KR20170070167A - Dispersed carbon-coated metal particles, articles, and uses - Google Patents

Dispersed carbon-coated metal particles, articles, and uses Download PDF

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KR20170070167A
KR20170070167A KR1020177013010A KR20177013010A KR20170070167A KR 20170070167 A KR20170070167 A KR 20170070167A KR 1020177013010 A KR1020177013010 A KR 1020177013010A KR 20177013010 A KR20177013010 A KR 20177013010A KR 20170070167 A KR20170070167 A KR 20170070167A
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substrate
aqueous
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amp
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KR1020177013010A
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카렌 엠 코시다
게리 엘 슬레이터
메리 크리스틴 브릭
크리스틴 조앤 랜드리-콜트레인
제임스 알버트 레첵
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이스트맨 코닥 캄파니
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Priority to US14/514,463 priority Critical
Priority to US14/514,514 priority
Priority to US14/514,492 priority patent/US9434852B2/en
Priority to US14/514,492 priority
Priority to US14/514,500 priority patent/US9650533B2/en
Priority to US14/514,514 priority patent/US9447501B2/en
Priority to US14/514,463 priority patent/US9359517B2/en
Priority to US14/514,500 priority
Application filed by 이스트맨 코닥 캄파니 filed Critical 이스트맨 코닥 캄파니
Priority to PCT/US2015/053428 priority patent/WO2016060856A1/en
Publication of KR20170070167A publication Critical patent/KR20170070167A/en

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    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/02Printing inks
    • C09D11/03Printing inks characterised by features other than the chemical nature of the binder
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00Inks
    • C09D11/02Printing inks
    • C09D11/03Printing inks characterised by features other than the chemical nature of the binder
    • C09D11/037Printing inks characterised by features other than the chemical nature of the binder characterised by the pigment
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/20Diluents or solvents
    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00Printed circuits

Abstract

The non-aqueous composition contains carbon-coated metal particles dispersed in the organic diluent in an amount of at least 10% by weight. The dispersed carbon-coated metal particles have a median diameter of 0.6 m or less and are dispersed using a particle dispersant having a particle average molecular weight (Mw) of 2,000 to 100,000, and include nitrogen-containing units. The median diameter of the dispersed particles is measured using a dynamic light scattering method. In addition, the non-aqueous composition does not exhibit visible sedimentation when subjected to a sedimentation test at 20 占 폚 for at least 24 hours when the dispersed carbon-coated metal particles contain 25% by weight or less. Such non-aqueous compositions may contain photo-curable components and are useful for preparing photo-curable and photo-curable electro-conductive patterns and layers in a variety of products, including touch screen devices with touch screen displays.

Description

DISCERSED CARBON-COATED METAL PARTICLES, ARTICLES, AND USES < RTI ID = 0.0 >

The present invention is directed to a non-aqueous composition containing dispersed carbon-coated metal particles and an uniquely selected particle dispersant. The present invention also relates to a non-aqueous photocurable composition containing such dispersed carbon-coated metal particles and a particle dispersant. Such non-aqueous photocurable compositions can be used to provide seed metal catalysts for electroless plating processes designed to provide a pattern of electro-conductive materials.

Rapid development is taking place in various electronic devices, particularly display devices used for various communication, financial and recording purposes. In applications such as touch screen panels, electrochromic devices, light emitting diodes, field effect transistors and liquid crystal displays, conductive films are essential and significant efforts are being made in the industry to improve the properties of such conductive films.

There is a need to provide a touch screen display and apparatus that includes an improved conductive film element. Current touch screen displays use ITO (Indium Tin Oxide) coatings to create an array of capacitance areas used to distinguish multiple contacts. ITO coatings have significant defects. Indium is an expensive rare earth metal, available in limited supply from several sources around the world. ITO conductivity is relatively low, and short line lengths are required to obtain adequate response speed. The touch screen of a large display is divided into smaller segments to reduce the conductive line length to an acceptable resistance. These small segments require additional driving and sensing electronics. In addition, ITO is a ceramic material and does not easily bend or warp, requiring vacuum deposition at high processing temperatures to produce a conductive layer.

Silver is an ideal conductor whose conductivity is 50 to 100 times larger than ITO. Silver is used in many commercial applications and is available from a variety of sources. While it is highly desirable to make conductive film members using silver as a source of electrical conductivity, considerable advancement is needed to achieve optimal properties.

Roll-to-roll manufacturing method on a flexible transparent substrate using an "additive process" for the deposition of an electro-conductive pattern that provides the function of the sensor, The production of other transparent conductive products is the subject of recent development in the art. Of particular importance is the ability to produce a touch screen sensor having both the desired electrical performance as well as the appropriate optical properties (transmittance) in the visible portion (touch region) of the touch screen sensor. In order to obtain the required conductivity and optical properties, the average line width of the electro-conductive lines in the electro-conductive grid of less than 10 [mu] m is highly required.

The flexible transparent substrate used in this process is optically transparent (high light transmittance) and colorless and exhibits low haze. The application of an electro-conductive pattern using an additional process, such as an electro-conductive material or a flexographic printing of a seed metal composition, allows the flexible transparent substrate to conform to the scale of the fine features (e.g., fine lines) to be applied It is necessary to have adequate surface energy and roughness. Much effort has been devoted to the electronics industry to achieve these essential features.

WO 2013/063188 (Petcavich et al.) Discloses a process for making a first master plate and a first ink ("printable composition") using a flexographic printing process, Described is a method of manufacturing a mutual capacitance touch sensor comprising a dielectric substrate by printing a pattern and curing the printed dielectric article. A second ink may similarly be applied and cured to form a second pattern on the second surface of the substrate. Both patterns can include a seed metal catalyst that can later be electroless plated with a conductive material. The resulting dielectric article is described as having a thickness of 1 [mu] m to 1 mm and a preferred surface energy of 20 Dynes / cm to 90 Dynes / cm. The inks used in this method are generally non-aqueous in nature and contain a variety of photo-curable components and dispersed metal particles.

It is known to use a variety of materials to disperse metal particles in an aqueous or non-aqueous composition. For example, U.S. Patent No. 8,506,849 (Li et al.) Describes a curable conductive ink comprising metallic nanoparticles and a separate polymeric dispersant. Magnetic inkjet printing inks comprising dispersed magnetic nanoparticles and polymeric dispersants are described in U.S. Patent No. 8,597,420 (Iftime et al.). In another technique, as described, for example, in U.S. Patent Application Publication 2008/0090082 (Shim et al.), The outer surface of the metallic nanoparticles may be used to improve dispersibility in organic solvents for inkjet printing The hydrophobic tail is modified to incorporate.

There is a need for an improved printable composition (also known as ink) containing a seed metal catalyst for electroless plating. It is desirable to apply (e.g., print) an improved composition, such as an electroconductive line pattern with desired pigmentation for optical effects, stability for successful manufacture, and electroless print performance.

Still, products with electro-conductive line patterns must be highly transparent and invisible when viewed under lighting conditions where reflective lines are visible. For this purpose, it has been decided to treat the outer surface of an electro-conductive line (e.g. made of copper) with a blackening agent in order to reduce the reflectivity of the metal lines.

However, in some display devices that include capacitive touchscreens that are provided with electro-conductive patterns on both sides of the transparent substrate, the top surface of the "blackened" electro-conductive wiring may become opaque, Which is visible and reflective.

In order to maintain a thin line in the electro-conductive pattern, it is desirable to apply a thin layer of seed metal catalyst ink, i. E., Only enough to induce electroless plating. If too much ink is applied, the transparency of the product will decrease because ink spreads and wider lines are produced. Also, thicker lines are better visible in end products and less durable. Thus, a thinner line in the pattern is preferred, but this makes the electrolessly plated metal more visible in the line through the transparent substrate.

Useful seed metal catalysts for use in such materials include metals such as silver or copper particles. For desirable properties, a sufficient amount of such metal particles can be from 10% to 50% of the total weight of the ink or printable composition. In this amount, the metal particles are generally reflective and readily visible through the transparent substrate, thereby increasing the visibility of the resulting electro-conductive pattern. One of the attempts to reduce the reflectivity of seed metal catalysts and electroless plated metals is to add sufficient colorant (such as carbon black) to the printable composition (ink) so that the seed metal catalyst is not visible. However, it is difficult to add a sufficient amount of such a colorant to the ink without undesirably increasing the viscosity and the clumping (aggregation or aggregation) of the metal particles in the ink.

Dispersants (or dispersing aids) have generally been used to keep particulate matter in suspension for as long as possible for a variety of uses. However, the known dispersants have not been readily usable with certain particles for minimizing settling and particle-particle interactions which can undesirably increase the viscosity of a given composition. Significant research and engineering are needed in various industries to find dispersants most suitable for selected particle materials, generally metal, organic or inorganic properties. This is particularly the case for seed metal catalysts designed for electroless plating operations.

Accordingly, seed metal catalyst prints having a reduced reflectance, a small and uniform particle size distribution with limited particle agglomeration, and a suitable viscosity, for example, using flexographic printing, to apply a pattern of thin lines, It is necessary to provide a possible composition (ink).

In order to solve the foregoing problems, the present invention provides a non-aqueous composition comprising carbon-coated metal particles dispersed in an organic diluent in an amount of at least 10% by weight, based on the total weight of the non- , Wherein the dispersed carbon-coated metal particles are dispersed with a particle dispersant having a median particle diameter of 0.6 탆 or less and a weight average molecular weight (Mw) of 2,000 or more and 100,000 or less and containing nitrogen-containing units, Wherein the non-aqueous composition comprises visible sedimentation when subjected to a sedimentation test at 20 占 폚 for at least 24 hours, when the dispersed carbon-coated metal particles contain not more than 25% by weight of the dispersed carbon- Not shown.

In some embodiments, the non-aqueous composition is a non-aqueous photocurable composition, each of which is a dispersed carbon-coated metal present in an amount of at least 10% by weight based on the total weight of the non- Wherein the dispersed carbon-coated metal particles have a median particle diameter of 0.6 탆 or less and a weight average molecular weight (Mw) of 2,000 or more and 100,000 or less Of the dispersed carbon-coated metal particles, wherein the intermediate diameter is determined by dynamic light scattering and the non-aqueous photo-curable composition comprises at least 25% by weight of the dispersed carbon- , There is no visible sedimentation when the sedimentation test is carried out at 20 占 폚 for 24 hours or more.

The present invention provides a number of advantages by the inherently dispersed carbon-coated metal particles described herein. In particular, these carbon-coated metal particles can be readily dispersed in a higher concentration (e.g., at least 10% by weight) in the non-aqueous composition by using an uniquely selected particle dispersant.

It is also possible to reduce the reflectance of the carbon-coated metal particles when incorporated into the pattern of the electro-conductive lines formed by the electroless plating method.

The use of the particle dispersing agent according to the invention minimizes particle-particle interactions which increase the viscosity of the non-aqueous composition. In particular, by better dispersing the carbon-coated metal particles, a greater amount of the particles can be "loaded" into the non-aqueous composition without increasing the undesirable viscosity.

The particle dispersing agent used in accordance with the present invention facilitates disruption and stabilization of smaller sized carbon-coated metal particles that are difficult to settle. This is a serious problem for metal particles such as silver nanoparticles because the sedimentation rate depends on the sedimentation rate induced by the Stokes Law as follows: metal particle size and particle density (10.5 for silver metal) g / cm < 3 >).

Figure pct00001

Here, Vs is the particle settling velocity (m / sec) (the ρ particles downwardly into larger vertical than ρ fluid is ρ particles upwards is less than ρ fluid), g is gravitational acceleration (m / sec 2), and , ρ particle mass density of the particles (kg / m 3) and, ρ fluid is the mass density of the fluid (kg / m 3), μ is the dynamic viscosity (kg / m * s) and, R is the radius of the particle ( m).

Therefore, it can be seen that the sedimentation rate of the metal particles increases with R 2 and greatly changes with the particle size.

In addition, it has been observed that the non-aqueous compositions of the present invention (including non-aqueous photocurable compositions) exhibit improved shelf life without sedimentation between printing operations or in areas of the printing system with little agitation.

When the non-aqueous composition of the present invention is "printed" using a suitable printing means as described below (e.g., a flexographic printing member), the resulting image is printed Exhibit improved uniformity. These advantages provide for better coverage of a given printing area using lesser amounts of costly carbon-coated metal particles, and improved uniformity provides a more opaque dark line as desired. As coatings of smaller carbon-coated metal particles become more uniform, the electroless plating activity is improved compared to the case where larger agglomerated metal particles are used.

While the following discussion is directed to various embodiments of the present invention and some embodiments may be more preferred for certain uses, it should be understood that the disclosed embodiments are to be construed as limiting the scope of the invention as set forth in the appended claims, It should not be considered. In addition, those skilled in the art will appreciate that the following disclosure is more broadly applicable than those described in the explicitly described and the disclosure of any embodiment.

Justice

When used herein to define various components of a non-aqueous composition and a non-aqueous photocurable composition, unless stated otherwise, the singular form is intended to include one or more components (i. E. ).

It is to be understood that each term not explicitly defined herein shall have the ordinary or generally accepted meaning of those skilled in the art. A term definition can be taken from a standard published dictionary if the composition of the term is not semantically meaningful or inherently meaningless in context.

Unless otherwise stated, the use of the various ranges of numerical values specified herein is to be regarded as approximation as if the word "about" preceded both the minimum and maximum values within the stated range. In this way, even slight variations in the upper and lower bounds of the specified range can achieve substantially the same result as values in the range. Also, the start of these ranges is intended to be a continuous range including all values between the minimum and maximum values.

The median particle diameter [Dv (50%)] is measured using a dynamic light scattering method. For example, this method can be performed using Malvern Zetasizer Nano ZS, commercially available from Malvern Instruments, Ltd. Instructions for using this equipment are available with the above equipment.

Unless otherwise indicated, the terms "particle dispersant "," dispersant ", and "dispersant aid" are used interchangeably.

The terms "epoxy monomer "," unsaturated monomer ", "functional oligomer "," metal particles ", and "crosslinking agent" are used herein in their conventional sense and will be understood by those skilled in the art.

All molecular weights used herein are weight average molecular weights (Mw), which can be determined using known procedures and equipment unless the value is already known from the literature. For example, Mw can be determined using size exclusion chromatography (SEC) and its value is reported herein as poly (methyl methacrylate) equivalent.

The term "photocuring ", as used herein, is intended to encompass both functional oligomers and monomers, or even polymers, that are capable of responding to irradiation of such materials, for example, irradiation with ultraviolet (UV), visible, Thereby polymerizing into a crosslinked polymer network. Photocuring can be carried out in the presence of a crosslinking agent.

The term "photocurable" is used to define a substance (or component) to be polymerized or cross-linked when irradiated with a suitable radiation such as ultraviolet (UV), visible or infrared in an appropriate environment.

The term " photocurable component "means an organic compound (polymeric or non-polymeric) capable of participating in a photo-curable reaction. Such compounds may be a single reactant that provides photo-curing upon irradiation or may be combined with other co-reactants (e.g., photoinitiators or acid catalysts) to provide photo-curing upon irradiation.

