CN106795384B

CN106795384B - Dispersed carbon-coated metal particles, articles and uses

Info

Publication number: CN106795384B
Application number: CN201580054980.6A
Authority: CN
Inventors: 凯伦·M·柯西达; 盖瑞·L·史雷特; 玛莉·克里斯廷·布理克; 克里斯廷·乔安·蓝卓-考特兰; 詹姆斯·阿尔贝特·雷切克
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 2014-10-15
Filing date: 2015-10-01
Publication date: 2020-10-30
Anticipated expiration: 2035-10-01
Also published as: TWI707011B; KR20170070167A; TW201631055A; WO2016060856A1; CN106795384A

Abstract

The present invention relates to a non-aqueous composition containing dispersed carbon-coated metal particles in an organic diluent in an amount of at least 10 wt.%. The dispersed carbon-coated metal particles have a median diameter equal to or less than 0.6 [ mu ] M and use a catalyst having a weight average molecular weight (M) of at least 2,000 and up to and including 100,000_w) And a particulate dispersant comprising nitrogen-containing units. The median diameter of the dispersed particles was measured using dynamic light scattering. Further, when the non-aqueous composition contains up to and including 25 wt.% of the dispersed carbon-coated metal particles, it does not appear visually to settle at 20 ℃ for at least 24 hoursAnd (4) settling. Such non-aqueous compositions may include photocurable components and are suitable for use in preparing photocurable and photocurable conductive patterns and layers in various articles, including touch screen devices having touch screen displays.

Description

Dispersed carbon-coated metal particles, articles and uses

Technical Field

The present invention relates to non-aqueous compositions containing dispersed carbon-coated metal particles and a uniquely selected particle dispersant. The invention also relates to non-aqueous photocurable compositions containing these dispersed carbon-coated metal particles and a particle dispersant. These non-aqueous photocurable compositions can be used to provide seed metal catalysts for electroless plating processes designed to provide patterns of conductive materials.

Background

Rapid progress has been made in various electronic devices, particularly display devices for various communication, financial and archival purposes. Conductive films are necessary for uses such as touch screen panels, electrochromic devices, light emitting diodes, field effect transistors, and liquid crystal displays, and efforts are being made in the industry to improve the properties of these conductive films.

It is particularly desirable to provide touch screen displays and devices that incorporate improved conductive film assemblies. Currently, touch screen displays use Indium Tin Oxide (ITO) coatings to create an array of capacitive regions for distinguishing multiple contacts. ITO coatings have a number of disadvantages. Indium is an expensive rare earth metal and is available in limited quantities from very few sources throughout the world. ITO conductivity is relatively low and requires short line lengths to achieve adequate reaction rates. Touch screens for large displays are broken into smaller segments to reduce wire length, achieving acceptable resistance. These smaller segments require additional drive and sense electronics. In addition, ITO is a ceramic material that is not easily bent or flexed, and requires vacuum deposition using high processing temperatures to fabricate the conductive layer.

Silver is an ideal conductor with a conductivity 50 to 100 times greater than ITO. Silver is used in a variety of commercial applications and is available from many sources. The use of silver as a conductive source to make conductive film assemblies is highly desirable, but considerable development is required to obtain optimum characteristics.

The production of touch screen sensors and other transparent conductive articles on flexible and transparent substrates using an "additive process" of depositing conductive patterns that provide the functionality of the sensor in a roll-to-roll production method has been the target of recent developments in this industry. The ability to produce a touch screen sensor that has both the desired electrical properties and the appropriate optical properties (transmissivity) in the visible portion (touch zone) of the touch screen sensor is particularly important. To achieve the desired electrical and optical properties, it is strongly desired that the average line width of the conductive lines in the conductive grid is less than 10 μm.

The flexible and transparent substrates used in these processes should be optically clear (high integrated transmission) and colorless and exhibit low haze. The application of conductive patterns using additive processes, such as flexographic printing of conductive materials or seed metal compositions, requires that the flexible and transparent substrate have a suitable surface energy and roughness that is consistent with the dimensions of the fine features (e.g., fine lines) intended to be applied. Considerable effort has been made in the electronics industry to achieve these desirable characteristics.

WO 2013/063188 (petvaich et al) describes a method of printing a first pattern on a first side of a dielectric substrate by using a flexographic printing process with at least a first master plate and a first ink ("printable composition"); and curing the printed dielectric article to produce a mutual capacitance type touch sensor comprising a dielectric substrate. A second ink may be similarly applied and cured to form a second pattern on the second surface of the substrate. Both patterns may contain a seed metal catalyst that may be followed by electroless plating with a conductive material. The resulting dielectric article is described as having a thickness of 1 μm to 1mm and a preferred surface energy of 20 dynes/cm to 90 dynes/cm. The inks used in these processes are generally non-aqueous and contain various photocurable components and dispersed metal particles.

It is known to use various materials to disperse metal particles in aqueous or non-aqueous compositions. For example, U.S. patent 8,506,849 (Li) et al) describes curable conductive inks containing metal nanoparticles and different polymeric dispersants. Magnetic ink jet printing inks comprising dispersed magnetic nanoparticles and polymeric dispersants are described in U.S. patent 8,597,420 (Iftime et al). In other techniques, the outer surface of the metal nanoparticles is modified to incorporate a hydrophobic tail to enhance dispersibility in organic solvents for inkjet printing, as described, for example, in U.S. patent application publication 2008/0090082 (sink, et al).

There is a need for improved printable compositions (also referred to as inks) comprising seed metal catalysts for electroless plating. It is desirable to apply (e.g., print) these improved compositions as a pattern of conductive lines with the coloration needed for optical effects, stability for successful fabrication, and electroless printing performance.

However, the resulting article with the pattern of conductive lines must be highly transparent and invisible when viewed under lighting conditions where the reflected lines are visible. For this purpose, it has been determined to treat the outer surface of the conductive wire (e.g., consisting of copper) with a blackening agent to reduce the reflectivity of the metal wire.

However, in some display devices containing capacitive touch screens that are provided with conductive patterns on both sides of a transparent substrate, the top surfaces of the "blackened" conductive threads may not be apparent, but the bottom surfaces are visible and reflected through the transparent substrate.

To maintain a thin line in the conductive pattern, a thin seed metal catalyst ink layer needs to be applied, i.e., only to an extent sufficient to cause electroless plating. If the ink lay-up is too large, the ink will spread and provide wider lines and thereby reduce the transparency of the article. In addition, these thicker threads are more visible and less durable in the final article. Thus, thinner lines are required in the pattern, but this makes the electroless plated metal more visible in the lines through the transparent substrate.

Useful seed metal catalysts for use in these materials comprise particles of a metal, such as silver or copper. Sufficient amounts of these metal particles can comprise from 10% to 50% of the total weight of the ink or printable composition for the desired properties. These amounts of metal particles are generally reflective and are readily visible through the transparent substrate, thereby increasing the visibility of the resulting conductive pattern. One attempt to reduce the reflectivity of the seed metal catalyst and the electroless plated metal is to add a sufficient amount of colorant (such as carbon black) to the printable composition (ink) such that the seed metal catalyst is not visible. However, it is difficult to add sufficient amounts of these colorants to the ink without undesirably increasing the viscosity and coalescence (aggregation or coalescence) of the metal particles in the ink.

Dispersants (or dispersing aids) are typically used to maintain the particulate material in suspension for as long as possible for various purposes. However, known dispersants have not been readily available for use with specific particles to minimize sedimentation and interparticle interactions that may undesirably increase the viscosity of a given composition. In general, a great deal of research and engineering is required in various industries to find the optimal dispersant for selected particulate materials, whether metallic, organic or inorganic. This is especially true for seed metal catalysts designed for electroless plating operations.

Accordingly, there is a need to provide a seed metal catalyst printable composition (ink) with reduced reflectivity, small uniform particle size distribution with limited particle agglomeration, and suitable viscosity for applying fine line patterns using, for example, flexography.

Disclosure of Invention

To solve the above problems, the present invention provides a non-aqueous composition containing dispersed carbon-coated metal particles having a median diameter equal to or less than 0.6 μm in an organic diluent in an amount of at least 10 wt.%, based on the total weight of the non-aqueous compositionAnd is prepared by using a monomer having a weight average molecular weight (M) of at least 2,000 and up to and including 100,000_w) And containing a dispersion of particulate dispersant comprising nitrogen-containing units, said median diameter being measured using dynamic light scattering,

wherein, when the non-aqueous composition contains up to and 25 wt% dispersed carbon-coated metal particles, it exhibits no visual sedimentation when subjected to a sedimentation test at 20 ℃ for at least 24 hours.

In some embodiments, these nonaqueous compositions are nonaqueous photocurable compositions, each of which comprises:

dispersed carbon-coated metal particles present in an amount of at least 10 wt% based on the total weight of the non-aqueous photocurable composition, and the dispersed carbon-coated metal particles have a median diameter equal to or less than 0.6 μ M and are of a weight average molecular weight (M) of at least 2,000 and up to and including 100,000_w) And containing a dispersion of particulate dispersant comprising nitrogen-containing units, said median diameter being measured using dynamic light scattering,

an organic diluent, and a water-soluble organic solvent,

a UV curable component, and

optionally a UV photoinitiator(s) is (are) present,

wherein, when the non-aqueous photocurable composition contains up to and including 25% by weight of the dispersed carbon-coated metal particles, it exhibits no visual sedimentation when subjected to a sedimentation test at 20 ℃ for at least 24 hours.

The present invention provides many of the advantages of the uniquely dispersed carbon-coated metal particles described herein. In particular, these carbon-coated metal particles can be readily dispersed in higher concentrations (e.g., at least 10 weight percent) in non-aqueous compositions by using uniquely selected particle dispersants.

The reflectivity of the carbon-coated metal particles can also be reduced when the carbon-coated metal particles are incorporated into a pattern of conductive lines formed by an electroless plating process.

The use of the particulate dispersant according to the present invention can minimize the interparticle interactions that would increase the viscosity of the non-aqueous composition. By dispersing the carbon-coated metal particles more thoroughly in particular, higher amounts of these particles can be "loaded" into the non-aqueous composition without an undesirable increase in viscosity.

The particulate dispersants used in accordance with the present invention also promote the disintegration and stabilization of smaller carbon-coated metal particles that do not readily settle. This is a serious problem for metal particles such as silver nanoparticles because the rate of sedimentation depends on the metal particle size and particle density (silver metal is 10.5 g/cm) according to the sedimentation velocity derived from Stokes' law as shown below³)：

Where Vs is the particle settling velocity (m/sec) (vertically downwards, if p)_Granules>ρ_{Fluid, especially for a motor vehicle}(ii) a Vertically upwards, if p_Granules<ρ_{Fluid, especially for a motor vehicle}) G is gravitational acceleration (m/sec)²)，ρ_GranulesIs the mass density (kg/m) of the particles³)，ρ_{Fluid, especially for a motor vehicle}Is fluid mass density (kg/m)³) μ is the dynamic viscosity (kg/m s) and R is the particle radius (m). Thus, the settling rate of the metal particles can be seen as a function of R²But increases and therefore varies greatly with particle size.

It has also been observed that the non-aqueous compositions of the present invention, including non-aqueous photocurable compositions, exhibit improved shelf life without settling between printing jobs or in areas of the printing system that are subject to little agitation.

When the non-aqueous composition of the present invention is "printed" using a suitable printing apparatus (e.g., a flexographic printing member) as described below, the resulting image exhibits improved uniformity of particle distribution in the printed line. This advantage enables better coverage of a given printed area with a smaller amount of expensive carbon-coated metal particles, and improved uniformity provides the desired, more opaque dark lines. In the case where the coverage uniformity of the smaller carbon-coated metal particles is larger, the electroless plating activity is improved as compared with the case where larger coalesced metal particles are used.

Detailed Description

The following discussion is directed to various embodiments of the invention, and the disclosed embodiments should not be interpreted, or otherwise regarded, as limiting the scope of the invention as claimed below, when some embodiments may be more desirable for a particular use. Furthermore, it should be apparent to one skilled in the art that the following disclosure has broader application than what is explicitly described and discussed in any of the embodiments.

Definition of

As used herein to define the various components of both the non-aqueous composition and the non-aqueous photocurable composition, the singular forms "a", "an" and "the" are intended to include one or more of the components (i.e., including the plural referents), unless the context clearly dictates otherwise.

Terms not explicitly defined in the present application should be understood to have meanings customary to or commonly accepted by those skilled in the art. A term definition may be looked up from a standard printing dictionary if the term is interpreted such that the term has no or substantially no meaning in its context.

Unless expressly indicated otherwise, the use of numerical values in the various ranges specified herein is understood to be approximate, as if the minimum and maximum values in the ranges were preceded by the word "about". As such, slight variations above and below the stated ranges can be used to achieve substantially the same results as values in the ranges. Further, the disclosure of these ranges is intended as a continuous range encompassing every value between the minimum and maximum values.

The median particle diameter [ Dv (50%) ] was measured using dynamic light scattering. This method may be performed, for example, using malverstath philosophy Nano zs (Malvern zetasizer Nano zs), which is commercially available from Malvern Instruments Ltd. Instructions for use of this apparatus may be obtained with the apparatus.

Unless otherwise indicated, the terms "particulate dispersant", "dispersant" and "dispersing aid" mean equivalents.

The terms "epoxy monomer", "unsaturated monomer", "functional oligomer", "metal particle" and "crosslinker" are used herein in their usual meaning and are well known to the skilled artisan.

As used herein, all molecular weights are weight average molecular weights (M) that can be measured using known procedures and equipment_w) Provided that the values are not already known in the literature. For example, M can be measured using Size Exclusion Chromatography (SEC)_wAnd values are expressed herein as poly (methyl methacrylate) equivalent weight.

As used herein, the term "photocured" means that functional oligomers and monomers or even polymers polymerize to form a crosslinked polymer network in response to irradiation of these materials (e.g., irradiation with Ultraviolet (UV), visible or infrared radiation of appropriate wavelength). The photocuring may be carried out in the presence of a crosslinking agent.

The term "photocurable" is used to define a material (or component) that will polymerize or crosslink upon irradiation with suitable radiation (e.g., irradiation with radiation such as Ultraviolet (UV), visible, or infrared radiation in a suitable environment).

The term "photocurable component" refers to an organic chemical compound (polymeric or non-polymeric) that can participate in a photocurable reaction. These compounds may be a single reactant that provides photocuring upon irradiation, or they may be combined with other coreactants (such as photoinitiators or acid catalysts) to provide photocuring upon irradiation.

