CN106795384A

CN106795384A - Carbon coated metallic particles, article and the purposes being dispersed through

Info

Publication number: CN106795384A
Application number: CN201580054980.6A
Authority: CN
Inventors: 凯伦·M·柯西达; 盖瑞·L·史雷特; 玛莉·克里斯廷·布理克; 克里斯廷·乔安·蓝卓-考特兰; 詹姆斯·阿尔贝特·雷切克
Original assignee: Eastman Kodak Co
Current assignee: Eastman Kodak Co
Priority date: 2014-10-15
Filing date: 2015-10-01
Publication date: 2017-05-31
Anticipated expiration: 2035-10-01
Also published as: KR20170070167A; TW201631055A; WO2016060856A1; TWI707011B; CN106795384B

Abstract

The present invention relates to a kind of non-aqueous composition, its carbon coated metallic particles being dispersed through in organic diluent for containing at least amount of 10 weight %.The carbon coated metallic particles being dispersed through has the median diameter for being equal to or less than 0.6 μm, and using with least 2,000 and at most and containing 100,000 weight average molecular weight (M_w) and comprising nitrogenous unit particle dispersants dispersion.The median diameter of the particle being dispersed through is measured using dynamic light scattering method.Additionally, when the non-aqueous composition contain at most and including be dispersed through described in 25 weight % carbon coated metallic particles when, it is not presented visual sedimentation when 20 DEG C of sedimentations for carrying out at least 24 hours are tested.Such non-aqueous composition may include photocurable component and the photocurable suitable for preparing various articles (including the touch screen device with touch screen display) and the conductive pattern and layer through photocuring.

Description

Carbon coated metallic particles, article and the purposes being dispersed through

Technical field

The present invention relates to contain the carbon coated metallic particles that is dispersed through and through the non-of unique particle dispersants selected Waterborne compositions.The present invention is also non-aqueous on the carbon coated metallic particles being dispersed through containing these and particle dispersants Photocurable composition.These non-aqueous Photocurable compositions can be used to provide for being designed to provide conductive material The seed metal catalyst of the electroless plating method of pattern.

Background technology

Obtained on various electronic installations (particularly for the display equipment of various communications, finance and archives purpose) fast Speed is progressive.The just such as use of kind of touch screen panels, electrochromic device, light emitting diode, field-effect transistor and liquid crystal display For way, conducting film is required, and the industrially positive property for making great efforts to improve these conducting films.

It is especially desirable to provide the touch screen display and device of the conductive membrane module for accommodating improved.At present, touch-screen Curtain display sets up the capacitive region array for distinguishing Multi-contact using tin indium oxide (ITO) coating.ITO coatings have to be permitted Many shortcomings.Indium is that expensive rare earth metal and the supply seldom originated from the whole world are limited.ITO electric conductivity is relatively low and needs Short-term length is realizing enough reaction rates.Touch screen for giant display resolves into smaller fragment and is led with reducing Line length, realizes acceptable resistance.These smaller fragments need extra driving and sensing electronic installation.Additionally, ITO is Ceramic material, not flexible or flexure, and the vacuum moulding machine of high disposal temperature is needed to use to manufacture conductive layer.

Silver is a kind of perfact conductor of the electrical conductivity with than big 50 to 100 times of ITO.Silver in various business applications and Can be obtained from many sources.Extremely be desirable for silver and manufacture conductive membrane module as conductive source, but need quite a lot of development with Obtain optimal properties.

" the addition technique " of functional conductive pattern of sensor is provided using deposition according to takeup type production method soft Property and transparent substrate on produce Touch screen sensor and other electrically conducting transparent articles and turned into latest development in this industry Target.Production has required electrical property and appropriate optical simultaneously in the visible part (Petting Area) of Touch screen sensor The ability of the Touch screen sensor of matter (transmissivity) is even more important.Conductive and optical property, is strongly required to lead for needed for realizing The average line width of conductor wire is less than 10 μm in power grid.

Flexible and transparent substrate in for these techniques answers optics clear (high synthesis transmissivity) and colourless and represent Low turbidity.Applying conductive pattern using addition technique (such as flexographic printing of conductive material or seed metal composition) needs flexibility And transparent substrate have appropriate surface can and it is consistent with the yardstick of the fine-feature (for example, fine lines) for being intended to apply thick Rugosity.Sizable effort is made in electronic device industry to obtain these required features.

WO 2013/063188 (Petrarch (Petcavich) et al.) descriptions are a kind of by using with least the first mainboard With the first pattern on flexography process printing dielectric substrate first side of the first ink (" printable compositions ")；With it is solid The method for changing dielectric article mutual capacitance type touch sensor of the production comprising dielectric substrate through printing.Can similarly apply Second ink and solidification on the second surface of substrate forming the second pattern.Two patterns can contain then to be entered with conductive material The seed metal catalyst of row electroless-plating.Description gained dielectric article has 1 μm and is arrived to the thickness of 1mm and 20 dynes/cm The preferred surface energy of 90 dynes/cm.It is generally non-aqueous for the ink in these methods and contains various photocurable components With the metallic particles being dispersed through.

It is known using various materials so that metallic particles is scattered in aqueous or non-aqueous composition.For example, United States Patent (USP) Curable conductive ink of 8,506,849 (Lee (Li) et al.) description comprising metal nanoparticle and different polymeric dispersants. Comprising the magnetic nanoparticle and polymer point being dispersed through described in United States Patent (USP) 8,597,420 (Yi Futan (Iftime) et al.) The magnetic ink jet inks of powder.In other technologies, the outer surface of metal nanoparticle is modified incorporating hydrophobicity Tail promotes dispersibility in organic solvent for ink jet printing, such as such as Patent Application Publication 2008/ Described in 0090082 (Shen (Shim) et al.).

Need the improved printable compositions comprising the seed metal catalyst for electroless-plating (also referred to as oily Ink).Wish that applying (for example, printing) these improved compositions is with the coloring required for optical effect, is directed into The stability and the conductive line pattern without electric printing performance of work(manufacture.

However, the produced article with conductive line pattern must highly transparent and when in the visible illumination bar of reflected ray Observe invisible at that time under part.For this purpose, it has been determined that process the outer surface of conductor wire (for example, being made up of copper) with black agent To reduce the reflectivity of tinsel.

However, some that conductive pattern is provided with the both sides of transparent substrates contain the display of capacitive touch screen In device, the top surface of " through melanism " conductive thread can not substantially, but basal surface is visible and is reflected through transparent substrates.

To maintain the fine rule in conductive pattern, it is necessary to apply thin seed metal catalyst oil layer of ink, i.e. be applied only to foot To cause the degree of electroless-plating.If ink laying is excessive, ink will spread and provide broader line and thus drop small thing The transparency of product.In addition, these thicker lines are more visible in finished article and are not durable more.Therefore, needed in pattern Thinner line, but this causes that the metal through electroless-plating is online middle more visible through transparent substrates.

