorption ( ASTM D 1510 ) 300 mg / g;
• Printex XE2 (Evonik): oil demand ( ASTM 2414 ) 380 ml / 100 g, ashing residue max. 1%, iodine adsorption ( ASTM D 1510 ) 1075 mg / g;
• Black Pearls 2000 (Cabot Company): Oil requirement ( ASTM 2414 330 ml / 100 g;
• Ensaco 250 G (Timcal): oil demand ( ASTM 2414 ) 192 ml / 100 g, ashing residue max. 0.05%, BET surface area 66.8 m ² / g;
• Ensaco 350 G (Timcal): oil demand ( ASTM 2414 ) 329 ml / 100 g, ashing residue max. 0.15%, BET surface area 780 m ² / g.

The electrical conductivity values for Printex XE2 are the best, since the smallest resistance was measured there and therefore the largest electrical conductivity is available. The circumstance is due to that Printex XE2 has the highest oil demand and thus the highest structure of the soot. The oil requirement is a measure of the structure of the soot, high oil demand shows a high soot structure, low oil demand one low soot structure.

QUOTES INCLUDE IN THE DESCRIPTION

This list The documents listed by the applicant have been automated generated and is solely for better information recorded by the reader. The list is not part of the German Patent or utility model application. The DPMA takes over no liability for any errors or omissions.

Cited patent literature

• EP 1826247 A1 [0003]
• - DE 69321366 T2 [0004]
• - DE 102007013276 A1 [0005]

Cited non-patent literature

• - Standard ASTM D 2414 [0015]
• - DIN IEC 60093 [0019]
• - DIN IEC 60093 [0020]
• - DIN IEC 60093 [0021]
• - DIN IEC 60093 [0022]
• - DIN IEC 60093 [0023]
• - DIN IEC 60093 [0028]
• - DIN IEC 60093 [0028]
• - DIN 53015 [0033]
• - DIN 53214 [0033]
• - DIN EN ISO 4629 [0033]
• - DIN 53241-1 [0034]
• ASTM D 1506 [0041]
• ASTM D 1509-95 [0041]
• ASTM D-2414 [0042]
• ASTM D-1506 [0042]
• - DIN 53553 [0042]
• - Standard ASTM 2414 [0048]
• - DIN 53214 [0058]
• - DIN 53214 [0062]
• - DIN 53214 [0062]
• - DIN 53214 [0070]
• - DIN EN ISO 4629 [0079]
• ASTM 2414 [0081]
• ASTM D 1510 [0081]
• ASTM 2414 [0081]
• ASTM D 1510 [0081]
• ASTM 2414 [0081]
• ASTM 2414 [0081]
• ASTM 2414 [0081]

Claims (26)