Unless otherwise indicated, the term "non-aqueous photocurable composition" refers to embodiments of the present invention that include one or more components that initiate or promote photocuring, which can be used to carry out the various methods described below and can be used to provide the articles described below. These non-aqueous photocurable compositions have predominantly organic solvents or liquid organic components and have less than 5% or even less than 1% by weight of water based on the total non-aqueous photocurable composition weight.

The term "polymerization" is used herein to refer to the formation of many smaller molecules, such as monomer combinations, into a large molecule, or polymer, e.g., by covalent bonding. The monomers may be combined to form only linear macromolecules or they may be combined 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 in the presence of a free radical polymerizable material and a suitable free radical generating photoinitiator. In some useful embodiments of the invention, both acid catalyzed polymerization and free radical polymerization may be employed.

The average dry thickness of a layer described herein can be determined by averaging at least 2 individual measurements taken for the dry layer, for example using electron microscopy.

Similarly, the average dry thickness or dry width of the lines, grid lines, or other pattern features described herein can be the average of at least 2 individual measurements, for example, using electron microscopy.

"actinic radiation" is used to refer to any electromagnetic radiation capable of producing photocuring or photopolymerization according to the invention and having a wavelength of at least 200nm and up to and including 1400nm, and typically at least 200nm and up to and including 750nm, or even at least 300nm and up to and including 700 nm. The term "exposure radiation" also refers to these actinic radiations.

The term "UV radiation" is used herein to refer to radiation having a wavelength (λ) of at least 200nm and up to and including 400nm_max) Of electromagnetic radiation.

Use of

Photocuring is possible in the practice of the present invention even when the non-aqueous photocurable composition contains a substantial amount of carbon-coated metal particles as described herein, and the non-aqueous photocurable composition can be used in a variety of techniques, such as graphic art imaging (e.g., as a photocurable ink for ink spray, or other imaging processes in color proofing systems), electronic conformal coatings, coated abrasives, magnetic media, and photocurable compositions, as well as in electroless plating processes as described herein.

In addition, the non-aqueous composition containing the dispersion of carbon-coated metal particles of the present invention can be advantageously used for producing electronic materials, magnetic recording materials, optical materials, gas sensing materials, catalytic materials, sintered materials, light reflecting films, light absorbing films or coatings, intermediate layers in functional components, and other materials that can be readily apparent to those skilled in the art with reference to 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 nonaqueous photocurable compositions of the present invention are particularly useful as nonaqueous photocurable compositions each containing at least one photocurable component. These non-aqueous photocurable compositions can be photocured in any useful form, for example, in coatings on various substrates, fibers, patterns on various substrates, photocurable forms, and molded articles and adhesives.

More specifically, the non-aqueous photocurable composition may be used in a variety of articles or devices for a variety of purposes requiring efficient photocuring. For example, these non-aqueous photocurable compositions may be designed to be sensitive to a selected wavelength of radiation and may be used, for example, to provide a seed metal catalyst which may then be further processed, for example, using an electroless plating procedure, to form a pattern of conductive metal patterns. These conductive metal patterns can be designed and incorporated into a variety of devices, including but not limited to touch screens or other display devices that can be used in many consumer, industrial, and commercial products.

Touch screen technology can include different touch sensor configurations, including capacitive and resistive touch sensors. The resistive touch sensor includes a plurality of layers facing each other with a gap between adjacent layers that can be maintained by spacers formed during processing. Resistive touch screen panels can comprise several layers, including two thin, metallic, conductive layers separated by a gap that can be established by a spacer. When an object such as a stylus, palm or fingertip presses down on a point on the outer surface of the panel, the two metal layers contact and form a connection causing a change in current. This touch event is sent to the controller for further processing.

Capacitive touch sensors may be used in electronic devices having features that are sensitive to touch. These electronic devices may include, but are not limited to, televisions, monitors, automated transfer machines, and projectors that may be adapted to display images including text, graphics, video images, movies, still images, and presentations. Image devices that may be used for these display devices may include cathode ray tubes (CRS), projectors, flat panel Liquid Crystal Displays (LCD), LED systems, OLED systems, plasma systems, electroluminescent displays (ECD), and Field Emission Displays (FED). For example, the present invention can be used to fabricate capacitive touch sensors that can be incorporated into electronic devices having touch-sensitive features to provide computing devices, computer displays, portable media players (including e-readers), mobile phones, and other portable communication devices.

Using the present invention, it is possible to implement systems and methods for manufacturing flexible and optically adaptive touch sensors in a high volume roll-to-roll manufacturing process that can create micro-conductive features in a single pass. The non-aqueous photocurable composition may be used in these systems and methods with a plurality of printing elements (e.g., a plurality of flexographic printing plates) to form a plurality of high resolution conductive images from a predetermined design of patterns provided in those plurality of printing elements. A plurality of patterns may be printed on one or both sides of the transparent substrate as described in more detail below. 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 or both sides of the transparent substrate, which may be further processed, for example using electroless metal plating, to provide a pattern of conductive metal.

Non-aqueous compositions

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

(a) Carbon-coated metal particles

Typically, only one type (composition) of carbon-coated metal particles is used in each non-aqueous composition, but mixtures of different types of carbon-coated metal particles from the same or different classes of metals that do not interfere with each other may also be included. Generally, each carbon-coated metal particle has a net neutral charge. Generally, the carbon-coated particles are non-magnetic, meaning that they do not exhibit significant magnetic properties, and thus, the non-aqueous compositions of the present invention are also generally non-magnetic.

Useful carbon-coated metal particles can include metal particles that are at least partially coated with carbon. The metal particles are composed of one or more metals (i.e., pure metals or metal alloys) selected from one or more classes of noble metals, semi-noble 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-noble 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. Noble metals such as silver, palladium and platinum are particularly useful, and semi-noble metals nickel and copper are also particularly useful. Among the group IV metal classes, tin is particularly useful. In many embodiments, pure silver or copper is used in the non-aqueous photocurable composition. Thus, in practicing the present invention, the term "metal" is intended to have the same meaning as "metallic", but the terms "metal" and "metallic" are not intended to include metal salts, metal oxides, and metal hydrides.

The metal particles comprising the metal are typically at least partially surface coated with carbon. The carbon may be amorphous, sp2 hybrid, or graphene-like in nature.

Thus, particularly useful materials for use in the non-aqueous composition are carbon-coated silver particles, carbon-coated copper particles, or (in some embodiments) a mixture of carbon-coated silver particles and carbon-coated copper particles, all dispersed in an organic solvent medium using one or more particle dispersants as described below.

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

These carbon-coated metal particles may be present in any geometric shape, including, but not limited to, spheres, rods, prisms, cubes, cones, pyramids, wires, flakes, platelets, and combinations thereof, and may be uniform or non-uniform in shape and size. The best advantages of the invention can be achieved using carbon-coated metal particles in the form of individual particles or agglomerates of a few particles.

The one or more particulate dispersants in the non-aqueous composition each serve to disperse the carbon-coated metal particles to prevent them from agglomerating or coalescing in a non-aqueous composition (as described below) that also contains an organic diluent. These particulate dispersants are carefully selected so that the present invention can provide the desired advantages. First, each particulate dispersant has a weight average molecular weight (M) of at least 2,000 and up to and including 100,000 or, more specifically, up to and including 50,000_w). The most useful particulate dispersants each have a M of at least 3,000 and up to and including 30,000_w。

In addition, each useful particulate dispersant comprises two or more nitrogen-containing units, such as amides (carboxylic, sulfonic, sulfinic, phosphoric, phosphonic, and many other acid that can form amides), amines (primary, secondary, tertiary), amine oxides, amidines (amidoimines), azos, carbamates (urethanes), carbodiimides, diazos (diazos), diazos (diazonium), enamines, guanidines (imines of urea), aromatic heterocycles (pyridine, pyrimidine, pyridazine, pyrazine, pyrrole, imidazole, pyrazole, oxazole (ozazole), isoxazole, thiazole, indole, indolizine, quinoline, isoquinoline, hydrazine, hydrazone, hydroxamic acid, imides, imine (Schiff) base), nitrates (esters of nitric acid), nitriles (cyanides), nitrites (esters of nitrous acid), nitro/nitrosos (nitrosobenzenes, nitrobenzene, nitromethane, nitro (nitro) amines, amines (primary, secondary, tertiary), amines, amidines (amidoimines), azos (amides), hydrazines (esters of many other acid that can form, N-nitrosoureas), nitrones (imine N-oxides), oximes (imines of hydroxylamines) or ureas (diamides of formic acid, such as N-methylurea, N-methylthiourea biuret allophanate, urazole) units or fragments. Some areParticularly useful nitrogen-containing units are amide, amine and imine units. Generally, each particulate dispersant has a plurality of nitrogen-containing units (since it is at least oligomeric) and has an M of at least 2,000_w. These nitrogen-containing units provide a strong anchoring of the particulate dispersant to the carbon-coated metal particles.

Each particulate dispersant also contains functional groups that are compatible with the organic polymer and 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.

Some particularly useful particulate dispersants are organic polymers comprising ester units, such as those found in polyesters or (meth) acrylic polymers (homopolymers and copolymers).

In other embodiments, the particulate dispersant is an organic polymer containing units selected from at least one (one or more) of the following classes (i) to (iv):

(i) pyridine units as in vinyl pyridine;

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

(iii) imide units [ -C (═ O) -NH-C (═ O) -units ]; and

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

Mixtures of these particulate dispersants from the same or different classes of materials may be used if desired.

Some examples of useful particulate dispersants having these characteristics are the following materials, including some commercially available products:

copolymers containing polyethyleneimine segments, e.g. sertraline

35000 and

39000 (Lubrizol);

is in a block form,Copolymers containing ester and amine units in the form of branched, hyperbranched and comb-like structures, e.g. Disbeck

-2155、

-2152、

-2013、

9077 (BYK/Altana) and efocara

PX 4731 and

PX 4732(BASF)；

acrylic block copolymers containing aliphatic or aromatic amine units, e.g.

PX 4701 (BASF); and

copolymers containing aliphatic or aromatic amine units, e.g.

2118 (BYK/Altana) and Terninic

150R(BASF)。

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

In addition to this, the amount of carbon-coated metal particles in each non-aqueous composition is at least 10 wt. -% or at least 15 wt. -% and up to and including 60 wt. -% or even up to and including 70 wt. -%, based on the total weight of the non-aqueous composition (comprising the organic diluent). Using this information, one skilled in the art can then determine the available and optimal amount of the selected particle dispersant for the selected carbon-coated metal particles.

In some particularly useful embodiments, the non-aqueous composition comprises dispersed carbon-coated silver particles present at a concentration of at least 15 weight% and up to and including 60 weight%, based on the total weight of the non-aqueous composition, and the dispersed carbon-coated silver particles have a median diameter of less than 0.5 μm, measured as described above.

Nonaqueous compositions, including the nonaqueous photocurable compositions described below, also typically comprise an organic diluent, which acts as a nonaqueous (organic) solvent or solvent combination, in which the components of the nonaqueous composition are dissolved or dispersed.

In some embodiments of the invention, the organic diluent is an organic solvent medium comprising one or more inert organic solvents such as: 2-ethoxyethanol, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 1-methoxy-2-propanol (Dowanol PM), 4-heptanone, 3-heptanone, 2-heptanone, cyclopentanone, cyclohexanone, diethyl carbonate, 2-ethoxyethyl acetate, N-butyl butyrate, 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 can be readily determined by one of ordinary skill in the art using the teachings provided herein. By "inert" is meant that the organic solvent does not significantly participate in any chemical reaction.

When one or more photocurable components (as described below) are present as liquid organic compounds, it may be unnecessary that these one or more photocurable components act as organic diluents and that the respective inert organic solvents. In these cases, the organic diluent may be considered a "reactive" diluent. Alternatively, one or more reactive diluents may be used in combination with one or more inert organic solvents (as described above) to form suitable organic diluents.

The amount of organic diluent can be judiciously selected depending on the particular material used, the apparatus used to apply the resulting non-aqueous composition, and the properties desired, including compositional uniformity.

For example, the organic diluent may provide at least 10 wt% and up to and including 90 wt% or at least 20 wt% and up to and including 80 wt%, based on the total weight of the non-aqueous composition. The organic diluent typically comprises little or no water, meaning that water is present in an amount of less than 5 wt% or even less than 1 wt%, based on the total weight of the non-aqueous composition.

While not a requirement of the nonaqueous composition, an optional and desirable component is carbon black in an amount of at least 0.5 weight percent and up to and including 20 weight percent, or typically at least 1 weight percent and up to and including 10 weight percent, based on the total weight of the nonaqueous composition.

As mentioned above, the non-aqueous photocurable composition of the present invention may be a non-aqueous photocurable composition further containing one or more photocurable components as described hereinafter. The amounts of these components can also be determined using the teachings provided below, but generally, only one or more photocurable components are present in an amount that provides sufficient photocuring in the particular application.

Some particularly useful non-aqueous photocurable compositions of the present invention comprise:

at least 10 wt% or even at least 15 wt% and up to and containing 60 wt% or up to and containing 70 wt% of dispersed carbon-coated metal particles, all by weight of the total non-aqueous photocurable composition, and the dispersed carbon-coated metal particles have a median diameter equal to or less than 0.6 μ M and pass a M of at least 2,000 and up to and containing 100,000_wAnd containing a dispersion of particulate dispersant comprising nitrogen-containing units, said median diameter being determined using dynamic light scattering, all as hereinbefore described,

an organic diluent (as described above),

a UV curable component (as described below), and

optionally a UV photoinitiator (as described below),

wherein, when the non-aqueous photocurable composition contains up to and including 25% by weight of the dispersed carbon-coated metal particles, it exhibits no visual sedimentation when subjected to a sedimentation test at 20 ℃ for at least 24 hours (the test being further defined above).

In these non-aqueous photocurable compositions, the dispersed carbon-coated metal particles can comprise dispersed carbon-coated silver particles or dispersed carbon-coated copper particles or a mixture of both dispersed carbon-coated silver particles and dispersed carbon-coated copper particles, all of which are described below.

In addition, the weight ratio of particulate dispersant to dispersed carbon-coated metal particles in these non-aqueous photocurable compositions can be at least 1:100 and up to and including 30: 100.

In some particularly useful non-aqueous photocurable compositions, the dispersed carbon-coated metal particles can be present in an amount of at least 15 weight% and up to and including 60 weight%, based on the total weight of the non-aqueous photocurable composition, and the dispersed carbon-coated metal particles (such as carbon-coated silver particles or carbon-coated copper particles) have a median diameter of less than 0.5 μm, as measured using dynamic light scattering as described above.