Unless otherwise stated, the term "non-aqueous photocurable composition" refers to an embodiment of the present invention that includes one or more components that initiate or facilitate photocuring, the non- Are useful in the practice of various methods and can be used to provide the products described below. Such non-aqueous photocurable compositions primarily contain an organic solvent or liquid organic component and have less than 5% water, or even less than 1% water by weight based on the total weight of the non-aqueous photocurable composition.

The term "polymerization" as used herein means to form very large molecules, i.e. macromolecules or polymers, by covalent bonding several small molecules such as, for example, monomers. The monomers can be combined to form only linear macromolecules or to form three-dimensional macromolecules, commonly referred to as crosslinked polymers. One type of polymerization that can be carried out in the practice of the present invention is acid-catalyzed (cationic) polymerization. Another type of polymerization is free radical polymerization where free radical polymerizable materials and suitable free radical generating photoinitiators are present. In some useful embodiments of the present invention, both the acid-catalyzed polymerization and the free radical polymerization can be used simultaneously.

The average dry thickness of the layers described herein can be determined from the average of at least two individual measurements taken for the dry layer using, for example, electron microscopy.

Similarly, the average dry thickness or width of the lines, grid lines, or other pattern features described herein may be the average of at least two individual measurements taken, for example, using electron microscopy.

 "Actinic radiation" refers to a material that is capable of undergoing photocuring or photopolymerization in accordance with the present invention and has a wavelength of at least 200 nm to less than 1400 nm, typically at least 200 nm to less than 750 nm, or even at least 300 nm to less than 700 nm Quot; is used to refer to any electromagnetic radiation having an < / RTI > The term "exposed radiation" also refers to such actinic radiation.

The term "ultraviolet radiation" is used herein to refer to electromagnetic radiation having a wavelength (? Max) of at least 200 nm to 400 nm or less.

Usage

Photocuring is also possible where the non-aqueous photocurable composition contains a large amount of the carbon-coated metal particles described herein, which can be applied to a variety of techniques, for example, graphic art imaging (e.g., Electronic conformal coatings, coated abrasives, magnetic media and photocurable composites as well as the electroless plating processes described herein (e.g., in color proofing systems such as chemical inks, or in other imaging processes) Lt; / RTI >

In addition, the non-aqueous compositions of the present invention containing dispersions of carbon-coated metal particles can be used in a wide variety of applications, including electronic materials, magnetic materials, magnetic recording materials, optical materials, gas sensor materials, catalyst materials, Absorbing films or coatings, intermediate layers in functional assemblies, and other materials that can be readily understood by those skilled in the art in view of this teaching.

Thus, the non-aqueous compositions of the present invention have a variety of uses in any situation where a dispersion of carbon-coated metal particles is required for any particular purpose.

The non-aqueous compositions of the present invention are particularly useful as non-aqueous photocurable compositions each containing at least one photocurable component. Such non-aqueous photocurable compositions can be photocured in any useful form, such as coatings on various substrates, fibers, patterns on various substrates, photocurable forms and molded articles, and adhesives.

More particularly, non-aqueous photocurable compositions can be used for various purposes that require efficient photocuring in a variety of articles or devices. For example, such a non-aqueous photocurable composition may be designed to be sensitive to a selected radiation wavelength and may be further processed, for example using an electroless plating process to form an electro-conductive metal pattern Which can be used to provide a pattern of seed metal catalysts. Such electro-conductive metal patterns can be designed and integrated into a variety of devices including, but not limited to, touch screens or other display devices that can be used in a number of consumer, industrial and commercial products.

Touch screen technology may include various touch sensor structures, including capacitive and resistive touch sensors. The resistive touch sensor includes several layers facing each other with a gap between adjacent layers that can be preserved by spacers formed during fabrication. The resistive touch screen panel may comprise several layers comprising two thin metal electro-conductive layers separated by a gap that may be produced by a spacer. When an object such as a stylus, palm or fingertip touches a point on the panel outer surface, the two metal layers come into contact and a connection is created that causes a change in current. This touch operation is transmitted to the controller for further processing.

The capacitive touch sensor may be used in an electronic device having a touch-sensitive feature. Such electronic devices may include, but are not limited to, televisions, monitors, automatic transmission devices, and projectors, which may be configured to display images including text, graphics, video images, movies, still images and presentations. Imaging devices that can be used in these display devices include cathode ray tubes (CRS), projectors, flat panel liquid crystal displays (LCDs), LED systems, OLED systems, plasma systems, electroluminescent displays (ECDs) and field emission devices . For example, the present invention may be used to fabricate a capacitive touch sensor, which may be integrated into an electronic device having touch-sensitive features to provide a portable media player including a computing device, a computer display, an e- , Mobile telephones, and other portable communication devices.

Using the present invention, a system and method for manufacturing a flexible and optically compliant touch sensor is possible with a high-capacity roll-to-roll manufacturing process in which the micro-electro-conductive feature can be produced in a single pass. A non-aqueous photocurable composition can be used in such systems and methods with multiple printing elements, such as multiple flexographic printing plates, to provide a number of high resolution electro-conductive Images can be formed. As will be described in more detail later, various patterns can be printed on one side or both sides of the transparent substrate. For example, one predetermined pattern may be formed on one side of the transparent substrate, and a different predetermined pattern may be formed on the opposite side of the transparent substrate. The printed pattern of the non-aqueous photocurable composition may then be "printed" as a pattern on one side or both sides of the transparent substrate and the printed pattern may be further processed, for example using electroless metal plating Thereby providing an electro-conductive metal pattern.

Non-aqueous composition

The non-aqueous composition of the present invention, in its simplest form, consists essentially of: (a) dispersed carbon-coated metal particles of the same or different composition as described below; (b) one or more particle dispersants as described below; And (c) an organic diluent (liquid organic material) as described below, for example an organic solvent medium, in which the carbon-coated metal particles (and potentially other components) are dispersed.

(a) carbon-coated metal particles

Generally, in each non-aqueous composition, only one type (composition) of carbon-coated metal particles is used, but other types of carbon-coated metal particles from the same or different classes of metals If not). Generally, each carbon-coated metal particle has a net neutral charge. Generally, the carbon-coated metal particles are non-magnetic, which is less magnetic, and therefore the non-aqueous composition of the present invention likewise has generally non-magnetic properties.

Useful carbon-coated metal particles can include metal particles that are at least partially coated with carbon. The metal particles are comprised of one or more metals (i.e., pure metals or metal alloys) selected from one or more classes of precious metals, semi- precious metals, Group IV metals or combinations thereof. Useful noble metals include, but are not limited to, gold, silver, palladium, platinum, rhodium, iridium, rhenium, mercury, ruthenium and osmium. Useful semi-precious metals include, but are not limited to, iron, cobalt, nickel, copper, carbon, aluminum, zinc and tungsten. Useful Group IV metals include, but are not limited to, tin, titanium, and germanium. Precious metals such as silver, palladium and platinum are particularly useful, and the semi-precious metals of nickel and copper are also particularly useful. Tin is particularly useful among the Group IV metal species. In many embodiments, pure silver or copper is used in the non-aqueous photocurable composition. Thus, in the practice of the present invention, the term "metal" has the same meaning as "metallic", with the terms "metal" and "metallic" not intended to include metal salts, metal oxides, and metal hydrides .

Metal particles composed of the above-mentioned metals are generally at least partially coated with carbon. Such carbon may be amorphous, sp2 hybrid or graphene-like.

Thus, materials particularly useful for use in non-aqueous compositions are mixtures of carbon-coated silver particles, carbon-coated copper particles, or in some embodiments carbon-coated silver particles and carbon-coated copper particles, All of which are dispersed in an organic solvent medium using one or more particle dispersing agents, as described below.

The carbon-coated metal particles are designed to have a median particle diameter of less than or equal to 0.6 탆, or less than 0.2 탆, or less than 0.1 탆, as measured in a suspension by dynamic light scattering techniques. These carbon-coated metal particles generally have a minimum median diameter of 0.005 占 퐉.

Such carbon-coated metal particles may be present in any geometric configuration including spheres, rods, prisms, cubes, cones, pyramids, wires, pieces, platelets, and combinations thereof , Which may be uniform or non-uniform in shape and size. The optimum advantage of the present invention can be achieved by using carbon-coated metal particles as individual particles or as aggregates of several particles.

Each of the one or more particle dispersants in the non-aqueous composition is used to disperse the carbon-coated metal particles such that clumping or aggregation is prevented in the non-aqueous composition also containing an organic diluent (described below). These particle dispersants are carefully selected and the present invention can provide the desired benefits. First, each of the particle dispersants has a weight average molecular weight (Mw) of 2,000 or more and 100,000 or less, more particularly 50,000 or less. The most useful particle dispersants each have a Mw of from 3,000 to less than 30,000.

In addition, each useful particulate dispersant may contain two or more nitrogen-containing units such as amides (carboxylic acid, sulfonic acid, sulfinic acid, phosphoric acid, phosphonic acid and many other acids capable of forming amides), amines (Amines), azo, carbamates (urethanes), carbodiimides, diazoes, diazoniums, enamines, guanidines (imines of urea), aromatic heterocycles Imidazole, imidazole, isoxazole, thiazole, indole, indolizine, quinoline, isoquinoline), hydrazine, hydrazone, hydroxamic acid, imide, (Esters of nitrous acid), nitrites (esters of nitric acid), nitriles (cyanides), nitrites (esters of nitrogens), nitrile / nitroso (nitrobenzene, nitrobenzene, N-nitrosourea), nitrone (imine N-oxide), ox (Imine of hydroxylamine) or urea (bisamides of carbonic acid, such as N-methylurea, N-methylthiourea buret alloysaccharide, urazole) units or segments. Some particularly useful nitrogen-containing units are amides, amines, and imine units. Generally, each of the particle dispersants has a plurality of nitrogen-containing units and is at least oligomeric and has a Mw of at least 2,000. These nitrogen-containing units provide strong anchoring of the particle dispersant to carbon-coated metal particles.

Each particle dispersant also contains a functional group that is compatible with the organic polymer and compatible with the organic solvent used in the organic solvent medium of the non-aqueous composition. For polar non-aqueous compositions, useful nitrogen-containing units include ester, acrylate or ether groups or combinations thereof.

Particularly useful particle dispersants are organic polymers including ester units such as those found in polyester or (meth) acrylate polymers (homopolymers and copolymers).

In another embodiment, the particle dispersant is an organic polymer comprising units selected from at least one (one or more) of the following classes (i) to (iv):

(i) pyridine units such as, for example, in vinyl pyridine;

(ii) an imine unit (e.g., -alkylene-NH- units), such as ethyleneimine and propyleneimine units as found in polyethyleneimine;

(iii) imide units [-C (= O) -NH-C (= O) - units]; And

(iv) amine units (primary, secondary and tertiary amine groups).

If desired, mixtures of these particle dispersants from the same or different classes of materials can be used.

Some examples of useful particle dispersants having these characteristics are the following materials (including some commercial products):

Copolymers containing polyethyleneimine segments such as Solsperse 占 35000 and Solsups 占 39000 (Lubrizol);

DISPERBYK-2152, DISPERBYK-2013, BYK®-9077 (BYK / ALTANA), and Efka® PX 4731 and EFKA PX 4732 Copolymers containing ester and amine units in the form of block, branched, multimeric, and comb structures, such as, for example, BASF);

Acrylic block copolymers containing aliphatic or aromatic amine units, such as EFKA PX 4701 (BASF); And

Copolymers containing aliphatic or aromatic amine units, such as Disperse Bike®-2118 (BYK / Altana) and Tetronic® 150R (BASF).

The following essential ingredients are included in the non-aqueous composition in an amount such that the weight ratio of the particle dispersant to the dispersed carbon-coated metal particles is at least 1: 100, or even at least 3: 100, or 10: 100 to 30: . These weights represent the total weight of all particle dispersants and the total weight of all carbon-coated metal particles in each non-aqueous composition.

In addition, the amount of carbon-coated metal particles in each non-aqueous composition may be at least 10 weight percent, or at least 15 weight percent, and at most 60 weight percent, based on the total weight of the non-aqueous composition (including organic diluent) Even 70% by weight or less. With this information, a skilled artisan can determine the useful and optimal amount of particle dispersant selected for the selected carbon-coated metal particles.

In some particularly useful embodiments, the non-aqueous composition comprises dispersed carbon-coated silver particles present in a concentration of from 15% to 60% by weight, based on the total weight of the non-aqueous composition, The carbon-coated silver particles have a median diameter less than 0.5 탆 determined as described above.

The non-aqueous composition (including the non-aqueous photocurable composition described below) also generally comprises a non-aqueous (organic) solvent in which the components of the non-aqueous composition are dissolved or dispersed, or an organic diluent .

In some embodiments of the present invention, the organic diluent is selected from the group consisting of 2-ethoxyethanol, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) Propanol (Dowanol PM), 4-heptanone, 3-heptanone, 2-heptanone, cyclopentanone, cyclohexanone, diethylcarbonate, 2-ethoxyethyl acetate, Is an organic solvent medium comprising at least one inert organic solvent such as acetone, dichloromethane, isopropanol, ethylene glycol and methyl lactate. Mixtures of these listed inert organic solvents may be used in the organic solvent medium in any suitable volume or weight ratio. Other useful organic solvents may be readily ascertainable by one of ordinary skill in the art using the teachings provided herein. By "inert" it is meant that the organic solvent is not involved in any chemical reaction.

If more than one photo-curable component (described below) is present as the liquid organic compound, then these one or more photo-curable components may serve as an organic diluent and may not require a separate inert organic solvent. In such cases, the organic diluent may be considered as a "reactive" diluent. Alternatively, the one or more reactive diluents may be combined with one or more inert organic solvents (as described above) to form suitable organic diluents.

The amount of organic diluent may be suitably selected depending on the particular material employed, the means for applying the resulting non-aqueous composition, and the desired properties, including composition uniformity.

For example, the organic diluent may provide from 10 wt% to 90 wt% or from 20 wt% to 80 wt%, based on the total weight of the non-aqueous composition. The organic diluent typically contains little or no water, which means that the water is present in an amount of less than 5% by weight, or even less than 1% by weight, based on the total weight of the non-aqueous composition.

An optional or preferred component, although not required for the non-aqueous composition, is carbon black in an amount of at least 0.5 wt% to 20 wt%, or typically at least 1 wt% to 10 wt%, based on the total amount of the non-aqueous composition .

As described above, the non-aqueous composition of the present invention may be a non-aqueous photocurable composition that additionally comprises at least one photo-curable component as described below. The amount of such components may also be determined using the teachings provided below, but in general, the one or more photo-curable components are present only to such an extent as to provide sufficient photo-curing in a particular application.

Particularly useful non-aqueous photocurable compositions of the present invention include,

Dispersed carbon-coated metal particles in an amount of not less than 10% by weight, or even not less than 15% by weight and not more than 60% by weight or not more than 70% by weight based on the total weight of the non-aqueous photo- The metal particles are all dispersed with a particle dispersant having a median diameter of 0.6 m or less and a Mw of 2,000 or more and less than 100,000 as described above, and contain nitrogen-containing units, and the median diameter is determined using a dynamic light scattering method ).