Useful seed metal catalyst in for these materials includes metal, such as particle of silver or copper.The property for needed for Matter, these enough metallic particles can account for the gross weight 10% to 50% of ink or printable compositions.The metal of this tittle Grain typically has reflectivity and can pass through transparent substrates to be seen easily, thus the visibility of increase gained conductive pattern.Reduce crystal seed Metallic catalyst and be the enough colouring agent (such as carbon black) of addition to can through reflexive a kind of trial of the metal of electroless-plating Printing composition (ink) is such that seed metal catalyst is invisible.However, enough these colouring agents of addition to ink without It is difficult that non-desired ground increases the viscosity of metallic particles in ink and condensation (aggregation is coalesced).

The time long is tried one's best for various use to maintain granular materials to suspend usually using dispersant (or dispersing aid) On the way.However, still known dispersant can not be used into specific particle easily minimize sedimentation and may increase to non-desired The particles' interaction of the viscosity of given group compound.In general, numerous studies and engineering are needed in various industry to seek The optimum dispersant of selected granular materials is sought, no matter the selected granular materials is metallicity, Organic or inorganic nature.This for Be designed for electroless-plating operation seed metal catalyst for it is especially true.

Accordingly, it is desirable to provide a kind of small uniform particle size point being restricted with reduced reflectivity, flocculation Cloth and use (for example) flexographic printing apply the seed metal catalyst printable compositions (oil of the appropriate viscosity of thread pattern Ink).

The content of the invention

To solve the above problems, the present invention provides a kind of non-aqueous composition, and it contains with non-aqueous composition gross weight The carbon coated metallic particles being dispersed through in organic diluent of the meter at least amount of 10 weight %, the warp being dispersed through The metallic particles of carbon coating has and is equal to or less than 0.6 μm of median diameter, and is with having at least 2,000 and at most and contain 100,000 weight average molecular weight (M_w) and containing nitrogenous unit particle dispersants dispersion, the median diameter be using dynamic Light scattering method is measured,

Wherein, when the non-aqueous composition contains at most and the carbon coated metal being dispersed through containing 25 weight % During grain, it is not presented visual sedimentation when 20 DEG C of sedimentations for carrying out at least 24 hours are tested.

In certain embodiments, these non-aqueous compositions are non-aqueous Photocurable composition, and they are respectively included：

Applied through carbon with being dispersed through of existing with the amount of non-aqueous Photocurable composition gross weight meter at least 10 weight % The metallic particles for covering, and the carbon coated metallic particles being dispersed through has the median diameter for being equal to or less than 0.6 μm, and It is with least 2,000 and at most and containing 100,000 weight average molecular weight (M_w) and contain the particle dispersants of nitrogenous unit Dispersion, the median diameter is measured using dynamic light scattering method,

Organic diluent,

UV-curable component, and

UV light triggers optionally,

Wherein, when the non-aqueous Photocurable composition contains at most and the warp including being dispersed through described in 25 weight % During the metallic particles of carbon coating, it is not presented visual sedimentation when 20 DEG C of sedimentations for carrying out at least 24 hours are tested.

The present invention provides many advantages of the carbon coated metallic particles through specific dispersion specifically described herein.Specifically Say, these carbon coated metallic particles can by using the particle dispersants of unique selection easily with higher concentration (for example, At least 10 weight %) it is scattered in non-aqueous composition.

Institute can also be reduced when carbon coated metallic particles is incorporated in the conductive line pattern formed by electroless plating method State the reflectivity of carbon coated metallic particles.

Phase between the particle of the viscosity by non-aqueous composition is increased can be minimized using particle dispersants of the invention Interaction." can load " and arrive non-aqueous by especially more fully disperseing carbon coated metallic particles, these particles of higher amount In property composition and viscosity increases without non-desired.

Particle dispersants used according to the invention also promote the not smaller carbon coated metallic particles of free settling point Split and stabilization.This is serious problems for metallic particles such as silver nano-grain, because being led from this according to following shown The sinking speed of lentor (Stokes) law, depending on metal particle size and grain density, (silver metal is 10.5g/ to the rate of settling cm³)：

Wherein Vs is particle sinking speed (m/sec) (vertically downward, if ρ_Particle>ρ_Fluid；Vertically upward, if ρ_Particle< ρ_Fluid), g is acceleration of gravity (m/sec²), ρ_ParticleIt is granular mass density (kg/m³), ρ_FluidIt is fluid mass density (kg/m³), μ For dynamic viscosity (kg/m*s) and R are particle radius (m).It is therefore seen that the rate of settling of metallic particles is with R²And increase And therefore greatly change with granularity.

Also it has been observed that non-aqueous composition of the invention (including non-aqueous Photocurable composition) represents improved Storage period, without sedimentation between printing work or in the region of little agitation of print system.

When of the invention non-aqueous using appropriate printing equipment (for example, flexographic printing element) " printing " as described below During composition, the improved particle distribution uniformity in gained picture showing track.This advantage is realized using lesser amount of Expensive carbon coated metallic particles more preferably covers given Printing Zone, and the improved uniformity provides desired more light tight Concealed wire.In the case where the covering uniformity of smaller carbon coated metallic particles is bigger, with using bigger through coalescence Situation during metallic particles is compared, electroless-plating activity improvement.

Specific embodiment

Discussion below is related to various embodiments of the present invention, and is used for special-purpose when that may be more desirable to some embodiments When, the disclosed embodiments are not necessarily to be construed as or are separately considered as the limitation scope advocated as follows of the invention.Additionally, affiliated neck The technical staff in domain should be apparent that disclosure below has compared to being expressly recited and the discussion of any embodiment broader is answered With.

Definition

When being used to define the various components of non-aqueous composition and non-aqueous Photocurable composition herein, unless Separately indicate, otherwise singulative " " and " described " are intended to include one or more described components (that is, including multiple indicants).

Each term in present application is not exactly defined to be interpreted as with those skilled in the art's custom or institute The implication that the technical staff in category field is generally received.If the explanation of term causes term thereon hereinafter without implication or base Without implication on this, then can be looked into from standard printing dictionary and take term definition.

Unless otherwise explicitly indicated, otherwise it is interpreted as approximately using the numerical value in the various scopes specified herein Value, as added wording " about " before the minimum value and maximum in the scope.In this way, scope change up and down slightly It is dynamic to can be used to realizing the result substantially the same with value in the scope.Additionally, the disclosure of these scopes is intended for bag Successive range containing each value between minimum value and maximum.

Median particle diameter [Dv (50%)] is measured using dynamic light scattering method.For example, can be used can have from Malvern instrument The Malvern ElWin Sietas wise man nanometer ZS (Malvern that limit company (Malvern Instruments, Ltd.) is commercially available Zetasizer Nano ZS) carry out the method.The operation instruction of this equipment can be obtained together with the equipment.

Unless otherwise indicated, otherwise term " particle dispersants ", " dispersant " and " dispersing aid " represents equivalent.

