TWI675744B - "electrically-conductive articles with protective polymeric coatings, method for providing the same, and electronic device comprising the same" - Google Patents

Abstract

The invention relates to an object, which includes a transparent substrate having a first supporting side and an opposite second supporting side. A conductive pattern is arranged on at least the first support side. The dried outermost polymer coating is disposed on at least a portion but not all of the conductive pattern. The dried outermost polymer coating has a dry thickness of less than 5 μm, an integrated transmittance of at least 80%, and includes a glass transition temperature (T _g ). Non-crosslinked thermoplastic polymer equal to or greater than 65 ° C. Such articles can be prepared and incorporated into various electronic devices.

Description

Conductive article with protective polymer coating, method for providing the same, and electronic device including the same

The present invention relates to a conductive object, which includes one or more conductive patterns that generally include one or more conductive metal patterns. The dry polymer coating is typically disposed on at least a portion of the conductive pattern for various protective and coloring features. Such conductive objects can be incorporated into various electronic devices to provide, for example, a touch screen display.

Various electronic devices are developing rapidly, especially display devices used for various communication, financial and archival purposes. For applications such as touch screen panels, electrochromic devices, light-emitting diodes, field-effect transistors, and liquid crystal displays, conductive films are extremely important and a lot of work has been done in the industry to improve the properties of their conductive films and especially Improves metal grid or line conductivity and provides greater consistency between the mask design and the resulting user metal pattern.

Conductive objects used in various electronic devices (including touch screens in electronic, optical, sensory and diagnostic devices (including but not limited to phones, computing devices, and other display devices)) have been designed to work against human fingertips or mechanical recording needles The touch is responsive. Generally, touch screen technology incorporates the use of resistive or capacitive sensor layers that form part of a display.

Generally, touch screen technology incorporates the use of resistive or capacitive sensor layers that form part of a display. There is a need to provide touch screen sensors and displays containing improved conductive film elements. Currently, these resistive and capacitive touch screen displays use an indium tin oxide (ITO) coating to create an array to distinguish multiple contact points. Struggling to find in industry Useful alternatives for ITO coatings include the use of various other conductive metal compositions.

As discussed, touch screens are often susceptible to damage due to increased direct contact (touch) by display users or due to moisture or water in the environment. Resistive and capacitive touch sensors can include translucent (or near-transparent) electrically insulating covering materials placed on the display structure to protect the touch screen sensor from environmental conditions (such as moisture), abrasion, oxygen, and Any harmful chemicals affect and isolate them.

There is also a need to protect the conductive portion of the sensor from environmental damage (such as moisture) and environmental and physical damage during manufacturing and integration operations.

These electrically insulating covering materials include a glass or polyester layer as a protective covering. Each of these materials has certain advantages and disadvantages. WO 2013/062630 (Petcavich) and WO 2013/063051 (Petcavich et al.) Both describe the use of light-curable compositions containing various light initiators and light-curable materials to form cross-links on touch sensors (and display screens). Protective layer of bipolymer.

U.S. Patent 7,569,250 (Nelson) describes applying a protective coating to a flex circuit having conductive traces on one surface and applying the protective coating in a The process of applying a liquid to a surface. Parts of the flex circuit remain exposed (uncoated) for attachment to an electronic device (such as a print head assembly). A protective coating may be applied to the surface of the flex circuit and then further processed, for example, by cross-linking or thermal curing.

Although these materials can provide a protective surface in touch sensors, it is desirable to avoid cross-linkable materials caused by other required processing procedures, as well as with photoinitiators or other chemicals that can remain in the final protective surface Potential problems with crosslinkers that are reactive and can cause yellowing when left in the protective coating as a protective coating.

In addition, residual photoinitiators used in photocuring operations for the preparation of protective coatings can cause adhesion and shrinkage problems, at least in part due to their low molecular weight, high flowability, and (again) high initial concentration, Therefore, the residual concentration after photocuring can be as high as 15% by weight of the final protective coating. These problems can be particularly noticeable in photocurable compositions that are applied to conductive patterns at high cure and printing speeds using printing methods such as flexography.

Therefore, there is a need to improve the protection of conductive patterns (especially in the presence of high concentrations of light-curable photoinitiators), thereby minimizing yellowing and other problems.

The invention provides an object, comprising: a transparent substrate having a first supporting side and an opposite second supporting side; a conductive pattern arranged on at least the first supporting side, and a dry outermost polymer coating arranged on at least On some but not all of the conductive pattern, the dried outermost polymer coating has a dry thickness of less than 5 μm, an integrated transmittance of at least 80%, and includes a non-crosslinked thermoplastic having a glass transition temperature (T _g ) equal to or greater than 65 ° C. polymer.

In some embodiments, the article of the present invention further comprises: a conductive pattern disposed on the opposite second support side of the transparent substrate, and a dry outermost polymer layer disposed on at least a portion of the transparent substrate on the opposite second support side But not all of the conductive patterns, the dried polymer coating has a dry thickness of less than 5 μm, an integrated transmittance of at least 80%, and includes a non-crosslinked thermoplastic polymer having a glass transition temperature (T _g ) equal to or greater than 65 ° C.

For example, an object as a conductive object may have a transparent substrate that is a continuous transparent polymer mesh, and the object may include at least a first portion and a second opposite support side disposed on the first transparent side of the continuous transparent polymer mesh. The same or different conductive patterns on at least the first portion.

In addition, in some other embodiments of the present invention, the continuous transparent polymer mesh includes: a plurality of portions on the first support side and a plurality of portions on the second support side Part; the same or different conductive patterns respectively arranged on the first support side and a plurality of parts opposite to the second support side in the transparent substrate; and a dry outermost polymer coating arranged on at least a part but not all of each conductive On the pattern.

The invention provides a number of advantages. Because the dried outermost polymer coating is not crosslinked (or crosslinkable), the dried outermost polymer coating does not require curing or post-treatment, thereby reducing the complexity of the printing device and process. In addition, problems related to photoinitiators and other cross-linking agents (such as yellowing from residual reactants) and other problems related to post-cure chemical reactions are avoided. In addition, potential problems from shrinkage and adhesion are avoided because low molecular weight materials (such as photoinitiators) are not needed. Finally, the dried outermost polymer layer is highly transparent and can be suitably used to cover all or only a portion of the conductive pattern so that a proper electrical connection can be achieved when desired.

definition

Unless otherwise indicated, as used herein to define the various components of the conductive pattern and dry outermost polymer coating, the singular forms "a, an" and "the" are intended to include one or more components (also That is, it includes a plurality of indicators).

As used herein, the term "light-curing" means subjecting functional oligomers and monomers or even polymers to exposure to such materials (e.g., irradiation with ultraviolet (UV), visible or infrared radiation at a suitable wavelength) ) Polymerize the crosslinked polymer network.

The term "photocuring" is used to define a material (or component) that polymerizes or crosslinks when exposed to suitable radiation in a suitable environment (eg, using radiation such as ultraviolet (UV), visible, or infrared radiation).

A "thermoplastic polymer" refers to a polymer that has no cross-linking sites between individual polymer macromolecules and becomes liquid, pliable, or moldable above a specific temperature and then returns to the solid state after cooling. In many cases, the thermoplastic polymer is also soluble in a suitable organic solvent medium.

The repeating units in the non-crosslinked thermoplastic polymers described herein are generally derived from polymerizable units used in condensation or radical polymerization processes, which polymerizable units have the desired properties and contribute to the desired polymer _Tg .

The average dry thickness of the layers described herein (e.g., the dried outermost polymer coating) can be, for example, the average of at least two separate measurements made in the dried layer using electron microscopy, light microscopy, or profiling Measured.

Similarly, the average dry thickness or width of a line, grid line, or other pattern feature described herein may be the average of at least two separate measurements, for example, using electron microscopy, light microscopy, or profiling .

"Actinic radiation" is used to mean any one that is capable of producing a photocuring or photopolymerization according to the present invention and has a wavelength of at least 200 nm and at most and including 1400 nm and usually at least 200 nm and at most and including 750 nm or even at least 300 nm and at most and including 700 nm An electromagnetic radiation. The term "exposure radiation" also refers to the actinic radiation.

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

Weight-average molecular weight ( _Mw ) was determined using size exclusion chromatography (SEC). The values reported herein are reported as poly (methyl methacrylate) equivalent weights.

Differential scanning calorimetry (DSC) can be used to determine the glass transition temperature (T _g ) and the values reported herein refer to the indium standard.

As used herein, the terms "transparent" and "transparency" referring to substrates, polymer layers (including dry outermost polymer coatings) refer to materials and structures with an integrated transmittance of at least 80% and more likely at least 90%. Integrated transmission is in the electromagnetic spectrum (e.g. 410nm to 700nm) The visible region is measured using a spectrophotometer and known techniques.

As used herein, the term "conductive pattern" refers to a predetermined or randomly arranged pattern of an electrical material having a function of carrying a current. In most embodiments, the conductive patterns are conductive metal patterns, but other conductive materials may be used. For example, conductive polymers, carbon nanotubes, graphene, and other conductive carbon structures may be used in other embodiments. . The conductive pattern can be composed of multiple regions, some of which are designed to be located in the "touch" region of a device (such as a touch screen sensor) incorporated into a conductive object. The other areas of the conductive pattern may be located outside the "touch" area and disposed in the boundary or electrical connection area. These areas may consist of conductive bus bars, probe pads, electrodes, and connectors. A connector or connector pad as defined for the present invention is a conductive region of a conductive pattern that is connected to an external electronic connection, a detector, a circuit, or other external component. For example, each conductive pattern may include a "conductive grid" or a "conductive metal grid" that can be arranged in a "touch" area. The conductive pattern may also include a "conductive connector" or a "conductive metal connector" located outside the "touch" area and being part of the connector pad. Other regions may include other conductive lines and interconnects that provide current paths within the device component.

use

The object of the present invention can be used in various technologies and devices, including but not limited to touch screen sensors, displays, integrated circuit components, microchips, thin-film transistor components, and others that can be used in many consumer, industrial and commercial products. Display or functional device. Imaging devices that can be used in these display devices can 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 prepare capacitive touch sensors that can be incorporated into electronic devices with 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 to produce flexible and optically compliant contacts in a high-volume roll-to-roll manufacturing process Systems and methods for controlling sensors are possible, in which micro-conductive features can be generated in a single pass. A plurality of high-resolution conductive patterns (or images) may be formed using a plurality of printed parts (eg, a plurality of flexographic printing plates) from predetermined designs or patterns provided in the plurality of printed parts. Printing multiple patterns on one or both sides of the transparent substrate can be explained in more detail below. For example, one predetermined pattern may be formed on one side of the transparent substrate and different predetermined patterns may be formed on opposite sides of the transparent substrate. The dry outermost polymer coating described herein may be incorporated or arranged in each of at least a portion, but not all of the plurality of conductive patterns.

Outermost polymer coating

The outermost polymer coating used in the present invention is derived from the mixing of one or more non-crosslinked thermoplastic polymers (hereinafter "polymers" unless otherwise indicated), each polymer or polymer mixture Has a glass transition temperature (T _g ) equal to or greater than 65 ° C.

Useful non-crosslinked thermoplastic polymers can be used to provide a transparent film as defined herein with the integrated transmittance described above.

These non-crosslinked thermoplastic polymers may be non-condensing polymers, including, but not limited to, polyesters, polyamides, polyimides, polycarbonates, polyurethanes, polyureas, and polyfluorenes. It is more likely that the non-crosslinked thermoplastic polymer is an addition polymer derived from one or more ethylenically unsaturated polymerizable monomers. These polymers include, but are not limited to, polyvinyl acetal, polyacrylic acid, and polypropylene. Amine, polystyrene, polyolefin, polyvinyl halide, polyvinylidene halide, polyfluorene and polyvinyl ether. Natural or synthetic cellulose can also be used.

Useful non-crosslinked thermoplastic polymers can be linear, branched, comb, or any other known polymer morphology. Also useful are block, graft, or cone copolymers or polymers containing multiple monomers in various morphologies, as long as the other properties described herein are achieved.

Particularly useful non-crosslinked thermoplastic polymers are "non-aromatic", which means that carbocyclic aromatic or heterocyclic aromatic moieties (or groups) are not intentionally included in the polymer.