The non-aqueous composition of the present invention may be prepared by suitably dispersing the carbon-coated metal particles with one or more of the described particle dispersants using a suitable dispersing device. The two essential components may be mixed or dispersed in an organic diluent (e.g., an organic solvent medium) (as described above) that is effective to disperse the carbon-coated metal particles.

Methods for dispersing the carbon-coated metal particles include, but are not limited to, ball milling, media milling, magnetic stirring, high speed homogenization, high pressure homogenization, shaker shaking, and sonication. Ultrasonic treatment is particularly useful for dispersing carbon-coated metal particles with a particle dispersant contained in an organic diluent.

Media milling techniques may also be used to break up solid particles, such as carbon-coated metal particles, used in the present invention. Media milling can be accomplished with an attritor, ball mill, media mill, or vibratory mill using suitable media comprising silica, silicon nitride, sand, zirconia, alumina, titania, yttria-stabilized zirconia, zirconium silicate, glass, steel, or any other material known for such uses.

The non-aqueous photocurable composition of the present invention may further comprise at least 0.5% by weight and up to and including 20% by weight or at least 1% by weight and up to and including 10% by weight of dispersed carbon black, based on the total amount of the non-aqueous photocurable composition.

Acid catalyzed photo-curable chemistry:

in some embodiments of the present invention, the non-aqueous photocurable composition comprises one or more UV-curable components, at least one of which is an acid-catalyzed photocurable component. These non-aqueous photocurable compositions may further comprise a photoacid generator.

Some useful acid catalyzed photocurable components may be photocurable epoxy materials. Cationically photocurable epoxy materials ("epoxides") useful in the present invention are organic compounds having at least one oxirane ring shown in the formula:

which can polymerize via a ring opening mechanism. These epoxy materials include monomeric epoxy compounds and epoxides of the polymeric type and can be aliphatic, cycloaliphatic, aromatic or heterocyclic. These materials generally have an average of at least one polymerizable epoxy group per molecule, or generally at least about 1.5 or even at least about 2 polymerizable epoxy groups per molecule. Polymeric epoxy materials include linear polymers having terminal epoxy groups (e.g., diglycidyl ethers of polyoxyalkylene glycols), polymers having backbone (main chain) ethylene oxide units (e.g., polybutadiene polyepoxides), and polymers having pendant 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 than two 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 vary from low molecular weight monomeric materials to high molecular weight polymers and they can vary greatly in backbone and substituent (or pendant) properties. For example, the backbone can be of any type and the substituents thereon can be any groups that do not substantially interfere with the desired cationic photocuring process at room temperature. Examples of permissible 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 at least 58 and up to and including 100,000 or even higher.

Useful epoxy materials include those containing cyclohexene oxide groups, such as epoxycyclohexanecarboxylates, e.g., 3, 4-epoxycyclohexylmethyl-3, 4-epoxycyclohexanecarboxylate, 3, 4-epoxy-2-methylcyclohexylmethyl-3, 4-epoxy-2-methylcyclohexanecarboxylate, and bis (3, 4-epoxy-6-methylcyclohexylmethyl) adipate. A more detailed list of useful epoxy materials of this nature is provided in U.S. patent No. 3,117,099 (promos et al).

Other useful epoxy materials include glycidyl ether monomers that are glycidyl ethers of polyhydric phenols obtained by reacting a polyhydric phenol with an excess of a chlorohydrin, such as epichlorohydrin [ e.g., the diglycidyl ether of 2, 2-bis- (2, 3-epoxypropoxyphenol) -propane ]. Other examples of Epoxy materials of these types are described in U.S. Pat. No. 3,018,262 (Schroeder) and "Handbook of Epoxy Resins" (Handbook of Epoxy Resins), "plum (Lee) and Neville (Neville), McGraw-Hill Book Co., N.Y. (1967).

Other useful epoxy materials are resins such as copolymers derived from the copolymerization of an acrylate ester (e.g., glycidyl acrylate and glycidyl methacrylate) reacted with glycidol and one or more ethylenically unsaturated polymerizable monomers.

Other useful epoxy materials are epichlorohydrin (e.g., epichlorohydrin), alkylene oxides (e.g., propylene oxide and styrene oxide), alkylene oxides (e.g., butadiene oxide), and glycidyl esters (e.g., ethyl glycerate).

Other useful epoxy materials are silicones having epoxy functionality or epoxy groups (e.g., cyclohexyl epoxy groups), especially those having a silicone backbone. Commercial examples of these epoxy materials include UV 9300, UV 9315, UV 9400, UV 9425 silicone materials available from Momentive (Momentive).

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

The photopolymerizable epoxy material may comprise a blend or mixture of two or more different epoxy materials. Examples of such blends include photopolymerizable epoxy materials of two or more molecular weight distributions, such as blends of one or more low molecular weight (less than 200) epoxy materials with one or more intermediate molecular weight (from 200 to 100,000) photopolymerizable epoxy materials or blends of one or more of the photopolymerizable epoxy materials with one or more higher molecular weight (greater than about 100,000) epoxy materials. Alternatively or additionally, the photopolymerizable epoxy material may comprise a blend of epoxy materials having different chemical properties (e.g., aliphatic and aromatic properties) or different functionalities (e.g., polar and non-polar properties). Other cationically polymerizable monomers or polymers may additionally be incorporated into the photopolymerizable epoxy material.

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

Various compounds can be used as photoacid generators for generating the appropriate acid to participate in the photocuring of epoxy materials. Some of these "photoacid generators" are acidic and others are nonionic. Other useful photoacid generators than those described below will be readily apparent to those of skill in the art, with reference to the teachings provided herein. Various compounds suitable for use as photoacid generators can be purchased from various commercial sources or prepared using known synthetic methods and starting materials.

Onium salt acid generators useful in the practice of the present invention include, but are not limited to, salts of diazonium, phosphonium, iodonium, or sulfonium salts, including polyaryl diazonium, phosphonium, iodonium, and sulfonium salts. Iodonium or sulfonium salts include, but are not limited to, diaryliodonium and triarylsulfonium salts. Useful counter anions include, but are not limited to, complex metal halides such as tetrafluoroborate, hexafluoroantimonate, triflate, hexafluoroarsenate, hexafluorophosphate and arenesulfonate. The onium salt can also be an oligomeric or polymeric compound having multiple onium salt moieties as well as a molecule having a single onium salt moiety.

Examples of useful aromatic iodonium salts include (but are not limited to) diphenyliodonium tetrafluoroborate; bis (4-methylphenyl) iodonium tetrafluoroborate; phenyl-4-methylphenylidine tetrafluoroborate; bis (4-heptylphenyl) iodonium tetrafluoroborate; bis (3-nitrophenyl) iodonium hexafluorophosphate; bis (4-chlorophenyl) iodonium hexafluorophosphate; di (naphthyl) iodonium tetrafluoroborate; bis (4-trifluoromethylphenyl) iodonium tetrafluoroborate; diphenyliodonium hexafluorophosphate; bis (4-methylphenyl) iodonium hexafluorophosphate; diphenyliodonium hexafluoroarsenate; bis (4-phenoxyphenyl) iodonium tetrafluoroborate; phenyl-2-thienyliodonium hexafluorophosphate; 3, 5-dimethylpyrazolyl-4-phenyliodonium hexafluorophosphate; diphenyliodonium hexafluoroantimonate; 2,2' -diphenyliodonium tetrafluoroborate; bis (2, 4-dichlorophenyl) iodonium hexafluorophosphate; bis (4-bromophenyl) iodonium hexafluorophosphate; bis (4-methoxyphenyl) iodonium hexafluorophosphate; bis (3-carboxyphenyl) iodonium hexafluorophosphate; bis (3-methoxycarbonylphenyl) iodonium hexafluorophosphate; bis (3-methoxysulfonylphenyl) iodonium hexafluorophosphate; bis (4-acetamidophenyl) iodonium hexafluorophosphate; bis (2-benzothiophenyl) iodonium hexafluorophosphate; and diphenyliodonium hexafluoroantimonate; and mixtures thereof. These compounds can be produced by metathesis of the corresponding aromatic iodonium monosalt (such as, for example, diphenyliodonium hydrogensulfate) according to the teachings of beliger (Beringer) et al, american society for chemistry (j.am.chem.soc.)81,342 (1959).

Other suitable iodonium salts include the compounds described in U.S. Pat. No. 5,545,676 (palazotto et al) column 2 (lines 28 to 46), and U.S. Pat. No. 3,729,313 (Smith)), 3,741,769 (Smith), 3,808,006 (Smith), 4,250,053 (Smith), and 4,394,403 (Smith).

A useful iodonium salt can be a single salt (e.g., containing an anion such as chloride, bromide, iodide, or C)₄H₅SO₃ ^-) Or metal complex salts (e.g., containing SbF)₆ ^-、PF₆ ^-、BF₄ ^-Tetrakis (perfluorophenyl) borate or SbF₅OH₃₁AsF₆ ^-). If desired, a mixture of any of these iodonium salts of the same or different classes can be used.

Exemplary sulfonium salts include, but are not limited to, triphenylsulfonium tetrafluoroborate, methyldiphenylsulfonium tetrafluoroborate, dimethylphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, diphenylnaphthylsulfonium hexafluoroarsenate, tritolylphenylsulfonium hexafluorophosphate, methoxyphenyldiphenylsulfonium hexafluoroantimonate, 4-butoxyphenyldiphenylsulfonium tetrafluoroborate, 4-chlorophenyldiphenyl-sulfonium hexafluorophosphate, tris (4-phenoxyphenyl) sulfonium hexafluorophosphate, bis (4-ethoxyphenyl) methylsulfinium hexafluoroarsenate, 4-acetonylphenyldiphenylsulfonium tetrafluoroborate, 4-thiomethoxyphenyl diphenylsulfonium hexafluorophosphate, bis (methoxysulfonylphenyl) methylsulfinium hexafluoroantimonate, bis (nitrophenyl) phenylsulfinium hexafluoroantimonate, bis (methoxyformylphenyl) methylsulfinium hexafluorophosphate, methylthiophenyl sulfonium hexafluorophosphate, 4-acetamidophenyldiphenylsulfonium tetrafluoroborate, dimethylnaphthylsulfonium hexafluorophosphate, trifluoromethyldiphenylsulfonium tetrafluoroborate, p- (phenylthienyl) diphenylsulfonium hexafluoroantimonate, p- (phenylthienyl) diphenylsulfonium hexafluorophosphate, bis- [ p- (phenylthienyl) ] phenylsulfonium hexafluoroantimonate, bis- [ p- (phenylthienyl) ] phenylsulfonium hexafluorophosphate, bis- (hexafluoroantimonate) diphenylsulfide bis (hexafluoroantimonate) 4,4' -bis (diphenylsulfonium) diphenylsulfide, bis (hexafluorophosphate), 10-methylphenoxathionium hexafluorophosphate, 5-methylthiothianthrene hexafluorophosphate, 10-phenyl-9, 9-dimethyl 9-oxathioxanthone hexafluorophosphate, 10-phenyl-9-oxo 9-oxathioxanthone tetrafluoroborate, sodium hexafluorophosphate, sodium borate, Tetrafluoroboric acid 5-methyl-10-oxothianthrene, hexafluorophosphoric acid 5-methyl-10, 10-dioxothianthrene and mixtures thereof.

Sulfonium salts are desirable for use and should be soluble in any inert organic solvent (described below) and also should be storage stable, meaning that they do not spontaneously promote polymerization when mixed with other components, particularly the electron acceptor photosensitizer and the electron donor co-initiator, prior to exposure to appropriate radiation. Thus, the selection of a particular onium salt can be made for optimum properties with respect to other components and amounts.

Particularly useful sulfonium salts include, but are not limited to, triaryl-substituted salts, such as mixed triarylsulfonium hexafluoroantimonate (e.g., available as UVI-6974 from Dow Chemical Company), mixed triarylsulfonium hexafluorophosphate (e.g., available as UVI-6990 from Dow Chemical Company), and aryl sulfonium hexafluorophosphate (e.g., available as SarCa^TMKI85 was obtained from Sartomer Company).

One or more onium salts (such as iodonium salts or sulfonium salts) can generally be present in non-aqueous photocurable composition in an amount of at least 0.05% by weight and up to and containing 10% by weight, or typically at least 0.1% by weight and up to and containing 10% by weight, or even at least 0.5% by weight and up to and containing 5% by weight, based on the total weight of non-aqueous photocurable composition.

Nonionic photoacid generators may also be used in the present invention, including, but not limited to, diazomethane derivatives such as, for example, bis (phenylsulfonyl) diazomethane, bis (p-toluenesulfonyl) diazomethane, bis (xylenesulfonyl) diazomethane, bis (cyclohexylsulfonyl) -diazomethane, bis (cyclopentylsulfonyl) diazomethane, bis (n-butylsulfonyl) diazomethane, bis (isobutylsulfonyl) diazomethane, bis (sec-butylsulfonyl) diazomethane, bis (n-propylsulfonyl) diazomethane, bis (isopropylsulfonyl) diazomethane, bis (tert-butylsulfonyl) diazomethane, bis (n-pentylsulfonyl) diazomethane, bis (isopentylsulfonyl) diazomethane, bis (sec-pentylsulfonyl) diazomethane, bis (tert-pentylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-butylsulfonyl) diazomethane, 1-cyclohexylsulfonyl-1- (tert-pentylsulfonyl) diazomethane and 1-tert-pentylsulfonyl-1- (tert-butylsulfonyl) diazomethane.