Term " epoxy monomer ", " unsaturated monomer ", " functional oligomers ", " metallic particles " and " crosslinking agent " is common with its Implication is with this article and known to general technology person.

As used herein, all molecular weight are the weight average molecular weight (M that can be used known procedure and equipment to measure_w), If described value is not yet for known in document.For example, can be used size exclusion chromatography method (SEC) to measure M_w, and value is herein It is expressed as poly- (methyl methacrylate) equivalent weight.

As used herein, term " photocuring " represents functional oligomers and monomer or even polymer in response to these Irradiation (for example, being irradiated using ultraviolet (UV) of appropriate wavelength, visible or infra-red radiation) polymerization of material forms cross-linked polymeric Thing network.Photocuring can in the presence of a crosslinking agent be carried out.

Defined using term " photocurable " by with appropriate radiation exposure (for example, using spoke in appropriate environment Penetrate such as ultraviolet (UV), the irradiation of visible or infra-red radiation) when be polymerized or crosslinking material (or component).

Term " photocurable component " refers to that the organic compound that may participate in photocurable reaction (is polymerized or non-poly- Close).These compounds can be to provide the monoreactant of photocuring in irradiation, or they can be with other co-reactants (such as light Initiator or acid catalyst) combination with irradiation when photocuring is provided.

Except as otherwise noted, otherwise term " non-aqueous Photocurable composition " refers to of the invention to draw including one or more Hair or promote photocuring component embodiment, the non-aqueous Photocurable composition can be used to implementing described below each Kind of method and can be used to provide article described below.These non-aqueous Photocurable compositions mainly have organic solvent or Liquid organic component and with terms of total non-aqueous Photocurable composition weight less than 5 weight % or even less than 1 weight % Water.

Term " polymerization " used herein for example make many more small molecule such as combination of monomers shapes by covalently bonded representing Great molecule as macromolecular or polymer.The monomer can be combined only to form linear macromolecule or they can be through group Close to form the three-dimensional macromolecular of commonly referred to cross-linked polymer.What can be carried out in the embodiment of this invention a type of is polymerized to Acid catalysis (cation) is polymerized.It is another type of to be polymerized to exist free redical polymerization material and appropriate free radical generation light draws Radical polymerization in the case of hair agent.In some useful embodiments of the invention, can simultaneously using acid catalyzed polymerisation and from It is polymerized two kinds by base and is polymerized.

Can be by least 2 average determinations of the individual measurements for for example being obtained for dried layer using electron microscopy herein Described in layer average dry thickness.

Similarly, the average dry thick or dry wide of line specifically described herein, grid lines or other pattern characteristics is at least 2 The individual measurements for for example being obtained using electron microscopy it is average.

Refer to produce photocuring of the invention or light polymerization and with least using " actinic radiation " 200nm and at most and containing 1400nm, and typically at least 200nm and at most and containing 750nm, or even at least 300nm and at most and Any electromagnetic radiation of the wavelength containing 700nm.Term " exposing radiation " also refers to these actinic radiations.

Wavelength (λ of the term " UV radiation " used herein with finger with least 200nm and at most and containing 400nm_max) electricity Magnetic radiation.

Purposes

Even if when non-aqueous Photocurable composition contains substantial amounts of carbon coated metallic particles specifically described herein, In the embodiment of this invention it may also happen that photocuring, and the non-aqueous Photocurable composition can be used for multiple technologies, such as scheme The imaging of shape art as light curable ink (for example, in color proofing system, being used for ink and spraying or other imaging works Skill), electronics conformal coating, coated abrasive material, magnetic medium and Photocurable composition and specifically described herein without electric In depositing process.

In addition, the non-aqueous composition of the dispersion liquid containing carbon coated metallic particles of the invention is advantageously used for Production electronic material, magnetic material, magnetic pipe recording material, optical material, gas sensing material, catalysis material, agglomerated material, light Intermediate layer in reflectance coating, light absorping film or coating, functional assembly and other operator is familiar with reference to this teaching when can be light The material being apparent from.

Therefore, during the dispersion liquid in carbon coated metallic particles needs any situation for any specific purpose, this The non-aqueous composition of invention has various uses.

Non-aqueous composition of the invention is particularly useful as respectively can containing at least one the non-aqueous of photocurable component Photocurable composition.These non-aqueous Photocurable compositions can be with any useful form photocuring, for example, being in various linings Coating, fiber on bottom, pattern on various substrates, photocurable form and molded articles and adhesive.

More specifically, the non-aqueous Photocurable composition can be used to need effective light in various articles or device Various purposes of solidification.For example, these non-aqueous Photocurable compositions can be designed with sensitive to selected radiation wavelength and can make With (such as) conduction is formed to provide further for example can then being processed using electroless-plating program for seed metal catalyst The pattern of metal pattern.These conductive metal patterns can be designed and are incorporated in various devices, including but not limited to Touch screen Or other display equipments that can be used in many consumption, industry and commercial product.

Touchscreen technology may include different touch sensor configurations, comprising capacitor type and resistive touch sensor.Electricity Resistance type touch sensor include several layers relative to each other, adjacent interlayer have one can by processing during formed dividing plate keep Gap.Resistive touch screen panel can include several layers, including two thin, the gold separated by the gap that can be set up by dividing plate Category, conductive layer.When object such as felt pen, palm or finger tip push the certain point on panel outer surface, the contact of this two metal level And form connection and cause curent change.This touch event is sent to controller for further treatment.

Capacitive touch sensor can be used in the electronic installation of the feature for having sensitive to touch.These electronic installations can Including but not limited to television set, monitor, automatically deliver machine and may be adapted to display image including word, figure, video figure The projector of picture, film, rest image and demonstration.The image device that can be used for these display equipments can be comprising cathode-ray tube (CRS), projector, plate of flat liquid crystal display (LCD), LED information display system, OLED systems, plasma system, electroluminescent display And Field Emission Display (FED) (ECD).For example, the present invention can be used to manufacture is incorporated with having the feature sensitive to touch Capacitive touch sensor in electronic installation, to provide computing device, computer display, portable electronic device (bag Containing electronic reader), mobile phone and other portable communication apparatus.

Using the present invention, may realize can one way set up micro conductive feature high-volume takeup type manufacturing process in manufacture The system and method for the flexible and touch sensor of optics adaptability.The non-aqueous Photocurable composition can print with multiple Part (such as multiple flexographic printing plates) is used in these system and method with from being provided in those multiple printing units together The predetermined design of pattern forms multiple high-resolution conductive pattern pictures.Multiple patterns can print transparent as described in more detail below On one or both sides of substrate.For example, a predetermined pattern can be formed on the side of transparent substrates, and a different predetermined patterns can It is formed on the opposite side of transparent substrates.It is transparent that the pattern of printed non-aqueous Photocurable composition then " can print " Pattern on substrate one or both sides, the printed pattern for example can plate further treatment and provide conduction using electroless metal Metal pattern.