Organic diluents (as described above),

UV-curable components (described below), and

If necessary, UV photoinitiators (described below)

Wherein the non-aqueous photocurable composition comprises a settling test at 20 占 폚 for at least 24 hours when the dispersed carbon-coated metal particle contains 25% by weight or less Lt; / RTI > does not exhibit visible sedimentation when tested with a < RTI ID = 0.0 >

In such a non-aqueous photocurable composition, the dispersed carbon-coated metal particles may be dispersed carbon-coated silver particles or dispersed carbon-coated copper particles, or dispersed carbon- A mixture of coated copper particles, all of which are described below.

Moreover, the weight ratio of the particle dispersant to the dispersed carbon-coated metal particles in such a non-aqueous photocurable composition may be from 1: 100 to 30: 100 or less.

In some particularly useful non-aqueous photocurable compositions, the dispersed carbon-coated metal particles may be present in an amount comprising at least 15 wt% to 60 wt%, based on the total weight of the non-aqueous photocurable composition, The dispersed carbon-coated metal particles (e.g., carbon-coated silver particles or carbon-coated copper particles) have a median diameter of less than 0.5 탆 as measured using the dynamic light scattering method as described above.

The non-aqueous compositions of the present invention can be prepared by suitably dispersing the carbon-coated metal particles with one or more particle dispersants using suitable dispersing means. All of these essential ingredients can be mixed or dispersed in an organic diluent such as an organic solvent medium (as described above) in which the carbon-coated metal particles can be effectively dispersed.

Methods used to disperse carbon-coated metal particles include, but are not limited to, ball milling, media milling, magnetic stirring, high speed homogenization, high pressure homogenization, shaking stirring and ultrasonication. Ultrasonic processing is particularly useful for dispersing carbon-coated metal particles as a particle dispersant in an organic diluent.

Media milling techniques are also useful for grinding solid particles such as carbon-coated metal particles used in the present invention. The media milling can be carried out using suitable media made of silica, silicon nitride, sand, zirconium oxide, alumina, titania, yttria, yttria-stabilized zirconia, zirconium silicate, glass, A ball mill, a medium mill or a vibrating mill.

The non-aqueous photocurable composition of the present invention may further comprise at least one of carbon black dispersed in an amount of 0.5 wt% to 20 wt%, or 1 wt% to 10 wt%, based on the total weight of the non- . ≪ / RTI >

Acid-catalyzed photochemistry

In some embodiments of the present invention, the non-aqueous photocurable composition comprises at least one UV-curable component, at least one of which is an acid-catalyzed photocurable component. Such a non-aqueous photocurable composition may further comprise a photoacid generator.

Some useful acid-catalyzed photocurable ingredients may be photocurable epoxy materials. The cationic photo-curable epoxy material ("epoxide") useful in the present invention is an organic compound having at least one oxirane ring, wherein the oxirane ring is represented by the following formula and is polymerizable by a ring-

Figure pct00002
.

These epoxy materials include monomeric epoxy compounds and polymeric epoxides, and may be aliphatic, alicyclic, aromatic, or heterocyclic. These materials generally have, on average, at least one polymerizable epoxy group per molecule, or typically at least about 1.5 or even at least about 2 polymerizable epoxy groups per molecule. The polymeric epoxy material may be a linear polymer having a terminal epoxy group (e.g., a diglycidyl ether of a polyoxyalkylene glycol), a polymer having a backbone (backbone) oxirane unit (e.g., a polybutadiene polyepoxy Side) and side chain epoxy groups (e.g., glycidyl methacrylate polymers or copolymers).

The photocurable epoxy material may be a single compound or it may be a mixture of different epoxy materials containing one, two or more epoxy groups per molecule. The "average" number of epoxy groups per molecule is determined by dividing the total number of epoxy groups in the epoxy material by the total number of epoxy-containing molecules present.

Epoxy materials can range from low molecular weight monomer materials to high molecular weight polymers, which can vary widely in the nature of the backbone and substituent (or side chain) groups. For example, the backbone can be of any type and the substituent groups on the backbone can be any group that does not substantially interfere with the desired cation photo-curing process at room temperature. Examples of acceptable substituents include, but are not limited to, halogens, ester groups, ethers, sulfonate groups, siloxane groups, nitro groups and phosphate groups. The molecular weight of the epoxy material may be greater than or equal to 58 and greater than or equal to 100,000.

Useful epoxy materials include, but are not limited to, cyclohexene oxide groups such as epoxy cyclohexane carboxylates such as 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-2-methylcyclohexyl Methyl-3,4-epoxy-2-methylcyclohexanecarboxylate and bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate. A more detailed list of useful epoxy materials is provided in U.S. Pat. No. 3,117,099 (Proops et al.).

Another useful epoxy material is the glycidyl ether of a polyhydric phenol obtained by reacting a polyhydric phenol with an excess of chlorohydrin (e.g., epichlorohydrin), such as 2,2-bis- (2,3-epoxyprop / RTI > phenoxy) -propane] glycidyl ether monomer. Other examples of this type of epoxy material are described in U.S. Patent No. 3,018,262 (Schroeder) and in Handbook of Epoxy Resins, Lee and Neville, McGraw-Hill Book Co., New York (1967) .

Another useful epoxy material is a copolymer derived from acrylic esters (e.g., glycidyl acrylate and glycidyl methacrylate) reacted with glycidol, copolymerized with one or more ethylenically unsaturated polymerizable monomers, and It is the same resin.

Other useful epoxy materials are epichlorohydrin such as epichlorohydrin, alkylene oxides such as propylene oxide and styrene oxide, alkenyl oxides such as butadiene oxide, and glycidyl esters such as ethyl glycidate.

Another useful epoxy material is silicone, especially an epoxy material having a silicone backbone, with epoxy functional groups or groups such as cyclohexylpropoxy groups. Commercial examples of such epoxy materials include UV 9300, UV 9315, UV 9400, UV 9425 silicone materials available from Momentive.

The polymeric epoxy material may optionally contain other functional groups that do not substantially interfere with the cationic curing of the non-aqueous photocurable composition at room temperature. For example, photopolymerizable epoxy materials may also include free radically polymerizable functional groups.

The photopolymerizable epoxy material may comprise a blend or a mixture of two or more different epoxy materials. Examples of such blends are blends of one or more low molecular weight (less than 200) epoxy materials and one or more intermediate molecular weight (200 to 100,000) photopolymerizable epoxy materials, or one or more of such photopolymerizable epoxy materials and one or more higher molecular weight 0.0 > 100,000 < / RTI > or more) of a photopolymerizable epoxy material. Alternatively or additionally, the photopolymerizable epoxy material may include blends of epoxy materials having different functionalities such as aliphatic and aromatic properties, or different functional groups such as polar and non-polar properties. Other cationic polymerizable monomers or polymers may be further incorporated into the photopolymerizable epoxy material.

One or more photocurable epoxy materials are included in the non-aqueous photocurable composition in an amount sufficient to provide the desired effective photocuring (or photopolymerization). For example, the at least one photopolymerizable epoxy material may be present in an amount of at least 5 weight percent to 50 weight percent, or typically at least 10 weight percent to 40 weight percent, based on the total weight of the non-aqueous photocurable composition .

Various compounds can be used as photoacid generators to generate acids suitable for participating in photocuring of epoxy materials. Some of these " photoacid generators "are acidic in character and others are nonionic in character. Other useful photoacid generators other than those described below will be readily apparent to those skilled in the art in view of the teachings provided herein. Various compounds useful as photoacid generators may be purchased from various commercial sources or may be prepared using known synthetic methods and starting materials.

Onium salt acid generating agents useful in the practice of the present invention include salts such as diazonium, phosphonium, iodonium or sulfonium salts, and polyaryldiazonium, phosphonium, iodonium and sulfonium salts, But is not limited thereto. The iodonium or sulfonium salts include, but are not limited to, diaryl iodonium and triarylsulfonium salts. Useful counter anions include complex metal halides such as tetrafluoroborate, hexafluoroantimonate, trifluoromethanesulfonate, hexafluoroarsenate, hexafluorophosphate and arenesulfonate. But is not limited thereto. The onium salt may also be a molecule having one onium salt residue as well as an oligomeric or polymeric compound having a plurality of onium salt residues.

Examples of useful aromatic iodonium salts include, but are not limited to, diphenyl iodonium tetrafluoroborate; Di (4-methylphenyl) iodonium tetrafluoroborate; Phenyl-4-methylphenyl iodonium tetrafluoroborate; Di (4-heptylphenyl) iodonium tetrafluoroborate; Di (3-nitrophenyl) iodonium hexafluorophosphate; Di (4-chlorophenyl) iodonium hexafluorophosphate; Di (naphthyl) iodonium tetrafluoroborate; Di (4-trifluoromethylphenyl) iodonium tetrafluoroborate; Diphenyl iodonium hexafluorophosphate; Di (4-methylphenyl) iodonium hexafluorophosphate; Diphenyl iodonium hexafluoroarsenate; Di (4-phenoxyphenyl) iodonium tetrafluoroborate; Phenyl-2-thienyl iodonium hexafluorophosphate; 3,5-dimethylpyrazolyl-4-phenyliodonium hexafluorophosphate; Diphenyl iodonium hexafluoroantimonate; 2,2'-diphenyl iodonium tetrafluoroborate; Di (2,4-dichlorophenyl) iodonium hexafluorophosphate; Di (4-bromophenyl) iodonium hexafluorophosphate; Di (4-methoxyphenyl) iodonium hexafluorophosphate; Di (3-carboxyphenyl) iodonium hexafluorophosphate; Di (3-methoxycarbonylphenyl) iodonium hexafluorophosphate; Di (3-methoxy-substituted fonylphenyl) iodonium hexafluorophosphate; Di (4-acetamidophenyl) iodonium hexafluorophosphate; Di (2-benzothienyl) iodonium hexafluorophosphate; And diphenyl iodonium hexafluoroantimonate; And mixtures thereof. Such compounds are described in Beringer et. al., J. Am. Chem. Soc. 81, 342 (1959)], by the metathesis of the corresponding aromatic iodonium simple salt, such as diphenyl iodonium bisulfate.

Other suitable iodonium salts are disclosed in US Pat. No. 5,545,676 (Palazzotto et al.), Column 2 (lines 28 to 46) and US Pat. No. 3,729,313 (Smith), US Pat. No. 3,741,769 (Smith) 3,808,006 (Smith), 4,250,053 (Smith) and 4,394,403 (Smith).

Useful iodonium salts include simple salts (e.g. containing chloride, bromide, iodide or an anion such as C 4 H 5 SO 3 - ) or metal complex salts (for example SbF 6 - , PF 6 - - , BF 4 - , tetrakis (perfluorophenyl) borate, or SbF 5 OH 31 AsF 6 - ). If desired, any mixture of these same or different classes of these iodonium salts may be used.

Exemplary sulfonium salts include, but are not limited to, triphenylsulfonium tetrafluoroborate, methyldiphenylsulfonium tetrafluoroborate, dimethylphenyl hexafluorophosphate, triphenylsulfonium hexafluorophosphate, triphenylsulfonium Hexafluoroantimonate, diphenylnaphthylsulfonium hexafluoroarsenate, tritolylsulfonium hexafluorophosphate, anisyldiphenylsulfonium hexafluoroantimonate, 4-butoxyphenyldiphenylsulfonium Tetra fluoroborate, 4-chlorophenyldiphenylsulfonium hexafluorophosphate, tri (4-phenoxyphenyl) sulfonium hexafluorophosphate, di (4-ethoxyphenyl) phenylsulfonium hexafluoroarsenate , 4-acetonylphenyldiphenylsulfonium tetrafluoroborate, 4-thiomethoxyphenyldiphenylsulfonium hexafluorophosphate (Methoxyphenyl) methylsulfonium hexafluoroantimonate, di (nitrophenyl) phenylsulfonium hexafluoroantimonate, di (carbomethoxyphenyl) methylsulfonium hexafluorophosphate, di 4-acetamidophenyldiphenylsulfonium tetrafluoroborate, dimethylnaphthylsulfonium hexafluorophosphate, trifluoromethyldiphenylsulfonium tetrafluoroborate, p- (phenylthiophenyl) diphenylsulfonium hexa (P- (phenylthiophenyl)] phenylsulfonium hexafluoroantimonate, di- [p- (phenylthiophenyl) diphenylsulfonium hexafluorophosphate, di [ Phenyl)] phenylsulfonium hexafluorophosphate, 4,4'-bis (diphenylsulfonium) diphenyl sulfide bis (hexafluoroantimonate), 4,4'-bis Sulfide bis (hexafluoro Phenyl-9,9-dimethylthiazonium hexafluorophosphate, 10-phenyl-9-t-butoxycarbonylphenylphosphonium hexafluorophosphate, 5-methyl-10-oxothianthrinium tetrafluoroborate, 5-methyl-10,10-dioxothitanthranium hexafluorophosphate, and mixtures thereof.

It is preferred to use a sulfonium salt and be soluble in any inert organic solvent (to be described later), and also to be stable in storage (i.e., when mixed with other components, particularly an electron acceptor sensitizer and an electron donor co- Lt; RTI ID = 0.0 > (i. E., ≪ / RTI > does not spontaneously promote polymerization prior to exposure). Thus, the selection of a particular onium salt can be made for optimal properties with other components and amounts.

Particularly useful sulfonium salts include, but are not limited to, mixed triarylsulfonium hexafluoroantimonates (e.g., sold as UVI-6974 from Dow Chemical Company), mixed triaryl sulfonium hexafluoroantimonates (Commercially available, for example, as UVI-6990 from Dow Chemical Company) and arylsulfonium hexafluorophosphate (e.g., commercially available as SarCaTM KI85 from Sartomer Company) ).

One or more onium salts (e.g., an iodonium salt or a sulfonium salt) may be present in the non-aqueous photo-curable composition in an amount of at least 0.05% by weight, based on the total weight of the non-aqueous photo- By weight or less, or typically from 0.1% by weight to 10% by weight, or even from 0.5% by weight to 5% by weight.

 Nonionic photoacid generators are also useful in the present invention and include, but are not limited to, diazomethane derivatives such as bis (benzenesulfonyl) diazomethane, bis (p- toluenesulfonyl) Bis (cyclopentylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (cyclopentylsulfonyl) diazomethane, bis Bis (t-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (S-amylsulfonyl) diazomethane, bis (isoamylsulfonyl) diazomethane, bis (sec-amylsulfonyl) diazomethane, bis 1-cyclohexylsulfonyl-1- (t-butylsulfonyl) 1-cyclohexylsulfonyl-1- (t-amylsulfonyl) Methane, and 1-t-amylsulfonyl-1- (t-butylsulfonyl) diazomethane.