Such useful non-crosslinked thermoplastic polymers include derivatives derived from at least one or more acrylic acids Ester or methacrylate Acrylic polymer of ethylenically unsaturated polymerizable monomer. Use of these monomers provides at least 5 mol% or at least 10 mol% and up to and including 100 mol% of "acrylic" repeating units (based on total repeating units) in the (co) polymer. If the "acrylic" repeating unit accounts for less than 100 mol%, the remaining repeating units may be derived from one or more ethylenically unsaturated polymerizable monomers familiar to those skilled in the art, as long as the repeating units do not include the ability to undergo a color change reaction Carbocyclic aromatic or heterocyclic aromatic moieties or other functional groups. Thus, useful acrylic polymers can be homopolymers or copolymers that include two or more different repeating units derived from two or more different ethylenically unsaturated polymerizable monomers.

Thus, acrylate or methacrylate vinyl-based unsaturated polymerizable monomers may include those which may be unsubstituted or substituted with one or more alkoxy, hydroxyalkoxy, alkoxyalkoxy, or haloalkoxy groups. Suitable for ester alkyl. For example, such useful ethylenically unsaturated polymerizable monomers include hydroxyalkyl methacrylates (such as methyl methacrylate), methyl methacrylate, ethyl methacrylate, methyl acrylate, Ethyl acrylate, n-butyl acrylate, n-butyl methacrylate, isobutyl methacrylate, third butyl acrylate, third butyl methacrylate, n-hexyl methacrylate, acrylic acid N-dodecyl ester, 2-ethylhexyl methacrylate, 2-ethylhexyl acrylate, cyclohexyl methacrylate, cyclohexyl acrylate, glycidyl methacrylate, glycidyl acrylate , Chloromethyl acrylate or hydroxyalkyl acrylate (such as hydroxyethyl acrylate or hydroxypropyl acrylate).

In many embodiments, non-crosslinked thermoplastic polymer-based copolymers (including terpolymers) each include a repeat derived from methyl (meth) acrylate (meaning methyl acrylate or methyl methacrylate) Units and repeating units derived from alkyl (meth) acrylates (wherein the alkyl group has at least 1 carbon atom and up to and including 18 carbon atoms), wherein the repeating units derived from alkyl (meth) acrylates account for At least 5 mol% and up to and including 25 mol% of the total copolymer repeat units, and repeat units derived from methyl methacrylate constitute the remaining total Polymer. Useful ethylenically unsaturated polymerizable monomers are described above and others will be readily apparent to those skilled in the art.

Other useful ethylenically unsaturated polymerizable monomers that can be used to provide repeating units in the copolymer include, but are not limited to, acrylamide, methacrylamide, acrylic acid, methacrylic acid, acrylonitrile, vinyl acetate, vinyl chloride And dichloroethylene or any other ethylenically unsaturated mono-aromatic polymerizable monomer capable of copolymerizing with (meth) acrylate.

Non-crosslinked thermoplastic polymers having one or more different types of repeating units derived from one or more of the aforementioned ethylenically unsaturated polymerizable monomers can be prepared, and the repeating units can be in any desired order (e.g., random, alternating, Block or other configurations known to those skilled in polymer chemistry) are disposed within the polymer.

The mol% amounts of the various repeat units defined herein for the polymers illustrated are intended to refer to the actual mole amounts present in the polymers. Those skilled in the art will understand that actual mol% values may differ from their theoretically possible values derived from the amount of ethylenically unsaturated polymerizable monomers used in the polymerization process. However, under most polymerization conditions that achieve high polymer yields and optimal reactions for all ethylenically unsaturated polymerizable monomers, the actual mol% of each ethylenically unsaturated polymerizable monomer is usually within the theoretical amount of ± 15mol% Inside.

Some representative non-crosslinked thermoplastic polymers include, but are not limited to, the following polymers, where the molar ratio is a theoretical (nominal) amount based on the actual molar ratio of the ethylenically unsaturated polymerizable monomer used in the polymerization process. If the polymerization reaction is not carried out completely, the actual molar amount of the repeating unit may be different from the theoretical (nominal) amount of the ethylenically unsaturated polymerizable monomer.

Poly (methyl methacrylate-co-n-butyl methacrylate) 90: 10 mole ratio; poly (methyl methacrylate-co-n-butyl methacrylate) 75: 25 mole ratio; Poly (methyl methacrylate-co-n-butyl methacrylate-co-methacrylic acid) 85: 15: 5 mole ratio; poly (methyl methacrylate-co-hexyl methacrylate) 90 : 10 mole ratio; poly (methyl methacrylate-co-octyl methacrylate) 90: 10 mole ratio; Poly (methyl methacrylate-co-lauryl methacrylate) 90: 10 mol ratio; poly (ethyl methacrylate-co-n-butyl methacrylate-co-methacrylic acid) 80: 15: 5 mole ratio; and poly (ethyl methacrylate-co-methacrylic acid) 90:10 mole ratio.

Useful non-crosslinked thermoplastic copolymers and terpolymers are commercially available. For example, poly (methyl methacrylate-co-n-butyl methacrylate) is obtained as ELVACITE ^® 4028; poly (methyl methacrylate-co-n-butyl methacrylate-co- methacrylic acid) -based obtained in the form of ELVACITE ^® 2614; and poly (methyl methacrylate - co - lauryl methacrylate ester) based to form ELVACITE ^® 2552 obtained from Lucite International.

Preparation of articles with dry outermost polymer coating

Generally speaking, the object of the present invention is prepared by first providing a suitable transparent substrate having a first support side and a second support side (opposite planar side opposite to the edge). A suitable transparent substrate may be composed of various materials.

Suitable transparent substrates include, but are not limited to, glass (including flexible glass), glass-reinforced epoxy laminates, cellulose triacetate, acrylate, polycarbonate, adhesive-coated polymer transparent substrates, polyester films, and transparent Composite material. Suitable transparent polymers for use as transparent polymer substrates include, but are not limited to, polyethylene and other polyolefins, polyesters (e.g., polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymer -1,4-cyclohexane dimethylene terephthalate, poly (butylene terephthalate) and its copolymers), polypropylene, polyvinyl acetate, polyurethane, Polyamines, polyimides, polyfluorenes, polycarbonates, poly (methyl methacrylate), and other materials readily understood by those skilled in the art. Other useful transparent substrates may be derived from cellulose derivatives (e.g., cellulose esters, cellulose triacetate, cellulose diacetate, cellulose acetate propionate, cellulose acetate butyrate, polyacrylates, polyetherimides, and mixtures thereof) Make up.

When presenting as a layer, the biaxially oriented sheet may also be provided with other layers that can be used to change the optical or other properties of the biaxially oriented sheet. These layers may contain colorants, antistatic Electrical or conductive materials or slips, as long as the desired integrated transmittance is maintained.

The use of flexible transparent substrates to manufacture flexible electronic devices or touch screen components facilitates rapid roll-to-roll manufacturing. ESTAR ^® poly (ethylene terephthalate) film, MELLINEX ^® poly (ethylene terephthalate) film and cellulose triacetate film are especially used for manufacturing flexible transparent substrates (including continuous substrate mesh). Useful materials.

The transparent substrate may have a thickness of at least 20 μm and up to and including 300 μm or typically at least 75 μm and up to and including 200 μm. If desired, antioxidants, antistatic or conductive agents, plasticizers, and other useful additives may be incorporated into the transparent substrate in suitable amounts.

The conductive pattern (such as a conductive metal pattern, which may include a conductive grid (such as a conductive metal grid) and a conductive connector (such as a conductive metal connector)) may be arranged in any desired manner (there are several techniques known in the industry) One or both of the first support side and the opposite second support side in the transparent substrate.

Some conductive patterns may be constructed from one or more conductive polymers, many of which are known in the art. For example, the conductive polymers may be selected from substituted or unsubstituted pyrrole-containing polymers [as described, for example, in US Patents 5,665,498 (Savage et al.) And 5,674,654 (Zumbalyadis et al.)]; Substituted or unsubstituted thiophene-containing polymers [e.g., in U.S. Patents 5,300,575 (Joans et al.), 5,312,681 (Muys et al.), 5,354,613 (Quinters et al.), 5,370,981 (Krafft et al.), 5,372,924 (Quinters et al. People), 5,391,472 (Muys et al.), 5,403,467 (Jonas et al.), 5,443,944 (Azoulay), 4,987,042 (Jonas et al., And 4,731,408 (Jasne)); and substituted or unsubstituted aniline containing polymers [As set forth, for example, in US Patents 5,716,550 (Gardner et al.), 5,093,439 (Epstein et al.), And 4,070,189 (Kelley et al.)].

Some conductive patterns may be composed of one or more conductive carbon structures, many of which are known in the industry and include, for example, conductive carbon black, carbon nanotubes, graphite, graphene, or combinations thereof.

In other embodiments, the conductive pattern is designed to have metallic features. For example, photosensitive silver halide technology can be used for this purpose on one or both support sides of a transparent substrate A conductive silver pattern is provided thereon, for example as set forth in U.S. Patent Application Publications 2011/0289771 (Kuriki) and 2011/0308846 (Ichiki). Other silver halide technologies used for this purpose are also described in co-filed and commonly assigned U.S. Patent Provisional Application No. 14 / 468,626 (filed by Lushington on August 26, 2014). In this technique, a silver halide emulsion can be designed on one or both supporting sides of a transparent substrate, exposed through a suitable mask, and then the pattern formed by this exposure can be processed to form a silver metal pattern and suitably remove non- Expose the silver halide emulsion. Various conductive silver patterns can be designed using predetermined masking elements having corresponding patterns to have a desired pattern.

In other embodiments, a light-curable composition that can provide a seed metal catalyst for an electroless plating process can be used to form a conductive pattern (such as a conductive metal pattern) on one or both support sides of a transparent substrate. For example, the photo-curable composition may include an acid-catalyzed photo-curable chemical substance, a radical photo-curable chemical substance, or these two types of chemicals, examples of which are described below, but the present invention is not limited to the described photo-curable Curing chemicals and can be implemented using any known photocurable composition that can further include a seed metal catalyst suitable for electroless metal plating processes.

Acid-catalyzed photo-curable chemicals:

In some embodiments, useful photo-curable compositions include one or more UV-curable components, at least one of which is an acid-catalyzed photo-curable component. The photocurable compositions may further include a photoacid generator that participates in generating acid radicals to cause photocuring of the photocurable component.

Some useful acid-catalyzed photocurable components are photocurable epoxy materials. The cationic photocurable epoxy material may be an organic compound having at least one ethylene oxide ring, which is shown in the following formula:

It can be polymerized (light-cured) by a ring-opening mechanism. These epoxy materials include monomeric epoxy compounds and epoxides of the polymer type and may be aliphatic, cycloaliphatic, aromatic or heterocyclic. Such materials typically have an average of at least one polymerizable epoxy group per molecule, or typically have at least about 1.5 or even at least about 2 polymerizable epoxy groups per molecule. Polymer epoxy materials include linear polymers with terminal epoxy groups (e.g. diglycidyl ether of polyoxyalkylene glycols), polymers with backbone (backbone) ethylene oxide units (e.g. polybutadiene Polyepoxides) and polymers with side chain epoxy groups (such as glycidyl methacrylate polymer or copolymer). The photocurable epoxy material may be a single compound or it may be a mixture of different epoxy materials containing one, two or more epoxy groups per molecule.

Epoxy materials can vary from low molecular weight monomer materials to high molecular weight polymers and the properties of their main chain and substituent (or side chain) groups can vary widely. For example, the main chain can be of any type and the substituents thereon can be any group that does not substantially interfere with the desired cationic photocuring process at room temperature. The permissible substituents illustrated include, but are not limited to, halogens, ester groups, ethers, sulfonate groups, siloxane groups, nitro groups, and phosphate groups.

Useful light epoxy materials include those containing epoxy cyclohexane groups, such as epoxy cyclohexane formate (e.g. 3,4-epoxycyclohexylmethyl-3,4-epoxy Cyclohexaneformate, 3,4-epoxy-2-methylcyclohexylmethyl-3,4-epoxy-2-methylcyclohexaneformate) and adipic acid bis (3 , 4-epoxy-6-methylcyclohexylmethyl) ester. A more detailed list of useful epoxy materials having this property is provided in US Patent 3,117,099 (Proops et al.).

Other useful epoxy materials include glycidyl ether monomers, which are glycidyl ethers of polyhydric phenols obtained by reacting polyhydric phenols with excess chlorohydrins such as epichlorohydrin [eg 2,2-bis- ( 2,3-epoxypropoxyphenol) -propane diglycidyl ether]. Other examples of such epoxy materials are described in US Patent 3,018,262 (Schroeder) and "Handbook of Epoxy Resins" by Lee and Neville, McGraw-Hill Book Company, New York (1967).