Non-aqueous composition

In the minimum form of non-aqueous composition of the present invention, the non-aqueous composition is mainly consisted of：A () such as The carbon coated metallic particles being dispersed through of identical or different composition hereinafter described；(b) one or more as mentioned below Particle dispersants；(c) such as organic diluent (liquid organic material), organic solvent medium as mentioned below, wherein disperseing The carbon coated metallic particles (and possible other components).

(a) carbon coated metallic particles

Generally, using only the carbon coated metallic particles of a type (composition) in each non-aqueous composition, but may be used also The mixture of the carbon coated metallic particles of the different type comprising the metal from identical or different classification not interfering with each other. In general, each carbon coated metallic particles has net neutral charge.In general, the carbon coated particle is non-magnetic Property, it is meant that it does not show obvious magnetic, and therefore, non-aqueous composition of the invention is equally generally non magnetic.

Available carbon coated metallic particles may include the metallic particles of carbon coating at least in part.The metallic particles It is (that is, pure by metal of one or more noble metal, semi-precious metal, Group IV metal or its combination that are selected from one or more classifications Metal or metal alloy) composition.Available noble metal includes but is not limited to gold, silver, palladium, platinum, rhodium, iridium, rhenium, mercury, ruthenium and osmium. Available semi-precious metal includes but is not limited to iron, cobalt, nickel, copper, carbon, aluminium, zinc and tungsten.Available Group IV metal include (but It is not limited to) tin, titanium and germanium.Noble metal is particularly useful such as silver, palladium and platinum, and semi-precious metal nickel and copper are also particularly useful.In iv In race's metal classification, tin is especially useful.In many examples, fine silver or copper are used in non-aqueous Photocurable composition. Therefore, in the embodiment of this invention, term " metal " is intended to identical with " metallicity " meaning, but term " metal " and " metallicity " are no Slaine to be included, metal oxide and metal hydride.

The general at least part of ground surface carbon coating of metallic particles comprising the metal.The carbon can be mixed for amorphous, sp2 Into or class Graphene property.

Therefore, for non-aqueous composition in the material being particularly useful be carbon coated Argent grain, carbon coated The mixture of copper particle or (in certain embodiments) carbon coated Argent grain and carbon coated copper particle, they are used One or more particle dispersants as mentioned below are dispersed in organic solvent medium.

The carbon coated metallic particles is designed to when the feelings measured by dynamic light scattering technique in suspension Have under condition and be equal to or less than 0.6 μm or less than 0.2 μm or the more likely median particle diameter less than 0.1 μm.These are applied through carbon The metallic particles for covering typically has 0.005 μm of minimum median diameter.

These carbon coated metallic particles in any geometry can be present, including but not limited to spheroid, bar, prism Body, cube, cone, pyramid, silk thread, thin slice, platelet and its combination, and its shapes and sizes can be uniform or non-equal It is even.Can be used in the carbon coated metallic particles of the agglomerated thing of individual particles or a little particle of the invention optimal excellent to realize Point.

One or more particle dispersants described in non-aqueous composition respectively be used for disperse carbon coated metallic particles in case Only its cohesion or coalescence in the non-aqueous composition (as described hereinafter) for also containing organic diluent.It is carefully chosen these Grain dispersant can provide required advantage so as to the present invention.First, each particle dispersants have at least 2,000 and at most and containing 100, 000 or more specifically at most and containing 50,000 weight average molecular weight (M_w).Most available particle dispersants respectively have at least 3, 000 and at most and containing 30,000 M_w。

In addition, each available particle dispersants include two or more nitrogenous units, for example acid amides (carboxylic acid, Sulfonic acid, sulfinic acid, phosphoric acid, phosphonic acids and many can form other acid of acid amides), amine (primary, secondary, uncle), amine oxide, (acid amides is sub- for amidine Amine), azo, carbamate (carbamate) (urethane (urethanes)), carbodiimide, diazonium (diazo), diazonium (diazonium), enamine, guanidine (imines of urea), aromatic heterocycle (pyridine, pyrimidine, pyridazine, pyrazine, pyrroles, imidazoles, pyrazoles, evil Azoles (ozazole), isoxazole, thiazole, indoles, indolizine, quinoline, isoquinolin), hydrazine, hydrazone, hydroxamic acid, acid imide, imines (west Buddhist (Schiff) alkali), nitrate (ester of nitric acid), nitrile (cyanide), nitrous acid ester (ester of nitrous acid), nitro/nitroso it is (sub- Nitrobenzene, nitrobenzene, nitromethane, N- nitroso ureas), nitrone (sub- amine n-oxide), oxime (imines of azanol) or urea (formic acid Bisamide, such as N- MUs, N- methylthiourea biurets allophanic acid, urazole) unit or fragment.Some are especially useful to contain Nitrogen unit is acid amides, amine and imines unit.In general, each particle dispersants have multiple nitrogenous units (because it is at least It is oligomeric) and with least 2,000 M_w.These nitrogenous units cause that particle dispersants strength is affixed to carbon coated metal Grain.

Each particle dispersants also containing it is compatible with organic polymer and with the organic solvent medium for non-aqueous composition In the compatible functional group of organic solvent.For polarity, non-aqueous composition, available nitrogenous unit includes ester, acrylic acid Ester or ether or its combination.

Some particle dispersants being particularly useful are that (such as they are in polyester or (methyl) acrylate copolymer comprising ester units Finder in (homopolymers and copolymer)) organic polymer.

In other embodiments, particle dispersants are containing selected from following classification (i) at least classification (in (iv) Or multiple classifications) unit organic polymer：

The pyridine unit of (i) such as in vinylpyridine；

(ii) the imines unit (such as-alkylidene-NH- units) that can be such as found in polyethyleneimine, including aziridine With propyleneimine unit；

(iii) acid imide unit [- C (=O)-NH-C (=O)-unit]；With

(iv) amine unit (primary, secondary and tertiary amido).

The mixture of these particle dispersants from identical or different classification material can be used if necessary.

Some examples of the available particle dispersants with these features are following material, including some commercially available prod：

Copolymer containing polyethyleneimine fragment, such as She Sibosi35000 Hes 39000 (Lu Borun (Lubrizol))；

In block, such as branched, hyperbranched and pectinate texture form the copolymer containing ester and amine unit, this Bick of enlightening-2155、-2152、-2013、- 9077 (BYK/ A Ertana ) and Ai Fuka (Altana)The Hes of PX 4731PX 4732(BASF)；

Acrylic block copolymers containing aliphatic series or aromatics amine unit, such asPX 4701(BASF)；With

Copolymer containing aliphatic series or aromatics amine unit, such as- 2118 (BYK/ A Ertana) and spy ask Buddhist nun Gram150R(BASF)。

Following required component is contained in non-aqueous composition, and its amount causes that particle dispersants are carbon coated with what is be dispersed through The weight ratio of metallic particles be at least 1:100 or even at least 3:100 and at most and containing 10:100 or at most and containing 30:100. These weight refer to the gross weight and all carbon coated metallic particles of all particle dispersants in each non-aqueous composition Gross weight.