The nonionic photoacid generator may also be a glyoxime derivative such as bis-o- (p-toluenesulfonyl) -α-dimethylglyoxime, bis-o- (p- toluenesulfonyl) (P-toluenesulfonyl) -2,3-pentanedione-glyoxime, bis-o (p-toluenesulfonyl) -? - dicyclohexylglyoxime, bis- - (p-toluenesulfonyl) -2-methyl-3,4-pentanedione-glyoxime, bis- (N-butanesulfonyl) -? - dicyclohexylglyoxime, bis-o- (n-butanesulfonyl) -2,3-pentanediol (Methanesulfonyl) -? - dimethylglyoxime, bis-o (n-butanesulfonyl) -2-methyl-3,4-pentanedionglyoxime, bis- - (1,1,1-trifluoroethanesulfonyl) -? - dimethylglyoxime, bis-o- (t-butoxycarbonyl) Butanesulfonyl) -? - dimethylglycine (Cyclohexanesulfonyl) -? - dimethylglyoxime, bis-o- (benzenesulfonyl) -? - dimethylsulfoxide, bis-o- (perfluorooctanesulfonyl) bis (p-butylbenzenesulfonyl) -? - dimethylglyoxime, bis-o- (p-fluorobenzenesulfonyl) o- (xylenesulfonyl) -? - dimethylglyoxime, or bis-o- (camphorsulfonyl) -? - dimethylglyoxime.

The photoacid generator may also be a bis-sulfone derivative, such as bisnaptylsulfonylmethane, bistrifluoromethylsulfonylmethane, bismethylsulfonylmethane, bisethylsulfonylmethane, bispropylsulfonylmethane, (P-toluenesulfonyl) propane (? -Ketosulfone derivative), and 2-isopropyl (2-isopropylphenyl) -Carbonyl-2- (p-toluenesulfonyl) propane (beta -ketosulfone derivative).

Another class of useful nonionic photoacid generators are the di- sulfono derivatives such as diphenyldisulfone and dicyclohexyldisulfone; Nitrobenzyl sulfonate derivatives such as 2,6-dinitrobenzyl p-toluenesulfonate and 2,4-dinitrobenzyl p-toluenesulfonate; Sulfonic acid ester derivatives such as 1,2,3-tris (methanesulfonyloxy) benzene, 1,2,3-tris (trifluoromethanesulfonyloxy) benzene, 1,2,3-tris (p - < / RTI > toluenesulfonyloxy) benzene; And sulfonic acid esters of N-hydroxyimides, such as N-hydroxysuccinimide methanesulfonate, N-hydroxysuccinimide trifluoromethane sulfonate, N-hydroxysuccinimide ethane sulfonate, N-hydroxysuccinimide 1-propanesulfonate, N-hydroxysuccinimide 2-propanesulfonate, N-hydroxysuccinimide 1-pentanesulfonate, N-hydroxysuccinimide 1-octanesulfo N-hydroxysuccinimide p-toluenesulfonate, N-hydroxysuccinimide p-methoxybenzenesulfonate, N-hydroxysuccinimide 2-chloroethanesulfonate, N-hydroxysuccinate N-hydroxysuccinimide 2,4,6-trifluoro-benzenesulfonate, N-hydroxysuccinimide 2,4,6-trimethyl-benzenesulfonate, N-hydroxy Succinimide 2,4,6-trichloro-benzenesulfonate, N- N-hydroxysuccinimide 1-naphthalenesulfonate, N-hydroxysuccinimide 2-naphthalenesulfonate, N-hydroxy-2-phenylsuccinimide Methanesulfonate, N-hydroxymaleimide methanesulfonate, N-hydroxyglutarimide methanesulfonate, N-hydroxyglutarimidebenzenesulfonate, N-hydroxyphthalimide methanesulfonate, N- N-hydroxyphthalimide trifluoromethanesulfonate, N-hydroxyphthalimide p-toluene sulfonate, N-hydroxynaphthalimide methanesulfonate, N-hydroxynaphthalene sulfonate, N-hydroxy-5-norbornene-2,3-dicarboximide methanesulfonate, N-hydroxy-5-norbornene-2,3-dicarboximide trifluro Methanesulfonate, N-hydroxy-5- Dicarboximide p-toluene sulfonate, N-hydroxynaphthalimide triflate and N-hydroxy-5-norbornene-2,3-dicarboximide perfluoro-1-butane Sulfonate.

The at least one nonionic photoacid generator can be present in the non-aqueous photocurable composition in an amount of at least 0.05 wt% to 10 wt%, or typically at least 0.1 wt% to 10 wt%, based on the total weight of the non- Or even at least 0.5% to 5% by weight of the composition.

The non-aqueous photocurable compositions containing some of the non-aqueous photocurable compositions described herein, particularly photocurable epoxy materials and photoacid generators, may contain one or more electron donor photosensitizers. Useful electron donor sensitizers should be soluble in non-aqueous photocurable compositions and should have no functional groups that substantially interfere with the cationic photocuring process and should have a light absorption (sensitivity) within the wavelength range of at least 150 nm to 1000 nm It should be possible.

A suitable electron donor photoresist initiates a chemical modification of the onium salt (or other photogenerator) in response to photons absorbed from the irradiation. In addition, the electron donor sensitizer should be capable of reducing the photoacid generator after the electron donor sensitizer absorbs light (i.e., after the photo-induced electron transfer). Thus, the electron donor sensitizer, when absorbing photons from irradiation, can generally provide electrons to the photoacid generator.

Very rapid curing - when required (for example, non-aqueous photo-cured thin coating film of a curable composition), the electron donor is a photosensitive agent, at the desired wavelength of irradiation using a photo-curing process, at least 1000 liter mole -1 cm -1 , typically at least 50,000 liters-mole- 1 cm- 1 .

For example, each electron donor sensitizer generally has an oxidation potential of at least 0.4 V to 3 V for SCE, or more generally at least 0.8 V to 2 V for SCE.

In general, many different classes of compounds can be used as electron donor sensitizers for various reactants. Useful electron donor sensitizers include aromatic compounds such as naphthalene, 1-methylnaphthalene, anthracene, 9,10-dimethoxyanthracene, benz [a] anthracene, pyrene, phenanthrene, benzo [c] phenanthrene, and fluoranthene But is not limited thereto.

Other useful electron donor sensitizers with triplet excited states are carbonyl compounds such as thioxanthone and xanthone. Coumarine dyes, such as ketokines, including aromatic ketones such as fluorenone, and ketocoumarins with strong electron donating moieties such as dialkylamino, may also be used as electron donor sensitizing agents. Other suitable electron donor sensitizing agents include, but are not limited to, azo dyes, acridine dyes, thiazole dyes, thiazine dyes, oxazine dyes, azine dyes, aminoketone dyes, porphyrin, aromatic polycyclic hydrocarbons, p- Aminotriaryl methane, merocyanine, squarylium dyes, and pyridinium dyes.

A mixture of electron donor sensitizers selected from the same or different classes of materials may be used.

A variety of useful electron donor sensitizers are available from various commercial sources for use in the present invention and can be readily found.

When used, the at least one electron donor sensitizer is present in the non-aqueous photocurable composition in an amount of from 0.000001% to 5% by weight, typically from 0.0001% to 2% by weight, based on the total weight of the non- ≪ / RTI > The exact amount of electron donor sensitizer required depends on the total non-aqueous photocurable composition, its intended use and extinction coefficient.

In some embodiments, the electron donor photoresist is a pyrene, benzopyrene, perylene, or benzopiperylene present in an amount of at least 0.0001 wt% to 2 wt%, based on the total weight of the non-aqueous photocuring agent.

In some non-aqueous photocurable compositions of the present invention, the electron donor photosensitizer may be replaced by a combination of one or more electron acceptor photosensitizers and one or more electron donor co-initiators.

Useful electron acceptor sensitizers should be soluble in non-aqueous photocurable compositions and should be free of functional groups that substantially interfere with the cationic photocuring process and should have a light absorption (sensitivity) within a wavelength range of at least 150 nm to at most 1000 nm, Be able to.

A suitable electron acceptor sensitizer initiates the chemical modification of the onium salt in response to photons absorbed from the irradiation. The electron acceptor sensitizer should be capable of oxidizing the electron donor co-initiator (described below) to the radical cation after the electron acceptor sensitizer has absorbed the light (i.e., after the photo-induced electron transfer). Therefore, the electron acceptor sensitizer, when absorbing photons from irradiation, can generally accept electrons from the electron donor co-initiator.

If very fast curing (e.g., curing of a thin coat of the composition) is desired, the electron acceptor sensitizer can be cured at a desired irradiation wavelength using a photocuring process of at least 1000 liters-mol -1 cm -1 , typically at least And an extinction coefficient of 100,000 liters-mole- 1 cm -1 .

In general, as long as the energy requirements discussed above are met, many different classes of compounds can be used as electron acceptor sensitizers for the various reactants. Useful electron acceptor sensitizers include, but are not limited to, 1-cyanonaphthalene, 1,4-dicyanonaphthalene, 9,10-dicyanoanthracene, 2,9,10-tricyanoanthracene, , Cyanoaromatic compounds such as 10-tetracyanoanthracene; Aromatic dicarboxylic acids such as 1,8-naphthalenedicarboxylic acid, 1,4,6,8-naphthalenetetracarboxylic acid, 3,4-perylene dicarboxylic acid, and 3,4,9,10-perylene tetracarboxylic acid anhydride or imide And imides; Quinolinium, quinolinium, quinolinium, quinolinium, isoquinolinium, phenanthridinium, acridinium and pyrylium salts.

Other useful electron acceptor sensitizers with triplet excited states include carbonyl compounds such as quinone such as benzo, naphtho, anthro-quinone with electron withdrawing substituents such as chloro and cyano to be. Ketones including aromatic ketones such as fluorenone and coumalin dyes such as ketocoumarin such as those having strong electron withdrawing moieties such as pyridinium can also be used as electron acceptor sensitizing agents . Other suitable electron acceptor sensitizers include, but are not limited to, azo dyes, acridine dyes, thiazole dyes, thiazine dyes, oxazine dyes, azine dyes, aminoketone dyes, porphyrin, aromatic polycyclic hydrocarbons, p-substituted aminostyryl ketone compounds , Aminotriaryl methane, merocyanine, squarylium dyes, and pyridinium dyes. Diarylketones and other aromatic ketones, such as fluorenone, are useful electron acceptor sensitizers.

As long as the electrochemical requirements described above are met, it is also possible to use mixtures of electron acceptor sensitizers selected from the same or different classes of materials.

A variety of useful electron acceptor sensitizers are available from a variety of commercial sources.

The one or more electron acceptor sensitizing agents may be present in the non-aqueous photocurable composition in an amount of from 0.000001 wt% to 5 wt%, typically from 0.0001 wt% to 2 wt%, based on the total weight of the non-aqueous photocurable composition have.

The use of electron acceptor photosensitizers is highly effective by incorporating one or more electron donor co-initiators into the non-aqueous photo-curable composition, each of which has an oxidation potential of at least 0.1 V to 3 V for the electron donor co-initiator . Thus, such electron donor co-initiators should be soluble in non-aqueous photocurable compositions. The electron donor co-initiator may also be selected in view of other factors such as storage stability and selected photopolymerizable epoxy materials, photoacid generators, and electron acceptor sensitizers.

Useful electron donor co-initiators include, but are not limited to, alkylaromatic polyether, arylalkylamino compounds wherein the aryl group is optionally substituted with one or more electron withdrawing groups such as, but not limited to, carboxylic acid, carboxylic acid ester, ketone, aldehyde, sulfonic acid, sulfonate, Lt; / RTI > For example, when aryl is a substituted or unsubstituted phenyl or naphthyl group (e.g., a phenyl or naphthyl group having one or more electron-withdrawing groups as mentioned above) and the two alkyl groups are independently substituted with 1 to 6 carbon atoms Lt; / RTI > are useful.

Useful electron donor co-initiators can be readily obtained from a number of commercial sources.

Generally, the at least one electron donor co-initiator is present in an amount of at least 0.001 wt% to 10 wt%, or more typically at least 0.005 wt% to 5 wt%, based on the total weight of the non-aqueous photo- Even at least 0.01% to 2% by weight.

As noted above, all of the non-aqueous photocurable compositions containing the various essential and optional ingredients will contain at least 0.5% to 20% by weight or at least 20% by weight of the dispersed carbon black, based on the total weight of the non- 1% by weight to 10% by weight.

Some embodiments of the non-aqueous photocurable compositions of the present invention comprise (a) a photopolymerizable epoxy material as described above, (b) a photoacid generator as described above, (c) an electron donor photostabilizer as described above, (d) dispersed carbon-coated metal particles as described above with optional particle dispersants as described above, (e) organic diluents such as those described above, such as an organic solvent medium, (f) free radically polymerizable materials , And (g) a free radical photoinitiator, wherein

The photopolymerizable epoxy material has at least two polymerizable epoxy groups per molecule,

Wherein the photoacid generator is iodonium or sulfonium,

The dispersed carbon-coated metal particles are dispersed carbon-coated silver particles having a median diameter of 0.5 μm or less, as measured using the dynamic light scattering method as described above.

Free radical Photocurable  chemistry

In another embodiment, the non-aqueous photocurable composition comprises one or more UV-curable components, one of which is a free radical photocurable component, and the non-aqueous photocurable composition is a free radical A photoinitiator may further be included.

The at least one free-radically polymerizable compound may be selected from the group consisting of ethylenically unsaturated polymerizable monomers, oligomers or polymers such as mono- or polyfunctional acrylates (including methacrylates) Can exist. Such free radically polymerizable compounds comprise at least one ethylenically unsaturated polymerizable linkage (residue), and in many embodiments may comprise two or more of these unsaturated moieties. Suitable materials of this type contain at least one ethylenically unsaturated polymerizable linkage and may undergo additional (or free radical) polymerization. These free radically polymerizable materials can be mono-, di- or poly-acrylates or methacrylates, including but not limited to methyl acrylate, methyl methacrylate, ethyl acrylate, isopropyl methacrylate, n-hexyl acrylate Butanediol diacrylate, triethylene glycol dimethacrylate, 1,3-propanediol diacrylate, stearyl acrylate, allyl acrylate, glycerol diacrylate, glycerol triacrylate, ethylene glycol diacrylate, Acrylate, 1,3-propanediol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate Trimethylol propane triacrylate, 1,2,4-butanetriol trimatak Acrylates such as 1,4-cyclohexanediol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, sorbitol hexaacrylate, Acrylate, bis [1- (2-acryloxy)] - p-ethoxyphenyldimethylmethane, bis [1- (3-acryloxy-2- hydroxy)] - p- Tris-hydroxyethyl-isocyanurate trimethacrylate; Bis-acrylates and bis-methacrylates of polyethylene glycols having a molecular weight of 200 to 500 or less, copolymerizable mixtures of acrylate monomers such as those described in U.S. Patent No. 4,652,274 (Boettcher et al.), And U.S. Patent No. 4,642,126 Acrylate oligomers such as those described in (Zader et al.); And vinyl compounds such as styrene and styrene derivatives, diallyl phthalate, divinyl succinate, divinyl adipate, and divinyl phthalate. Mixtures of two or more of these free radically polymerizable materials may be used if desired.

Such materials may be purchased from a number of commercial sources or may be prepared using known synthetic methods and starting materials.

The amount of the at least one free radically polymerizable material is not particularly limited, but is preferably at least 10% by weight to 90% by weight, or typically at least 20% by weight, based on the total weight of the non-aqueous photo- And may be present in an amount of up to 85% by weight and may be optimized based on the desired properties of composition solubility and mechanical strength of the resulting photocured composition.