The nonionic photoacid generator can also include glyoxime derivatives such as, for example, bis-o- (p-toluenesulfonyl) - α -dimethylglyoxime, bis-o- (p-toluenesulfonyl) - α -diphenylglyoxime, bis-o- (p-toluenesulfonyl) - α -dicyclohexylglyoxime, bis-o- (p-toluenesulfonyl) -2, 3-pentanedionato glyoxime, bis-o- (p-toluenesulfonyl) -2-methyl-3, 4-pentanedionato glyoxime, bis-o- (n-butanesulfonyl) - α -dimethylglyoxime, bis-o- (n-butanesulfonyl) - α -diphenylglyoxime, bis-o- (n-toluenesulfonyl) - α -diphenylglyoxime, bis-O- (n-butanesulfonyl) - α -diphenylglyoxime, bis, Bis-o- (n-butanesulfonyl) - α -dicyclohexylglyoxime, bis-o- (n-butanesulfonyl) -2, 3-pentanedione glyoxime, bis-o- (n-butanesulfonyl) -2-methyl-3, 4-pentanedione glyoxime, bis-o- (methanesulfonyl) - α -dimethylglyoxime, bis-o- (trifluoromethanesulfonyl) - α -dimethylglyoxime, bis-o- (1,1, 1-trifluoroethanesulfonyl) - α -dimethylglyoxime, bis-o- (tert-butanesulfonyl) - α -dimethylglyoxime, bis-o- (perfluorooctanesulfonyl) - α -dimethylglyoxime, bis-o- (n-butanesulfonyl) - α -dimethylglyoxime, bis-o- (perfluorooctanesulfonyl) - α -dimethylglyoxime, bis-, Bis-o- (cyclohexanesulfonyl) - α -dimethylglyoxime, bis-o- (benzenesulfonyl) - α -dimethylglyoxime, bis-o- (p-fluorophenylsulfonyl) - α -dimethylglyoxime, bis-o- (p-tert-butylbenzenesulfonyl) - α -dimethylglyoxime, bis-o- (xylenesulfonyl) - α -dimethylglyoxime, or bis-o- (camphorsulfonyl) - α -dimethylglyoxime.

These photoacid generators may also include bis sulfone derivatives, such as, for example, bis naphthylsulfonylmethane, bis trifluoromethylsulfonylmethane, bis methylsulfonylmethane, bis ethylsulfonylmethane, bis propylsulfonylmethane, bis isopropylsulfonylmethane, bis-p-toluenesulfonylmethane, bis phenylsulfonylmethane, 2-cyclohexyl-carbonyl-2- (p-toluenesulfonyl) propane (. beta. -ketosulfone derivative) and 2-isopropyl-carbonyl-2- (p-toluenesulfonyl) propane (. beta. -ketosulfone derivative).

Other classes of useful nonionic photoacid generators include disulfo derivatives such as, for example, diphenyl disulfone and dicyclohexyl disulfone; nitrobenzyl sulfonate derivatives such as, for example, 2, 6-dinitrobenzyl p-toluenesulfonate and 2, 4-dinitrobenzyl p-toluenesulfonate; sulfonate derivatives such as, for example, 1,2, 3-tris (methylsulfonyloxy) benzene, 1,2, 3-tris (trifluoromethylsulfonyloxy) benzene and 1,2, 3-tris (p-toluenesulfonyloxy) benzene; and sulfonates of N-hydroxysuccinimide, such as, for example, N-hydroxysuccinimide methanesulfonate, N-hydroxysuccinimide trifluoromethanesulfonate, N-hydroxysuccinimide ethanesulfonate, N-hydroxysuccinimide 1-propanesulfonate, N-hydroxysuccinimide 2-propanesulfonate, N-hydroxysuccinimide 1-pentanesulfonate, N-hydroxysuccinimide 1-octanesulfonate, N-hydroxysuccinimide p-toluenesulfonate, N-hydroxysuccinimide p-methoxybenzenesulfonate, N-hydroxysuccinimide 2-chloroethanesulfonate, N-hydroxysuccinimide benzenesulfonate, N-hydroxysuccinimide 2,4, 6-trifluorobenzenesulfonate, N-hydroxysuccinimide 2,4, 6-trimethylbenzenesulfonate, N-hydroxysuccinimide 2,4, 6-trichlorobenzenesulfonate, N-hydroxysuccinimide 4-cyano-benzenesulfonate, N-hydroxysuccinimide 1-naphthalenesulfonate, N-hydroxysuccinimide 2-naphthalenesulfonate, N-hydroxy-2-phenylsuccinimide methanesulfonate, N-hydroxymaleimide ethanesulfonate, N-hydroxy-2-phenylmaleimide methanesulfonate, N-hydroxyglutarimide benzenesulfonate, N-hydroxyphthalimide methanesulfonate, N-hydroxyphthalimide benzenesulfonate, N-hydroxyphthalimide trifluoromethanesulfonate, N-hydroxyphthalimide, N-hydroxyphthalimide p-toluenesulfonate, N-hydroxynaphthalimide methanesulfonate, N-hydroxynaphthalimide benzenesulfonate, N-hydroxy-5-norbornene-2, 3-dicarboximide methanesulfonate, N-hydroxy-5-norbornene-2, 3-dicarboximide trifluoromethanesulfonate, N-hydroxy-5-norbornene-2, 3-dicarboximide p-toluenesulfonate, N-hydroxynaphthalimide trifluoromethanesulfonate and N-hydroxy-5-norbornene-2, 3-dicarboximide perfluoro-1-butanesulfonate.

One or more nonionic photoacid generators may be present in the non-aqueous photocurable composition in an amount of at least 0.05 wt% and up to and including 10 wt%, or typically at least 0.1 wt% and up to and including 10 wt%, or even at least 0.5 wt% and up to and including 5 wt%, based on the total weight of the non-aqueous photocurable composition.

Some of the non-aqueous photocurable compositions described herein, particularly those containing a photopolymerizable epoxy material and a photoacid generator, can contain one or more electron donor photosensitizers. Useful electron donor photosensitizers should be soluble in the non-aqueous photocurable composition, free of functionality that would substantially interfere with the cationic photocuring process, and have the ability to absorb (sensitivity) light over a wavelength range of at least 150nm and up to and including 1000 nm.

Suitable electron donor photosensitizers initiate a chemical transformation of an onium salt (or other photoacid generator) in response to photons absorbed from radiation. The electron donor photosensitizer should also have the ability to reduce the photoacid generator after the electron donor photosensitizer has absorbed light (i.e., photo-electron transfer). Therefore, the electron donor photosensitizer has substantially the ability to donate electrons to the photoacid generator immediately after absorbing photons from radiation.

When extremely rapid curing is desired (e.g., curing of a thin applied film of a non-aqueous photocurable composition), the electron donor photosensitizer may have at least 1000 l-moles at the desired wavelength of radiation using a photocuring process^-1cm^-1And usually at least 50,000 liter-moles^-1cm^-1The extinction coefficient of (a).

For example, each electron donor photosensitizer typically has an oxidation potential of at least 0.4V and up to and including 3V (versus SCE) or more typically at least 0.8V and up to and including 2V (versus SCE).

In general, many different classes of compounds are useful as electron donor photosensitizers for a variety of reactants. Useful electron donor photosensitizers include, but are not limited to, aromatic compounds such as naphthalene, 1-methylnaphthalene, anthracene, 9, 10-dimethoxyanthracene, benzo [ a ] anthracene, pyrene, phenanthrene, benzo [ c ] phenanthrene, and fluoranthene (fluoranthene).

Other electron donor photosensitizers that can be used with respect to the triplet excited state are carbonyl compounds such as 9-thioxanthone and xanthone. Ketones (including aromatic ketones such as fluorenones) and coumarin dyes (such as ketocoumarins, as those having a strong electron donor moiety such as a dialkylamino group) can also be used as electron donor photosensitizers. It is believed that other suitable electron donor photosensitizers include xanthene dyes, acridine dyes, thiazole dyes, thiazine dyes, oxazine dyes, azine dyes, aminoketone dyes, porphyrins, aromatic polycyclic hydrocarbons, para-substituted aminostyryl ketone compounds, aminotriarylmethanes, merocyanines, squaraine dyes, and pyridinium dyes.

Mixtures of electron donor photosensitizers selected from the same or different classes of materials may also be used.

Various useful electron donor photosensitizers are commercially available from various sources and can be readily found for use in the present invention.

When used, the one or more electron donor photosensitizers may be present in the non-aqueous photocurable composition in an amount of at least 0.000001% by weight and up to and including 5% by weight and typically at least 0.0001% by weight and up to and including 2% by weight, based on the total weight of the non-aqueous photocurable composition. The precise amount of electron donor photosensitizer required will vary depending upon the overall non-aqueous photocurable composition, its intended use, and the extinction coefficient.

In some embodiments, the electron donor photosensitizer is pyrene, benzopyrene, perylene, or benzoperylene, which is present in an amount of at least 0.0001 weight% and up to and including 2 weight%, based on the total weight of the non-aqueous photocurable composition.

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 photosensitizers should be soluble in the non-aqueous photocurable composition, free of functionality that would substantially interfere with the cationic photocuring process, and have the ability to absorb (sensitivity) light over a wavelength range of at least 150nm and up to and including 1000 nm.

Suitable electron acceptor photosensitizers initiate chemical transformation of onium salts in response to photons absorbed from radiation. The electron acceptor photosensitizer should also have the ability to oxidize an electron donor co-initiator (described below) to a cationic radical after the electron acceptor photosensitizer has absorbed light (i.e., photo-induced electron transfer). Thus, electron acceptor photosensitizers generally have the ability to accept electrons from electron donor co-initiators immediately after absorbing photons from radiation.

When extremely rapid curing is desired (e.g., curing of a thin film of the applied composition), the electron acceptor photosensitizer may have at least 1000 liter-moles at the desired wavelength of radiation using a photocuring process^-1cm^-1And usually at least 10,000 liter-moles^-1cm^-1The extinction coefficient of (a).

In general, many different classes of compounds are useful as electron acceptor photosensitizers for a variety of reactants, provided that the energy requirements described above are met. Useful electron acceptor photosensitizers include, but are not limited to, cyanoaromatic compounds such as 1-cyanonaphthalene, 1, 4-dicyanonaphthalene, 9, 10-dicyanoanthracene, 2,9, 10-tricyanoanthracene, 2,6,9, 10-tetracyanoanthracene; aromatic anhydrides and imides, such as 1, 8-naphthalenedicarboxylic acid, 1,4,6, 8-naphthalenetetracarboxylic acid, 3, 4-perylenedicarboxylic acid and 3,4,9, 10-perylenetetracarboxylic anhydride or imide; condensed pyridinium salts, such as quinolinium, isoquinolinium, phenanthridinium, acridinium, and pyrylium salts.

Other useful electron acceptor photosensitizers for triplet excited states are carbonyl compounds such as quinones, e.g., benzene-, naphthalene-, anthracene-quinones with electron withdrawing substituents such as chlorine and cyano. Ketones (including aromatic ketones such as fluorenones) and coumarin dyes (such as ketocoumarins, as those having a strong electron moiety such as pyridinium) may also be used as electron acceptor photosensitizers. Other suitable electron acceptor photosensitizers are believed to include xanthene dyes, acridine dyes, thiazole dyes, thiazine dyes, oxazine dyes, azine dyes, aminoketone dyes, porphyrins, aromatic polycyclic hydrocarbons, para-substituted aminostyrone compounds, aminotriarylmethanes, merocyanines, squaraine dyes, and pyridinium dyes. Diaryl ketones and other aromatic ketones (e.g., fluorenones) are useful electron acceptor photosensitizers.

Mixtures of electron acceptor photosensitizers selected from the same or different classes of materials may also be used, provided that the above electrochemical requirements are met.

Various electron acceptor photosensitizers are available commercially from various sources.

The one or more electron acceptor photosensitizers may be present in the non-aqueous photocurable composition in an amount of at least 0.000001% by weight and up to and including 5% by weight and typically at least 0.0001% by weight and up to and including 2% by weight, based on the total weight of the non-aqueous photocurable composition.

The use of electron acceptor photosensitizers is highly efficient by incorporating into the non-aqueous photocurable composition one or more electron donor co-initiators, each having an oxidation potential of at least 0.1V and up to and including 3V (vs SCE). Thus, these electron donor co-initiators should be soluble in the non-aqueous photocurable composition. The electron donor co-initiator may also be selected by taking into account other factors such as storage stability and the nature of the photopolymerizable epoxy material, photoacid generator, and electron acceptor photosensitizer selected.

Useful electron donor co-initiators are alkyl aromatic polyethers, aryl alkyl amino compounds wherein the aryl group is substituted with one or more electron withdrawing groups including, but not limited to, carboxylic acid ester, ketone, aldehyde, sulfonic acid ester, and nitrile groups. For example, aryldialkyldiamino compounds are suitable, wherein the aryl group is a substituted or unsubstituted phenyl or naphthyl group (e.g., a phenyl or naphthyl group having one or more electron withdrawing groups as described above), and the two alkyl groups independently comprise from 1 to 6 carbon atoms.

Useful electron donor coinitiators are readily available from a variety of commercial sources.

In general, the one or more electron donor co-initiators may be present in an amount of at least 0.001 wt% and up to and including 10 wt%, or more typically at least 0.005 wt% and up to and including 5 wt%, or even at least 0.01 wt% and up to and including 2 wt%, based on the total weight of the non-aqueous photocurable composition.

As noted above, all of the non-aqueous photocurable compositions containing the various necessary and optional components may comprise at least 0.5% by weight and up to and including 20% by weight or at least 1% by weight and up to and including 10% by weight of the dispersed carbon black, based on the total weight of the non-aqueous photocurable composition.

Some embodiments of the non-aqueous photocurable compositions of the present invention may comprise the following components: (a) a photopolymerizable epoxy material as described above, (b) a photoacid generator as described above, (c) an electron donor photosensitizer as described above, (d) dispersed carbon-coated metal particles as described above with any particle dispersant as described above, (e) an organic diluent, as described above, an organic solvent medium, (f) a free-radically polymerizable material, and (g) a free-radical photoinitiator, wherein:

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

the photoacid generator is iodonium or sulfonium, and

the dispersed carbon-coated metal particles are dispersed carbon-coated silver particles having a median diameter equal to or less than 0.5 μm as measured using dynamic light scattering as described above.

Free radical photo-curable chemistry:

in other embodiments, the non-aqueous photocurable composition comprises one or more UV-curable components, at least one of which is a free-radical photocurable component and the non-aqueous photocurable composition may further comprise a free-radical photoinitiator to provide free radicals during photocuring.