In addition, the amount of metallic particles carbon coated in each non-aqueous composition is (to be included with non-aqueous composition Organic diluent) gross weight meter at least 10 weight % or at least 15 weight % and at most and containing 60 weight % or even up to and contain 70 weight %.Using this information, being familiar with operator can then determine selected particle dispersants for selected carbon coated metal The available and optimal amount of particle.

In some embodiments being particularly useful, non-aqueous composition is included to be pressed with non-aqueous composition gross weight meter at least 15 weight % and at most and the carbon coated Argent grain being dispersed through that exists of concentration containing 60 weight %, and described be dispersed through Carbon coated Argent grain has the median diameter less than 0.5 μm for measuring as described above.

Non-aqueous composition (including non-aqueous Photocurable composition hereinafter described) also generally comprises non-aqueous combination The component dissolving of thing disperses the organic diluent for useing non-aqueous (organic) solvent or solvent combination as therein.

In some embodiments of the invention, organic diluent is such as following inert organic solvents containing one or more Organic solvent medium：Cellosolvo, 2- (2- methoxy ethoxies) ethanol, 2- (2- ethoxy ethoxies) ethanol, 1- first Epoxide -2- propyl alcohol (ten thousand promises more (Dowanol) PM), 4- heptanone, 3- heptanone, 2-HEPTANONE, cyclopentanone, cyclohexanone, diethyl carbonate, 2-ethoxyethyl acetate, butyric acid N- butyl esters, acetone, dichloromethane, isopropanol, ethylene glycol and methyl lactate.These are listed lazy Property organic solvent mixture can with any appropriate volume or weight ratio be used for organic solvent medium in.Can be by art Technical staff judges other available organic solvents easily using teaching presented herein.So-called 'inertia' represents organic Solvent will not substantially participate in any chemical reaction.

In the presence of one or more photocurable components (as mentioned below) are in a liquid state organic compound, these one or more It is probably nonessential that photocurable component can use organic diluent and indivedual inert organic solvents as.In such cases, have Machine diluent can be considered " reactivity " diluent.Or, one or more reactive diluents can be organic with one or more inertia molten Agent (as described above) is applied in combination to form appropriate organic diluent.

Can carefully according to the certain material for being used, the device for applying gained non-aqueous composition and required property (including composition uniformity) selects the amount of organic diluent.

For example, organic diluent can be provided with non-aqueous composition gross weight meter at least 10 weight % and at most and containing 90 weights Measure % or at least 20 weight % and at most and containing 80 weight %.Organic diluent generally comprises little water or without water, it is meant that Water is existed by the amount with non-aqueous composition gross weight meter less than 5 weight % or even less than 1 weight %.

Although not being the necessary condition of non-aqueous composition, optional and desired component is with non-aqueous composition gross weight Gauge at least 0.5 weight % and at most and containing 20 weight % or typically at least 1 weight % and at most and containing 10 weight % contents Carbon black.

As described above, non-aqueous composition of the invention can be further containing one or more as mentioned below can light consolidate Change the non-aqueous Photocurable composition of component.The amount that the teaching for hereinafter providing judges these components is it is also possible to use, but typically For, only exist one or more photocurable components of the amount of the photocuring for providing enough in special-purpose.

Some especially useful non-aqueous Photocurable compositions of the invention are included：

At least 10 weight % or even at least 15 weight % and at most and containing 60 weight % or at most and containing 70 weight % contain Amount the carbon coated metallic particles being dispersed through, all contents be with non-aqueous Photocurable composition gross weight meter, and The carbon coated metallic particles being dispersed through has and is equal to or less than 0.6 μm of median diameter, and by least 2,000 and At most and containing 100,000 M_wAnd the particle dispersants dispersion containing nitrogenous unit, the median diameter is dissipated using dynamic optical Method judgement is penetrated, as described above,

Organic diluent (as described above),

UV-curable component (as mentioned below), and

UV light triggers (as mentioned below) optionally,

Wherein, when the non-aqueous Photocurable composition contains at most and the warp including being dispersed through described in 25 weight % During the metallic particles of carbon coating, it is (described that it is not presented visual sedimentation when 20 DEG C of sedimentations for carrying out at least 24 hours are tested Test is further in defined above).

In these non-aqueous Photocurable compositions, the carbon coated metallic particles being dispersed through may include what is be dispersed through Carbon coated Argent grain or the carbon coated copper particle being dispersed through or the carbon coated Argent grain that is dispersed through and it is dispersed through Carbon coated copper particle both mixture, they are set forth in hereinafter.

In addition, particle dispersants and the carbon coated metal being dispersed through in these non-aqueous Photocurable compositions The weight ratio of particle can be at least 1:100 and at most and containing 30:100.

In some especially useful non-aqueous Photocurable compositions, the carbon coated metallic particles being dispersed through can be by With non-aqueous Photocurable composition gross weight meter at least 15 weight % and at most and the amount containing 60 weight % is present, and the warp Scattered carbon coated metallic particles (such as carbon coated Argent grain or carbon coated copper particle) has as using as above The median diameter less than 0.5 μm that dynamic light scattering method described in text is measured.

Can suitably disperse carbon coated using appropriate dispersal device by with particle dispersants one or more described Metallic particles prepares non-aqueous composition of the invention.This two kinds of required components can mix or be scattered in and can effectively disperse through carbon The organic diluent (such as organic solvent medium) of the metallic particles of coating is in (as described above).

For disperseing method including but not limited to ball milling, medium milling, the magnetic of carbon coated metallic particles Stirring, high speed homogenisation, high pressure homogenizing, electromagnetic shaker vibration and ultrasonication.Ultrasonication is used especially for being contained in Particle dispersants in organic diluent disperse carbon coated metallic particles.

Medium milling technology can be additionally used in the solid particle that comminution is used in the present invention, such as carbon coated metallic particles. Grater, ball mill, medium grinder or oscillating mill can be used using appropriate comprising silica, silicon nitride, sand, oxidation Zirconium, aluminum oxide, titanium oxide, yittrium oxide, yttria stabilised zirconia, zirconium silicate, glass, steel or any other known use Medium milling is realized in the medium of the material of these purposes.

Non-aqueous Photocurable composition of the invention can further include in terms of non-aqueous Photocurable composition total amount At least 0.5 weight % and at most and containing 20 weight % or at least 1 weight % and being dispersed through at most and containing 10 weight % contents Carbon black.

Through acid catalyzed photocurable chemistry：

In some embodiments of the invention, non-aqueous Photocurable composition includes one or more UV-curable components, Wherein at least one is through acid catalyzed photocurable component.These non-aqueous Photocurable compositions can further include light acid Producing agent.