One or more free radical photoinitiators may also be present in the non-aqueous photocurable composition to produce free radicals. Such free radical photoinitiators include any compound capable of generating free radicals upon exposure to photo-curing radiation used in the practice of the present invention, such as ultraviolet or visible light. For example, the free radical photoinitiator may be prepared from a triazine compound, a thioxanthone compound, a benzoin compound, a carbazole compound, a diketone compound, a sulfonium borate compound, a diazo compound and a biimidazole compound and other compounds apparent to those skilled in the art Can be selected. A mixture of such compounds may be selected from the same or different classes.

Benzophenone, benzoyl benzoate, methyl benzoyl benzoate, 4-phenyl benzophenone, hydroxyl benzophenone, acrylated benzophenone, 4,4'-bis (dimethylamino) benzophenone and 4,4'- Ethylamino) benzophenone, anthraquinone compounds, and 2,2'-dioxyacetophenone, 2,2'-dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, pt -Butyl trichloroacetophenone, pt-butyldichloroacetophenone, benzophenone, 4-chloroacetophenone, 4,4'-dimethylaminobenzophenone, 4,4'-dichlorobenzophenone, 3,3'- 2-methoxybenzophenone, 2,2'-dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one are also useful. Other useful compounds of this type are described, for example, in U.S. Patent No. 7,875,416 (Park et al.).

Most of these free radical photoinitiators can be obtained from a variety of commercial sources.

The at least one free radical photoinitiator is present in the non-aqueous photocurable composition in an amount of from 0.3 wt% to 10 wt%, or typically from 0.4 wt% to 10 wt%, or even 0.5 wt%, based on the total weight of the non- % ≪ / RTI > to 5% by weight or less.

In some of these embodiments, the non-aqueous photocurable composition comprises one or more free radically polymerizable materials as described above, one or more free radical photoinitiators as described above, dispersed carbon-coated silver particles as described above, organic Solvent medium, wherein acrylate is present as one of the free radically polymerizable components.

Non-aqueous Photocurable  Preparation of composition

In order to prepare the non-aqueous photocurable composition of the present invention, the photocurable component may be present in a suitable organic diluent (for example, an organic solvent medium), as long as it does not act as an organic diluent (as described above) Various ingredients, including components and optional ingredients, are combined in any suitable manner. Thus, such a compounding process may involve incorporating into the organic diluent, a suitable dispersed carbon-coated metal particle as described above (including a particle dispersant as described above) and at least one photo-curable component (as described above) . These photocurable components may include a UV-curable component and a UV photoinitiator. Alternatively, the photocurable component may comprise a polymerizable epoxy material and a photoacid generator.

The resulting non-aqueous photocurable composition may be provided as a fluid, gel or paste having a viscosity of at least 1 centipoise to 100,000 centipoise at 25 占 폚. The non-aqueous photocurable composition can be applied to a variety of substrates (described below) by conventional means and can be photocured to a non-stick state within 1 second or 10 minutes or more using various curing means and irradiation sources . At the same time as photocuring or prior to photocuring, the inert organic solvent can be removed using suitable drying means.

Particularly useful inert organic solvents for this mixing are acetone, methanol, ethanol, isopropanol, 1-methoxy-2-propanol (Dowanol PM), methylene chloride, and mixtures thereof, But does not appreciably react with any reactive component of the < RTI ID = 0.0 >

article

The non-aqueous photocurable composition of the present invention may be formulated as described above and applied to one or both sides of the paper (flat side) of any suitable substrate (the following description) using any suitable method. For example, the non-aqueous photocurable composition can be applied to various substrates such as dip coating, roll coating, hopper coating, spray coating, spin coating, ink jetting, photolithographic imprinting, Flexographic printing using flexographic printing plates and flexographic printing sleeves, lithographic printing using lithographic printing plates, and gravure or intaglio printing using appropriate printing elements, Or may be applied in a pattern manner. Flexographic printing using a flexographic printing element is particularly useful for providing a predetermined pattern of non-aqueous photocurable composition, which method comprises applying the same or different non- Can be used to provide multiple patterns of the Mars composition. Details of these processes are provided below.

The applied non-aqueous photocurable composition can be formed into a uniform layer and can be dried or dried in a predetermined pattern. The resulting article may be regarded as a "precursor" article before photocuring is performed as described below.

 As will be described in more detail below, the substrate for such articles may be comprised of any useful material (s) and may be any suitable material (s), for example, a metal material, glass, paper stock (any type of cellulosic material) Size and shape of the individual films or sheets, or it may be a continuous web of material, such as a continuous polymer web.

Various amounts of the essential and optional ingredients of the non-aqueous composition (including non-aqueous photocurable compositions) are described above, but it should be understood that it is meant to refer to a solution or dispersion containing such ingredients. However, it should be understood that when applied to a suitable substrate and optionally dried and then photo-cured, the amounts of the various components differ within the applied non-aqueous composition. The individual amounts and relative amounts of residual components (e.g., when the inert organic solvent is removed) can be readily calculated from information on the amount of components in the non-aqueous composition prior to application to the substrate.

For example, in a dried non-aqueous composition (including a dried non-aqueous photo-curable composition), the carbon-coated metal particles may be present in an amount of 10 wt% to 90 wt% To about 30% by weight, and the carbon particles can be present in an amount of up to 20% by weight, and the photocurable component (described above, before curing) can be present in an amount of up to 90% by weight.

Non-aqueous Photocurable  Use of composition

The non-aqueous photocurable compositions described herein can be photocured (or photopolymerized) using suitable radiation, including ultraviolet light or visible light, or both. One or more suitable light sources may be used in the exposure process. Each precursor article can be exposed individually as an element or in an alternative embodiment described below, a web (e.g., a roll-to-roll web) containing a plurality of precursor articles (including multiple photocurable patterns) A continuous web of two-roll continuous webs of polymer is applied to the continuous polymer web at multiple portions on one or both of the support surfaces, when the continuous polymer web passes through the exposure zone, or when the exposure apparatus passes a desired path over a continuous polymer web, The same or different non-aqueous photocurable compositions can be applied to both support surfaces of the substrate, whether the substrate is in the form of a single element or in the form of a continuous polymer web (see, for example, In many embodiments, a non-aqueous photocurable composition as described herein is used to coat a substrate (or a continuous polymeric web) A different electro-conductive metal pattern may be formed.

Preferred photocuring is a UV or visible light irradiation with a wavelength of at least 184.5 nm to 700 nm and an intensity of at least 1 mJ / cm 2 to 1000 mJ / cm 2 or typically at least 1 mJ / cm 2 to 800 mJ / cm 2 . ≪ / RTI >

When the non-aqueous photocurable composition is uniformly applied to a suitable substrate, the resulting uniform dry layer is exposed to radiation through a suitable photomask (masking element) having the desired pattern, and then exposed to radiation through a non- &Quot; imaged "or selectively exposed (or patterned) by appropriately removing the non-crosslinked (non-cured) photocurable composition using a" developer "solution suitable for solubilizing or dispersing the photocurable composition. These features or steps may be performed on both (opposing) supporting surfaces of the substrate. In addition, if desired, multiple patterns can be formed on the dried layer using the same or different photomasks.

 More specifically, a predetermined pattern of one or more non-aqueous photocurable compositions may be formed on a suitable substrate using the methods described below.

Suitable substrates useful in providing precursor articles (also known in the art as "receptor elements") can be composed of any suitable material, so long as they do not interfere with the purpose of the non-aqueous photocurable composition. For example, useful substrates include, but are not limited to, polymer films, metals, paper stock, rigid or flexible glass (such as those treated or not treated with a tetrafluorocarbon plasma, a hydrophobic fluorine or siloxane water repellent material) Or a material comprising ceramic wafers, fabrics, and combinations thereof (e.g., laminates of various films or laminates of paper and films), wherein a uniform layer or pattern of non-aqueous photocurable compositions Is then formed thereon in an appropriate manner so that a uniform photocured layer or one or more photocured patterns are formed on the at least one receptor (support) surface. The substrate may be transparent, translucent or opaque, rigid or flexible. Many useful substrates are transparent and have an integrated transmittance of at least 90%, and such transparent substrates may also be flexible, such as a continuous polymer web.

The substrate may comprise one or more auxiliary polymers or one or more patterns of non-polymeric layers or other materials applied before the non-aqueous photocurable composition is applied. For example, one or both of the support (planar) surfaces of the substrate may be treated with, for example, a primer layer or with an electrical or mechanical treatment (e.g., graining) Surface "to improve the adhesion of the non-aqueous photocurable composition and the resulting photocurable layer or photocurable pattern. The adhesive layer may be disposed on a substrate to provide a variety of properties in response to stimulation (e. G., Can be thermally activated, solvent activated, or chemically activated) Layer. ≪ / RTI >

In some embodiments, the substrate may comprise a separate receptive layer, such as a receptor surface disposed on the substrate, which may be a material such as a suitable polymeric material that highly accommodates the non-aqueous photocurable composition Lt; / RTI > Such a receptive layer may have a dry thickness of from 0.05 탆 to 10 탆 measured at 25 캜 or typically from 0.05 탆 to 3 탆.

The support surface of the substrate (especially the polymeric substrate) can be treated by corona discharge, mechanical abrasion, flame treatment, or exposure to oxygen plasma or by coating with various polymeric films such as poly (vinylidene chloride) or aromatic polysiloxane, U.S. Patent No. 5,492,730 (Balaba et al.) And 5,527,562 (Balabar et al.) And U.S. Patent Application Publication No. 2009/0076217 (Gommans et al.).

Suitable substrate materials for forming precursor articles as continuous webs include, but are not limited to, metal films or foils, metal films on polymers (e.g., metal films on electro-conductive polymer films), flexible glasses, semiconducting organic or inorganic Films, organic or inorganic dielectric films, or laminates of two or more layers of such materials. For example, useful continuous web substrates include films such as poly (ethylene terephthalate) films, poly (ethylene naphthalate) films, polyimide films, polycarbonate films, polyacrylate films, polystyrene films, polyolefin films and polyamide films Polymer foils, metal foils such as aluminum foils, cellulosic or resin-coated or glass-coated papers, cardboard webs and metallized polymeric films.

Particularly useful substrates are transparent polyester films composed of poly (ethylene terephthalate), poly (ethylene naphthalate), polycarbonate or poly (vinylidene chloride), which have not been surface treated as mentioned above.

In some embodiments, the first polymer latex and the second polymer latex are mixed to form a dried primer layer on the substrate to adhere the patterned material having fine lines formed using the non-aqueous photocurable composition can do. The first polymer latex may comprise a first polymer and a first surfactant such that the dried coating of the first polymer latex has a surface polarity of at least 50%. The second polymer latex may comprise a second polymer and a second surfactant such that the dried coating of the second polymer latex has a surface polarity of 27% or less. Moreover, the dried coating of the mixture may have a surface polarity of greater than or equal to 15% and less than or equal to 50%.

At least one of the first and second polymers described herein may be a polymeric material that is at least partially composed of repeating units derived from glycidyl (meth) acrylate (meaning glycidyl acrylate, glycidyl methacrylate, or both) Units, and in most embodiments, at least one of the first polymer and the second polymer is at least partially derived from glycidyl (meth) acrylate. In addition, at least one of the first polymer and the second polymer is crosslinkable and can be crosslinked after being coated on a suitable support, for example during drying of the substrate or during various heat treatments.

Particularly useful first polymers are vinyl polymers that are at least partially derived from one or more glycidyl-functional ethylenically unsaturated polymerizable monomers such as glycidyl acrylate and glycidyl methacrylate. Thus, the first polymer may be a homopolymer derived from glycidyl (meth) acrylate, but may also be a copolymer derived from glycidyl (meth) acrylate and one or more other ethylenically unsaturated polymerizable monomers Lt; / RTI > The term "glycidyl" refers to an oxirane ring attached to an alkyl group having 1 to 4 carbon atoms (linear or branched alkyl group which may be further substituted) such as methyl, ethyl, isopropyl and t- Quot;

The first polymer is specifically designed by copolymerizing one or more glycidyl (meth) acrylates with one or more alkyl (meth) acrylates, wherein the ester alkyl group has at least two carbon atoms, including, but not limited to, ethyl acrylate , Ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, allyl methacrylate, Acrylate, acrylate, and others apparent to those skilled in the art. Particularly useful co-monomers are alkyl (meth) acrylates in which the alkyl ester group has 4 or more carbon atoms, such as, but not limited to, n-butyl acrylate, n-butyl methacrylate, , n-hexyl methacrylate, and cyclohexyl methacrylate.

The second polymer latex may include one or more second polymers and one or more second surfactants (described below) such that the dried coating of the second polymer latex has a surface polarity of 28% or less or 27% or less .

Particularly useful second polymers include, as described above for the first polymer, one or more glycidyl-functional ethylenically unsaturated polymerizable monomers such as glycidyl (meth) acrylates, such as glycidyl Acrylate, and glycidyl methacrylate. Thus, the second polymer can be a homopolymer derived from glycidyl (meth) acrylate, or a copolymer derived from glycidyl (meth) acrylate and one or more other ethylenically unsaturated polymerizable monomers. The term "glycidyl" is as defined above.

The second polymer is specifically designed by copolymerizing one or more glycidyl (meth) acrylates with one or more co-monomers, such as one or more alkyl (meth) acrylates, wherein the ester alkyl group has two or more carbon atoms, Such as, but not limited to, ethyl acrylate, ethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate , Allyl methacrylate, hydroxyethyl methacrylate, hydroxyethyl acrylate, and others as would be apparent to one skilled in the art. Particularly useful co-monomers are alkyl (meth) acrylates in which the alkyl ester group has 4 or more carbon atoms, such as, but not limited to, n-butyl acrylate, n-butyl methacrylate, , n-hexyl methacrylate, and cyclohexyl methacrylate.

The first polymer latex comprises at least one first surfactant, wherein each first surfactant is an alkyl sulphonate sodium salt, wherein the alkyl group has at least 10 carbon atoms. For example, the first surfactant may be sodium alpha-olefin (C 14 -C 16 ) sulfonate or the first surfactant may be R-CH 2 -CH = CH-CH 2 -S (= O) 2 O - a compound represented by Na + , wherein R is a C 10 , C 11 or C 12 hydrocarbon group, or a mixture of such compounds having different R groups that are any of C 10 to C 12 hydrocarbon groups. One useful commercial product containing a first surfactant is Rhodacal A 246 L (e.g., available from Rhodia). Mixtures of such first surfactants can be used if desired.

The second polymer latex comprises at least one second surfactant and each second surfactant is an alkylphenol sulfate ammonium salt having at least three ethylene oxide units. For example, the second surfactant may be a salt of ethoxy nonylphenol sulfate to poly or second surfactant R'- phenyl - (O-CH 2 CH 2 ) n S (= O) O 2 - NH 4 + (wherein, R 'is C 8 To C 12 hydrocarbon group, and n is 3 or more and 10 or less, or n is 3 or more and 6 or less). One useful commercial product containing a second surfactant is Rhodapex® CO-436 (available from Rhodia, for example). Mixtures of such second surfactants can be used if desired.

Each of the first polymer latex and the second polymer latex may be prepared using emulsion polymerization or may be obtained as an aqueous dispersion of the particulate emulsion polymer.