The one or more free radically polymerizable compounds can be present to provide free radically polymerizable functionality, including ethylenically unsaturated polymerizable monomers, oligomers, or polymers (such as mono-or multifunctional acrylates (also including methacrylates)). These free radically polymerizable compounds contain at least one ethylenically unsaturated polymerizable bond (moiety) and they may contain two or more of these unsaturated moieties in many embodiments. Suitable materials of these types contain at least one ethylenically unsaturated polymerizable bond and have the ability to undergo addition (or free radical) polymerization. These free radically polymerizable materials include mono-, di-, or poly-acrylates and methacrylates, including but not limited to methyl acrylate, methyl methacrylate, ethyl acrylate, isopropyl methacrylate, n-hexyl acrylate, stearyl acrylate, allyl acrylate, glyceryl diacrylate, glyceryl triacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate, 1, 3-propylene glycol diacrylate, 1, 3-propylene glycol dimethacrylate, 1, 4-butylene glycol diacrylate, 1, 6-hexanediol diacrylate, neopentyl glycol dimethacrylate, trimethylolpropane triacrylate, 1,2, 4-butylene glycol trimethacrylate, ethylene glycol dimethacrylate, ethylene glycol diacrylate, propylene glycol diacrylate, 1, 4-cyclohexanediol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, sorbitol hexaacrylate, bis [1- (2-acryloyloxy) ] -p-ethoxyphenyl dimethylmethane, bis [1- (3-acryloyloxy-2-hydroxy) ] -p-propoxyphenyl dimethylmethane and tris-hydroxyethyl-isocyanurate trimethacrylate; the diacrylates and dimethacrylates of the polyethylene glycol have a molecular weight of 200 to (including) 500, a copolymerizable mixture of acrylate monomers (as described in U.S. Pat. No. 4,652,274 (Boettcher et al)) and acrylate oligomers (as described in U.S. Pat. No. 4,642,126 (Zadaer 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 can be used if desired.

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

While the amount of the one or more free radically polymerizable materials is not particularly limited, they may be present in the non-aqueous photocurable composition in an amount of at least 10% by weight and up to and including 90% by weight, or typically at least 20% by weight and up to and including 85% by weight, based on the total weight of the non-aqueous photocurable composition, and may be optimized based on the desired composition solubility and mechanical strength properties of the resulting photocurable composition.

One or more free radical photoinitiators may also be present in the non-aqueous photocurable composition to generate free radicals. These free radical photoinitiators include any compound that has the ability to generate free radicals upon exposure to the photocuring radiation (e.g., ultraviolet or visible radiation) used in the practice of the present invention. For example, the free radical photoinitiator may be selected from triazine compounds, 9-oxathiolane compounds, benzoin compounds, carbazole compounds, diketone compounds, sulfonium borate compounds, diazo compounds, and bisimidazole compounds, and other compounds that will be readily apparent to those skilled in the art. Mixtures of these compounds may be selected from the same or different classes.

Also useful are benzophenone compounds (e.g., benzophenone, benzoylbenzoate, benzoylmethyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4 '-bis (dimethylamino) benzophenone and 4,4' -bis (diethylamino) benzophenone), anthraquinone compounds and acetophenone compounds (e.g., 2 '-diethoxyacetophenone, 2' -dibutoxyacetophenone, 2-hydroxy-2-methylpropiophenone, p-tert-butyltrichloroacetophenone, p-tert-butyldichloroacetophenone, benzophenone, 4-chloroacetophenone, 4 '-dimethylaminobenzophenone, 4' -dichlorobenzophenone, 3 '-dimethyl-2-methoxybenzophenone, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, hydroxy-2' -bis (dimethylamino) benzophenone, acrylated benzophenone, 2-hydroxy-2-methyl acetophenone, p-tert-butyltrichloroacetophenone, benzophenone, 2,2' -dichloro-4-phenoxyacetophenone, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one and 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one). Other useful compounds of these types are described, for example, in U.S. Pat. No. 7,875,416 (Park et al).

Many of these free radical photoinitiators are available from various commercial sources.

One or more free radical photoinitiators may be present in the non-aqueous photocurable composition in an amount of at least 0.3% by weight and up to and including 10% by weight, or typically at least 0.4% by weight and up to and including 10% by weight, or even at least 0.5% by weight and up to and including 5% by weight, based on the total weight of the non-aqueous photocurable composition.

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

Preparation of non-aqueous Photocurable compositions

To prepare the non-aqueous photocurable composition of the present invention, the various components (including the essential and optional components) are combined in any suitable manner, for example, in a suitable organic diluent (such as an organic solvent medium), with the exception of the photocurable component serving as the organic diluent (as described above). Thus, these combined processes may mix the appropriate dispersed carbon-coated metal particles as described above (including the particle dispersants as described above) and one or more photocurable components (as described above) in an organic diluent. These photocurable components may include a UV curable component and a UV photoinitiator. Alternatively, the photocurable component may include a polymerizable epoxy material and a photoacid generator.

The resulting non-aqueous photocurable composition may be a fluid, gel or paste having a viscosity of at least 1 centipoise and up to and including 100,000 centipoise at 25 ℃. The non-aqueous photocurable composition can be applied to a variety of substrates (described below) by conventional methods and photocured to a tack-free state in 1 second or up to 10 minutes or more using various curing devices and radiation sources. Any inert organic solvent may be removed using a suitable drying method, either simultaneously with or prior to photocuring.

Particularly useful inert organic solvents (other than those described above) that can be used for such mixing include, but are not limited to, acetone, methanol, ethanol, isopropanol, 1-methoxy-2-propanol (Dunaunox PM), dichloromethane, and mixtures thereof that do not significantly react with any reactive component of the non-aqueous photocurable composition.

Article with a cover

The non-aqueous photocurable composition of the present invention may be formulated as described above and applied to one or both supporting sides (planar sides) of any suitable substrate (described below) using any suitable method. For example, the non-aqueous photocurable composition can be applied to either or both support sides in a uniform or pattern-by-pattern process using, for example, dip coating, roll coating, funnel coating, spray coating, spin coating, ink spray coating, photolithographic imprinting, flexographic printing using flexographic printing elements (e.g., flexographic printing plates and flexographic printing sleeves), photolithographic printing using photolithographic printing plates, and gravure or intaglio printing using appropriate printing elements. Flexographic printing using a flexographic printing member is particularly useful for providing a predetermined pattern of a non-aqueous photocurable composition, and the method can be used to provide a plurality of patterns of the same or different non-aqueous photocurable composition on one or both supporting sides of a substrate. Further details of these processes are provided below.

The applied non-aqueous photocurable composition may be formed and dried into a uniform layer or dried into a predetermined pattern. The resulting article may be considered a "precursor" article prior to photocuring as described below.

As described in more detail below, the substrates for these articles may be constructed of any useful material and may be individual films or sheets of any suitable size and shape, for example constructed of metallic materials, glass, paper stock (cellulosic materials of any type), or ceramics, or they may be continuous webs of material, such as continuous polymeric webs.

Various amounts of the essential and optional components of the non-aqueous composition (including the non-aqueous photocurable composition) are described above, but it should be understood that the amounts refer to solutions or dispersions containing these components. However, it should be understood that the amounts of the various components in the applied non-aqueous composition are different after application to an appropriate substrate, and optionally drying, and then photocuring. The individual amounts and relative amounts of the remaining components (if, for example, the inert organic solvent has been removed) can be readily calculated from information on the amounts of the 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 photocurable composition), the carbon-coated metal particles may be present in an amount of at least 10% by weight and up to and including 90% by weight, the particle dispersant may be present in an amount of at least 1% by weight and up to and including 30% by weight, the carbon particles may be present in an amount of up to and including 20% by weight, and the photocurable component (described above, prior to curing) may be present in an amount of up to and including 90% by weight.

Use of non-aqueous photocurable compositions

The non-aqueous photocurable compositions described herein may be photocured (or photopolymerized) using suitable radiation, including ultraviolet light or visible actinic light or both. One or more suitable light sources may be used for the exposure process. Each precursor item may be individually exposed as a single component, or in an alternative embodiment described below, a web (e.g., a wound continuous polymeric web) comprising a plurality of precursor items (comprising a plurality of photocurable patterns) in a plurality of portions on one or both support sides of the continuous polymeric web may be individually exposed as the continuous polymeric web passes through an exposure station or as an exposure device passes through the continuous polymeric web in a desired path. The same or different non-aqueous photocurable compositions can be applied (e.g., using flexographic printing) on both supporting sides of a substrate, whether the substrate is in the form of a single component or in the form of a continuous polymeric web. In many embodiments, different patterns of conductive metal can be formed on opposing support sides of a substrate (or continuous polymer network) using the non-aqueous photocurable compositions described herein.

Wavelengths of at least 184.5nm to (including) 700nm and at least 1mJ/cm can be used²And up to and including 1000mJ/cm²Or more typically at least 1mJ/cm²And up to and including 800mJ/cm²UV or visible radiation of an intensity to achieve the desired photocuring.

When the non-aqueous photocurable composition is uniformly applied to an appropriate substrate, the resulting uniformly dried layer can be "imaged" or selectively exposed (or patterned) by exposure radiation through an appropriate reticle (masking member) having the desired pattern, and then the uncrosslinked (uncured) photocurable composition is suitably removed using an appropriate "developing" solution that dissolves or disperses the uncured material. These features or steps may be performed on both (opposite) support sides of the substrate. In addition, multiple patterns may be formed in the dried layer using the same or different masks, as desired.

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 (also referred to in the related art as "receiving assemblies") that may be used to provide the precursor articles may be constructed of any suitable material, so long as the material does not inhibit the purpose of the non-aqueous photocurable composition. For example, useful substrates may be formed from materials including (but not limited to): polymeric films, metals, paper stock, rigid or flexible glass (untreated or treated via, for example, carbon tetrafluoride plasma, hydrophobic fluorine or silicone repellent materials), silicon or ceramic wafers, fabrics, and combinations thereof (such as laminates of various films or laminates of paper and films), provided that a uniform layer or pattern of the non-aqueous photocurable composition can be formed thereon and then irradiated to form a uniform cured layer or one or more photocured patterns on at least one receiving (support) surface thereof in a suitable manner. The substrate may be transparent, translucent or opaque and rigid or flexible. Many useful substrates are transparent and have an overall transmission of at least 90%, and these transparent substrates can also be flexible, such as a continuous polymer web.

The substrate may comprise one or more auxiliary polymeric or non-polymeric layers or one or more patterns of other materials applied prior to application of the non-aqueous photocurable composition. For example, either or both supporting (planar) surfaces of the substrate may be treated, e.g., with a primer layer or electrically or mechanically treated (e.g., pelletized) to impart a "receiving surface" to the surface to improve adhesion of the non-aqueous photocurable composition to the resulting photocurable layer or photocurable pattern. An adhesive layer may be disposed on the substrate to provide various properties in response to a stimulus (e.g., the stimulus may be thermally activated, solvent activated, or chemically activated) and may serve as a receiving layer.

In some embodiments, the substrate may comprise individual receiving layers disposed on the substrate as receiving surfaces, the receiving layers and substrate may be comprised of materials that are highly receptive to the non-aqueous photocurable composition (such as suitable polymeric materials). These receiving layers may have a dry thickness of at least 0.05 μm and up to and including 10 μm or typically at least 0.05 μm and up to and including 3 μm when measured at 25 ℃.

The support side of the substrate, particularly a polymeric substrate, may be treated by exposure to corona discharge, mechanical abrasion, flame treatment, or oxygen plasma as described, for example, in U.S. patent 5,492,730 (Balaba et al) and 5,527,562 (Balaba et al) and U.S. patent application publication 2009/0076217 (gemmans (Gommans et al)) or by coating with various polymeric films such as poly (vinylidene chloride) or aromatic polysiloxanes.

Suitable substrate materials for forming the precursor article in a continuous web include, but are not limited to, metal films or foils, metal films on polymers (e.g., metal films on conductive polymeric films), flexible glass, semiconductive organic or inorganic films, organic or inorganic dielectric films, or laminates of two or more layers of these materials. For example, useful continuous web substrates can include polymeric films (e.g., poly (ethylene terephthalate) films, poly (ethylene naphthalate) films, polyimide films, polycarbonate films, polyacrylate films, polystyrene films, polyolefin films, and polyamide films), metal foils (e.g., aluminum foil, cellulose paper, or resin-coated or glass-coated paper), paperboard 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) with or without surface treatment as described above.

In some embodiments, the first polymer latex and the second polymer latex may be mixed to form a dried base coat on the substrate to adhere the patterned material with the fine lines formed using the non-aqueous photocurable composition. The first polymer latex may include a first polymer and a first surfactant such that a dried coating of the first polymer latex has a surface polarity of at least 50%. The second polymer latex can include a second polymer and a second surfactant such that a dried coating of the second polymer latex has a surface polarity of less than or equal to 27%. In addition, the dried coating of the mixture may have a surface polarity of at least 15% and up to and including 50%.

At least one of the first and second polymers described herein comprises a vinyl polymer comprising repeat units derived at least in part from glycidyl (meth) acrylate (representing glycidyl acrylate, glycidyl methacrylate, or both), and in most embodiments, the first and second polymers are each derived at least in part from glycidyl (meth) acrylate. Furthermore, at least one of the first and second polymers is crosslinkable and may be crosslinked, for example, after application to a suitable support, such as during drying or various thermal treatments of the substrate.

Particularly useful first polymers are vinyl polymers derived at least in part from one or more ethylenically unsaturated polymerizable monomers having glycidyl functionality, such as glycidyl acrylate and glycidyl methacrylate. Thus, the first polymer may be a homopolymer derived from glycidyl (meth) acrylate, but it is more likely a copolymer derived from glycidyl (meth) acrylate and one or more other ethylenically unsaturated polymerizable monomers. The term "glycidyl" refers to a group containing an oxirane ring attached to an alkyl group (linear or branched alkyl groups which may be further substituted) having 1 to 4 carbon atoms, such as methyl, ethyl, isopropyl, and tert-butyl.

The first polymer is especially designed to copolymerize one or more glycidyl (meth) acrylates with one or more alkyl (meth) acrylates having at least 2 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, hydroxyethyl acrylate, and others that will be readily apparent to those skilled in the art. Particularly useful co-monomers are alkyl (meth) acrylates wherein the alkyl group has at least 4 carbon atoms, including but not limited to n-butyl acrylate, n-butyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate, and cyclohexyl methacrylate.

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

Particularly useful second polymers are vinyl polymers derived at least in part from one or more ethylenically unsaturated polymerizable monomers having glycidyl functionality, such as glycidyl (meth) acrylate, e.g., glycidyl acrylate and glycidyl methacrylate, as described above for the first polymer. Thus, the second polymer may 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 defined above.

The second polymer is especially designed by copolymerizing one or more glycidyl (meth) acrylates with one or more comonomers such as one or more alkyl (meth) acrylates having at least 2 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, hydroxyethyl acrylate, and others that will be readily apparent to those skilled in the art. Particularly useful comonomers are alkyl (meth) acrylates in which the alkyl group has at least 4 carbon atoms, such as n-butyl acrylate, n-butyl methacrylate, n-hexyl acrylate, n-hexyl methacrylate and cyclohexyl methacrylate.