It can be photocurable epoxy material through acid catalyzed photocurable component that some are available.Can be used in the present invention Cationic photocurable epoxy material (" epoxides ") is the organic compound with least one oxirane ring, the ring Oxidative ethane ring is shown in following formula：

It can be polymerized by open loop mechanism.These epoxy materials include the epoxidation of monomeric epoxide compound and polymeric type Thing and can be aliphatic series, cyclic aliphatic, aromatics or heterocycle.The general per molecule of these materials averagely has at least one polymerizable epoxy Base, or generally per molecule has at least about 1.5 or even at least about 2 polymerizable epoxy bases.Polymeric epoxy materials include tool Have the linear polymer (for example, diglycidyl ether of polyether polyols) of terminal epoxy groups, with skeleton (main chain) ring The polymer (for example, polybutadiene polyepoxide) and the polymer with side ring epoxide of oxirane unit are (for example, methyl-prop Olefin(e) acid ethylene oxidic ester polymer or copolymer).

Photocurable epoxy material can for single compound or its for different per molecules can contain one, two or be more than Two mixtures of the epoxy material of epoxy radicals.It is total containing epoxy molecule divided by existing by the total epoxy radix in epoxy material To judge " average " epoxy radix of per molecule.

Epoxy material can change from low molecular weight monomers material to heavy polymer and it can be in main chain and substitution base (or side base) is differed considerably in nature.For example, main chain can for any types and substitution base thereon can be at room temperature will not be big Any group of cation photocuring technique needed for being disturbed on body.The example of the substitution base of permission include but is not limited to halogen, Ester group, ether, sulfonate group, siloxy group, nitro and phosphate-based.The molecular weight of epoxy material can be at least 58 and at most and contain 100,000 or even more high.

Available epoxy material includes those epoxy materials containing cyclohexene oxide group, such as 7-oxa-bicyclo[4.1.0 carboxylic acid Ester, such as 3,4- epoxycyclohexyl-methyl -3,4- epoxycyclohexane carboxylates, 3,4- epoxy -2- methylcyclohexylmethyl -3,4- rings Oxygen -2- methylcyclohexanecarboxylic acids ester and double (3,4- epoxy -6- methylcyclohexylmethyls) adipate esters.Available this kind of property of tool The more detailed list of epoxy material be provided in United States Patent (USP) 3,117,099 (Pu Lupusi (Proops) et al.).

Other available epoxy materials include being many by what is reacted polyhydric phenols and the chloropharin such as epichlorohydrin of excess and obtain The glycidyl ether monomers of first phenol glycidol ether are [for example, two shrinks of 2,2- double-(2,3- epoxypropoxyphenol)-propane Glycerin ether].Other examples of the epoxy material of these types be set forth in United States Patent (USP) 3,018,262 (Schroeder (Schroeder)) and " epoxy resin handbook (Handbook of Epoxy Resins) ", Lee (Lee) and Neville (Neville), McGraw-Xi Er Books Co., Ltd (McGraw-Hill Book Co.), in New York (1967).

Other available epoxy materials are resin, as derived from acrylate (such as acrylic acid contracting reacted with glycidol Water glyceride and GMA) with the copolymerization of one or more ethylenic unsaturated polymerizable monomer combined polymerizations Thing.

Other available epoxy materials are epichlorohydrin class (such as epichlorohydrin), alkylene oxide (such as expoxy propane and Oxybenzene second Alkene), alkylene oxide (such as butadiene oxide) and ethylene oxidic ester (such as ethyl glycerate).

Other available epoxy materials are the poly- silica with epoxy functional or epoxy radicals (such as cyclohexyl ring epoxide), especially It is that those have the epoxy material of poly- silicon-oxygen backbone.The commercial embodiments of these epoxy materials are included purchased from figure advanced in years (Momentive) the poly- silica material of UV 9300, UV 9315, UV 9400, UV 9425.

Polymeric epoxy materials optionally will not can generally disturb non-aqueous photocurable to combine at room temperature comprising other The functionality of the cation photocuring of thing.For example, photopolymerization epoxy material can also include free redical polymerization functionality.

Photopolymerization epoxy material can include two kinds or more than two kinds of admixtures or mixture of different epoxy materials.These The example of admixture includes two kinds or more than two kinds of photopolymerization epoxy materials of molecular weight distribution, such as one or more low-molecular-weights The admixture of (being less than 200) epoxy material and one or more intermediate molecular weight (from 200 to 10,000) photopolymerization epoxy materials Or one or more described photopolymerization epoxy materials and one or more higher molecular weight (greater than about 10,000) epoxy materials are mixed Compound.Or or in addition, photopolymerization epoxy material can be comprising with different chemical property (such as aliphatic series and aromatics property) or not The admixture of the epoxy material of same functionality (such as polarity and non-polar nature).Other cationic polymerizable monomers or polymer Can be incorporated into addition in photopolymerization epoxy material.

One or more photocurable epoxy materials are included in non-aqueous Photocurable composition to provide with appropriate amount Required effective photocuring (or photopolymerization).For example, described one or more photopolymerization epoxy materials can by with it is non-aqueous can Photocurable composition gross weight meter at least 5 weight % and at most and containing 50 weight % or typically at least 10 weight % and at most and contain The amount of 40 weight % is present.

Various compounds can be used as light acid producing agent for producing the appropriate sour photocuring to participate in epoxy material.These Some in " light acid producing agent " are for acid and other are nonionic.Those skilled in the art is with reference to presented herein Teaching will be readily appreciated by except they hereinafter described in addition to other available light acid producing agents.It is suitable for light acid producing agent Various compounds can be bought from various commercial sources or are obtained using known synthetic method and parent material.

Can be used to implement salt the acid producing agent of the invention including but not limited to salt of diazonium, Phosphonium, Iodonium or sulfonium salt, including Poly- aryldiazonium, Phosphonium, Iodonium and sulfonium salt.Iodonium or sulfonium salt include but is not limited to Er Fang Ji Iodonium and triarylsulfonium salt.It is available relative Anion includes but is not limited to complexing metal halogen ion, such as tetrafluoroborate, hexafluoroantimonic anion, TFMS root, hexafluoro Arsenate, hexafluoro-phosphate radical and arene-sulfonic acids root.Salt can also be the oligomeric or polymerizable compound with multiple salt parts with And the molecule with single salt part.