The useful substrate may have a desired dry thickness, depending on the end use of the article formed therefrom. For example, the dry thickness of the substrate (including all treatments and auxiliary layers) may be 0.001 mm or greater and 10 mm or less, and in the case of a transparent polymer film, the dry thickness of the substrate may be 0.008 mm or greater and 0.2 mm or less.

The substrate used to make the articles described herein may be in the form of a continuous web of transparent polymer-based materials, including, for example, individual sheets of any size or shape, and transparent polyester webs suitable for roll- Can be provided in a continuous web form. Such a continuous polymer web can be divided or formed into individual first, second and further portions that can be used to form the same or different photocured patterns.

After application of the non-aqueous photocurable composition, any inert organic solvent of the organic diluent may be removed by a drying or prebaking process, so as not to adversely affect the remaining components or cause premature photocuring. Useful drying conditions may be as low as room temperature for as short as 5 seconds to several hours, depending on the manufacturing process. In most processes, such as the roll-to-roll process described below, the drying conditions may be high enough to remove at least 90% of the inert organic solvent (s) in at least 5 seconds.

Any applied uniform layer of the non-aqueous photocurable composition may have a dry thickness of from greater than or equal to 0.1 μm and less than or equal to 10 μm, or typically greater than or equal to 0.2 μm and less than or equal to 1 μm, Layer, which generally has a dry thickness that is approximately the same as a uniform layer of non-photocurable non-aqueous photocurable composition. This uniform layer may be applied to both (opposite) supporting surfaces of the substrate, and the uniform layer may have the same or different chemical composition or dry thickness.

Any applied pattern of non-aqueous photocurable composition includes a grating line (or other shape including a circular or irregular network) having an average dry width of from 0.2 탆 or more to 100 탆 or less, typically 5 탆 or more to 10 탆 or less , And the optimum dry width is selected to suit the intended use of the resulting uniform photocured layer having a photocured electro-conductive grid line having dimensions essentially identical to those of the non- Lt; / RTI >

Thus, the present invention can be used to provide an article comprising a substrate and a uniform layer or pattern composed of the non-aqueous photocurable composition of the present invention, which article generally comprises an article formed prior to photocuring Quot; precursor "article which means " precursor ". When photocuring a non-aqueous photocurable composition, the precursor article is considered an intermediate (photo-cured) article.

In some embodiments, the same or different non-aqueous photocurable compositions can be applied in a suitable manner on the support surface (planar surface) of the substrate to form a "double-sided" or double-sided precursor article, The aqueous photocurable composition may be in the form of a uniform layer or a predetermined pattern, which may be the same or different.

In many embodiments, the pattern of non-aqueous photocurable composition is applied using a relief member such as an elastomeric relief member (e.g., a flexographic printing member) derived from a flexographic printing plate precursor (e.g., (As a roll-to-roll continuous web) on one or both (opposing) support surfaces of a substrate, many of which are known in the art and some of which are available from DuPont, Cyrel® Flexographic Such as the Flexographic Photopolymer Plate and the Flexcel SR and NX Flexographic Plate and Flexcel Direct Flexographic Plate from Eastman Kodak Company, Available.

Particularly useful elastomeric relief members are derived from a flexographic printing plate precursor and a flexographic printing sleeve precursor, each of which can be suitably imaged to provide a relief member for "printing" or applying an appropriate pattern It can be processed.

For example, useful elastomeric relief members can be composed of one or more elastomeric layers with or without a substrate on which a relief image can be produced using appropriate imaging means.

For example, an elastomeric relief member having a relief layer that includes a top relief surface and an average relief image depth of at least about 50 microns relative to the top relief surface, typically an average relief image depth (pattern height) (E.g., flexographic printing elements) are described, for example, in U.S. Patent No. 7,799,504 (Zwadlo et al.) And 8,142,987 (Ali et al.) And U.S. Patent Application Publication No. 2012/0237871 Can be prepared from an image forming exposure of an elastomeric photopolymerizable layer in an elastomeric relief member precursor, such as a flexographic printing member precursor. Such an elastomeric photopolymerizable layer may be imaged through an appropriate mask image to provide an elastomeric relief member (e.g., a flexographic printing plate or a flexographic printing sleeve). In some embodiments, a relief layer comprising a relief pattern may be disposed on a suitable substrate as described in the Ali et al. Patents. Other useful materials and methods of image formation (including development) for providing elastomeric relief images are also described in the above-referenced Ali et al. Patents. The relief layer (and flexographic printing member) may be different to provide different patterns of non-aqueous photocurable compositions on the same or opposite supporting surfaces of the substrate.

In another embodiment, the elastomeric relief member can be made from a material having an elastomeric material such as, for example, those described in U.S. Patent No. 5,719,009 (Fan), 5,798,202 (Cushner et al.), 5,804,353 (Kushner et al), 6,090,529 Gelbart), 6,159,659 (gelbart), 6,511,784 (Hiller et al.), 7,811,744 (Figov), 7,947,426 (defibbro et al.), 8,114,572 Landry-Coltrain et al., U.S. Patent No. 8,153,347 (Veres et al.), 8,187,793 (Regan et al.), And U.S. Patent Application Publication No. 2002/0136969 2003/0180636 (Kanga et al.), And 2012/0240802 (Landry-Coltrain et al., ≪ RTI ID = 0.0 & (Or wear) laser-engravable elastomeric relief member precursor in the presence or absence of an integral mask as described in US Pat. A directly engraved relief member can be made without solvent processing or development required for the photopolymerizable elastomer material.

When an elastomeric relief member is used, the non-aqueous photocurable composition can be applied in an appropriate manner to the top relief surface (raised surface) of the elastomeric leaf member. This application can be accomplished using suitable means, and it is preferred that as little as possible is coated on the sides (slopes) or recesses of the relief. Anilox roller systems or other roller application systems, especially low volume Anilox rollers and associated skive knives of less than 2.5 bilion cubic micrometers per square inch (6.35 bilion cubic micrometers per square centimeter) Can be used. Optimum metering of the non-aqueous photocurable composition onto the top relief surface can be achieved by controlling the viscosity or thickness or by selecting suitable application means.

For example, a non-aqueous photocurable composition may be formulated to have a viscosity for such use of less than or equal to 1 cps (centipoise) and less than or equal to 5000 cps, or less than or equal to 1 cps and less than or equal to 1500 cps. The thickness of the non-aqueous photocurable composition on the relief image is generally limited to an amount sufficient to allow easy transfer to the substrate but not too much flow over the edge of the elastomeric relief member in the recess during application.

Thus, a non-aqueous photocurable composition can be supplied in an amount (as a uniform layer or pattern) measured for each printed precursor article from anilox or other roller ink application system. In one embodiment, a first roller may be used to transfer the non-aqueous photocurable composition from the "ink" pan or metering supply system to the metering feed roller or the anilox roller. The non-aqueous photocurable composition is generally metered into a uniform thickness when it is transported from the anilox roller to the printing plate cylinder. When the substrate as a continuous web is moved from the printing plate cylinder to the impression cylinder through the roll-to-roll handling system, the impression cylinder applies pressure to the printing plate cylinder to cause an image of the non- aqueous photocurable composition to be deposited from the elastomeric relief member .

After the non-aqueous photocurable composition is applied to the uppermost relief surface (or raised surface) of the elastomeric relief member, at least 25% by weight of any inert organic solvent is removed to form a higher viscosity deposition on the uppermost relief surface of the relief image It may be useful for water to form. This removal of the inert organic solvent may be accomplished in any manner, for example, by injection of hot air, by evaporation at room temperature, or by heating in a hot oven or other means known in the art for solvent removal have.

When applied in a uniform layer on the substrate or in a grid line of a predetermined pattern or in another form (on one or both of the support surfaces of the substrate), the non-aqueous photocurable composition in the precursor article, Or an appropriate source such as an LED, to provide a photocured layer or one or more light cured patterns on the substrate. For example, photocuring may be achieved by the use of ultraviolet-visible light radiation having a wavelength (? Max ) of at least 190 nm to 700 nm and an intensity of at least 1,000 micro watts / cm 2 to 80,000 micro watts / cm 2 . The illumination system used to generate such radiation may be, for example, a low-pressure, medium-pressure or low-pressure system having a desired operating pressure of from 1 to 50 discharge lamps, such as xenon, metal halide, metal arc High-pressure mercury vapor discharge lamp). The lamp may include an envelope capable of transmitting light at a wavelength of 190 nm or more and 700 nm or less or typically 240 nm or more and 450 nm or less. The lamp cover may be composed of quartz (eg spectrocil or pyrex). Typical lamps that can be used to provide ultraviolet light are, for example, a medium pressure mercury arc, such as GE H3T7 and Hanovia 450W arc lamps. Photocuring may be performed using a combination of various lamps, some or all of which may operate in an inert atmosphere. When using a UV lamp, the irradiance flux that impinges on the substrate (or the applied layer or pattern) may cause a sufficient rapid sight of the applied non-aqueous photocurable composition, for example in a roll-to-roll operation May be designed to be sufficient to carry out the continuous cycle in 1 to 20 seconds.

The LED illuminating device used for photo-curing may have an emission peak wavelength of 350 nm or more. The LED device may comprise two or more types of devices having different emission peak wavelengths of 350 nm or more. A commercial example of an LED device having an ultraviolet light emitting diode (UV-LED) with an emission peak wavelength of 350 nm or more is NCCU-033 available from Nichia Corporation.

The result of such an investigation of the precursor article is that it comprises a substrate (e.g., a separate sheet or a continuous web) and is coated on one or both of the support surfaces of the substrate with a photocured layer or one or more It is an intermediate article having a photocured pattern.

The resulting intermediate article can be used in this form for some applications, but in most embodiments it is further treated to include an electro-conductive metal on a uniform photocured layer or photocured pattern (s) Each of these includes carbon-coated metal particles as a "seed" material for further applying an electro-conductive metal, for example, using an electroless metal plating procedure. For example, the electroless "seed" carbon-coated metal particles as described above may comprise palladium or platinum particles that may be electroless plated with copper, platinum, palladium or other metals as described below.

One useful method is to use a plurality of flexographic printing plates (e.g., as described above) in a stack of printing zones, each stack having its own printing plate cylinder, The flexographic printing plate may be used to print an individual substrate, or the stack of printing plates may be used to print multiple portions of a continuous polymer web (either or both supporting surfaces). The same or different non-aqueous photocurable compositions (on the same or opposite support surfaces) can be "printed" or applied to these substrates using multiple flexographic printing plates.

In another embodiment, a central impression cylinder can be used with a single impression cylinder mounted on a print press frame. As the substrate (or receiver member) enters the printing press frame, it comes into contact with the impression cylinder and an appropriate pattern is printed with the non-aqueous photocurable composition. Alternatively, an in-line flexographic printing process in which the printing zones are arranged in a horizontal line and driven by a common line shaft can be used. The printing zone may be connected to the exposure zone, the cutting zone, the folder and other post-processing equipment. The skilled artisan can readily determine other useful configurations of equipment and areas using information available in the art. For example, an in-the-round imaging process is described in WO 2013/063084 (Jin et al.).

The intermediate articles described herein having the described photocured patterns containing dispersed carbon-coated metal particles can be directly immersed in an aqueous electroless metal plating bath or solution, Continuous web) can be stored with only the photocured pattern for later use.

For example, each intermediate article may be contacted with an electroless plating metal that is the same as or different from the metal in the carbon-coated metal particles incorporated into the photocured pattern (s). However, in most embodiments, the electroless plating metal is a metal other than the metal used for the dispersed carbon-coated metal particles in the photocured pattern (s).

In most embodiments, the electroless plating metal may be, for example, copper (II), silver (I), silver (II), and the like, although any metal that is likely to be electrolessly & ), Gold (IV), palladium (II), platinum (II), nickel (II), chromium (II) and combinations thereof. Copper (II), silver (I) and nickel (II) are electroless plating metals which are particularly useful for carbon-coated silver, copper or palladium particles.

The one or more electroless plating metals may be present in the aqueous electroless plating bath or solution in an amount of from 0.01 wt% to 20 wt%, based on the total solution weight.

Electroless plating can be performed using known temperature and time conditions, which conditions are well known in the various references and scientific literature. It is also known to incorporate various additives such as metal complexing agents or stabilizers into the aqueous electroless plating solution. Changes in time and temperature can be used to change the metal electroless plating thickness or metal electroless plating deposition rate.

Useful aqueous electroless plating solutions or baths are electroless copper (II) plating baths which may contain formaldehyde as a reducing agent. Ethylenediaminetetraacetic acid (EDTA) or a salt thereof may be present as a copper complexing agent. For example, copper electroless plating may be performed at room temperature for several seconds to several hours, depending on the desired deposition rate and plating rate and plating metal thickness.

Other useful waterborne electroless plating solutions or baths include silver (I), EDTA and sodium tartrate, silver (I) and ammonia and glucose, copper (II) and EDTA and dimethylamine borane, copper And hypophosphites, nickel (II) and lactic acid, acetic acid and hypophosphites, and other industry standard aqueous electroless baths or solutions such as those described in Mallory et al., Electroless Plating: Fundamentals and Applications .

After the electroless plating process to provide the electro-conductive metal pattern on one or more portions of the substrate or the opposing support surface, the resulting article of manufacture may be removed from the aqueous electroless plating bath or solution, Or other aqueous solutions to remove any residual electroless plating chemistry. At this point, the electroless plated metal is generally stable and is intended for the intended purpose of forming a variety of electro-conductive products with the desired electro-conductive metal grid lines or electro-conductive metal connectors (or BUS connectors or electrodes) Can be used.

In some embodiments, the resulting article of manufacture can be obtained, for example, with water at room temperature as described in U.S. Patent Application Publication No. 2014/0071356 (Petcavich), or in WO 95/169345 (La Rinsed or cleaned with deionized water at a temperature of less than 70 ° C, as described in [0027] for example, in Ramakrishnan et al.

In order to change the surface of the electroless plated metal for reasons of visual or durability, a surface plating of at least another (third or more) metal such as nickel or silver on the electroless plated layer (this process is sometimes referred to as & metal sulfide or metal selenide layer suitable for varying the surface color and scattering properties without reducing the conductivity of the electrolessly plated (second) metal, Postprocessing can be used. Depending on the metals used in the various capping procedures of the process, it may be desirable to treat the electroless plated metal with another seed metal catalyst in the aqueous seed metal catalyst solution to promote deposition of the additional metal.

Furthermore, the same or different conditions can be used to sequentially perform several treatments with the aqueous electroless metal plating solution. If appropriate, a continuous washing or rinsing step may be carried out at room temperature or below 70 < 0 > C.

In addition, the electroless plating procedure may be performed several times in sequence using the same or different electroless plating metals and the same or different electroless plating conditions.

Some details of methods and apparatus useful for carrying out some embodiments of the present invention are described, for example, in US 2014/0071356 (mentioned above) and WO 2013/169345 (mentioned above). Other details of a useful manufacturing system for making conductive articles, particularly in a roll-to-roll fashion, are described in WO 2014/070131 (filed October 29, 2012 by Petkovich and Jean ).

Additional equipment systems and step features that may be used to practice the present invention are described in U.S. Patent Application No. 14 / 146,867 (filed on January 3, 2014 by Shifley).