Other useful epoxy-based resins, such as propylene derived from reacting with glycidol Copolymers of acrylates (such as glycidyl acrylate and glycidyl methacrylate) copolymerized with one or more ethylenically unsaturated polymerizable monomers. Other useful epoxy materials are epichlorohydrin, alkylene oxides (such as propylene oxide and styrene oxide), alkenyl oxides (such as butadiene oxide), and glycidyl esters (such as ethyl glycidyl ester) . Other useful epoxy materials are polysiloxanes having epoxy functional groups or groups such as cyclohexyl epoxy groups, especially their epoxy materials having a polysiloxane backbone. Commercial examples of these epoxy materials include UV 9300, UV 9315, UV 9400, UV 9425 polysiloxane materials available from Momentive.

The polymeric epoxy material may optionally contain other functional groups that do not substantially interfere with the cationic photocuring of the photocurable composition at room temperature. For example, a photopolymerizable epoxy material may also include free radical polymerizable functionality.

The photopolymerizable epoxy material may include a blend or mixture of two or more different epoxy materials. Examples of such blends include two or more molecular weight distribution photopolymerizable epoxy materials, such as one or more low molecular weight (less than 200) epoxy materials and one or more medium molecular weight (200 to 10,000) light Polymerizable epoxy materials or blends of one or more of these photopolymerizable epoxy materials with one or more higher molecular weight (greater than 10,000) epoxy materials. Alternatively or additionally, the photopolymerizable epoxy material may include a blend of epoxy materials having different chemical properties (such as aliphatic and aromatic properties or different functional groups (such as polar and non-polar properties)).

The photocurable composition comprises one or more amounts of a photocurable epoxy material suitable to provide the desired effective photocuring (or photopolymerization). For example, based on the total weight of the photocurable composition, the one or more photopolymerizable epoxy materials may be at least 5% by weight and up to and including 50% by weight or usually at least 10% by weight and up to and including 40% by weight. presence.

Various compounds can be used as photoacid generators to generate suitable acids to participate in photocuring in epoxy materials. Some of these "photoacid generators" are acidic and others are non-ionic. Those skilled in the art can easily understand according to the teaching provided in this article except that they are explained below. Other useful photoacid generators other than those mentioned.

The onium hydrochloride generators that can be used as photoacid generators in the practice of the present invention include, but are not limited to, diazonium salts, sulfonium, iodonium, or phosphonium salts, including polyaryldiazonium, phosphonium, iodonium, and sulfonium salts. Iodonium or sulfonium salts include, but are not limited to, diaryl iodonium and triarylsulfonium salts. Useful counter anions include, but are not limited to, complex metal halides such as tetrafluoroborate, hexafluoroantimonate, trifluoromethanesulfonate, hexafluoroarsenate, hexafluorophosphate, and aromatic sulfonates ( arenesulfonate). An onium salt may also be an oligomer or polymer compound having multiple onium salt moieties and a molecule having a single onium salt moiety.

Useful iodonium salt may be a simple salt (e.g., containing an anion (e.g. chloride, bromide, iodide, or ^{_{C 4 H 5 SO 3 -)}} ) or a metal complex salt (e.g., containing _{^{SbF 6 -, PF 6 -,}} BF ₄ ^-, tetrakis (perfluorophenyl) borate or ^{_{SbF 5 OH 31 AsF 6 -)}} . If desired, a mixture of any of these same or different iodonium salts can be used. The use of phosphonium salt is desirable and it should be soluble in any inert organic solvent (as explained below) and it should also be shelf-stable, which means that it is compatible with other components (especially electron acceptors) before exposure to suitable radiation. Bulk photosensitizers and electron donor co-initiators) do not spontaneously promote polymerization when mixed. Particularly useful phosphonium salts include, but are not limited to, triaryl substituted salts, such as mixed hexafluoroantimonate triarylsulfonium (for example, commercially available from Dow Chemical Company as UVI-6974), mixed hexafluorophosphate triarylsulfonium (for example, UVI-6990 (available from Dow Chemical Co.) and arylfluorene hexafluorophosphate (for example from Sartomer).

Based on the total weight of the photocurable composition, the one or more onium salts (e.g., iodonium or sulfonium salts) may generally be at least 0.05% by weight and up to and including 10% by weight or usually at least 0.1% by weight and up to and including 10% by weight Or even present in the photocurable composition in an amount of at least 0.5% by weight and up to and including 5% by weight.

Non-ionic photoacid generators can also be used in the present invention. These compounds include, but are not limited to, diazomethane derivatives. The non-ionic photoacid generator may also include an ethylenedioxime derivative. Useful photoacid generators may also include difluorene derivatives. Other useful nonionic photoacids The generating agent contains a disulfo derivative.

Based on the total weight of the photocurable composition, the one or more non-ionic photoacid generators may be at least 0.05% by weight and up to and including 10% by weight or usually at least 0.1% by weight and up to and including 10% by weight or even at least 0.5% by weight Is present in the photocurable composition in an amount of up to and including 5% by weight.

Some of the photocurable compositions described herein, especially those containing photopolymerizable epoxy materials and photoacid generators, may contain one or more electron donor photosensitizers to improve photocuring efficiency. Useful electron donor photosensitizers should be soluble in the photo-curable composition, contain no functional groups that substantially interfere with the cationic photo-curing process, and can absorb (sensitivity) light of at least 150 nm and up to and including wavelengths in the 1000 nm range. .

Suitable electron-donor photosensitizers initiate chemical conversion of onium salts (or other photoacid generators) in response to photons absorbed from irradiation. After the electron donor photosensitizer absorbs light, the electron donor photosensitizer should also be able to reduce the photoacid generator (ie, light-induced electron transfer). Therefore, electron donor photosensitizers are generally capable of donating electrons to photoacid generators after absorbing photons from irradiation.

When extremely fast curing is desired (e.g., curing of the applied photo-curable composition film), the electron donor photosensitizer may have at least 1000 liters-Mole ^-1 cm ^-1 at a desired irradiation wavelength using a photo-curing process, and Usually an extinction coefficient of at least 50,000 liters-Mole ^-1 cm ^-1 . For example, each electron donor photosensitizer typically has an oxidation potential (relative to SCE) of at least 0.4V and up to and including 3V.

In general, many different kinds of compounds can be used as electron donor photosensitizers for various 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. Other useful electron donor photosensitizers involving triplet excited states are carbonyl compounds such as thioxanthone and xanthone. Ketones (including aromatic ketones (e.g. fluorenone)) and coumarin dyes (e.g. ketocoumarin) (e.g. those with a strong electron donating moiety (e.g. dialkylamino)) can also be used as electron donor Body photosensitizer. It is believed that other suitable electron donor photosensitizers contain Xanthene dye, acridine dye, thiazole dye, thiazine dye, oxazine dye, azine dye, amine ketone dye, porphyrin, aromatic polycyclic hydrocarbon, para-substituted amine styryl ketone compound, amine group Triarylmethane, meroanthocyanins, squaraine dyes and pyridinium dyes.

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

Based on the total weight of the photo-curable composition, one or more electron donor photosensitizers may be present in the photo-curable in an amount of at least 0.000001 wt.% And up to and including 5 wt.% And usually at least 0.0001 wt.% And up to and including 2 wt.%. In the composition.

In some embodiments, the electron donor photosensitizer is fluorene, benzofluorene, fluorene, or benzofluorene, which is present in an amount of at least 0.0001% by weight and up to and including 2% by weight based on the total weight of the photocurable composition.

In other embodiments, a combination of one or more electron acceptor photosensitizers and one or more electron donor co-initiators may be used instead of the electron donor photosensitizer.

Suitable electron acceptor photosensitizers are responsible for the chemical conversion of onium salts caused by photons absorbed from irradiation. The electron acceptor photosensitizer should also be able to oxidize the electron donor co-initiator (as explained below) to free radical cations (ie, light-induced electron transfer) after the electron acceptor photosensitizer absorbs light. Therefore, electron acceptor photosensitizers are usually able to accept electrons from the electron donor co-initiator after absorbing photons from radiation.

When extremely fast curing is desired (e.g., curing of applied composition films), the electron acceptor photosensitizer may have at least 1000 liters-Mole ^-1 cm ^-1 and typically at least 10,000 at the desired irradiation wavelength using a photo-curing process. Extinction coefficient of liter-Mole ^-1 cm ^-1 .

In general, many different kinds of compounds can be used as electron acceptor photosensitizers for various reactants, provided that the energy requirements discussed above are met. Useful electron acceptor photosensitizers include, but are not limited to, cyano aromatic compounds, aromatic acid anhydrides, and imidamines and condensed pyridinium salts. Other useful electron acceptor photosensitizers involving triplet excited states are carbonyl compounds, such as quinones. Ketones (including aromatic ketones (such as fluorenone)) and coumarin dyes (such as ketocoumarin) (such as those with a strong electron-withdrawing moiety (such as pyridinium)) can also be used as electron acceptor photosensitizers Agent. It is believed that other suitable electron acceptor photosensitizers include xanthene dye, acridine dye, thiazole dye, thiazine dye, oxazine dye, azine dye, amino ketone dye, porphyrin, aromatic polycyclic hydrocarbon, para-substitution Amine styryl ketone compounds, amine triarylmethanes, merocyanin, squaraine dyes and pyridinium dyes. Diaryl ketones and other aromatic ketones (such as fluorenone) are useful electron acceptor photosensitizers.

Based on the total weight of the photo-curable composition, one or more electron acceptor photosensitizers may be present in the photo-curable in an amount of at least 0.000001 wt% and up to and including 5 wt% and usually at least 0.0001 wt% and up to and including 2 wt%. In the composition.

By including one or more electron donor co-initiators in the photocurable composition, the use of electron acceptor photosensitizers is highly effective. Each electron donor co-initiator has at least 0.1V and at most and contains 3V. Oxidation potential (relative to SCE). These electron donor co-initiators should be soluble in the photocurable composition.

Useful electron donor co-initiators are alkyl aromatic polyethers, aryl groups via one or more electron withdrawing groups (including but not limited to carboxylic acids, carboxylic acid esters, ketones, aldehydes, sulfonic acids, sulfonic acid esters) And nitrile groups) substituted arylalkylamino compounds. For example, aryldialkyldiamine compounds are useful in which the aryl group is a substituted or unsubstituted phenyl or naphthyl group (e.g., a benzene having one or more electron withdrawing groups as described above). Or naphthyl), and the two alkyl groups independently include 1 to 6 carbon atoms.

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

As mentioned above, all photocurable compositions containing various basic and optional components may be further at least 0.5% by weight and up to and including 20% by weight or at least 1% by weight based on the total weight of the photocurable composition. Contained in an amount of 10% by weight including dispersed carbon black.

Free radical photocurable chemicals:

In other embodiments, the photocurable composition may include one or more UV curable components, at least one of which is a radical photocurable component and the photocurable composition may further include a radical photoinitiator. To provide free radicals during light curing.

One or more free radical polymerizable compounds may be present to provide free radical polymerizable functional groups, including ethylenically unsaturated polymerizable monomers, oligomers, or polymers (such as monofunctional or polyfunctional acrylates) (also containing methyl groups) Acrylate). The radical polymerizable compounds include at least one ethylenically unsaturated polymerizable bond (portion) and in many embodiments it may include two or more of the unsaturated portions. Such suitable materials contain at least one ethylenically unsaturated polymerizable bond and are capable of addition (or radical) polymerization. The free radical polymerizable materials include mono-, di- or polyacrylates and methacrylates, including but not limited to methyl acrylate, methyl methacrylate, ethyl acrylate, isopropyl methacrylate, acrylic acid N-hexyl ester, stearyl acrylate, allyl acrylate, glycerol diacrylate, glycerol triacrylate, ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol dimethacrylate , 1,3-propanediol diacrylate, 1,3-propanediol dimethacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, neopentyl glycol diacrylate , Neopentyl glycol dimethacrylate, trimethylolpropane triacrylate, 1,2,4-butanetriol trimethacrylate, 1,4-cyclohexanediol diacrylate, neopentyl Tetraol triacrylate, neopentaerythritol tetraacrylate, neopentaerythritol tetramethacrylate, dipentaerythritol hexaacrylate, sorbitol hexaacrylate, bis [1- (2-propenyloxy) )]-P-ethoxyphenyldimethylmethane, bis [1- (3-propenyloxy-2-hydroxy)]-p-propoxyphenyldimethyl Methane and trihydroxyethyl isocyanurate trimethacrylate; diacrylates and bismethacrylates of polyethylene glycol having a molecular weight of 200 to 500 and containing 500; copolymerizable mixtures of acrylate monomers , Such as those described in U.S. Patent 4,652,274 (Boettcher et al.); And acrylate oligomers, such as those described in U.S. Patent 4,642,126 (Zader et al.); And vinyl compounds such as styrene and styrene derivatives, Diallyl phthalate, divinyl succinate, diethylene adipate And divinyl phthalate.