The example of available Fang Zu Iodonium salt includes but is not limited to tetrafluoro boric acid Er Ben Ji Iodonium；(the 4- methyl of tetrafluoro boric acid two Phenyl) Iodonium；Tetrafluoro boric acid phenyl -4- Jia base Ben Ji Iodonium；Tetrafluoro boric acid two (4- heptyl phenyl) Iodonium；(the 3- nitros of hexafluorophosphoric acid two Phenyl) Iodonium；(the 4- chlorphenyl) Iodonium of hexafluorophosphoric acid two；(the naphthyl) Iodonium of tetrafluoro boric acid two；Tetrafluoro boric acid two (4- trifluoromethyls) Iodonium；Hexafluorophosphoric acid Er Ben Ji Iodonium；(the 4- aminomethyl phenyl) Iodonium of hexafluorophosphoric acid two；Hexafluoroarsenate Er Ben Ji Iodonium；(the 4- benzene of tetrafluoro boric acid two Phenyl) Iodonium；Hexafluorophosphoric acid phenyl -2- Sai fen Ji Iodonium；Hexafluorophosphoric acid 3,5- dimethyl pyrazole oxazolyl -4- benzene bases Iodonium；Hexafluoro antimony Sour Er Ben Ji Iodonium；Tetrafluoro boric acid 2,2'- bis- Ben Ji Iodonium；(the 2,4 dichloro benzene base) Iodonium of hexafluorophosphoric acid two；(the 4- bromobenzenes of hexafluorophosphoric acid two Base) Iodonium；(the 4- methoxyphenyl) Iodonium of hexafluorophosphoric acid two；(the 3- carboxyl phenyl) Iodonium of hexafluorophosphoric acid two；(the 3- methoxyl groups of hexafluorophosphoric acid two Carbonyl phenyl) Iodonium；(the 3- methoxysulfonyl phenyl) Iodonium of hexafluorophosphoric acid two；(the 4- acetamidophenyl) Iodonium of hexafluorophosphoric acid two；Six (the 2- benzothienyl) Iodonium of fluorophosphoric acid two；And hexafluoro-antimonic acid Er Ben Ji Iodonium；With its mixture.Can be according to Beling (Beringer) etc. People, corresponding Fang Zu Iodonium mono-salts (e.g., the example of teaching double decomposition of JACS (J.Am.Chem.Soc.) 81,342 (1959) Such as, sulfuric acid diphenyl hydrogen base Iodonium) these compounds are obtained.

Other Shi Dang Iodonium salt include being set forth in United States Patent (USP) 5,545,676 (para assistant support (Palazzotto) et al.) the 2 columns (the 28th row to the 46th row) and United States Patent (USP) 3,729,313 (Smith (Smith)), 3,741,769 (Smiths), 3, Compound in 808,006 (Smiths), 4,250,053 (Smiths) and 4,394,403 (Smiths).

You Iodonium salt can for mono-salt (for example, contain anion, such as chlorion, bromide ion, iodide ion or C₄H₅SO₃ ^-) or Metallic complex salt is (for example, contain SbF₆ ^-、PF₆ ^-、BF₄ ^-, wantonly (perfluorophenyl) borate or SbF₅OH₃₁AsF₆ ^-).If desired, The mixture of any these identical or different classification Iodonium salt then can be used.

Exemplary sulfonium salt includes but is not limited to tetrafluoro boric acid triphenylsulfonium, tetrafluoro boric acid methyldiphenyl base sulfonium, hexafluoro phosphorus Sour 3,5-dimethylphenyl sulfonium, hexafluorophosphoric acid triphenylsulfonium, hexafluoro-antimonic acid triphenylsulfonium, hexafluoroarsenate diphenyl naphthyl sulfonium, hexafluoro phosphorus Sour trimethylphenyl sulfonium, hexafluoro-antimonic acid anisyl diphenyl sulfonium, tetrafluoro boric acid 4- butoxy phenyl diphenyl sulfonium, hexafluorophosphoric acid 4- Chlorphenyl diphenyl-sulfonium, hexafluorophosphoric acid three (4- Phenoxyphenyls) sulfonium, hexafluoroarsenate two (4- ethoxyl phenenyls) methyl sulfonium, four Fluoboric acid 4- acetonyl phenyl diphenyl sulfonium, hexafluorophosphoric acid 4- sulfenyl methoxyphenyl diphenyl the sulfonium, (methoxyl group of hexafluoro-antimonic acid two Sulfonvlphenyl) methyl sulfonium, (nitrobenzophenone) phenyl of hexafluoro-antimonic acid two sulfonium, hexafluorophosphoric acid two (carbomethoxvphenvl) methyl Sulfonium, tetrafluoro boric acid 4- acetylamino phenyl diphenyl sulfonium, hexafluorophosphoric acid dimethyl naphthyl sulfonium, tetrafluoro boric acid trifluoromethyl diphenyl P- (tolylthiophene base) the diphenyl sulfonium of sulfonium, hexafluoro-antimonic acid, p- (tolylthiophene base) the diphenyl sulfonium of hexafluorophosphoric acid, hexafluoro-antimonic acid Double (the diphenyl of two-[p- (tolylthiophene base)] phenyl sulfoniums, hexafluorophosphoric acid two-[p- (tolylthiophene base)] phenyl sulfonium, 4,4'- Sulfonium) diphenyl sulfide double (hexafluoroantimonic anion), double (diphenyl sulfonium) diphenylsulfides of 4,4'- double (hexafluoro-phosphate radical), hexafluorophosphoric acids 10- methyl phenoxazines sulfonium, hexafluorophosphoric acid 5- methyl thianthrene, hexafluorophosphoric acid 10- phenyl -9,9- dimethyl 9- oxygen sulphur xanthone, four Fluoboric acid 10- phenyl -9- oxo 9- oxygen sulphur xanthone, tetrafluoro boric acid 5- methyl isophthalic acid 0- oxos thianthrene, hexafluorophosphoric acid 5- methyl - 10,10- dioxos thianthrene and its mixture.

It is that sulfonium salt is desirable to for use and should dissolve in any inert organic solvents (being set forth in hereafter) and its also Should be storage stabilization, it is meant that it is when mixed with other components (particularly electron acceptor sensitising agent and electron donor common initiator) Will not spontaneously promote polymerization before appropriate radiation during conjunction.Therefore, the selection of specific salts can be for regard to other Optimal properties are carried out for component and amount.

Especially useful sulfonium salt includes but is not limited to the salt of triaryl substitution, such as blended hexafluoro-antimonic acid triaryl matte (for example, being bought from Dow Chemical (Dow Chemical Company) with UVI-6974), blended hexafluorophosphoric acid three Aryl sulfonium (for example, being bought from Dow Chemical with UVI-6990) and hexafluorophosphoric acid aryl sulfonium are (for example, with SarCa^TM KI85 From Sartomer, (Sartomer Company) buys).

One or more salt (such as Iodonium salt or sulfonium salt) can press with non-aqueous Photocurable composition gross weight meter at least 0.05 weight % and at most and containing 10 weight % or typically at least 0.1 weight % and at most and containing 10 weight % or even at least 0.5 weight % and at most and the amount containing 5 weight % is stored in non-aqueous Photocurable composition.

Nonionic light acid producing agent can be additionally used in the present invention, and the compound includes but is not limited to diazomethane derivative Thing, such as (e.g.) double (benzenesulfonyl) diazomethanes, double (ptoluene-sulfonyl) diazomethanes, double (ditosyls) weight N-formyl sarcolysine alkane, double (cyclohexylsulfonyl)-diazomethanes, double (Cyclopentylsulfonyl) diazomethanes, double (normal-butyl sulfonyls) weight N-formyl sarcolysine alkane, double (iso-butylsulfonyl) diazomethanes, double (sec-butylsulfonyl) diazomethanes, double (n-propyl sulfonyl) diazonium Methane, double (isopropelsulfonyl) diazomethanes, double (tert. butylsulfonyl) diazomethanes, double (n-pentyl sulfonyl) diazonium first Alkane, double (isopentyl sulfonyl) diazomethanes, double (sec-amyl sulfonyl) diazomethanes, double (tertiary pentyl sulfonyl) diazonium first Alkane, 1- cyclohexylsulfonyls -1- (tert. butylsulfonyl) diazomethane, 1- cyclohexylsulfonyls -1- (tertiary pentyl sulfonyl) weights N-formyl sarcolysine alkane and 1- tertiary pentyl sulfonyl -1- (tert. butylsulfonyl) diazomethane.