The non-aqueous photocurable compositions of the present invention may be used in a method of providing one or more electro-conductive articles. The method includes providing a continuous web of transparent substrate, examples of which are described above and may in particular be a continuous web of poly (ethylene terephthalate).

The method also includes forming a photocurable pattern of a non-aqueous photocurable composition comprising at least a photocurable component as described above and dispersed carbon-coated metal particles on at least a first portion of a continuous web of a transparent substrate Step (described herein). The photocurable pattern is then photocured to form a photocured pattern on the first portion of the continuous web, the photocured pattern comprising the dispersed carbon-coated metal particles (as described above) as a seed metal catalyst site . The photocured pattern can then be electroless plated onto the first portion of the continuous web with an electro-conductive metal (as described above).

The method may further comprise the steps of forming, shaping, photo-curing and electrolessing the features described above for one or more additional times on one or more additional portions of the continuous web different from the first portion using the same or different non-aqueous photocurable compositions. And performing a plating process. In this manner, multiple photocured and electroless plated patterns can be formed on the same or different support surfaces of the substrate. The resulting electro-conductive pattern may have the same composition, pattern or electrical conductivity, or some or all of these characteristics may be different (predetermined according to customer needs).

Thus, the method can be used to provide a plurality of precursor articles,

Forming a first photocurable pattern on a first portion of the continuous web by applying a non-aqueous photocurable composition to the first portion using a flexographic printing member;

Advancing a continuous web comprising a first photocurable pattern proximate the exposure radiation thereby forming a first photocured pattern on the first portion,

Forming a second photocurable pattern on the second portion of the continuous web by applying the same or different non-aqueous photocurable compositions to the second portion using the flexographic printing member,

Advancing a continuous web comprising a second photocurable pattern proximate the exposure radiation thereby forming a second photocurable pattern on the second portion,

Optionally forming one or more additional photocured patterns in a similar manner in one or more additional portions of the continuous web using the same or different non-aqueous photocurable compositions and the same or different flexographic printing elements ; And

Winding a continuous web comprising a plurality of photocured patterns, or immediately using a continuous web for further processing such as electroless plating

.

Thus, the method may further comprise:

Forming a plurality of electro-conductive articles from a continuous web comprising a plurality of photocured patterns, and

Assembling the individual conductive articles to the same or different individual devices (e.g., the same or different touch screen displays or devices)

.

The method may also include electroless plating each of the plurality of photocured patterns in the continuous web to form a plurality of electro-conductive articles that can be assembled into the same or different individual devices by the same or different users . ≪ / RTI > Such devices may be touch screens, or other display devices including controllers, housings, and software suitable for the type of communication desired over the Internet. Alternatively, the device may be a subcomponent of such a touch screen or other display device.

In some embodiments, the method can be used to manufacture an apparatus comprising a touch screen,

Assembling one or more individual electro-conductive articles into the device housing to form a touch screen area

Wherein each of the one or more individually electrically-conductive articles comprises an electrically-conductive material comprising an electroless-plated electro-conductive metal on a photocured pattern derived from the non-aqueous photocurable composition of the present invention, Pattern.

Useful products made using the present invention may be formed of capacitive touchscreen sensors including an electro-conductive metal grid line, an electro-conductive metal connector (electrical lead or BUS connector) in a suitable pattern. For example, after printing the non-aqueous photocurable composition of the present invention in a predetermined pattern, the printed pattern is electroless plated with a suitable metal as described above to form an electro-conductive metal grid line and an electro- Can be formed.

The present invention provides at least the following embodiments and combinations thereof, but combinations of other features are considered within the scope of the present invention as those skilled in the art will appreciate from the teachings of this disclosure.

1. A non-aqueous composition comprising carbon-coated metal particles dispersed in an organic diluent in an amount of at least 10% by weight based on the total weight of the non-aqueous composition,

Wherein the dispersed carbon-coated metal particles are dispersed in a particle dispersing agent having a median diameter of 0.6 mu m or less and a weight average molecular weight (Mw) of 2,000 or more and 100,000 or less and containing nitrogen-containing units, Lt; / RTI >

Wherein the non-aqueous composition does not exhibit visible sedimentation when subjected to sedimentation tests at 20 占 폚 for more than 24 hours, when the dispersed carbon-coated metal particles contain 25% by weight or less of the dispersed carbon-coated metal particles.

2. A process as claimed in claim 1 wherein the ratio of the carbon-coated silver particles dispersed or dispersed carbon-coated copper particles, or mixtures comprising dispersed carbon-coated silver particles and dispersed carbon- - aqueous composition.

3. The non-aqueous composition of claim 1 or 2, wherein the weight ratio of the particle dispersant to the dispersed carbon-coated metal particles is at least 1: 100 to 30: 100.

4. The non-aqueous composition of any one of embodiments 1-3 wherein the dispersed carbon-coated metal particles are present in an amount of at least 15% by weight to 70% by weight, based on the total weight of the non- Composition.

5. The non-aqueous composition of any one of embodiments 1-4 wherein the particulate dispersant has a Mw of 2,000 to 50,000.

6. The non-aqueous composition of any of embodiments 1-5 further comprising carbon black dispersed in an amount of up to 20% by weight based on the total weight of the non-aqueous composition.

7. The non-aqueous composition of any one of embodiments 1-6 wherein the particle dispersant is an organic polymer comprising an ester unit.

8. The non-aqueous composition according to any one of embodiments 1 to 7, wherein the particle dispersant is an organic polymer comprising units selected from at least one of the following classes (i) to (iv): (i) pyridine units; (ii) an immigration unit; (iii) imide units; And (iv) an amine unit.

The dispersed carbon-coated metal particles of any of embodiments 1-8, wherein the dispersed carbon-coated metal particles are present in a concentration of from 15% to 60% by weight, based on the total weight of the non- Wherein the dispersed carbon-coated silver particles have a median diameter of less than 0.5 占 퐉 as measured using dynamic light scattering.

10. The method of any one of embodiments 1-9 wherein the organic diluent is selected from the group consisting of 2-ethoxyethanol, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) One of either of propyl alcohol, isopropanol, 4-heptanone, 3-heptanone, 2-heptanone, cyclopentanone, cyclohexanone, diethyl carbonate, 2-ethoxyethyl acetate, N-butyl butyrate and methyl lactate Of the total weight of the composition.

11. The non-aqueous composition of any of embodiments 1 to 10, wherein the composition is a non-aqueous photocurable composition further comprising a photo-curable component and, if desired, an ultraviolet photoinitiator.

12. The non-aqueous composition of embodiment 11 wherein said photo-curable component is a UV-curable component.

13. The non-aqueous composition of embodiment 11 or 12, wherein said photo-curable component is an acid catalyzed photo-curable component, and wherein said non-aqueous composition further comprises a photoacid generator.

14. The non-aqueous composition of any one of embodiments 11-13 wherein the photo-curable component is a photopolymerizable epoxy material.

15. The photoresist composition of any one of embodiments 11-14, wherein the photocurable component is a photopolymerizable epoxy material having at least two polymerizable epoxy groups per molecule, wherein the photoacid generator is an iodonium or a sulfonium compound, - aqueous composition.

16. The non-aqueous composition of embodiment 11 or 12, wherein said photo-curable component is a free radical photo-curable component, and wherein said non-aqueous composition further comprises a free radical photoinitiator.

17. The non-aqueous composition of embodiment 16 wherein the photocurable component comprises an acrylate.

18. An article comprising a substrate and having a dry layer or a dry pattern of the non-aqueous composition of any of embodiments 1 to 17 on one or both of the support surfaces of the substrate.

19. The article of embodiment 18, wherein the substrate is a continuous polymer web.

20. The article of embodiment 18 wherein the substrate comprises a metal, glass, paper stock or ceramic.

21. The article of embodiment 18 or 19 wherein the substrate is a continuous web comprising polyester.

22. The article of any one of embodiments 18,19, or 21, wherein the substrate is a continuous polymer web and the non-aqueous composition is disposed in multiple patterns on both support surfaces of the substrate.

23. An article comprising a substrate and having a dried layer or a dried pattern of a photocured composition derived from the non-aqueous composition of any of embodiments 11 to 17 on one or both of the support surfaces of the substrate.

24. The article of embodiment 23 wherein said substrate is a continuous polymer web.

25. The article of embodiment 23 or 24, wherein the photocured composition is disposed as one or more patterns on one or both of the support surfaces of the substrate.

26. The article of any one of embodiments 23-25, wherein the substrate is a continuous polymer web and the photocured composition is disposed in multiple patterns on both support surfaces of the substrate.

27. The article of any one of embodiments 23-26 wherein the substrate is a continuous web of polyester.

28. A method of providing a precursor article,

Providing a continuous web of transparent substrate,

Forming at least one photocurable pattern from one of the non-aqueous photocurable compositions of any one of embodiments 11 to 17 on at least one portion of at least one support surface of the continuous web,

≪ / RTI >

29. The method of embodiment 28 wherein < RTI ID =

Curing one or more photocurable patterns to form one or more photocured patterns on at least one portion of the continuous web, wherein each of the one or more photocured patterns comprises a carbon- Comprising coated metal particles; and

Electroless plating each of the one or more photocured patterns on at least one portion of the continuous web with an electro-conductive metal,

≪ / RTI >

30. The process of embodiment 29 wherein < RTI ID =

Forming a plurality of features on the plurality of portions of the continuous web, photocuring and electroless plating, wherein the plurality of portions comprise the same or different non-aqueous photocurable compositions, The steps, which are different

≪ / RTI >

31. The method of any one of embodiments 28-30, wherein a plurality of precursor articles are provided,

Forming a plurality of photocurable patterns on a plurality of portions on one or both of the support surfaces of the continuous web by applying the non-aqueous photocurable composition to the plurality of portions using one or more flexographic printing elements,

Advancing the continuous web comprising the plurality of photocurable patterns proximate the exposure radiation, thereby forming a plurality of photocured patterns; and

Winding the continuous web including the plurality of photocured patterns

≪ / RTI >

32. The method of any one of embodiments 28 to 31, wherein the substrate is a continuous polyester web.

33. The method of embodiment 32 wherein said substrate is a continuous polyester web comprising poly (ethylene terephthalate).

34. A method of forming a plurality of electro-conductive patterns on a substrate,

Providing a precursor article, wherein the precursor article comprises a substrate, and on one or both of the support surfaces of the substrate, a plurality of photocured patterns comprising the dispersed carbon-coated metal particles as a seed metal catalyst Wherein said plurality of photocured patterns are provided from at least one non-aqueous photocurable composition as defined in any one of embodiments 11 to 17,

Electroplating each of the plurality of photocured patterns to form a plurality of electro-conductive patterns

≪ / RTI >

35. A method of forming a plurality of electronic devices,

Providing an article, the article comprising a substrate, wherein a plurality of electroless plated and photocured patterns, including the dispersed carbon-coated metal particles, are disposed on one or both of the support surfaces of the substrate Wherein the plurality of electroless plating and photocured patterns are provided from one or more of the non-aqueous photocurable compositions defined in any one of embodiments 1 to 17, and

Forming a plurality of electro-conductive articles from the plurality of electroless plated and photo-cured patterns, and

Forming the plurality of electro-conductive articles to form a plurality of electronic devices

≪ / RTI >

The following examples are provided to illustrate the practice of the invention and are not intended to be limiting in any way.

The following dispersant screening test was used to determine the particle dispersant useful in dispersing carbon-coated silver particles in the practice of the present invention. This test can similarly be used to determine particle dispersants useful for appropriately dispersing carbon-coated copper particles and other carbon-coated metal particles such as carbon-coated platinum particles.

Early Dispersant  Screening test (0.5 wt% carbon-coated silver particles)

This test was carried out using a small amount of carbon-coated silver particles and an excess of the tested particle dispersant ("dispersant") (weight of 10: 1 weight of particle dispersant to weight of carbon-coated silver particles) Was carried out using silver particles. By adding 2.5 g of the desired dispersant to 47.5 g of 1-methoxy-2-propanol (Sigma-Aldrich) with stirring until the dispersant is completely dissolved and forming a dispersant solution, To prepare a dispersant solution. Then, while stirring in a 20 ml glass vial, 4 g of the 5 wt% dispersant solution was coated with carbon-coated silver particles (NovaCentrix, Ag-25-ST3, Austin, Average particle diameter) of 0.02 g was added. The resulting non-aqueous composition was treated with an ultrasonic probe system (Vibra-Cell VC600, Sonics & Materials, Inc.) for two minutes at room temperature, The sedimentation was visually evaluated. This was carried out by visual observation after the suspension was allowed to stand at room temperature (20 ° C) for 24 hours. The following rating scale was used to evaluate the settling of dispersed carbon-coated silver particles:

5 = fully precipitated clear solution;

4 = almost completely precipitated light gray solution;

3 = Wide gray band on partially submerged black suspension.

2 = Narrow gray band on black suspension with fewer subsidence but less than grade "3"; And

1 = black suspension without pronounced settling.

The results of the dispersant screening test are summarized in Table I below.

[Table I]

Figure pct00003

* Weight average molecular weight as reported by the manufacturer or as determined by size exclusion chromatography

SMA = styrene-maleic anhydride copolymer

PVP = poly (vinylpyrrolidone)

Dispersants providing a settling grade of 3 or less in Table 1 were selected for a concentrated dispersant test (higher concentration of carbon-coated silver particles) as described below as an additional test.

Enriched Dispersant  The test (50 wt% carbon-coated silver particles)

This evaluation was designed to evaluate the dispersant in a more concentrated formulation with much lower dispersant to carbon-coated silver particle weight ratio (4 or 5 wt% dispersant to carbon-coated silver particle weight%). Because they are too concentrated to visually evaluate the sedimentation behavior, they were characterized only for the median particle size. The particle size distribution derived from the light scattering measurement provides a good measure of the effectiveness of the particle dispersant (dispersant) by showing the degree of agglomeration in the suspension in the non-aqueous composition.

A 5 wt% solution of the tested dispersant was prepared by adding 2.5 g of the desired dispersant to 47.5 g of 1-methoxy-2-propanol with stirring until the dispersant was completely dissolved and provided a dispersant solution. Subsequently, carbon-coated silver particles (NovaCentrix, Ag-25-ST3, 25 from Austin, Texas) were added to 8 g of a 5 wt% dispersant solution in a 60 ml bottle (LDPE from Nalgene) nm) was added. The resulting non-aqueous composition was applied to an ultrasonic probe system (Vibra-Cell VC600, Sonics & Materials, Inc.) for 2 to 4 minutes at room temperature (20 ° C) Lt; / RTI > The median particle diameter was measured by dynamic light scattering (expressed as Dv (50%)) using a Mallvern Zetasizer Nano-ZS ("ZEN" All size data were based on the volume weighted distribution and the equivalent spherical diameter model. The results are shown in Table II.

Table II

Figure pct00004

* TLTM = "Too large to measure" when using "ZEN" device

The results shown in Table II indicate that the evaluated dispersant identified in Tests 2-2 to 2-17 effectively dispersed the carbon-coated silver particles having a preferably small median diameter (0.6 탆 or less) ≪ / RTI > of the non-aqueous composition.