Although the amount of the one or more radical polymerizable materials is not particularly limited, it may be at least 30% by weight and up to and including 90% by weight or usually at least 40% by weight and up to and including 85 based on the total weight of the photocurable composition. An amount by weight is present in the photocurable composition.

One or more free radical photo initiators may also be present in the photocurable composition to generate free radicals. The free radical photoinitiators include any compound capable of generating free radicals upon exposure to photocuring radiation, such as ultraviolet or visible radiation. For example, the radical photoinitiator may be selected from the group consisting of triazine compounds, thioxanthone compounds, benzoin compounds, carbazole compounds, dione compounds, sulfonium borate compounds, diazo compounds, benzophenone compounds, and biimidazole Compounds and other compounds readily understood by those skilled in the art.

Based on the total weight of the photocurable composition, the one or more free radical photoinitiators may be at least 0.3% by weight and up to and including 10% by weight or usually at least 0.4% by weight and up to and including 10% by weight or even at least 0.5% by weight And is present in the photocurable composition in an amount up to and including 5% by weight.

The photocurable compositions (acid-catalyzed chemicals or free-radical chemicals) described herein generally include suitable metal particles that can be used as seed metal catalytic sites for electroless plating processes. Generally, only one type of metal particles is used, but a mixture of metal particles from the same or different metal types that do not interfere with each other can also be included. The metal particles typically have a net neutral charge.

Useful metal particles may be selected from one or more types of precious metals, semi-precious metals, Group IV metals, or combinations thereof. Useful metal particles include, but are not limited to, particles of gold, silver, palladium, platinum, rhodium, iridium, osmium, mercury, ruthenium, osmium, iron, cobalt, nickel, copper, aluminum, zinc, and tungsten. Useful Group IV metal particles include, but are not limited to, particles of tin, titanium, and germanium. Precious metal particles (such as particles of silver, palladium, and platinum) are particularly useful, as are semi-precious particles of nickel and copper. Tin particles are particularly useful in Group IV metal species. In many embodiments, light can be fixed Silver particles or copper particles are used in the chemical composition.

Surfactants, polymers, or carbon can be used to coat and separate metal particles that can be used in the present invention. The carbon on the carbon-coated metal particles can have amorphous, sp2-mixed, or graphene-like properties. The carbon can be used to prevent the aggregation of metal particles and provide improved dispersibility in the photopolymerizable composition. Useful carbon-coated metal particles include carbon-coated silver particles and carbon-coated copper particles or a mixture of carbon-coated silver particles and carbon-coated copper particles.

The metal particles that can be used in the photocurable composition can be dispersed in various organic solvents and can be in the presence of other components of the photocurable composition (such as a multifunctional polymer epoxy material) or in optional components (such as The multifunctional acrylate resins described below have improved dispersibility. Useful dispersants are known in the art and may also be present if desired. Methods for dispersing metal particles include, but are not limited to, ball milling, magnetic stirring, high-speed homogenization, high-pressure homogenization, and ultrasonic processing.

The metal particles that can be used in these embodiments can exist as individual particles in the photocurable composition, but in many embodiments, the metal particles exist as agglomerates of two or more metal particles. These metal particles can exist in any geometric shape, including but not limited to spherical, rod-shaped, prism-shaped, cubic, cone-shaped, pyramid-shaped, wire-shaped, lamellar, platelet-shaped, and combinations thereof, and their shapes and sizes It can be uniform or non-uniform. The average particle size of the individual and agglomerated metal particles may vary from at least 0.01 μm and up to and including 25 μm or more likely at least 0.02 μm and up to and including 5 μm. Although the size of the metal particles is not particularly limited, the best benefit can be achieved using metal particles in the form of individual particles or aggregates having an average particle size of at least 0.02 μm and up to and including 10 μm. The particle size distribution is desirably narrow, as defined by a particle size in which more than 50% or usually at least 75% of the particles is in the range of 0.2 to 2 times the average particle size. The average particle size (same as the mean particle size) can be determined from any suitable procedure and equipment (including those purchased from Coulter or Horiba) and the appropriate mathematical calculations used for the equipment Diameter distribution.

When carbon-coated metal particles are used, they can be designed to have a median particle diameter that is equal to or less than 0.6 μm or less than 0.2 μm or more possibly less than 0.1 μm. The carbon-coated metal particles typically have a minimum median diameter of 0.005 μm. The median particle diameter [Dv (50%)] can be determined using a dynamic light scattering method. For example, this method can be implemented using a Malvern Zetasizer Nano ZS commercially available from Malvern Instruments Ltd.

Photocurable compositions are typically provided in a suitable organic diluent that is a non-aqueous (organic) solvent or solvent combination used as a component to dissolve or disperse the photocurable composition. In many embodiments, 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 ^TM PM organic solvent), 4-heptanone, 3-heptanone, 2-heptanone, cyclopentanone, cyclohexanone, Diethyl carbonate, 2-ethoxyethyl acetate, n-butyl butyrate, acetone, dichloromethane, isopropanol, ethylene glycol, and methyl lactate. "Inert" means that the organic solvent does not significantly participate in any chemical reaction.

Based on the total weight of the photocurable composition, the organic diluent (such as an organic solvent medium) may account for up to and including 1% by weight or up to at least 70% by weight or at least 10% by weight and up to and including 30% by weight. Organic diluents usually contain little or no water (usually less than 5% by weight of the total photocurable composition), so that the photocurable composition can be considered a "photocurable composition."

When one or more photocurable components (as set forth above) are present as liquid organic compounds, their one or more photocurable components can be used as organic diluents and may not require a separate inert organic solvent. In these cases, organic diluents can be considered "reactive" diluents. Alternatively, one or more reactive diluents can be used in combination with one or more inert organic solvents to form a suitable organic diluent.

object

The light-curable composition described above can be formulated as described above and used at any time. A suitable method is applied to one or both support sides (planar sides) of any suitable substrate (described below) to form a "precursor article". For example, dip coating, roll coating, hopper coating, spray coating, spin coating, inkjet, photolithography, and the use of flexographic printing components such as flexographic printing plates and flexographic printing sleeves can be used )) Flexographic printing, lithographic printing using lithographic printing plates, and gravure or intaglio printing with appropriate printed parts, apply the photocurable composition to one or two supporting sides in a uniform or pattern-wise manner. Flexographic printing using flexographic printing components can be used to provide multiple patterns of the same or different photocurable compositions on one or both of the substrate's supporting sides and one or more portions of either of the substrate's supporting sides (e.g., in When it is a continuous transparent polymer mesh).

The applied photo-curable composition may be formed and dried into a uniform layer or dried into a predetermined pattern. The resulting article can be considered as a "precursor" article prior to photocuring as explained below.

As described in more detail below, the substrates used for such objects can be constructed from any useful material and can be individual films or sheets of any suitable size and shape (e.g., metallic materials, glass, paper (any type of Cellulosic material) or ceramic), or it may be a continuous web of material (eg, a continuous transparent polymer mesh, such as a continuous poly (ethylene terephthalate) mesh).

In the dry photocurable composition, metal particles (such as carbon-coated metal particles) may be present in an amount of at least 10% by weight and up to and including 90% by weight, and the particle dispersant may be at least 1% by weight and up to and including 30% by weight The amount is present, individual carbon particles may be present in an amount of up to and including 20% by weight, and the photocurable component (explained above, before curing) may be present in an amount of up to and including 90% by weight.

After the photo-curable composition is applied on one or both of the supporting sides of the transparent substrate in a suitable manner (for example, in a pattern-by-pattern manner), the resulting intermediate article may be appropriately processed to photo-curable the photo-curable composition in a suitable pattern to Provide a conductive pattern with a seed metal catalyst.

A suitable dry outermost polymer coating may be disposed on the entire surface of each conductive metal pattern, but in most embodiments, it is disposed on only a portion of the conductive metal pattern. For example, a non-crosslinked thermoplastic polymer as set forth above can be used to place the entire conductive metal grid, but only on a portion of the conductive metal connector. This configuration of the dried outermost polymer layer may be arranged on only one of the first supporting side and the opposite second supporting side, or on both of the supporting sides.

The dried outermost polymer coating may have a dry thickness of less than 5 μm or more possibly less than 3 μm or even less than 1 μm. The maximum dry thickness is not limited, but for practical purposes, the maximum dry thickness is a maximum of 20 μm. The dried outermost polymer coating also has an integrated transmittance of at least 80% or more likely of at least 90% (as measured using the techniques set forth above) and a glass transition temperature of at least 65 ° C (as set forth above). In some embodiments, the dried outermost polymer coating has a dry thickness of less than 3 μm and an integrated transmittance of greater than 90%, and the non-crosslinked thermoplastic polymer is a non-crosslinked thermoplastic non-crosslinked thermoplastic acrylic polymer. Aromatic polymer.

In some particularly useful embodiments, the objects include a conductive pattern (such as a conductive metal pattern) on one or both of the first support side and the opposite second support side of the transparent substrate, including a conductive metal pattern, For example, they are composed of metal wires, which are composed of silver, copper, palladium or platinum, and especially copper or silver. In addition, the conductive metal patterns can be obtained by electrolessly plating carbon-coated metal particles (such as carbon-coated silver particles) and individual carbon particles mixed with the carbon-coated metal particles as appropriate. In the case where the conductive metal pattern has a conductive metal grid and a conductive metal connector, the conductive metal connector may have a similar configuration, except that it may not substantially include individual carbon particles (this means that there are individual carbon particles less than 5% by weight) ).

Therefore, after subjecting the intermediate article to conditions for photo-curing a photo-curable composition disposed on a supporting side of a transparent substrate and forming a dry outermost polymer coating using the procedures and equipment described below, the resulting product can be Objects incorporated into touch screens that require conductive patterns Or other devices.

Uses of photocurable compositions

After the dry outermost polymer coating is provided, the light-curable composition described herein can be photocured (or photopolymerized) using suitable radiation (including ultraviolet or visible light or both). One or more suitable light sources may be used for the exposure process. Each precursor article may be individually exposed as a single element, or in alternative embodiments described below, when passing a continuous polymer web through an exposure station, or when passing an exposed device through a continuous transparent polymer in a desired path When above the mesh, continuous meshes (such as roll-to-roll continuous transparent polymer meshes) can be exposed individually or collectively. Body (including multiple photo-curable patterns). The same or different photocurable compositions can be applied (eg, printed using flexography and flexographic printing components) on the two supporting sides of the substrate, whether the substrate is in the form of a single element or a continuous transparent polymer mesh. In many embodiments, the photo-curable composition described herein can be used to form different conductive patterns on opposite support sides of a substrate (or continuous polymer mesh).

When the photocurable composition is uniformly applied to a suitable substrate, the resulting uniform dry layer can be "imaged" or selectively exposed (or patterned) via a suitable light mask (masking element) with a desired pattern using exposure radiation, and A suitable "developer" solution that dissolves or otherwise removes the non-photocurable material is then used to properly remove the non-crosslinked (non-cured) photocurable composition. These features or steps may be implemented on two (opposite) support sides of the substrate. If desired, multiple conductive and photo-curable patterns can be formed in the dried layer using the same or different photomasks.

It is more likely that a predetermined pattern of one or more photocurable compositions can be formed on a suitable substrate using a method as described below.

A suitable substrate (also known in the industry as a "receiver element") that can be used to provide a precursor substrate can be composed of any suitable material as long as it does not inhibit the purpose of the photocurable composition. For example, useful substrates can be formed from materials that include but are not limited to: polymer films, gold Metal, paper, rigid or flexible glass (untreated or treated with, for example, a Teflon plasma, hydrophobic fluorine or silicone waterproofing material), silicon or ceramic wafers, fabrics and combinations thereof (e.g. various membranes Lamination or lamination of paper and film) provided that a uniform layer or pattern of photocurable composition can be formed on the substrate in a suitable manner and then irradiated to form uniform light on at least one of its receiving (supporting) surfaces. A cured layer or one or more light-cured patterns. The substrate may be transparent, translucent or opaque, and rigid or flexible. Many useful substrates are transparent and have an integrated transmittance of at least 90%, and the transparent substrates can also be flexible continuous transparent polymer meshes.