The first polymer latex comprises one or more first surfactants, each of which is a sodium salt of an alkyl sulfonic acid, wherein the alkyl group has at least 10 carbon atoms. For example, the first surfactant may be an alpha-olefin (C)₁₄-C₁₆) Sodium sulfonate, or the first watchThe surfactant may be selected from the group consisting of R-CH₂-CH＝CH-CH₂-S(＝O)₂O^-Na⁺A compound of (wherein R is C)₁₀、C₁₁Or C₁₂Hydrocarbon radicals) or these have the formula C₁₀To C₁₂Mixtures of compounds of different R groups of any one of the hydrocarbyl groups. One commercially available product that may be used that contains a first surfactant is a Rodcard

A246L (available, for example, from Rhodia). Mixtures of these first surfactants may be used if desired.

The second polymer latex comprises one or more second surfactants each of which is an ammonium salt of an alkyl phenol sulfate having at least 3 ethylene oxide units. For example, the second surfactant may be an ammonium salt of polyethoxy nonylphenol sulfate, or the second surfactant may be composed of R' -phenyl- (O-CH)₂CH₂)_n-S(＝O)O₂ ^-NH₄ ⁺Is represented by, wherein R' is C₈To C₁₂Hydrocarbyl and n is at least 3 and up to and including 10, or n is more likely at least 3 and up to and including 6. One commercially available product that may be used that contains a secondary surfactant is Rodopek

CO-436 (available, for example, from Rhodia). Mixtures of these secondary surfactants may be used if desired.

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

Useful substrates can have a desired dry thickness depending on the end use of the article formed therefrom. For example, the substrate dry thickness (including all processing and auxiliary layers) may be at least 0.001mm and up to and including 10mm, and particularly in the case of transparent polymeric films, the substrate dry thickness may be at least 0.008mm and up to and including 0.2 mm.

The substrate used to prepare the articles described herein can be provided in various forms, such as, for example, individual sheets and continuous webs of any size or shape (e.g., continuous webs of transparent polymeric substrates suitable for roll-to-roll operations, including transparent polyester webs). These continuous polymer webs may be divided or formed into individual first, second, and additional portions that may be used to form the same or different photocured patterns.

Any inert organic solvent of the organic diluent may be removed after application of the non-aqueous photocurable composition by a drying or pre-baking procedure that does not adversely affect the remaining components or prematurely cause photocuring. Useful drying conditions can be as low as room temperature, lasting as short as 5 seconds, and up to and including hours, depending on the manufacturing process. In most processes (roll-to-roll processes as described below), the drying conditions may be at a temperature sufficiently high to remove at least 90% of the inert organic solvent in at least 5 seconds.

Any applied layer of the uniform non-aqueous photocurable composition may have a dry thickness of at least 0.1 μm and up to and including 10 μm or typically at least 0.2 μm and up to and including 1 μm, and the optimum dry thickness may be tailored to the intended use of the resulting uniform photocurable layer, which layer typically has a dry thickness about the same as a uniform layer of the non-photocurable non-aqueous photocurable composition. Such a uniform layer, which may have the same or different chemical composition or dry thickness, may be applied to both (opposite) supporting sides of the substrate.

Any applied pattern of the non-aqueous photocurable composition, which typically has photocured and electrically conductive gridlines that are substantially the same size as the non-photocured gridlines, may comprise a grid (or other shape, including a circular or irregular network), having lines with an average dry width of at least 0.2 μm and up to and including 100 μm, or typically at least 5 μm and up to and including 10 μm, and the optimum dry width may be tailored to the intended use of the resulting uniform photocured layer.

Thus, the present invention may be used to provide articles comprising a substrate and a uniform layer or pattern comprising the non-aqueous photocurable composition of the present invention, wherein such articles may be considered "precursor" articles, meaning that they are generally the first articles to be formed prior to photocuring. After photocuring the non-aqueous photocurable composition, the precursor article is now considered an intermediate (photocured) article.

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

In many embodiments, a relief assembly derived from a flexographic printing plate precursor, such as an elastic relief assembly (flexographic printing member), is used to apply a pattern of a non-aqueous photocurable composition on one or both (opposing) supporting sides of a substrate (e.g., in a rolled continuous web), many of which are known in the art and some of which may be, for example, in cyrillic form

Flexographic Photopolymer Plates (Flexographic Photopolymer Plates) are commercially available from DuPont (DuPont) and from Islam Kodak Company (Eastman Kodak Company) as Flexcell SR and NX Flexographic Plates (Flexographic Plates) and Flexcell direct Flexographic Plates (Flexcell direct Flexgraphic Plates).

Particularly useful elastic relief members are derived from flexographic printing plate precursors and flexographic printing sleeve precursors, each of which can be appropriately imaged (and processed as needed) to provide relief members for "printing" or applying an appropriate pattern.

For example, useful elastic relief components may include one or more elastic layers with or without a substrate, wherein a relief image may be generated using a suitable imaging device.

For example, an elastic relief assembly (e.g., flexographic printing member) having an embossed layer constituting the uppermost relief surface and having an average relief image depth (pattern height) of at least 50 μm relative to the uppermost relief surface, or typically having an average relief image depth of at least 100 μm, can be made from an elastic photopolymerizable layer in an imagewise exposed elastic relief assembly precursor (e.g., flexographic printing member precursor), as described, for example, in U.S. patent 7,799,504 (Wadlo et al) and 8,142,987 (Alli et al) and U.S. patent application publication 2012/0237871 (Wadlo). These elastomeric photopolymerizable layers may be imaged with a suitable mask image to provide an elastomeric relief element (e.g., a flexographic printing plate or a flexographic printing sleeve). In some embodiments, an embossing layer comprising an embossing pattern may be disposed on a suitable substrate as described in the Ali et al patent. Other useful materials and image forming methods for providing an elastic relief image, including development, are also described in the ali et al patent. The embossing layer (and flexographic printing element) may be different to provide different patterns of the non-aqueous photocurable composition to the same or opposite support side of the substrate.

In other embodiments, such as, for example, U.S. Pat. Nos. 5,719,009 (Fan)), 5,798,202 (Cushner et al), 5,804,353 (Cuxina et al), 6,090,529 (Gelbart), 6,159,659 (Gebart), 6,511,784 (Hiller et al), 7,811,744 (Figov)), 7,947,426 (Ferford et al), 8,114,572 (Landri) -spring (Coltrain et al), 8,153,347 (Weleses (Veres) et al), 8,187,793 (Rigen (Regan et al) and U.S. patent application publication 2002/0136969 (Hiller et al), 2003/0129530 (Leinerback et al), 2003/0136285 (Tesser et al), 2003/0180636 (Kanga et al) and 2012/0240802 (Landri-spring et al), the elastomeric relief elements are provided from a directly (or excisable) laser-engravable elastomeric relief element with or without the use of a one-piece mask. Directly engraved relief elements can be made without solvent treatment or development as required for photopolymerizable elastic materials.

When an elastic relief member is used, the non-aqueous photocurable composition can be applied to the uppermost embossed surface (raised surface) of the elastic relief member in an appropriate manner. This application can be achieved using suitable means and it is desirable to apply as little as possible to the sides (oblique portions) or recesses of the relief recesses. An anilox roller system or other roller application system (particularly a low volume anilox roller, below 25 hundred million cubic microns per square inch (63.5 hundred million cubic microns per square centimeter)) and associated skive knifes may be used. Optimal metering of the non-aqueous photocurable composition onto the uppermost embossed surface can be achieved by controlling the viscosity or thickness or selecting an appropriate application device.

For example, the non-aqueous photocurable composition may be formulated to have a viscosity for such coating of at least 1cps (centipoise) and up to and including 5000cps or at least 1cps and up to and including 1500 cps. The thickness of the non-aqueous photocurable composition on the relief image is generally limited by the sufficient amount that it can be easily transferred to the substrate, but does not flow too much past the edges of the elastic relief members in the recesses during application.

Thus, the non-aqueous photocurable composition may be fed from a web or other roll feeding system in an amount to yield each print precursor article (in a uniform layer or pattern). In one embodiment, a first roller may be used to transfer the non-aqueous photocurable composition from an "ink" pan or metering system to a metering or anilox roller. The non-aqueous photocurable composition is generally metered to achieve a uniform thickness when it is transferred from the anilox roll to the printing plate cylinder. As the substrate in a continuous web is transferred from the printing plate cylinder to the impression cylinder by the roll-to-roll processing system, the impression cylinder applies pressure to the printing plate cylinder that transfers the image of the non-aqueous photocurable composition from the elastic relief assembly to the substrate.

After the non-aqueous photocurable composition has been applied to the uppermost embossed surface (or raised surface) of the elastic relief assembly, it may be useful to remove at least 25% by weight of any inert organic solvent to form a more tacky deposit on the uppermost embossed surface of the embossed image. This removal of the inert organic solvent may be accomplished by any method, such as, for example, using a hot air jet, evaporation at room temperature, or heating in an oven at elevated temperatures, or other methods known in the art for removing solvents.

When the non-aqueous photopolymerizable composition in the precursor article is present in a uniform layer or predetermined pattern of grid lines or other shapes on the substrate (on one or both supporting sides of the substrate), it can be irradiated with appropriate radiation from an appropriate light source such as fluorescent lamps or LEDs as described above to provide a photocured layer or one or more photocured patterns on the substrateA method for preparing a medical liquid. For example, photocuring can be carried out by using a composition having a wavelength (. lamda.) of at least 190nm and at most 700nm_max) And at least 1,000 microwatts/cm²And up to and including 80,000 microwatts/cm²Is irradiated with UV-visible light of an intensity of (a). The radiation system used to generate this radiation may consist of one or more ultraviolet lamps, for example in the form of 1 to 50 discharge lamps, for example xenon, metal halides, metal arcs (e.g. low, medium or high pressure mercury vapor discharge lamps with the required operating pressure of from a few millimetres to about 10 atmospheres). The lamp may comprise an envelope capable of transmitting light of a wavelength of at least 190nm and up to and including 700nm, or typically at least 240nm and up to and including 450 nm. The lamp envelope may be composed of quartz (e.g., spetrocil (specrocil) or Pyrex (Pyrex)) as in serbeceae. Typical lamps that can be used to provide ultraviolet radiation are, for example, medium pressure mercury arcs, such as the GE H3T7 arc and hannover (Hanovia)450W arc lamps. Photocuring can be performed using a combination of various lamps, some or all of which can be operated in an inert atmosphere. When using a UV lamp, the radiation flux impinging on the substrate (or applied layer or pattern) may be designed to be sufficient to achieve sufficiently rapid photocuring of the applied non-aqueous photocurable composition in a continuous process (e.g., in a roll-to-roll operation) within 1 to 20 seconds.

The LED radiation devices used in photocuring can have a peak emission wavelength of 350nm or greater. The LED device can include two or more types of components having different peak emission wavelengths greater than or equal to 350 nm. A commercial example of an LED device having a peak emission wavelength of 350nm or greater and having an ultraviolet-light emitting diode (UV-LED) is NCCU-033 available from riya chemical Corporation (Nichia Corporation).

This irradiation for the precursor article results in an intermediate article comprising a substrate (e.g., an individual sheet or a continuous web) and having thereon a photocured layer or any of one or more photocured patterns derived from a non-aqueous photocurable composition on one or both supporting sides of the substrate.

The resulting intermediate article may be used in this form in some applications, but in most embodiments the intermediate article is further processed to incorporate conductive metal on a uniform photocured layer or photocured pattern, each of which comprises carbon-coated metal particles with a "seed" material for further application of the conductive metal, e.g., using an electroless metal plating procedure. For example, the electroless "seed" carbon-coated metal particles described above may comprise silver, palladium, or platinum particles that may be electrolessly plated with copper, platinum, palladium, or other metals as described below.

One useful method is to use multiple flexographic printing plates (e.g., made as described above) in stacks in a printing station, where each stack has its own printing plate cylinder for printing individual substrates using each flexographic printing plate, or the stack of printing plates can be used to print portions (on one or both support sides) in a continuous polymer web. The same or different non-aqueous photocurable compositions may be "printed" or applied to such a substrate (on the same or opposite support side) using a plurality of flexographic printing plates.

In other embodiments, the central pressure cylinder may be used with a single pressure cylinder mounted on the printing press frame. As the substrate (or receiving assembly) enters the printing press frame, it contacts the pressure cylinder and prints the appropriate pattern with the non-aqueous photocurable composition. Alternatively, an in-line flexographic printing process with the printing stations arranged in a horizontal line and driven by a common spool member may be used. The printing station may be coupled to an exposure station, a cutting station, a folder, and other post-processing equipment. Those skilled in the art can readily determine other suitable apparatus and station configurations using the information available in the art. For example, the round (in-the-round) imaging process is described in WO 2013/063084 (gold (Jin et al).

The intermediate article described herein having the pattern of the photocured dispersed carbon-coated metal particles-containing can be immediately immersed in a water-based electroless metal plating bath or solution, or the intermediate article (e.g., in a rolled continuous web) can simply be stored along with the photocured pattern for use at a later time.

For example, each intermediate article can be contacted with the same or different electroless plating metal as the metal incorporated in the carbon-coated metal particles in the photocured pattern. In most embodiments, however, the electroless-plated metal is a different metal than the metal used in the carbon-coated metal particles dispersed in the photocured pattern.

Any metal that will likely be "electrolessly" plated onto the carbon-coated metal particles may be used at this time, but in most embodiments the electrolessly plated metal may be, for example, copper (II), silver (I), gold (IV), palladium (II), platinum (II), nickel (II), chromium (II), and combinations thereof. Copper (II), silver (I) and nickel (II) are particularly suitable electroless plating metals for carbon-coated silver, copper or palladium particles.

The one or more electroless plating metals can be present in the aqueous-based electroless plating bath or solution in an amount of at least 0.01 weight percent and up to and including 20 weight percent based on the total solution weight.

The electroless plating can be carried out using known conditions of temperature and time, as these conditions are well known in various textbooks and scientific literature. It is also known to include various additives (e.g., metal complexing agents or stabilizers) in aqueous-based electroless plating solutions. Time and temperature variations may be used to vary the metal electroless plating thickness or the metal electroless plating deposition rate.

One useful water-based electroless plating solution or bath is an electroless copper (II) plating bath that may include 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 can be carried out at room temperature for a few seconds up to several hours depending on the desired deposition rate and plating rate and plated metal thickness.