Non-aqueous Photocurable  Composition 21 % By weight  Dispersed carbon-coated silver particles)

A non-aqueous photocurable composition was formulated using each of the particle dispersant (dispersant) and dispersed carbon-coated silver particles shown in Table III below, and each of these non-aqueous photocurable compositions was used to form an electro- .

A 5 wt% solution of the tested dispersant was prepared by adding 2.5 g of the desired dispersant to 47.5 g of 1-methoxy-2-propanol with stirring until the dispersant was completely dissolved and provided a dispersant solution. Carbon-coated silver particles (Nova Centrix, Ag-25-ST3, 25 nm, specific mean particle diameter of 25 nm) were added to 8 g of a 5 wt% dispersant solution in a 60 ml bottle (LDPE, 8 g was added. The resulting non-aqueous composition was treated with an ultrasonic probe system (Vibra-Cell VC 600, Sonics & Materials, Inc.) at room temperature (20 ° C) for 4 minutes.

The solution of the photocurable component was a solution of 27.33 wt% epoxy acrylate CN 153 (6.02 g, Sartomer), 18.82 wt% poly (ethylene glycol) diacrylate (4.15 g, 250 M n , Sigma- Aldrich), 4.04% by weight poly (ethylene glycol) diacrylate (0.89 g, 575 M n , Sigma-Aldrich), 20.62% pentaerythritol tetraacrylate (4.55 g, 1.52 wt% triarylsulfonium salt hexafluorophosphate (0.34 g, Sigma-Aldrich) mixed in carbonate, 1.52 wt% triarylsulfonium salt hexafluoro-antimonate (0.34 g, g, Sigma-Aldrich), 4.55 weight percent free radical photoinitiator hydroxycyclohexyl phenyl ketone (1.0 g, Sigma-Aldrich), 2.32 weight percent free radical photoinitiator methyl-4'- (methylthio) N-propyophenone (0.51 g, Sigma- (0.0004 g, Sigma-Aldrich), 3.81 wt% ethyl-4- (dimethylamino) benzoate (0.84 g, Sigma-Aldrich) and 15.42 wt% of 1 -Methoxy-2-propanol (3.4 g, Sigma-Aldrich).

A sample (22.04 g) of this photocurable component solution was added to the non-aqueous composition containing carbon-coated silver particles (16 g) with stirring. Each non-aqueous photocurable composition was applied to a PRO 300D benchtop homogenizer with a rotor-stator probe operated at 100,000 rpm for 5 minutes under cooling of the non-aqueous photocurable composition (PRO Scientific Inc., (Scientific, Inc.).

Approximately 0.2 g of the suspension was removed and the median particle diameter was measured by dynamic light scattering (expressed as Dv (50%)) using a Malvern Zetasizer Nano-ZS ("ZEN") apparatus. All size data were based on the volume weighted distribution and the equivalent spherical diameter model. The results are shown in Table III.

About 2 grams of a non-aqueous photocurable composition sample (also referred to as "ink ") was taken in a narrow glass vial and the sedimentation and clarification was evaluated after 24 hours and about 7 days. A clear band of colorless fluid on top of the black non-aqueous photocurable composition produced after 24 hours indicated that the carbon-coated silver particles failed to maintain a suspended state. If the sediment is present in the bottom of the vial without purification, it represents a partially stabilized suspension of carbon-coated silver particles. The results of these evaluations are shown in Table III below.

Table III

Figure pct00005

TLTM = Too large to measure

PVP = poly (vinylpyrrolidone)

* Inv = non-aqueous photocurable composition of the present invention

** Comp = comparative non-aqueous photocurable composition

The results shown in Table III indicate that only the particle dispersants (dispersants) defined herein provide suitably small median diameters for the carbon-coated silver particles dispersed in the non-aqueous photocurable composition. In addition, the non-aqueous photocurable compositions of the present invention did not exhibit sedimentation or sedimentation during formulation and use.

Examples of Inventive Invention: Use of non-aqueous photocurable compositions to provide patterned articles

Embodiments of the present invention illustrate the use of the non-aqueous photocurable compositions of the present invention for producing precursor articles having a photocurable pattern on a suitable substrate.

A flexographic printing member was used to print the non-aqueous photocurable composition of the present invention, which was printed using a Kodak Square Spot laser technology with a resolution of 12,800 dpi, (Kodak Flexcel) NX flexographic printing plate precursor (Eastman Kodak Company) imaged using a commercially available < RTI ID = 0.0 > The flexographic printing plate precursor was exposed to UV and processed (developed) by the manufacturer using the known conditions proposed for these flexographic printing elements. The resulting flexographic printing plate was 1.14 mm thick (including PET film). The backing tape used to mount the flexographic plates to the printing form cylinders was a 20 mil (0.051 cm) thick 1120 beige tape (3M Campbell) with a Shore A of 55. The relief image design produced in the flexographic printing member included a grid pattern with fine lines having a width of 7 [mu] m at the top relief surface.

The non-aqueous photocurable composition 3-1 (Inv) of the present invention described in the above Table III was coated on a PET (poly (ethylene terephthalate) film [MELLY IGT Testing Systems Inc. (IGT Testing Systems Inc., Illinois, USA) on a bench top test press "Melinex® ST505, DuPont Teijin Films" Heights material) in flexographic mode. The Anilox roller system used to apply the non-aqueous photocurable composition to a flexographic printing member had a value of 1.3 BCMI and 1803 lpi as defined by IGT Testing Systems. The printed pattern was formed at ambient temperature using aniloxus force of 20 N, a printing force of 10 N and a printing speed of 0.20 m / s. The printed average line width on the substrate was obtained from the pattern printed on the flexographic printing element with the mentioned grid pattern.

The results of this practice were articles containing printed patterns of non-aqueous photocurable compositions on PET substrates.

Each printed pattern of the non-aqueous photocurable composition was irradiated with UV radiation at an exposure of approximately 298 mJ / cm < 2 > using a Fusion 300 WPI medium pressure mercury lamp providing a radiation wavelength of 190 to 1500 nm , And each printed pattern was photocured. The printed and photocured average line width of the cured pattern was measured in both the transmission and reflection modes using an Olympus BH-2 optical microscope.

This embodiment can be successfully used to provide precursor articles in which the non-aqueous photocurable composition has a non-photocured pattern on a suitable substrate, which can then be used to provide an intermediate article having a photocured pattern .

Inventive Examples: Use of non-aqueous photocurable compositions to provide electro-conductive articles

The above described articles containing photocured patterns can be used as intermediate articles for further work. Specifically, the above intermediate product was immersed in a beaker containing Enplate 占 Cu-406 electroless plating solution (Enthone) at 35 占 폚 for 10 minutes, rinsed with distilled water, and dried with nitrogen to prepare electroless copper plating To form an article having an electro-conductive pattern disposed on the PET substrate.

While the invention has been described in detail with reference to certain preferred embodiments, it will be understood that variations and modifications can be effected within the spirit and scope of the invention.

Claims (35)

  1. A non-aqueous composition comprising carbon-coated metal particles dispersed in an organic diluent in an amount of at least 10% by weight based on the total weight of the non-aqueous composition,
    The dispersed carbon-coated metal particles are dispersed in a particle dispersing agent having a median diameter of 0.6 占 퐉 or less and a weight average molecular weight (Mw) of 2,000 or more and 100,000 or less and containing nitrogen-
    The intermediate diameter is determined by a dynamic light scattering method,
    The non-aqueous composition, when containing 25 wt% or less of the dispersed carbon-coated metal particles, exhibits visual settling when subjected to a settling test at < RTI ID = 0.0 > 20 C & Non-aqueous composition.
  2. The method according to claim 1,
    A non-aqueous composition comprising dispersed carbon-coated silver particles or dispersed carbon-coated copper particles, or a mixture of dispersed carbon-coated silver particles and dispersed carbon-coated copper particles.
  3. The method according to claim 1,
    Wherein the weight ratio of the particle dispersant to the dispersed carbon-coated metal particles is at least 1: 100 to 30: 100 or less.
  4. The method according to claim 1,
    Wherein the dispersed carbon-coated metal particles are present in an amount of at least 15 weight percent to 70 weight percent, based on the total weight of the non-aqueous composition.
  5. The method according to claim 1,
    Wherein the particulate dispersant has an M w of at least 2,000 to less than or equal to 50,000.
  6. The method according to claim 1,
    Further comprising a dispersed carbon black in an amount of up to 20 weight percent based on the total weight of the non-aqueous composition.
  7. The method according to claim 1,
    Wherein the particle dispersant is an organic polymer comprising an ester unit.
  8. The method according to claim 1,
    Wherein the particle dispersant is an organic polymer comprising units selected from at least one of the following classes (i) to (iv): non-aqueous composition:
    (i) pyridine units;
    (ii) an immigration unit;
    (iii) imide units; And
    (iv) amine units.
  9. The method according to claim 1,
    The dispersed carbon-coated metal particles are dispersed carbon-coated silver particles present in a concentration of at least 15 wt.% To 60 wt.%, Based on the total weight of the non-aqueous composition,
    Wherein the dispersed carbon-coated silver particles have a median diameter of less than 0.5 [mu] m as measured using dynamic light scattering.
  10. The method according to claim 1,
    Wherein the organic diluent is selected from the group consisting of 2-ethoxyethanol, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 1-methoxy- Which is an organic solvent medium comprising at least one of heptanone, 2-heptanone, cyclopentanone, cyclohexanone, dimethyl carbonate, 2-ethoxyethyl acetate, N-butyl butyrate and methyl lactate, Composition.
  11. The method according to claim 1,
    A non-aqueous photocurable composition further comprising a photocurable component and, if desired, an ultraviolet photoinitiator.
  12. 12. The method of claim 11,
    Wherein the photocurable component is a UV-curable component.
  13. 12. The method of claim 11,
    Wherein the photo-curable component is an acid-catalyzed photo-curable component, and wherein the non-aqueous composition further comprises a photoacid generator.
  14. 14. The method of claim 13,
    Wherein the photocurable component is a photopolymerizable epoxy material.
  15. 15. The method of claim 14,
    The photocurable component is a photopolymerizable epoxy material having at least two polymerizable epoxy groups per molecule,
    Wherein the photoacid generator is an iodonium or a sulfonium compound.
  16. 12. The method of claim 11,
    Wherein the photocurable component is a free radical photocurable component and the non-aqueous composition further comprises a free radical photoinitiator.
  17. 17. The method of claim 16,
    Wherein the photocurable component comprises an acrylate.
  18. An article comprising a substrate and having a dry layer or a dry pattern of the non-aqueous composition of claim 1 or 11 on one or both of the support surfaces of the substrate.
  19. 19. The method of claim 18,
    Wherein the substrate is a continuous polymer web.
  20. 19. The method of claim 18,
    Wherein the substrate comprises metal, glass, paperstock or ceramic.
  21. 19. The method of claim 18,
    Wherein the substrate is a continuous web comprising a polyester.
  22. 19. The method of claim 18,
    Wherein the substrate is a continuous polymer web and the non-aqueous composition is disposed in multiple patterns on both support surfaces of the substrate.
  23. 1. An article comprising a substrate and having on the one or both sides of the substrate a dried layer of a photocured composition derived from the non-aqueous composition of claim 11 or a drying pattern.
  24. 24. The method of claim 23,
    Wherein the substrate is a continuous polymer web.
  25. 24. The method of claim 23,
    Wherein the photocured composition is disposed as one or more patterns on one or both of the support surfaces of the substrate.
  26. 24. The method of claim 23,
    Wherein the substrate is a continuous polymer web and the photocured composition is disposed in a plurality of patterns on both support surfaces of the substrate.
  27. 24. The method of claim 23,
    Wherein the substrate is a continuous web of polyester.
  28. CLAIMS What is claimed is: 1. A method of providing a precursor article,
    Providing a continuous web of transparent substrate, and
    Forming at least one photocurable pattern from the non-aqueous photocurable composition of claim 11 on at least one portion of at least one support surface of the continuous web,
    ≪ / RTI >
  29. 29. The method of claim 28,
    Curing the at least one photocurable pattern to form one or more photocured patterns on at least a portion of the continuous web, wherein each of the one or more photocured patterns comprises a seed metal catalyst site site, the dispersed carbon-coated metal particles, and
    Electroless plating each of the one or more photocured patterns on at least one portion of the continuous web with an electro-conductive metal,
    ≪ / RTI >
  30. 30. The method of claim 29,
    Forming a plurality of features on the plurality of portions of the continuous web, photocuring and electroless plating, wherein the plurality of portions comprise the same or different non-aqueous photocurable compositions, The steps, which are different
    ≪ / RTI >
  31. 29. The method of claim 28,
    A method of providing a plurality of precursor articles,
    Forming a plurality of photocurable patterns on a plurality of portions on one or both of the support surfaces of the continuous web by applying the non-aqueous photocurable composition to the plurality of portions using one or more flexographic printing elements,
    Advancing the continuous web comprising the plurality of photocurable patterns proximate the exposure radiation, thereby forming a plurality of photocured patterns; and
    Winding the continuous web including the plurality of photocured patterns
    ≪ / RTI >
  32. 29. The method of claim 28,
    Wherein the substrate is a continuous polyester web.
  33. 33. The method of claim 32,
    Wherein the substrate is a continuous polyester web comprising poly (ethylene terephthalate).
  34. A method of forming a plurality of electro-conductive patterns on a substrate,
    Providing a precursor article, wherein the precursor article comprises a substrate, and on one or both of the support surfaces of the substrate, a plurality of photocured patterns comprising the dispersed carbon-coated metal particles as a seed metal catalyst And wherein the plurality of photocured patterns are provided from one or more of the non-aqueous photocurable compositions defined in claim 11,
    Electroplating each of the plurality of photocured patterns to form a plurality of electro-conductive patterns
    ≪ / RTI >
  35. 1. A method of forming a plurality of electronic devices,
    Providing an article, the article comprising a substrate, wherein a plurality of electroless plated and photocured patterns, including the dispersed carbon-coated metal particles, are disposed on one or both of the support surfaces of the substrate Wherein the plurality of electroless plating and photocured patterns are provided from one or more of the non-aqueous photocurable compositions defined in claim 1, and
    Forming a plurality of electro-conductive articles from the plurality of electroless plated and photo-cured patterns, and
    Forming the plurality of electro-conductive articles to form a plurality of electronic devices
    ≪ / RTI >
KR1020177013010A 2014-10-15 2015-10-01 Dispersed carbon-coated metal particles, articles, and uses KR20170070167A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
US14/514,514 2014-10-15
US14/514,492 US9434852B2 (en) 2014-10-15 2014-10-15 Photocurable compositions with dispersed carbon-coated metal particles
US14/514,492 2014-10-15
US14/514,500 US9650533B2 (en) 2014-10-15 2014-10-15 Articles containing carbon-coated metal particles
US14/514,514 US9447501B2 (en) 2014-10-15 2014-10-15 Forming articles and devices with carbon-coated metal particles
US14/514,463 2014-10-15
US14/514,463 US9359517B2 (en) 2014-10-15 2014-10-15 Non-aqueous compositions of dispersed carbon-coated metal particles
US14/514,500 2014-10-15
PCT/US2015/053428 WO2016060856A1 (en) 2014-10-15 2015-10-01 Dispersed carbon-coated metal particles, articles and uses

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