In some embodiments, the substrate may include a separate receiving layer as a receiving surface disposed on the substrate, and the receiving layer and the substrate may be composed of a material such as a suitable polymer material that highly receives the light-curable composition. The dry thickness of the receiving layers when measured at 25 ° C may be at least 0.05 μm and up to and including 10 μm, or usually at least 0.05 μm and up to and including 3 μm.

More particularly, suitable substrate materials for forming precursor objects in the form of continuous transparent polymer mesh include, but are not limited to, metal films or foils, metal films on polymers (e.g., metal films on conductive polymer films), Flexible glass, semi-conductive organic or inorganic film, organic or inorganic dielectric film or a laminate of two or more layers of these materials. For example, a useful continuous transparent polymer mesh substrate may include a polymeric film (e.g., a poly (ethylene terephthalate) film, a poly (ethylene naphthalate) film, a polyimide film, a polycarbonate Film, polyacrylate film, polystyrene film, polyolefin film, and polyamide film), metal foils (such as aluminum foil), cellulose or resin-coated or glass-coated paper, paperboard mesh, and metalized polymers membrane.

A particularly useful substrate is a transparent polyester film having an integrated transmittance of greater than 90% as explained above.

In some embodiments, the first polymer latex and the second polymer latex may be mixed to form a dry primer layer on a substrate, thereby adhering a patterned material having fine conductive lines formed using a photo-curable composition. The first polymer latex may include a first polymer and a first polymer A surfactant, so that the dry coating of the first polymer latex has a surface polarity of at least 50%. The second polymer latex may include a second polymer and a second surfactant, so that the dry coating of the second polymer latex has a surface polarity of less than or equal to 27%.

At least one of the first and second polymers described herein includes containing at least a portion derived from glycidyl (meth) acrylate (meaning glycidyl acrylate, glycidyl methacrylate, or both) ) Of vinyl polymer. In addition, at least one of the first polymer and the second polymer is cross-linkable, and the polymer may be, for example, after a polymer mixture is coated on a suitable carrier (for example, drying on a substrate or various heat treatments) Period).

The first polymer may be a homopolymer derived from glycidyl (meth) acrylate, but more likely, it is derived from glycidyl (meth) acrylate and one or more other ethylenically unsaturated polymers. Copolymer of polymerized monomers.

The second polymer latex may include one or more second polymers and one or more second surfactants (described below) so that the dry coating of the second polymer latex has less than or equal to 28% or less than or equal to 27% surface polarity. As explained above for the first polymer, a particularly useful second polymer is derived at least in part from one or more glycidyl-functional ethylenically unsaturated polymerizable monomers (eg, glycidyl (meth) acrylate, Examples are vinyl polymers of glycidyl acrylate and glycidyl methacrylate). Therefore, 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. Thing.

The first polymer latex includes one or more first surfactants, each of which is a sodium alkylsulfonic acid salt, wherein the alkyl group has at least 10 carbon atoms. For example, the first surfactant may be an α-olefin (C ₁₄ -C ₁₆ ) sodium sulfonate, or the first surfactant may be R-CH ₂ -CH = CH-CH ₂ -S (= O ) ₂ O ^- Na ⁺ (wherein R is a C ₁₀ , C ₁₁ or C ₁₂ hydrocarbon group) or a mixture of these compounds (wherein different R groups are any of C ₁₀ to C ₁₂ hydrocarbon groups) .

The second polymer latex includes one or more second surfactants, each of which is an alkylphenol ammonium sulfate having at least 3 ethylene oxide units. For example, the second surfactant may be polyethoxynonylphenol ammonium sulfate, or the second surfactant may be R'-phenyl- (O-CH ₂ CH ₂ ) _n -S (= O) O ₂ ^- NH ₄ ⁺ representatives, where R 'based C ₈ to C ₁₂ hydrocarbyl group and n is at least 3 and up to 10, and comprising, or more likely, n is at least 3 and up to 6, and comprising.

The substrates used to prepare the articles described herein can be provided in various forms, such as individual sheets and continuous meshes of any size or shape (e.g., continuous transparent polymer meshes suitable for roll-to-roll operations (including continuous transparent polyester meshes) Film) of continuous network). These continuous polymer meshes can be divided or formed into individual first, second, and other portions, and these portions can be used to form the same or different light-curable conductive patterns.

After the photo-curable composition is applied pattern by pattern, any remaining organic solvents can be removed by evaporation, such as a drying or pre-baking process that does not adversely affect the remaining components or cause photo-curing prematurely. In most of the processes described below (eg, roll-to-roll processes), the drying conditions can be at a sufficiently high temperature and suitable drying equipment to remove at least 90% of all inert organic solvents in at least 5 seconds. For example, a suitable removal of the inert organic solvent can be achieved by using hot air spray, evaporation at room temperature, or heating in an oven at an elevated temperature.

The dry thickness of any of the applied uniform photo-curable composition layers may be at least 0.1 μm and at most and includes 10 μm or usually at least 0.2 μm and at most and includes 1 μm, and the optimal dry thickness may be for the resulting uniform photo-curable layer. The application is intended to be adjusted, which typically has a dry thickness of about the same as a uniform non-photocurable photocurable composition layer.

Any of the applied photo-curable composition patterns may include 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 line grids (or other shapes (including circles, diamonds, or ovals or Pattern of irregular network), and the optimal drying width can be adjusted for the intended use of the obtained uniform photo-curable layer, which is uniform The photo-curable layer typically has a photo-curable and conductive metal wire having substantially the same size as the non-photo-curable conductive metal wire.

In some embodiments, the same or different light-curable compositions may be applied to the two support sides (planar surfaces) of the substrate in a suitable manner to form a "two-way" or two-sided precursor object, and each applied light The curable composition may be in the form of the same or different uniform layers or predetermined patterns.

In many embodiments, any known printing method is used (e.g., inkjet printing, gravure printing, or flexographic printing (where a relief element (e.g., an elastic relief element (flexographic printing component) is derived from a flexographic printing plate precursor)) The pattern of the photocurable composition is applied to one or both (opposite) support sides of a substrate (e.g., as a roll-to-roll continuous web), many of these printed components are known in the industry and some are, for example, CYREL ^® flexographic photopolymer plates were purchased from DuPont and Flexcel SR and NX flexographic plates and Flexcel direct flexographic plates were purchased from Eastman Kodak.

Particularly useful elastic letterpress elements are derived from flexographic printing plate precursors and flexographic printing sleeve precursors, each of which can be appropriately imaged (and processed (if needed)) to provide letterpress elements for "printing" or application Suitable patterns for photocurable compositions.

In other embodiments, an elastic letterpress element is provided from a direct (or ablated) laser engravable elastic letterpress element precursor with or without the use of an integral mask, as set forth in the following patents: for example, US Patent No. 5,719,009 (Fan ), 5,798,202 (Cushner et al.), 5,804,353 (Cushner et al.), 6,090,529 (Gelbart), 6,159,659 (Gelbart), 6,511,784 (Hiller et al.), 7,811,744 (Figov), 7,947,426 (Figov et al.), 8,114,572 (Landry-Coltrain) Et al.), 8,153,347 (Veres et al.), 8,187,793 (Regan et al.) And U.S. Patent Application Publication 2002/0136969 (Hiller et al.), 2003/0129530 (Leinenback et al.), 2003/0136285 (Telser et al.), 2003/0180636 (Kanga et al.) And 2012/0240802 (Landry-Coltrain et al.).

When using an elastic relief member, the photocurable composition can be applied to the uppermost relief surface (convex surface) of the elastic relief member in a suitable manner. You can use appropriate methods It is now applied and it is desirable to apply as little as possible to the sides (slopes) or recesses of the relief of the relief. Anilox roll systems or other roll application systems can be used, especially low capacity anilox rolls (less than 2.5 billion cubic micrometers per square inch (6.35 billion cubic micrometers per square centimeter)) and related abrasive knives. Optimal metering of the photocurable composition to the uppermost relief surface can be achieved by controlling the viscosity or thickness or selecting an appropriate application method. For example, a photocurable composition can be formulated to have a viscosity of at least 1 cps (centipoise) for such applications and up to and including 5000 cps. The thickness of the photo-curable composition on the letterpress image is generally limited to a sufficient amount that can be easily transferred to the substrate during application but not so much as to flow over the edges of the elastic letterpress element in the recess.

Thus, the photocurable composition can be supplied from an anilox or other roller inkjet system in an amount measurement for each printed precursor object (in the form of a uniform layer or pattern). In one embodiment, a first roll can be used to transfer the photocurable composition from an "ink" tray or metering system to a metering or anilox roll. The photocurable composition is typically metered to a uniform thickness as it is transferred from the anilox roll to the printing plate cylinder. When the substrate is moved from the printing plate cylinder to the impression cylinder via a roll-to-roll processing system in a continuous web, the impression cylinder applies pressure to the printing plate cylinder, thereby transferring the image of the photocurable composition from the elastic letterpress element. To the substrate.

After being on the substrate, in a uniform layer or predetermined pattern of grid lines or other shapes (on one or two opposite sides of the substrate), the It is suitable to irradiate the photo-curable composition in the precursor object to provide a photo-curable layer or one or more photo-curable patterns on a substrate. For example, photocuring may be used by the wavelength (λ _max) of at least 190nm and 700nm and containing up to and intensity of at least 000 microwatt (microwatt) / cm ² and up to 80,000 and comprising microwatt / cm UV- ² it visible Irradiation to reach. The irradiation system used to generate the radiation may consist of one or more UV lamps in the form of, for example, 1 to 50 discharge lamps, such as xenon, metal halides, metal arcs (e.g. Low pressure, medium pressure or high pressure mercury vapor discharge lamp with the desired operating pressure). Such lamps may include a shell capable of transmitting light having a wavelength of at least 190 nm and up to and including 700 nm or typically at least 240 nm and up to and including 450 nm. The lamp housing may be composed of quartz, such as spectrocil or Pyrex. Typical lamps that can be used to provide UV radiation are, for example, medium pressure mercury arcs, such as the GE H3T7 arc and Hanovia 450W arc lamps. Light curing can be implemented using a combination of various lamps, and some or all of these lamps can be operated in an inert atmosphere. When using a UV lamp, the radiation flux impinging on the substrate (or the applied layer or pattern) may be designed to be sufficient for the applied photo-curable composition to be applied in a continuous manner (e.g., in a roll-to-roll operation) at 1 Sufficiently fast light curing within seconds to 20 seconds.

The LED irradiation device to be used in photo-curing may have an emission peak wavelength of 350 nm or more. The LED device may include two or more types of elements having different emission peak wavelengths greater than or equal to 350 nm. A commercial example of an LED device having an emission peak wavelength of 350 nm or more and having an ultraviolet light emitting diode (UV-LED) is NCCU-033 from Nichia Corporation.

This irradiation of the precursor article results in a light-curing layer or one or more light comprising a substrate (e.g., individual sheets or continuous webs) having a light-curable composition derived from one or two supporting sides on the substrate thereon The middle object of the cured pattern. Each photo-curable pattern typically contains "seed" metal particles that can be electrolessly plated as described below.

The resulting intermediate objects can be further processed to incorporate electrical conductivity on a uniform photo-curable layer or photo-curable pattern (each of which contains metal particles as a "seed" material for further, for example, applying a conductive metal using an electroless metal plating process) metal. For example, the electroless "seed" metal particles as described above may include silver, palladium, or platinum particles or mixtures thereof and the carbon-coated metal particles described above, which may use silver, copper, Electroless plating of platinum, palladium or other metals.

A useful method of the present invention uses a plurality of flexographic printing plates in a stack (e.g., made as explained above) in a printing station, where each stack itself has a printing plate cylinder, thereby using each flexographic printing plate To print individual substrates, or a stack of printing plates can be used to print multiple portions of a continuous transparent polymer mesh (on one or two support sides). Multiple flexographic printing plates can be used to "print" or apply the same or different photocurable compositions. Add to this one substrate (on the same or opposite support side).

In other embodiments, a central impression cylinder may be used with a single impression cylinder mounted on a printing press frame. As the substrate (or receiver element) enters the printer frame, it is brought into contact with the impression cylinder and a suitable pattern is printed with the photo-curable composition. Alternatively, an on-line flexographic printing process can be used, in which the printing stations are arranged in horizontal lines and driven by common spools. Printing stations can be coupled to exposure stations, cutting stations, folding machines and other post-processing equipment. Those skilled in the art can easily determine other useful configurations of equipment and stations using information available in the industry. For example, an in-the-round process is described in WO 2013/063084 (Jin et al.).