Other useful aqueous Electroless Plating solutions or baths include silver (I) with EDTA and sodium tartrate, silver (I) with ammonia and glucose, copper (II) with EDTA and dimethylamine borane, copper (II) with citrate and hypophosphite, nickel (II) with lactic acid, acetic acid and hypophosphite, and other industry standard aqueous Electroless baths or solutions (e.g., those described by Marolly et al in Electroless Plating: basic principles and Applications (electrolyte Plating: Fundamentals and Applications) 1990).

After the electroless plating process to provide a conductive metal pattern on one or more portions of one or the opposing support sides of the substrate, the resulting product article may be removed from the aqueous-based electroless plating bath or solution and may be washed with distilled or deionized water or another aqueous-based solution to remove any residual electroless plating chemistry. At this point, the electroless plated metal is generally stable and can be used for its intended purpose to form a variety of conductive articles having the desired conductive metal grid lines or conductive metal connectors (or BUS connectors or electrodes).

In some embodiments, the resulting product article may be rinsed or washed with deionized water at a temperature below 70 ℃ as described, for example, in [0048] of US2014/0071356 (pelts) with water at room temperature or as described in [0027] of WO 2013/169345 (lomacrlisnan (Ramakrishnan) et al).

To modify the surface of the electroless plated metal for visual or durability reasons, a variety of post-treatments may be used, including surface plating of yet at least another (third or more) metal (such as nickel or silver) onto the electroless plated metal (this procedure is sometimes referred to as "cladding"), or establishing a metal oxide, metal sulfide, or metal selenide layer sufficient to modify the surface color and scattering properties without reducing the conductivity of the electroless plated (second) metal. Depending on the metal used in the various coating procedures of the method, it may be desirable to treat the electroless-plated metal with another seed metal catalyst in a water-based seed metal catalyst solution to facilitate additional metal deposition.

Further, the aqueous electroless metal plating solution treatment may be performed a plurality of times sequentially using the same or different conditions. The continuous washing or rinsing step may also be carried out at room temperature or at a temperature below 70 ℃ where appropriate.

In addition, the electroless plating process may be sequentially performed a plurality of times using the same or different electroless plating metals and the same or different electroless plating conditions.

Some details of methods and apparatus suitable for carrying out some embodiments of the present invention are described in, for example, US2014/0071356 (as described above) and WO 2013/169345 (as described above). Further details of manufacturing systems suitable for manufacturing conductive articles, in particular in a winding process, are provided in WO2014/070131 (filed by petrak and gold at 10/29 of 2012).

Another system that can be used to perform the apparatus and step features of the present invention is described in U.S. serial No. 14/146,867 (filed by seifley (Shifley) on 1/3 2014).

The non-aqueous photocurable composition of the present invention may be used in a process to provide one or more electrically conductive articles. This method includes providing a continuous web of transparent substrate [ examples of which are described above, and can be, inter alia, a continuous web of poly (ethylene terephthalate) ].

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

The method may further comprise:

the formation, photocuring, and electroless plating features as described above are performed one or more additional times on one or more other portions of the continuous web different from the first portion using the same or different non-aqueous photocurable composition. In this manner, multiple photocured and electroless plated patterns can be formed on the same or different support sides of the substrate. The composition, pattern, or conductivity of the resulting conductive patterns may be the same, or any or all of these characteristics may be different (as predetermined by customer needs).

Accordingly, the method may be used to provide a plurality of precursor articles, including:

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 element,

advancing the continuous web comprising the first photocurable pattern to approach the exposure radiation and thereby form a first photocurable pattern on the first portion,

forming a second photocurable pattern on a second portion of the continuous web by applying the same or a different non-aqueous photocurable composition to the second portion using a flexographic printing element,

advancing the continuous web comprising a second photocurable pattern to approach the exposure radiation and thereby form a second photocurable pattern on a second portion,

optionally, forming one or more other photocured patterns on one or more other respective portions of the continuous web in a similar manner using the same or different non-aqueous photocurable composition and the same or different flexographic printing element, and

the continuous web comprising the plurality of photocured patterns is rolled up or used at once for further processing, such as electroless plating.

Accordingly, the method may further comprise:

forming a plurality of conductive articles from a continuous web comprising a plurality of photocured patterns, and

the individual conductive articles are assembled into the same or different individual devices (e.g., the same or different touch screen displays or devices).

The method may further comprise:

the plurality of photocured patterns in the continuous web are each electrolessly plated to form a plurality of conductive articles that can be assembled by the same or different users into the same or different individual devices. The device may be a touch screen or other display device that also includes appropriate controls, a housing, and software for any type of desired internet communication. Alternatively, the device may be a sub-component of such a touch screen or other display device.

In some embodiments, the method may be used to manufacture a device comprising a touch screen, the method comprising:

assembling one or more individual conductive articles into a device housing to form a touch screen area,

the one or more individual conductive items each comprise a conductive pattern comprising a conductive metal that has been electrolessly plated onto a photocured pattern derived from the non-aqueous photocurable composition of the present invention.

A useful product article made in accordance with the present invention can be formulated into a capacitive touch screen sensor containing an appropriate pattern of conductive metal grid lines, conductive metal connectors (electrical leads or BUS connectors). For example, the pattern of conductive metal gridlines and conductive metal connectors can be formed by printing the non-aqueous photocurable composition of the invention in a predetermined pattern, followed by electroless plating of the printed pattern with an appropriate metal as described above.

The present invention provides at least the following embodiments and combinations thereof, but other combinations of features are considered to be within the invention as will be apparent to those skilled in the art from the teachings of the invention:

1. a non-aqueous composition comprising dispersed carbon-coated metal particles in an organic diluent in an amount of at least 10 wt% based on the total weight of the non-aqueous composition, the dispersed carbon-coated metal particles having a median diameter equal to or less than 0.6 μ ι η and having a weight average molecular weight (M) of at least 2,000 and up to and including 100,000_w) And containing a dispersion of particulate dispersant comprising nitrogen-containing units, said median diameter being measured using dynamic light scattering,

2. The non-aqueous composition of example 1 containing dispersed carbon-coated silver particles or dispersed carbon-coated copper particles, or a mixture of both dispersed carbon-coated silver particles and dispersed carbon-coated copper particles.

3. The non-aqueous composition of embodiment 1 or 2 wherein the weight ratio of the particulate dispersant to the dispersed carbon-coated metal particles is at least 1:100 and up to and including 30: 100.

4. The non-aqueous composition of any of embodiments 1 through 3, wherein the dispersed carbon-coated metal particles are present in an amount of at least 15 weight percent and up to and including 70 weight percent, based on the total weight of the non-aqueous composition.

5. The non-aqueous composition of any of embodiments 1 through 4 wherein the particulate dispersant has a M of at least 2,000 and up to and including 50,000_w。

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

7. The non-aqueous composition of any of embodiments 1 through 6 wherein the particulate dispersant is an organic polymer containing ester units.

8. The non-aqueous composition of any of embodiments 1 through 7 wherein the particulate dispersant is an organic polymer containing units selected from at least one of the following categories (i) through (iv):

(i) a pyridine unit;

(ii) an imine unit;

(iii) an imide unit; and

(iv) an amine unit.

9. The non-aqueous composition of any of embodiments 1 through 8, wherein the dispersed carbon-coated metal particles are dispersed carbon-coated silver particles present at a concentration of at least 15 weight% and up to and including 60 weight%, based on the total weight of the non-aqueous composition, and the dispersed carbon-coated silver particles have a median diameter of less than 0.5 μ ι η as measured using dynamic light scattering.

10. The non-aqueous composition of any of embodiments 1-9, wherein the organic diluent is an organic solvent medium comprising at least one of 2-ethoxyethanol, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 1-methoxy-2-propanol, 4-heptanone, 3-heptanone, 2-heptanone, cyclopentanone, cyclohexanone, diethyl carbonate, 2-ethoxyethyl acetate, N-butyl butyrate, and methyl lactate.

11. The non-aqueous composition of any one of embodiments 1 through 10, which is a non-aqueous photocurable composition, further comprising a photocurable component and optionally a UV photoinitiator.

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

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

14. The non-aqueous composition as in any one of embodiments 11-13, wherein the photocurable component is a photopolymerizable epoxy material.

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

16. The non-aqueous composition of embodiment 11 or 12, wherein the photocurable component is a free-radical photocurable component and the 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 on one or both supporting sides of the substrate any of a dried layer or dried pattern of a non-aqueous composition as in any of embodiments 1-18.

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

20. The article of embodiment 18, wherein the substrate comprises 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 polymeric web and the non-aqueous composition is disposed in a plurality of patterns on both support sides of the substrate.

23. An article comprising a substrate and having on one or both supporting sides of the substrate either a dried layer or a dried pattern of a photocurable composition derived from the non-aqueous composition of any of embodiments 11-17.

24. The article of embodiment 23, wherein the substrate is a continuous polymeric web.

25. The article of embodiment 23 or 24, wherein the photocurable composition is arranged in one or more patterns on one or both supporting sides of a substrate.

26. The article of one or more of embodiments 23-25, wherein the substrate is a continuous polymeric web and the photocurable composition is disposed in a plurality of patterns on both supporting sides of the substrate.

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

28. A method of providing a precursor article, the method comprising:

a continuous web of a transparent substrate is provided,

forming one or more photocurable patterns derived from the non-aqueous photocurable composition of any of embodiments 11-17 on one or more portions of at least one supporting side of the continuous web.

29. The method of embodiment 28, further comprising:

photocuring one or more photocurable patterns to form one or more photocured patterns on one or more portions of the continuous web, the one or more photocured patterns each comprising dispersed carbon-coated metal particles as seed metal catalyst sites, and

electrolessly plating each of the one or more photocured patterns with a conductive metal onto one or more portions of a continuous web.

The method of embodiment 29, further comprising:

the formation, photocuring, and electroless plating features are performed multiple times on multiple portions of a continuous web, the multiple portions being the same or different, using the same or different non-aqueous photocurable compositions.

31. The method of any of embodiments 28 to 30, being for providing a plurality of precursor articles, the method comprising:

applying a non-aqueous photocurable composition to portions on one or both supporting sides of a continuous web using one or more flexographic printing elements to form a plurality of photocurable patterns on the portions,

advancing the continuous web comprising a plurality of photocurable patterns to approach exposure radiation and thereby form a plurality of photocurable patterns, and

rolling up the continuous web comprising a plurality of photocured patterns.

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

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

34. A method for forming a plurality of conductive patterns on a substrate, the method comprising:

providing a precursor article comprising a substrate and arranging a plurality of photocured patterns comprising dispersed carbon-coated metal particles as seed metal catalyst on one or both support sides of the substrate,

the plurality of photocured patterns is provided by one or more non-aqueous photocurable compositions as defined in any of examples 11 to 17, and

electroless plating each of the plurality of photocured patterns to form a plurality of conductive patterns.

35. A method of forming a plurality of electronic devices, the method comprising:

providing an article comprising a substrate and arranging a plurality of electroless-plated and photocured patterns comprising dispersed carbon-coated metal particles on one or both supporting sides of the substrate,

the plurality of electroless-plated and photocured patterns is provided by one or more non-aqueous photocurable compositions as defined in any of examples 1 to 17, and

forming a plurality of conductive objects by the plurality of electroless-plated and photocured patterns, and

the plurality of conductive articles are fabricated to form a plurality of electronic devices.

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

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

Initial dispersant screen test (0.5 wt% carbon coated silver particles):

this test was performed using carbon-coated silver particles, with a small amount of carbon-coated silver particles and an excess of the particle dispersant tested ("dispersant") (the ratio of the weight of the particle dispersant to the weight of the carbon-coated silver particles was 10: 1). A solution of 5% by weight of the dispersant tested was prepared by adding 2.5g of the desired dispersant to 47.5g of 1-methoxy-2-propanol (Sigma-Aldrich) with stirring until the dispersant was completely dissolved to form a dispersant solution. Next, 0.02g of carbon-coated silver particles (NovaCentrix, Ag-25-ST3,25nm specific mean particle size, Ostin (Austin) TX) were added with stirring to 4g of a 5% by weight dispersant solution in a 20ml glass vial. The resulting non-aqueous compositions were each treated with an ultrasonic probe system (weibra-cello (Vibra-Cell) VC600, sonic & Materials Inc.) at ambient temperature for 2 minutes and then visually assessed for sedimentation. This was done by visual observation after allowing the suspension to stand at room temperature (20 ℃) for 24 hours. The following rating scale was used to evaluate the settling of the dispersed carbon-coated silver particles:

5, completely settling as a transparent solution;

4-light grey solution, almost completely settled;

3, the wide gray color band is positioned above the black suspension liquid and partially subsides;

2-narrow gray band above black suspension, some local settling but less than rating "3"; and

the black suspension had no apparent sedimentation.

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

TABLE I

Weight average molecular weight, reported by manufacturer or measured by size exclusion chromatography

Styrene-maleic anhydride copolymer

PVP ═ poly (vinylpyrrolidone)

The dispersant in table I, which provided a settling rating of 3 or less, was then selected for another round of testing, but the concentration of carbon-coated silver particles was higher, and the concentrated dispersant tested as follows.

Concentrated dispersant test (50 wt% carbon coated silver particles):

this evaluation was designed to evaluate the dispersant in concentrated formulations with much less weight ratio of dispersant to carbon-coated silver particles (4 or 5 wt% dispersant to carbon-coated silver particles wt%). Only its median particle size was characterized because it was too concentrated to visually assess sedimentation behavior. The particle size distribution derived from light scattering measurements provides a good indication of the effectiveness of the particulate dispersant (dispersant) by showing the large degree of agglomeration contained in the suspension in the non-aqueous composition.

A solution of 5 wt% of the dispersant tested was prepared by adding 2.5g of the desired dispersant to 47.5g of 1-methoxy-2-propanol with stirring until the dispersant was completely dissolved to provide a dispersant solution. Next, 8g of carbon-coated silver particles (Novassex Ag-25-ST3, average particle size determined at 25nm, Ostin TX) were added with stirring to 8g of a 5 wt% dispersant solution in a 60ml bottle (LDPE, available from Nalgene). The resulting non-aqueous composition was treated with an ultrasonic probe system (Webela-Siro VC600, supersonic & materials Co., Ltd.) at ambient temperature (20 ℃ C.) for 2 to 4 minutes. About 0.2g of the suspension was removed and the median particle size was measured by dynamic light scattering using a malverett philosophy nano-ZS ("ZEN") device and expressed as Dv (50%). All size data are based on volume weighted distribution and equivalent spherical diameter models. The results are shown in table II below.