Electrically conductive ink composition for the production of electrically conductive, functional structures by means of A mass printing process, wherein the ink composition comprises: a) an electrically nonconductive polymer, b) an oxidative polymerizable material which differs from the electrically non-conductive Polymer a) differs, c) a siccative, d) at least an electrically conductive carbon component made of electrically conductive graphite d1), structured electrically conductive carbon black d2) and mixtures thereof, and e) optionally at least one non-aqueous Solvent in the form of a drying or non-drying oil. The ink composition of claim 1, wherein the electrically nonconductive polymer a) a polymer resin is. The ink composition of claim 2, wherein the electrically non-conductive polymer resin a) is selected is made of a modified rosin, in particular a phenol-modified rosin resin and a maleinate-modified Rosin resin, a modified hydrocarbon resin and mixtures from that. Printing ink composition according to one of the claims 1 to 3, wherein the oxidatively polymerizable material b) selected is made from a linseed-based alkyd resin, an alkyd resin based on soya oil, a linseed oil varnish, drying and semi-drying vegetable oils and mixtures thereof. Printing ink composition according to one of the claims 1 to 4, wherein the siccative c) is selected from a Manganese salt, a cobalt salt and mixtures thereof. Printing ink composition according to one of the claims 1 to 5, wherein the electrically conductive carbon component d) an electrically conductive graphite d1) is selected from a synthetic graphite and mixtures of several synthetic ones Graphites. Printing ink composition according to one of the claims 1 to 6, wherein the electrically conductive carbon component d) is selected from a structured electrically conductive Carbon black d2) and mixtures of several structured electrical conductive carbon black d2) with an oil requirement from 100-700 ml / 100 g, measured according to ASTM D 2414. Printing ink composition according to one of the claims 1 to 7, wherein the electrically conductive graphite d1) a average particle size from 0.1 μm to 100 microns. Printing ink composition according to one of the claims 1 to 8, wherein the structured electrically conductive Carbon black d2) an oil requirement of 100-550 ml / 100 g. Printing ink composition according to one of the claims 1 to 9, wherein the solvent e) selected is from a mineral oil, a vegetable oil or mixtures thereof. Printing ink composition according to one of the claims 1 to 10, wherein the ink composition comprises: a) 10-40 wt .-% of an electrically non-conductive Polymers, b) 20-50 wt .-% of an oxidatively polymerizable material, c) 0.01-2% by weight of a siccative, d) 10-50% by weight of an electrically conductive carbon component, selected from electrically conductive graphite d1), structured electrically conductive carbon black d2) and mixtures thereof, and e) optionally 10-50% by weight at least one non-aqueous solvent in the form of a drying or non-drying oil, each based on the total weight of the ink composition. The ink composition according to any one of claims 1 to 11, wherein the ink composition is less than 2.0% by weight of electrically conductive polymers having an electrical conductivity of 10 ^-1 S / m and greater (measured according to DIN IEC 60093 (measured as resistance)), based on the total weight the electrically conductive hydrocarbon component. Process for the preparation of an ink composition according to one of claims 1 to 12, comprising following steps: A) producing a binder from a electrically non-conductive polymer a), an oxidative polymerizable material b) other than polymer a), a siccative c) and optionally at least one non-aqueous Solvent in the form of a drying or non-drying oil e) by heating and mixing these components, B) Mixing the composition obtained in step A) with at least an electrically conductive carbon component d), selected from electrically conductive graphite d1), structured electrically conductive carbon black d2) and mixtures thereof, optionally with the addition of nonaqueous Solvent in the form of a drying or non-drying oil e) C) mixing the composition obtained in step B) by means of a dissolver and then D) mixing the composition obtained in step C) in a three-roll mill, High shear mixer or extruder. The method of claim 13, wherein mixing in step B) by means of a stirrer, Knürührers, butterfly mixer or Ankerrührers done. Layered, electrically conductive Structure obtained by using an ink composition according to any one of claims 1 to 12 becomes. Layered, electrically conductive Structure according to claim 15, which is by mass pressure and optionally subsequent drying of an ink composition according to any one of claims 1 to 12 becomes. An article comprising a fixed or flexible one Carrier and a layered, electrically conductive Structure according to claim 15 or 16. An article according to claim 17, the carrier being selected from paper, cardboard, Wood, polymers, polymer resins, glass, textiles and composites. An article according to claim 16 or 17, wherein the article is a layered, electrically conductive structure in the form of a printed circuit includes. A method of making an article comprising a carrier and a layered, electric conductive structure, the method comprising: A) Providing an ink composition according to a of claims 1 to 12, B) provide a solid or flexible support, optionally with at least a part of the surface to which the ink composition is to be applied, pretreated, C) Apply the provided ink composition by a mass printing method in the form of one or more electrically conductive, functional structures and D) optionally subsequent drying of applied printing ink composition. The method of claim 20, wherein the mass printing method is selected from offset printing, Flexographic printing and gravure printing. A method according to claim 20 or 21, wherein the drying by means of a hot air drying he follows. Method according to one of the claims 20 to 22, wherein the carrier is selected from Paper, cardboard, wood, polymers, polymer resins, glass, textiles and paper Composite materials, in particular paper and cardboard. Method according to one of the claims 20 to 23, wherein the pretreatment of at least part of the Surface of the carrier increasing the Surface roughness, the application of a primer or Adhesive and Corona Pretreatment for Plastics and Plastic Films includes. Use of an ink composition according to a of claims 1 to 12 for producing an electrical conductive, functional structure on a substrate. Use of an ink composition according to any one of claims 1 to 12 in a mas send printing method, selected from offset, flexo and gravure, for printing.