Intermediate articles described herein having a photocurable conductive pattern containing metal particles can be immediately immersed in a water-based electroless metal plating bath or solution, or intermediate articles with only photocurable patterns can be stored (e.g., rolled up Continuous mesh format) for subsequent use.

For example, each intermediate object can be brought into contact with an electroless plated metal that is the same as or different from the metal contained in the metal particles in the photo-curable pattern. In most embodiments, however, the electroless plated metal is a metal different from the metal used in the metal particles dispersed in the photo-curable pattern.

Any metal that may be electrolessly "plated" on the metal particles may be used at this time, but in most embodiments, the electroless 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 useful electroless plated metals for silver, copper, platinum, or palladium seed metal catalysts. In some embodiments, the resulting conductive metal pattern is composed of silver, copper, palladium, or platinum or a combination thereof in the form of a seed metal catalyst or a plated metal or both.

Electroless plating can be performed using known temperature and time conditions because these conditions are well known in various textbooks and scientific literature. It is also known to include various additives such as metal complexing agents or stabilizers in aqueous-based electroless plating solutions. Changes in time and temperature Can be used to change metal electroless plating thickness or metal electroless plating deposition rate.

After an electroless plating procedure for providing a conductive pattern on one or more portions of one or both support sides of the substrate, the resulting product article can be removed from an aqueous based electroless plating bath or solution and distilled or deionized water or Another aqueous-based solution washes to remove any residual electroless plating chemicals. At this time, electroless plated metal is generally relatively stable and can be used for its intended purpose to form various conductive objects having a desired conductive metal pattern.

In some embodiments, the resulting product article may use water at room temperature as described in, for example, [0048] of US 2014/0071356 (Petcavich) or as in [0027] of WO 2013/169345 (Ramakrishnan et al.) Rinse or rinse with deionized water at temperatures less than 70 ° C.

To change the surface of electroless plated metal for visual or durability reasons, various post-treatments can be used, including electroplating on the top surface of electroless plated metal and then at least another (third or more) metal (such as nickel or silver) (this procedure (Sometimes referred to as "covering"), or a layer of metal oxide, metal sulfide, or metal selenide sufficient to alter the surface color and scattering properties without reducing the conductivity of the electroless (second) metal.

Some details of useful methods and devices for implementing some embodiments of the invention are set forth, for example, in US 2014/0071356 (described above) and WO 2013/169345 (described above). Further details of a useful manufacturing system for the preparation of conductive objects, especially in a roll-to-roll manner, are provided in PCT / US / 062366, filed by Petcavich and Jin on October 29, 2012.

Additional systems that can be used to implement the features of the apparatus and steps of the present invention are described in US Patent No. 14 / 146,867 (filed by Shifley on January 3, 2014).

The photocurable compositions described herein can be used in a method of providing one or more conductive articles. This method includes providing a continuous transparent polymer mesh [for example, composed of poly (ethylene terephthalate)].

On a first portion of a continuous mesh of at least a transparent substrate, the method also includes forming a package Including the photo-curable components of the photo-curable composition as described above and the photo-curable composition of the dispersed metal particles (as described herein). The photocurable pattern is then photocured to form a photocurable pattern on the first portion of the continuous mesh, the photocurable pattern including dispersed metal particles (described above) as seed metal catalyst sites. The photocurable pattern can then be electrolessly plated on the first portion of the continuous mesh using a conductive metal (as set forth above).

This method may further include: using the same or different photo-curable composition on one or more parts of the continuous web different from the first part and then implementing one or more of the formation, photo-curing, and electroless plating features described above Times. In this way, multiple photo-curable and electroless plating patterns can be formed on the same or different support sides of the substrate. The resulting conductive patterns may have the same composition, pattern, or conductivity, or they may be different in any or all of these characteristics (such as predetermined by the consumer). The plurality of electroless plate patterns may be formed as a plurality of conductive grids and a plurality of conductive connectors connected to each of the plurality of portions on one or two supporting sides in the transparent polymer mesh, respectively. As described in more detail below, a dry outermost polymer coating can be formed on at least a portion but not all of each conductive pattern in any of a plurality of portions. The conductive metal pattern formed on one or both of the first support side and the opposite second support side in the transparent substrate in this manner may include a conductive metal wire including silver, copper, palladium, or platinum or the like. Two or more of them.

Therefore, the method of the present invention can be used to provide a plurality of precursor objects, including: forming a first on the first portion by applying a photocurable composition to a first portion of a continuous transparent polymer mesh using a flexographic printing member. The photo-curable pattern advances a continuous transparent polymer mesh including the first photo-curable pattern to approximate exposure to radiation, and thereby forms a first photo-curable pattern on the first portion by using the flexographic printing member to convert the same or A different photo-curable composition is applied to the second part of the continuous transparent polymer mesh to form a second photo-curable pattern on the second part, A continuous transparent polymer mesh including a second photo-curable pattern is advanced to approximate exposure to radiation, and a second photo-curable pattern is thereby formed on the second portion, using the same or different light-curables in a similar manner, as appropriate, The composition and the same or different flexographic printing parts form one or more other photo-curable patterns on one or more other respective portions of the continuous transparent polymer mesh, and rolls a continuous transparent pattern including a plurality of photo-curable patterns A polymer mesh, or a continuous mesh is immediately used for further processing (eg, electroless plating) and a dry outermost polymer coating is provided before assembly into an electronic device.

Therefore, the method may further include forming a plurality of conductive objects from a continuous transparent polymer mesh including a plurality of photo-curable patterns, and forming a dry layer on at least a portion but not all of each of the plurality of photo-curable patterns An outer polymer coating (as explained herein), and the assembly of individual conductive objects into the same or different individual electronic devices (eg, the same or different touch screen displays or devices).

The method may also include: electrolessly plating each of a plurality of photo-curable conductive patterns in a continuous transparent polymer mesh to form a plurality of conductive objects, and forming a desired outermost polymer coating that may be dried by the same Or different users assemble the obtained conductive objects into the same or different individual electronic devices. These devices may be touch screens or other display devices, which also include suitable controllers, housings, and software for any type of desired communication over the Internet. Alternatively, the device may be a sub-component of these touch screens or other display devices. In some embodiments, the devices provided by the present invention are touch screens, each of which has a viewing area of at least 1 cm ² and up to and including 100 m ² . The size and shape of the touch screen can vary depending on the intended use.

In some embodiments, the method of the present invention can be used to prepare an electronic device including a touch screen. Device, the method comprising: assembling one or more individual conductive objects into a device housing to form a touch screen area, each of the one or more individual conductive objects including a conductive metal (electrolessly electroplated derived from that described herein On the photocurable conductive pattern of the photocurable composition), and the dried outermost polymer coating is disposed on at least a portion but not all of the conductive metal pattern.

The dry outermost polymer coatings described herein can be prepared by first dissolving one or more suitable non-crosslinked thermoplastic polymers in a suitable solvent (or mixture thereof), and then coating the resulting outermost polymer The layer formulation is printed or applied on a portion of the conductive pattern. Suitable non-crosslinked thermoplastic polymers include those detailed above.

Suitable solvents for non-crosslinked thermoplastic polymers include, but are not limited to, alcohols, ethers, and glycol ethers, such as dipropylene glycol methyl ether, 1-methoxy-2-propanol, and 2-methoxy-1-methyl acetate Ethyl ester. Other materials can be added to the outermost polymer coating formulation to impart its desired properties, and these materials can be used to control viscosity or they can be surfactants used to modify surface tension.

According to the present invention, the outermost polymer coating formulation can be arranged on at least a portion of the conductive pattern on one or two support sides in a substrate using various deposition or printing techniques known in the art. These technologies include, but are not limited to, flexographic printing, screen printing, gravure printing, inkjet printing, and slit deposition. The deposition method can be used to apply the outermost polymer coating formulation to one conductive pattern at a time (eg, a batch process) or to multiple conductive patterns in a continuous roll-to-roll process.

A useful product article made according to the present invention can be formulated into a suitable pattern including a conductive metal pattern and a capacitive touch screen sensor with an inventive dry outermost polymer coating. For example, a conductive metal grid and a conductive metal connector can be formed in a conductive pattern by printing a photo-curable composition in a predetermined pattern and then printing the pattern using a suitable metal electroless plating as described above. You can also use flexo printing as explained above The dry outermost polymer coating formulation is applied only to the conductive metal pattern.

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

1. A conductive object comprising: a transparent substrate having a first support side and an opposite second support side; a conductive pattern disposed on at least the first support side, and a dry outermost polymer coating layer disposed on On at least a portion but not all of the conductive pattern, the dried outermost polymer coating has a dry thickness of less than 5 μm, an integrated transmittance of at least 80%, and includes non-crosslinked glass transition temperature (T _g ) equal to or greater than 65 ° C. Thermoplastic polymer.

2. The conductive object according to embodiment 1, wherein the conductive pattern includes at least: a conductive grid; and a conductive connector connected to the conductive grid.

3. The conductive article according to embodiment 2, wherein the dry outermost polymer coating is arranged on the conductive grid of 100% or less, but the dry outermost polymer coating is arranged on the conductive connection less than 100% Device.

4. The conductive object according to embodiment 2 or 3, wherein the conductive grid is a conductive metal grid and the conductive connector is a conductive metal connector connected thereto.

5. The conductive article according to any one of embodiments 1 to 4, further comprising: a conductive pattern arranged on the opposite second support side of the transparent substrate, and a dry outermost polymer layer arranged on the transparent substrate On at least a part but not all of the conductive pattern on the opposite second supporting side, the dried polymer coating has a dry thickness of less than 5 μm, an integrated transmittance of at least 80%, and includes a glass transition temperature (T _g ) equal to or Non-crosslinked thermoplastic polymers above 65 ° C.

6. The conductive object of embodiment 5, wherein the conductive pattern includes at least: a conductive grid, and A conductive connector connected to the conductive grid.

7. The conductive article according to embodiment 6, wherein the dry outermost polymer coating is arranged on the conductive grid of 100% or less, but the dry outermost polymer coating is arranged on the conductive connection less than 100% On the device, they are all located on the opposite second supporting side of the transparent substrate.

8. The conductive article according to any one of embodiments 1 to 7, wherein the non-crosslinked thermoplastic polymer is a non-crosslinked, non-aromatic thermoplastic polymer.

9. The conductive article according to any one of embodiments 1 to 8, wherein the dried outermost polymer coating has a dry thickness of less than 3 μm.

10. The conductive article according to any one of embodiments 1 to 9, wherein the non-crosslinked thermoplastic polymer is a non-crosslinked thermoplastic acrylic polymer.

11. The conductive article according to any one of embodiments 1 to 10, wherein the non-crosslinked thermoplastic polymer includes at least repeating units derived from methyl (meth) acrylate and repeats derived from alkyl (meth) acrylate Unit, wherein the alkyl group has 1 to 18 carbon atoms, wherein the repeating units derived from the alkyl (meth) acrylate account for at least 5 mol% and up to and including 25 mol% of the total polymer repeating units.

12. The conductive article according to any one of embodiments 1 to 11, wherein the conductive pattern arranged at least on the first support side of the transparent substrate includes a conductive metal wire composed of at least silver, copper, palladium, or platinum.

13. The conductive object according to any one of embodiments 5 to 12, wherein the conductive pattern disposed on the opposite second support side of the transparent substrate includes a conductive metal wire composed of at least silver, copper, palladium, or platinum.

14. The conductive object according to any one of embodiments 1 to 13, wherein the transparent substrate is a continuous transparent polymer mesh, and the object includes the same or different ones of the first in the continuous transparent polymer mesh. A conductive pattern on at least a first portion of the support side and at least a first portion of the opposite second support side.

15. The conductive article according to embodiment 14, wherein the continuous transparent polymer mesh comprises: a plurality of portions on the first support side and a plurality of portions on the opposite second support side; and each of the portions is disposed on the transparent portion. The same or different conductive patterns on the first support side and the plurality of portions on the opposite second support side in the substrate; and a dry outermost polymer coating disposed on at least a portion but not all of each conductive pattern on.

16. An electronic device comprising a conductive object as in any one of embodiments 1 to 15 as a touch screen.

17. The electronic device of embodiment 16, wherein the touch screen has a viewing area of at least 1 cm ² and up to and including 100 m ² .