TABLE II

TLTM ═ too large to measure using "ZEN" equipment "

The results shown in table II illustrate that the dispersants identified as tests 2-2 to 2-17 evaluated can effectively disperse carbon-coated silver particles having a desirably small median diameter (equal to or less than 0.6 μm) and are thus examples of non-aqueous compositions of the present invention.

Non-aqueous photocurable composition (21 wt% dispersed carbon-coated silver particles):

non-aqueous photocurable compositions were formulated using each of the particle dispersants (dispersants) shown in table III below and dispersed carbon-coated silver particles, and each of these non-aqueous photocurable compositions was used to manufacture electrically conductive articles.

A5% by weight solution of the desired dispersant was prepared by adding 2.5g of the dispersant to 47.5g of 1-methoxy-2-propanol with stirring until the dispersant was completely dissolved to form a dispersant solution. Next, 8g of carbon-coated silver particles (Novassex Ag-25-ST3, average particle size determined at 25nm, Ostin TX) were added with stirring to 8g of a 5 wt% dispersant solution in a 60ml bottle (LDPE, available from Nalon). The resulting non-aqueous composition was treated with an ultrasonic probe system (Weibull-Sailor VC600, supersonic & materials Co., Ltd.) at ambient temperature (20 ℃ C.) for 4 minutes.

A solution of photocurable components was prepared by mixing the following components: 27.33 wt% epoxy acrylate CN153(6.02g, Saedoma), 18.82 wt% poly (ethylene glycol) diacrylate (4.15g, M)_nIs 250, Westgamma-Aldrich), 4.04 wt% poly (ethylene glycol) diacrylate (0.89g, M)_n575, sigma-aldrich), 20.62% by weight of pentaerythritol tetraacrylate (4.55g, Saedo), 1.52% by weight of triarylsulfonium salt hexafluorophosphate (0.34g, sigma-aldrich) mixed in 50% propylene carbonate, 1.52% by weight of triarylsulfonium salt hexafluoroantimonate (0.34g, sigma-aldrich) mixed in 50% propylene carbonate, 4.55% by weight of the free-radical photoinitiator hydroxycyclohexylphenylketone (1.0g, sigma-aldrich), 2.32% by weight of the free-radical photoinitiator methyl-4' - (methylthio) -2-morpholinophenylpropanone (0.51g, sigma-aldrich), 0.002% by weight of 9-fluorenone (0.0004g, sigma-aldrich), 3.81% by weight of ethyl 4- (dimethylamino) benzoate (0.84g, sigma-aldrich) and 15.42 wt% 1-methoxy-2-propanol (3.4g, sigma-aldrich).

A sample (22.04g) of this photocurable component solution was added with stirring to a non-aqueous composition containing carbon-coated silver particles (16 g). Each of the non-aqueous photocurable compositions was then mixed using a PRO 300D bench top homogenizer with a rotor-stator probe (PRO Scientific, Inc.) operating at 10,000rpm for 5 minutes while allowing the non-aqueous photocurable composition to cool.

About 0.2g of the suspension was removed and the median particle size was measured by dynamic light scattering using a malverett philosophy nano-ZS ("ZEN") device and expressed as Dv (50%). All size data are based on volume weighted distribution and equivalent spherical diameter models. The results are shown in table III below.

About 2g samples of the non-aqueous photocurable composition (also referred to as "ink") were removed and placed in narrow glass vials to evaluate sedimentation and clarification after 24 hours to about 7 days. A clear band of colorless fluid on top of the resulting black non-aqueous photocurable composition after 24 hours indicated that the carbon-coated silver particles could not be maintained in suspension. The presence of sediment at the bottom of the vial without clarification indicates a suspension of partially stabilized carbon-coated silver particles. The results of these evaluations are shown in table III below.

TABLE III

Too large to measure TLTM

PVP ═ poly (vinylpyrrolidone)

Inv ═ non-aqueous photocurable compositions of the invention

Comparative non-aqueous photocurable composition

The results shown in table III illustrate that only the particulate dispersants (dispersants) defined herein provide a suitably small median diameter of the dispersed carbon-coated silver particles in the non-aqueous photocurable composition. In addition, the non-aqueous photocurable compositions of the present invention do not exhibit sedimentation or sedimentation during formulation and use.

Article invention example: use of non-aqueous photocurable compositions to provide patterned articles

The present examples demonstrate the use of the non-aqueous photocurable composition of the present invention in the manufacture of a precursor article having a photocurable pattern on a suitable substrate.

A flexographic printing member, a sample of a commercially available Kodak Flexcel NX flexographic printing plate precursor (eastman Kodak) was used to print the non-aqueous photocurable composition of the present invention (as described below), which had been imaged using a mask having a predetermined pattern written at a resolution of 12,800dpi using Kodak Square Spot laser technology. The flexographic printing plate precursor is UV exposed and treated (developed) using known conditions suggested by the manufacturer for these flexographic printing members. The resulting flexographic printing plate was 1.14mm thick (including PET film). The backing tape used to secure the flexographic printing plate to the plate cylinder was a 1120 Beiger (1120Beige) tape (3M company) 20 mils (0.051cm) thick with a Shore A hardness of 55. The resulting relief image design in the flexographic printing member comprised a grid pattern with fine lines having a width of 7 μm at the top relief surface.

Using the patterned flexographic printing member (described below), a benchtop test printer in flexographic mode "IGTF 1Printability Tester (IGT F1 printing Tester)" (IGT test Systems Inc. (IGTTesting Systems Inc.), Arlington mountain, IL) was used to print the non-aqueous photocurable composition 3-1(Inv) of the present invention described in Table III above onto a PET [ poly (ethylene terephthalate) film [ Melinaxox ]

ST505, Dupont emperor film (DuPont Teijin Films)]On a substrate. The anilox roller system used to apply the non-aqueous photocurable composition to the flexographic printing element has a value of 1.3BCMI and 1803lpi as determined by the IGT test system. The print pattern was made at ambient temperature using a screen force of 20N, a printing force of 10N and a printing speed of 0.20 m/s. The average line width printed on the substrate is obtained from the pattern printed by the grid pattern on the flexographic printing element.

These operations result in an article comprising a pattern of non-aqueous photocurable composition printed on a PET substrate.

Each of the non-aqueous photocurable compositions was irradiated with UV radiation using a Foundry (Fusion)300WPI medium pressure mercury lamp providing a radiation wavelength between 190 and 1500nm at an approximate exposure of 298mJ/cm²The printed patterns are cured by light. The printed and photocured average line widths of the cured patterns were measured using an Olympus BH-2 light microscope in both transmission and reflection modes.

This working example demonstrates that non-aqueous photocurable compositions can be successfully used to provide a precursor article having an uncured pattern on an appropriate substrate, which in turn can be used to provide an intermediate article having a photocured pattern.

Example of the invention: use of non-aqueous photocurable compositions for providing electrically conductive articles

The article comprising the photocured pattern described above can be used as an intermediate article for further operations. Specifically, by incorporating Nnaparlite

The intermediate article was subjected to electroless copper plating by soaking the intermediate article in a beaker of Cu-406 electroless plating solution (lesh (Enthone)) at 35 ℃ for 10 minutes, followed by rinsing with distilled water and drying with nitrogen gas to form a product article having a conductive pattern disposed on a PET substrate.

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

Claims

1. A non-aqueous composition comprising dispersed carbon-coated non-magnetic metal particles in an organic diluent in an amount of at least 10 weight% based on the total weight of the non-aqueous composition, said dispersed carbon-coated non-magnetic metal particles being treated with a catalyst having a weight average molecular weight (M) of at least 2,000 and up to and including 100,000_w) And a particulate dispersant comprising nitrogen-containing units dispersed therein,

wherein, when the non-aqueous composition contains up to and including 25 wt.% of the dispersed carbon-coated non-magnetic metal particles, it exhibits no visual sedimentation when subjected to a sedimentation test at 20 ℃ for at least 24 hours, and

when the dispersed carbon-coated non-magnetic metal particles are dispersed in a ratio of the dispersed carbon-coated non-magnetic metal particles to the particle dispersant of 20: 1 at 50% by weight in 1-methoxy-2-propanol, the median diameter of the dispersed carbon-coated non-magnetic metal particles being less than or equal to 0.24 μm as measured using dynamic light scattering.

2. The non-aqueous composition of claim 1, wherein the dispersed carbon-coated non-magnetic metal particles are dispersed carbon-coated silver particles or dispersed carbon-coated copper particles, or a mixture of both dispersed carbon-coated silver particles and dispersed carbon-coated copper particles.

3. The non-aqueous composition of claim 1, wherein the weight ratio of the particulate dispersant to the dispersed carbon-coated non-magnetic metal particles is at least 1:100 and up to and including 30: 100.

4. The non-aqueous composition of claim 1, wherein the dispersed carbon-coated non-magnetic metal particles are present in an amount of at least 15 weight% and up to and including 70 weight%, based on the total weight of the non-aqueous composition.

5. The non-aqueous composition of claim 1, wherein the particulate dispersant has a M of at least 2,000 and up to and including 50,000_w。

6. The non-aqueous composition of claim 1, further comprising dispersed carbon black in an amount up to and including 20 weight percent based on the total weight of the non-aqueous composition.

7. The non-aqueous composition of claim 1, wherein the particulate dispersant is an organic polymer comprising ester units.

8. The non-aqueous composition of claim 1, wherein the particulate dispersant is an organic polymer comprising units selected from at least one of the following classes (i) to (iv):

(i) a pyridine unit;

(ii) an imine unit;

(iii) an imide unit; and

(iv) an amine unit.

9. The non-aqueous composition of claim 1, wherein the dispersed carbon-coated non-magnetic metal particles are dispersed carbon-coated silver particles present at a concentration of at least 15 weight% and up to and including 60 weight%, based on the total weight of the non-aqueous composition.

10. The non-aqueous composition of claim 1, wherein the organic diluent is an organic solvent medium comprising at least one of 2-ethoxyethanol, 2- (2-methoxyethoxy) ethanol, 2- (2-ethoxyethoxy) ethanol, 1-methoxy-2-propanol, 4-heptanone, 3-heptanone, 2-heptanone, cyclopentanone, cyclohexanone, diethyl carbonate, 2-ethoxyethyl acetate, n-butyl butyrate, and methyl lactate.

11. The non-aqueous composition of claim 1, which is a non-aqueous photocurable composition further comprising a photocurable component and optionally a UV photoinitiator.

12. The non-aqueous composition of claim 11, wherein the photocurable component is a UV curable component.

13. The non-aqueous composition of claim 11, wherein the photocurable component is an acid-catalyzed photocurable component and the non-aqueous composition further comprises a photoacid generator.

14. The non-aqueous composition of claim 13, wherein the photocurable component is a photopolymerizable epoxy material.

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

16. The non-aqueous composition 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. The non-aqueous composition of claim 16, wherein the photocurable component comprises an acrylate.

18. An article comprising a substrate and having on one or both supporting sides of the substrate a dried layer of the non-aqueous composition of claim 1 or 11.

19. An article comprising a substrate and having on one or both supporting sides of the substrate a dried pattern of the non-aqueous composition of claim 1 or 11.

20. The article of claim 18 or 19, wherein the substrate is a continuous polymer web.

21. The article of claim 18 or 19, wherein the substrate comprises metal, glass, paper stock, or ceramic.

22. The article of claim 18 or 19, wherein the substrate is a continuous web comprising polyester.

23. The article of claim 18 or 19, wherein the substrate is a continuous polymeric web and the non-aqueous composition is arranged in a plurality of patterns on both supporting sides of the substrate.

24. An article comprising a substrate and having on one or both supporting sides of the substrate a dried layer of a photocurable composition derived from the non-aqueous composition of claim 11.

25. An article comprising a substrate and having on one or both supporting sides of the substrate a dried pattern of a photocurable composition derived from the non-aqueous composition of claim 11.

26. The article of claim 24 or 25, wherein the substrate is a continuous polymer web.

27. The article of claim 24 or 25, wherein the photocurable composition is arranged in one or more patterns on one or both supporting sides of the substrate.

28. The article of claim 24 or 25, wherein the substrate is a continuous polymeric web and the photocurable composition is arranged in a plurality of patterns on both supporting sides of the substrate.

29. The article of claim 24 or 25, wherein the substrate is a continuous web of polyester.

30. A method of providing a precursor article, the method comprising:

a continuous web of a transparent substrate is provided,

forming one or more photocurable patterns derived from the non-aqueous composition of claim 11 on one or more portions on at least one supporting side of the continuous web.

31. The method of claim 30, further comprising:

photocuring the one or more photocurable patterns to form one or more photocured patterns on the one or more portions of the continuous web, the one or more photocured patterns each comprising dispersed carbon-coated non-magnetic metal particles as seed metal catalyst sites, and

electrolessly plating each of the one or more photocured patterns on the one or more portions of the continuous web with a conductive metal.

32. The method of claim 31, further comprising:

performing the forming, photocuring, and electroless plating a plurality of times on a plurality of portions of the continuous web, the plurality of portions being the same or different, using the same or different nonaqueous composition.

33. The method of claim 30 for providing a plurality of precursor articles, the method comprising:

forming a plurality of photocurable patterns on a plurality of portions on one or both supporting sides of the continuous web by applying the nonaqueous composition to the portions using one or more flexographic printing elements,

advancing the continuous web comprising the plurality of photocurable patterns to approach exposure radiation and thereby form a plurality of photocured patterns, and

rolling up the continuous web comprising the plurality of photocured patterns.

34. The method of claim 30, wherein the substrate is a continuous polyester web.

35. The method of claim 34, wherein the substrate is a continuous polyester web comprising poly (ethylene terephthalate).

36. A method for forming a plurality of conductive patterns on a substrate, the method comprising:

providing a precursor article comprising a substrate and arranging on one or both supporting sides of the substrate a plurality of photocured patterns comprising dispersed carbon-coated non-magnetic metal particles as seed metal catalyst,

the plurality of photocured patterns is provided from one or more non-aqueous compositions according to claim 11, and

37. A method of forming a plurality of electronic devices, the method comprising:

providing an article comprising a substrate and arranging a plurality of electroless-plated and photocured patterns comprising dispersed carbon-coated nonmagnetic metal particles on one or both support sides of the substrate,

the plurality of electroless-plated and photocured patterns are provided from one or more non-aqueous compositions according to claim 1, and

forming a plurality of conductive objects from the plurality of electroless-plated and photocured patterns, and