18. A method of providing a conductive article as in any one of embodiments 1 to 15, the method comprising: forming a conductive pattern on a first support side of a transparent substrate, the transparent substrate also including an opposite second support side; and A dry outermost polymer coating is formed on at least a portion but not all of the conductive pattern, the dry polymer coating having a dry thickness of less than 5 μm, an integrated transmittance of at least 80%, and including a glass transition temperature (T _g ) equal to or greater than 65 ° C non-crosslinked thermoplastic polymer.

19. The method of embodiment 18, wherein the conductive pattern comprises at least: a conductive grid, and a conductive connector connected to the conductive grid.

20. The method of embodiment 19, comprising forming the dry outermost polymer coating on the conductive grid at or below 100%, but the dry outermost polymer coating is disposed at less than 100% of the conductive connection Device.

21. The method of embodiment 19, wherein the conductive grid is a conductive metal grid and the conductive connector is a conductive metal connector connected thereto.

22. The method of any one of embodiments 18 to 21, further comprising: forming a conductive pattern on the opposite second support side of the transparent substrate, and at least on the opposite second support side of the transparent substrate. A part, but not all, of the conductive pattern forms a dry outermost polymer coating. The dry polymer coating has a dry thickness of less than 5 μm, an integrated transmittance of at least 80%, and includes a glass transition temperature (T _g ) equal to or greater than 65. Non-crosslinked thermoplastic polymer at ℃.

23. The method of embodiment 22, wherein the conductive pattern on the opposite second support side includes a conductive grid and a conductive connector connected to the conductive grid.

24. The method of any one of embodiments 22 or 23, comprising forming the dry outermost polymer coating on the conductive grid at 100% or less, but the dry outermost polymer coating is disposed at less than 100% of the conductive connectors are located on the opposite second support side of the transparent substrate.

25. The method of any one of embodiments 18 to 24, comprising forming the outermost polymer coating on the first support side using a flexographic printing member.

26. The method of any one of embodiments 18 to 25, comprising forming the conductive pattern on a first portion of the substrate that is a continuous transparent polymer mesh.

27. The method of any one of embodiments 18 to 26, comprising: forming a plurality of conductive patterns on respective plurality of portions on the first support side of the substrate of the continuous transparent polymer mesh, and A dry outermost polymer coating is formed on at least a portion but not all of each of the conductive patterns in the plurality of portions, the dry outermost polymer coating being disposed in the plurality of conductive patterns Non-crosslinked thermoplastic polymers having a dry thickness of less than 5 μm, an integrated transmittance of at least 80%, and a glass transition temperature (T _g ) equal to or greater than 65 ° C. on each.

28. A method of providing a conductive article according to any one of embodiments 1 to 15, the method comprising: (i) providing a substrate in the form of a continuous transparent polymer mesh; (ii) using a photo-curable comprising metal particles The composition forms a first photo-curable pattern on at least a first portion on a first support side of the continuous transparent polymer mesh; (iii) exposing the photo-curable pattern to photo-curable radiation to the first support side Forming a photo-curable pattern on the first portion; (iv) electrolessly plating the photo-curing pattern on the first portion of the first support side with a conductive metal to form a conductive metal pattern on the first portion of the first support side; And (v) forming a dry outermost polymer coating on at least a portion, but not all, of the first pattern of the first support side of the conductive pattern.

29. The method of embodiment 28, further comprising: using the same or different photocurable composition and the same or different dry outermost polymer coating on the first supporting side of the continuous transparent polymer mesh Features (ii) to (v) are repeated on the previous part or parts different from the first part.

30. The method of embodiment 28 or 29, comprising: applying the photocurable composition to a first portion on the first support side of the continuous transparent polymer mesh by using a first flexographic printing member Forming the first photo-curable pattern on the first portion, advancing the continuous transparent polymer mesh including the first portion containing the first photo-curable pattern to approximate exposure to radiation, and thereby on the first portion Forming a first photo-curable pattern by applying the same or different photo-curable composition to a second portion on the first support side of the continuous transparent polymer mesh using the same or different flexographic printing members simultaneously Or sequentially forming a second photo-curable pattern on the second portion; including the second portion on the first support side containing the second photo-curable pattern The continuous transparent polymer mesh is advanced to approach the exposure radiation, and thereby a second photo-curable pattern is formed on the second portion of the first support side; using the same or different photo-curable compositions as appropriate and The same or different flexographic printing parts form one or more other photo-curable patterns simultaneously or sequentially on one or more other parts on the first supporting side in the continuous transparent polymer mesh; electroless plating of the first Supporting each of the photo-cured patterns on the side to form a plurality of conductive metal patterns; and forming the dry outermost polymer on at least a portion but not all of each of the plurality of conductive metal patterns coating.

31. The method of embodiment 30, further comprising after forming the dry outermost coating on at least a portion, but not all, of each of the plurality of conductive metal patterns: winding the continuous polymer mesh.

32. The method of any one of embodiments 28 to 30, further comprising after forming the dry outermost coating on at least a portion but not all of each of the plurality of conductive metal patterns: The individual conductive metal patterns of the continuous transparent polymer mesh are assembled into the same or different individual devices in the form of individual objects.

33. The method according to any one of embodiments 28 to 32, further comprising: using a photo-curable composition including metal particles to form light on at least a first portion of the continuous transparent polymer mesh opposite the second support side Curable pattern; exposing the photo-curable pattern to radiation to form a photo-curable pattern on the first portion of the opposite second support side; electroless plating of the light on the first portion of the opposite second support side with a conductive metal Curing the pattern to form a conductive metal pattern on the first portion of the opposite second support side; and forming a dry outermost polymer coating on at least a portion but not all of the conductive metal pattern, the dried polymer coating having a size of less than 5 μm The non-crosslinked thermoplastic polymer has a dry thickness, an integrated transmittance of at least 80%, and includes a glass transition temperature (T _g ) equal to or greater than 65 ° C.

34. The method of embodiment 33, further comprising: using the same or different photo-curable composition and the same or different dry outermost polymer coating, which is different from the relative transparent polymer web in the continuous transparent polymer web. On one or more other parts of the first part on the two supporting sides and on the opposite second supporting side, photocurable patterns are repeatedly formed, exposure, electroless plating, and dry outer polymer coating features are formed.

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

Representative Photocurable Composition 1: This representative photocurable composition includes at least the following components (formed into 100g aliquots): 14.4g epoxy acrylate (CN 153 from Sartomer), 9.9g poly ( Ethylene glycol) diacrylate (258 _n , Sigma-Aldrich), 2.1 g poly (ethylene glycol) diacrylate (575 _n , Sigma-Aldrich), 10.8 g neopentaerythritol tetraacrylate ( Sigma-Aldrich), 0.8 g hexafluorophosphate triarylphosphonium salt mixed in 50% propylene carbonate, Sigma-Aldrich, 0.8 g hexafluoroantimonate triarylphosphonium salt mixed in 50% propylene carbonate (Sigma-Aldrich), 2.4 g of radical photoinitiator hydroxycyclohexylphenyl ketone (Sigma-Aldrich), 1.2 g of radical photoinitiator methyl-4 '-(methylthio) -2-morpholine Phenylacetone (Sigma-Aldrich), 19.5g "seed" silver particles (from NovaCentrix, 20-25nm average particle size, Ag-25-ST3), 1.1g carbon particles (US1074, from US Nano), 0.001g 9 -Fluorenone (Sigma-Aldrich) and 35 g of 1-methoxyisopropanol (Sigma-Aldrich) solvent.

Printing light curable composition:

A desktop test printing press "IGT F1 Printability Tester" (from IGT Testing Systems, Arlington Heights, IL) was used to obtain poly (ethylene terephthalate) PET substrates (MELLINEX ^® 561, available from DuPont Teijin Films) as a sample of the printed pattern of the photocurable composition described above. The anilox system used to apply the photocurable composition to flexographic printing plates has values of 1.3BCMI and 1803 lpi, as specified by IGT. A printing pattern was formed at ambient temperature using an anilox force of 20 N, a printing force of 10 N, and a printing speed of 0.20 m / sec.

The flexographic printing plate used to print the photo-curable composition was a sample of a commercially available KODAK ^® Flexcel NX photopolymer plate (from Eastman Kodak), which had been imaged with UV radiation using a mask having the use of KODAK ^® SQUARE SPOT laser technology for predetermined patterns written at a resolution of 12,800dpi. The exposed flexographic photopolymer plate was processed (developed) using known conditions proposed by the manufacturer. The resulting flexographic printing plates (or parts) were each 1.14 mm thick (including PET). The backing tape used to mount each flexographic printing plate to a printing form cylinder was a 1120 meter colored tape from 3M Company, which was 20 mils (0.051 cm) thick and had a Shore A value of 55. The relief image design in a flexographic printing plate included a grid pattern with fine lines with a width of 7 μm on the top relief surface. The resulting corresponding printed photo-curable composition pattern has an average line width arranged on a primer PET substrate.

After being applied to the substrate, each of the Fusion 300 WPI medium pressure mercury lamps (providing an irradiation wavelength between 190-1500 nm) was used with UV radiation to approximate each of the 298 mJ / cm ² of the irradiated light curable composition using UV radiation. The printed patterns (ie, printed patterns) cure each printed pattern with light. The printed average line width of the obtained photo-cured pattern in the obtained precursor object was measured in a transmission and reflection mode using an Olympus BH-2 optical microscope.

Electroless metal plating:

By previously having the cured pattern body object at 45 ℃ containing Enplate Cu-406 beakers electroless plating solution (ENTHONE ^® Corporation) was immersed for 7 minutes in an electroless copper plating it includes a variety of light on the primed substrate cured pattern before the body The object is then rinsed with distilled water and dried with nitrogen to form an object having a conductive pattern disposed on a substrate.

Outermost polymer coating formulation:

Preparing a 10% by weight present in the 1-methoxy-2-propanol (DOWANOL ^® PM organic solvent) of ELVACITE ^® 4028 resin (Lucite International) the most outer polymeric coating formulations. The formulation is clear and has a viscosity of 25 cps at 22 ° C.

Printed outermost polymer coating formulation:

According to the present invention, a dry outermost polymer coating is provided by using a flexographic printing press (Performance Series P7, available from Mark Andy) in a continuous roll-to-roll operation and using a single flexographic station. This flexographic station includes a tray (filled with 300 grams of the outermost polymer coating formulation), an elastic metering roller (with a hardness of about 30 Shore A), a ceramic anilox roller (with a steel medical doctor blade), and a flexographic plate Plate roll. In this process, the outermost polymer coating formulation is delivered from the tray to the anilox roll by an elastic metering roll. Excessive outermost polymer coating formulation was removed from the anilox roller by a steel medical doctor blade. The anilox roll system has a value of 2.0 BCMI (billion μm ³ / in ² ), which is equivalent to 0.31 billion μm ³ / cm ² .

The outermost polymer coating formulation is then transferred to a flexographic printing plate obtained as described below and then to a moving mesh containing the electroless metal plating conductive pattern described above in the continuous mesh process. All printing, drying and winding operations were performed at 18 ° C and 50% relative humidity at a linear speed of 0.10 m / sec. The final dried conductive article has a dried outermost polymer coating disposed on at least a portion but not all of each conductive pattern, the dried coating having a thickness of 0.3 μm.

A commercially available KODAK ^® Flexcel NX photopolymer plate (Eastman Kodak company) imaged using a mask (having a predetermined pattern written at a resolution of 12,800 dpi using KODAK ^® SQUARE SPOT laser technology) for application (printing) Flexographic printing plate with outermost polymer coating formulation. UV exposure flexographic photopolymer plates were processed (developed) using known conditions proposed by the manufacturer. The resulting flexographic printing plate was approximately 1 mm thick. Except for the rectangular relief area (2 × 35 mm) in the area marked as the outermost part of the conductive pattern, the surface of the flexographic printing plate remains smooth (ie, in the receiving state). This relief area does not receive (or transmit) the outermost polymer coating formulation and therefore a smaller portion of each conductive pattern in the resulting conductive object remains "open" (uncoated). This uncoated area corresponds to the area of the printed conductive connector.

Environmental exposure of the sample:

All conductive objects made as described above were incubated in an environmental chamber maintained at 65 ° C and 90% RH (relative humidity) for 4 weeks. The conductive objects are suspended vertically in the environmental chamber and taken out at different time intervals for evaluation of electrical properties.

Measurement of electrical continuity:

The conductive pattern of this conductive object includes multiple conductive grid networks, where the end of each conductive grid network is connected to two probe pads, and one probe pad (near probe pad) is connected to the BUS conductive line, which in turn can Connects to a "connector" pad (which is connected to an external circuit). A "connector" may include multiple connector engagement pads. The second probe pad (remote probe pad) is connected to the conductive grid at the farthest point in the electrical path from the "connector" bonding pad. For this example, the connector bonding pads are not coated with the outermost polymer coating formulation to provide a connector that can be used to measure electrical resistance.

Test the cultivated conductive objects described above by applying a pulse voltage (25 volts, DC) to each conductive connector in each conductive pattern and measuring the current between the connector pads and the corresponding end probe pads Electrical continuity. Therefore, the current path is from the external circuit to the connector bonding pad, which passes through the BUS line, through the near probe pad, through the conductive grid network (about 300 mm in length), and reaches the end probe pad. Ohm's Law was then used to determine the resistance. A resistance greater than 1000 ohms in this path is considered a failure and is considered an "open circuit". For each conductive object used in these examples, there are 34 bond pad sites and 34 lattice column networks. Therefore, the maximum number of possible "break" results in each conductive object (and thus each conductive pattern) is 34.

Measurement of transparency:

The transparency of each conductive object was evaluated by measuring the integrated transmittance of radiation at 550 nm as explained above.

Comparative example:

The conductive article made as explained above was sent to the flexographic printing press without applying the outermost polymer coating formulation. The resulting comparative conductive article thus does not include a dry outermost polymer coating on the conductive pattern. The initial electrical continuity of each comparative conductive article was then tested as explained above. The initial average integrated transmittance of each of the three comparative conductive objects was 84%.

Then, as explained above for the conductive article of the present invention, a comparative article is cultivated in an environmental chamber and periodically removed to assess electrical continuity. Table I below shows the increase in the number of "open circuit" assessments for comparative objects. As shown in Table I, the average number of "open circuit" evaluations per conductive object increased gradually by 5 during the 4-week incubation period.

Examples of the invention:

Nine conductive objects made as described above were sent to the flexographic printing press, which flexibly engaged the printing station containing the outermost polymer coating formulation. Therefore, in addition to the smaller rectangular area (2 mm x 35 mm) of the conductive pattern, each of these conductive objects of the present invention includes a dry outermost polymer coating applied to a conductive pattern that includes a conductive metal grid. The outermost protective coating has a dry thickness of 0.3 μm. The initial integrated transmittance of all 9 conductive objects was determined to be 84%.

As explained above, the objects of the invention are cultivated in an environmental chamber and periodically taken out to assess electrical continuity. Table I below shows an increase in the number of "open circuit" evaluations of the conductive articles of the present invention. As shown in Table I, the average number of "open circuit" assessments did not increase during the 4-week incubation period. Therefore, it has been determined that the dry outermost polymer coating disposed on at least a part but not all of the conductive patterns in each conductive object will well protect the conductive patterns from contaminants such as water and oxygen, even under harsh conditions. Environmental conditions.

Claims (34)

A conductive object includes: a transparent substrate having a first support side and an opposite second support side; a conductive pattern disposed on at least the first support side, and a dry outermost polymer coating disposed on at least a portion But not all of the conductive patterns, the dried outermost polymer coating has a dry thickness of less than 5 μm, an integrated transmittance of at least 80%, and includes a non-crosslinked thermoplastic polymerization having a glass transition temperature (T _g ) equal to or greater than 65 ° C. Thing. The conductive object of claim 1, wherein the conductive pattern includes at least: a conductive grid; and a conductive connector connected to the conductive grid. The conductive article of claim 2, wherein the dry outermost polymer coating is arranged on the conductive grid of 100% or less, but the dry outermost polymer coating is arranged on the conductive connector less than 100% . The conductive article of claim 2, wherein the conductive grid is a conductive metal grid and the conductive connector is a conductive metal connector connected thereto. The conductive article of claim 1, further comprising: a conductive pattern disposed on the opposite second support side of the transparent substrate, and a dry outermost polymer coating disposed on the opposite second support side of the transparent substrate On at least a part but not all of the conductive pattern, the dried outermost polymer coating has a dry thickness of less than 5 μm, an integrated transmittance of at least 80%, and includes a non-glass transition temperature (T _g ) equal to or greater than 65 ° C. Crosslinked thermoplastic polymer. The conductive object of claim 5, wherein the conductive pattern includes at least a conductive grid, and a conductive connector connected to the conductive grid. The conductive article of claim 6, wherein the dry outermost polymer coating is arranged on the conductive grid 100% or less, but the dry outermost polymer coating is arranged on the conductive connector less than 100% Are all located on the opposite second supporting side of the transparent substrate. The conductive article according to any one of claims 1 to 7, wherein the non-crosslinked thermoplastic polymer is a non-crosslinked, non-aromatic thermoplastic polymer. The conductive article of any one of claims 1 to 7, wherein the dried outermost polymer coating has a dry thickness of less than 3 μm. The conductive article according to any one of claims 1 to 7, wherein the non-crosslinked thermoplastic polymer is a non-crosslinked thermoplastic acrylic polymer. The conductive article according to any one of claims 1 to 7, wherein the non-crosslinked thermoplastic polymer includes at least repeating units derived from methyl (meth) acrylate and repeating units derived from alkyl (meth) acrylate, Wherein the alkyl group has 1 to 18 carbon atoms, wherein the repeating units derived from the alkyl (meth) acrylate account for at least 5 mol% and up to and including 25 mol% of the total polymer repeating units. The conductive article according to any one of claims 1 to 7, wherein the conductive pattern arranged at least on the first supporting side of the transparent substrate includes a conductive metal wire composed of at least silver, copper, palladium, or platinum. The conductive article according to any one of claims 5 to 7, wherein the conductive pattern disposed on the opposite second supporting side of the transparent substrate includes a conductive metal wire composed of at least silver, copper, palladium, or platinum. The conductive object according to any one of claims 1 to 7, wherein the transparent substrate is a continuous transparent polymer mesh, and the object includes the same or different ones disposed on the first supporting side of the continuous transparent polymer mesh. At least a first portion and a conductive pattern on at least a first portion of the opposite second support side. The conductive article as claimed in claim 14, wherein the continuous transparent polymer mesh includes: a plurality of portions on the first support side and a plurality of portions on the opposite second support side; and each of the portions is disposed on the transparent substrate. The same or different conductive patterns on the plurality of portions on the first support side and the opposite second support side; and a dry outermost polymer coating disposed on at least a portion but not all of each conductive pattern . An electronic device includes a conductive object as in any one of claims 1 to 15 as a touch screen. The electronic device of claim 16, wherein the touch screen has a viewing area of at least 1 cm ² and at most including 100 m ² . A method of providing a conductive object as in any of claims 1 to 15, the method comprising: forming a conductive pattern on a first support side of a transparent substrate, the transparent substrate also including an opposite second support side; and at least a portion But not all of the conductive patterns form a dry outermost polymer coating. The dry polymer coating has a dry thickness of less than 5 μm, an integrated transmittance of at least 80%, and includes a glass transition temperature (T _g ) equal to or greater than 65 ° C. Non-crosslinked thermoplastic polymer. The method of claim 18, wherein the conductive pattern includes at least: a conductive grid, and a conductive connector connected to the conductive grid. The method of claim 19, comprising forming the dry outermost polymer coating on the conductive grid at or below 100%, but the dry outermost polymer coating is disposed on the conductive connector at less than 100% . The method of claim 19, wherein the conductive grid is a conductive metal grid and the conductive connector is a conductive metal connector connected thereto. The method of any one of claims 18 to 21, further comprising: forming a conductive pattern on the opposite second support side of the transparent substrate, and at least a part of the opposite second support side of the transparent substrate but Not all of the conductive patterns form a dry outermost polymer coating. The dry polymer coating has a dry thickness of less than 5 μm, an integrated transmittance of at least 80%, and includes a glass transition temperature (T _g ) equal to or greater than 65 ° C. Non-crosslinked thermoplastic polymer. The method of claim 22, wherein the conductive pattern on the opposite second support side includes a conductive grid and a conductive connector connected to the conductive grid. The method of claim 23, comprising forming the dry outermost polymer coating on the conductive grid at or below 100%, but the dry outermost polymer coating is disposed on the conductive connector at less than 100% Are all located on the opposite second supporting side of the transparent substrate. The method of any of claims 18 to 21, comprising forming the outermost polymer coating on the first support side using a flexographic printing member. The method of any one of claims 18 to 21, comprising forming the conductive pattern on a first portion of the substrate that is a continuous transparent polymer mesh. The method of any one of claims 18 to 21, comprising: forming a plurality of conductive patterns on respective multiple portions on the first support side of the substrate of the continuous transparent polymer mesh sheet, and A dry outermost polymer coating is formed on at least a portion but not all of each of the conductive patterns in the plurality of portions, the dry outermost polymer coating being disposed on each of the plurality of conductive patterns This is a non-crosslinked thermoplastic polymer having a dry thickness of less than 5 μm, an integrated transmittance of at least 80%, and including a glass transition temperature (T _g ) equal to or greater than 65 ° C. A method of providing a conductive article as claimed in any one of claims 1 to 15, the method comprising: (i) providing a substrate in the form of a continuous transparent polymer mesh; (ii) using a photo-curable composition including metal particles Forming a first photo-curable pattern on at least a first portion on a first support side of the continuous transparent polymer mesh; (iii) exposing the photo-curable pattern to photo-curable radiation to provide the Forming a photo-curable pattern on the first portion; (iv) electrolessly plating the photo-curable pattern on the first portion of the first support side with a conductive metal to form a conductive metal pattern on the photo-curable pattern; and (v) A dry outermost polymer coating is formed on at least a portion, but not all, of the first portion of the supporting side of the conductive pattern. The method of claim 28, further comprising: using the same or different photocurable composition and the same or different dry outermost polymer coating on the first support side of the continuous transparent polymer mesh. Features (ii) to (v) are repeated on one or more other parts different from the first part. The method of claim 28 or 29, comprising: applying the photocurable composition to a first portion on the first support side of the continuous transparent polymer mesh by using a first flexographic printing member on the continuous transparent polymer mesh. Forming the first photo-curable pattern on the first portion; advancing the continuous transparent polymer mesh including the first portion containing the first photo-curable pattern to approach exposure to radiation, and thereby forming a first portion on the first portion A photo-curable pattern; simultaneously or in accordance with applying the same or different photo-curable composition to a second portion on the first support side of the continuous transparent polymer mesh using the same or different flexographic printing members Sequentially forming a second photo-curable pattern on the second portion; advancing the continuous transparent polymer mesh including the second portion on the first support side containing the second photo-curable pattern to approximate exposure to radiation And thereby forming a second photo-curable pattern on the second portion of the first support side; optionally using the same or different photo-curable composition and the same or different flexographic printing components in the company One or more other photo-curable patterns are formed simultaneously or sequentially on one or more other portions on the first support side of the transparent polymer mesh sheet; the photo-curable patterns on the first support side are electrolessly plated Each forming a plurality of conductive metal patterns; and forming the dry outermost polymer coating on at least a portion but not all of each of the plurality of conductive metal patterns. The method of claim 30, further comprising, after forming the dry outermost coating on at least a portion but not all of each of the plurality of conductive metal patterns: winding the continuous polymer mesh. The method of claim 30, further comprising, after forming the dry outermost coating on at least a portion, but not all, of each of the plurality of conductive metal patterns: The individual conductive metal patterns are assembled into the same or different individual devices as individual objects. The method of claim 28 or 29, further comprising: using a photo-curable composition including metal particles to form a photo-curable pattern on at least a first portion of the continuous transparent polymer mesh opposite to a second support side; The photo-curable pattern is exposed to radiation to form a photo-curable pattern on the first portion of the opposite second support side; the photo-curable pattern on the first portion of the opposite second support side is electrolessly plated with a conductive metal to form the photo-curable pattern on the opposite second support side. Forming a conductive metal pattern on the first portion of the second support side; and forming a dry outermost polymer coating on at least a portion but not all of the conductive metal pattern, the dry polymer coating having a dry thickness of less than 5 μm, at least An integrated transmittance of 80% and includes a non-crosslinked thermoplastic polymer having a glass transition temperature (T _g ) equal to or greater than 65 ° C. The method of claim 33, further comprising: using the same or different photocurable composition and the same or different dry outermost polymer coating on the opposite second support side of the continuous transparent polymer mesh Unlike one or more other portions of the first portion on the opposite second support side, the photocurable pattern is repeatedly formed, exposed, electrolessly plated, and the dry outermost polymer coating feature is formed.