Nonionic light acid producing agent may also include glyoxime derivative, such as (e.g.) double-o- (ptoluene-sulfonyl)-α- Dimethyl glyoxime, double-o- (ptoluene-sulfonyl)-α-diphenyl glyoxime, double-o- (ptoluene-sulfonyl) rings of-α-two Hexyl glyoxime, double-o- (ptoluene-sulfonyl) -2,3- pentanediones glyoxime, double-o- (ptoluene-sulfonyl) -2- methyl - 3,4- pentanediones glyoxime, double-o- (normal butane sulfonyl)-alpha-alpha-dimethyl glyoxime, double-o- (normal butane sulfonyl)-α-two Phenyl glyoxime, double-o- (normal butane sulfonyl)-α-dicyclohexyl glyoxime, double-o- (normal butane sulfonyl) -2,3- penta 2 Ketone glyoxime, double-o- (normal butane sulfonyl) -2- methyl -3,4- pentanediones glyoxime, double-o- (methane sulfonyl)-alpha, alpha-dimethyl Base glyoxime, double-o- (trifluoromethane sulfonyl group)-alpha-alpha-dimethyl glyoxime, double-o- (1,1,1- HFC-143as sulfonyl)-α- Dimethyl glyoxime, double-o- (tertiary butane sulfonyl)-alpha-alpha-dimethyl glyoxime, double-o- (PFO sulfonyl)-alpha, alpha-dimethyl Base glyoxime, double-o- (Cyclohexanesulfonyl)-alpha-alpha-dimethyl glyoxime, double-o- (benzenesulfonyl)-alpha-alpha-dimethyl glyoxime, Double-o- (p- fluorophenylsulphonyl)-alpha-alpha-dimethyl glyoximes, double-o- (p- tert-butyl benzene sulfonyl)-alpha-alpha-dimethyl glyoxime, Double-o- (ditosyl)-alpha-alpha-dimethyl glyoximes or double-o- (camphor sulfonyl)-alpha-alpha-dimethyl glyoxime.

These light acid producing agents may also include bis sulfone derivative, such as (e.g.) double Naphthylsulfonyl methane, bis trifluoromethyl Sulfonyl methane, double methyl sulfonyl methanes, double ethylsulfonyl methane, double sulfonyl propyl methylmethanes, double isopropelsulfonyls Methane, double-tolysulfonyl methylmethane, double benzenesulfonyl methane, 2- cyclohexyl-carbonyl -2- (ptoluene-sulfonyl) propane (beta-keto sulfone derivative) and 2- isopropyls-carbonyl -2- (ptoluene-sulfonyl) propane (beta-keto sulfone derivative).

The available nonionic light acid producing agent of other classifications includes disulfo derivative, such as (e.g.) the sulfone of diphenyl two and The sulfone of dicyclohexyl two；Sulfonic acid p-Nitrobenzyl derivative, such as (e.g.) p-methyl benzenesulfonic acid 2,6- dinitros benzyl ester and p-methyl benzenesulfonic acid 2,4- dinitro benzyl esters；Sulfonate derivatives, such as (e.g.) 1,2,3- tri- (mesyl epoxide) benzene, 1,2,3- tri- (fluoroforms Sulfonyl epoxide) benzene and 1,2,3- tri- (p-toluenesulfonyl epoxide) benzene；And the sulphonic acid ester of N- hydroxy imides, such as (e.g.) N- HOSu NHS methanesulfonates, N-hydroxy-succinamide triflate, N-hydroxy-succinamide esilate, N-hydroxy-succinamide 1- propane sulfonic acid ester, N-hydroxy-succinamide 2- propane sulfonic acid ester, the sulphurs of N-hydroxy-succinamide 1- penta Acid esters, the pungent sulphonic acid esters of N-hydroxy-succinamide 1-, N-hydroxy-succinamide p-methyl benzenesulfonic acid ester, N-hydroxy-succinamide To methoxy benzenesulfonic acid ester, N-hydroxy-succinamide 2- chloroethenes sulphonic acid ester, N-hydroxy-succinamide benzene sulfonate, N- hydroxyls Succinimide 2,4,6- trifluoros benzene sulfonate, N-hydroxy-succinamide 2,4,6- tri-methyl p-toluenesulfonates ester, N- hydroxysuccinimidyls Acid imide 2,4,6- trichlorines benzene sulfonate, N-hydroxy-succinamide 4- cyano group-benzene sulfonate, N-hydroxy-succinamide 1- naphthalenes Sulphonic acid ester, N-hydroxy-succinamide 2- napsylates, N- hydroxyl -2- phenyl succinimides methanesulfonates, N- hydroxyls Malaysia Acid imide methanesulfonates, N- hydroxy maleimides esilate, N- hydroxyl -2- phenyl maleimides methanesulfonates, N- hydroxyls Base glutarimide methanesulfonates, N- glutarimides benzene sulfonate, HP methanesulfonates, N- Hydroxyphthalimide benzene sulfonate, HP triflate, N- hydroxyl phthalyls Imines p-methyl benzenesulfonic acid ester, N- hydroxyl naphthalimides methanesulfonates, N- hydroxyl naphthalimides benzene sulfonate, N- hydroxyls Base -5- ENB -2,3- dicarboximides methanesulfonates, N- hydroxyl -5- ENB -2,3- dicarboximide fluoroform sulphurs Acid esters, N- hydroxyl -5- ENB -2,3- dicarboximide p-methyl benzenesulfonic acid ester, N- hydroxyl naphthalimide fluoroform sulphurs Acid esters and N- hydroxyl -5- ENB -2,3- dicarboximide perfluor -1- fourth sulphonic acid esters.

One or more nonionic light acid producing agents can be by with non-aqueous Photocurable composition gross weight meter at least 0.05 weight Amount % and at most and containing 10 weight % or typically at least 0.1 weight % and at most and containing 10 weight % or even at least 0.5 weight Amount % and at most and the amount containing 5 weight % is stored in non-aqueous Photocurable composition.

The non-aqueous Photocurable composition of some specifically described herein (particularly they contain photopolymerization epoxy material and Light acid producing agent person) one or more electron donor sensitising agents can be contained.Available electron donor sensitising agent should dissolve in non-aqueous In Photocurable composition, without the functionality by cation photocuring technique is generally disturbed, and with least 150nm and The ability of the light absorbs (sensitiveness) at most and in the wave-length coverage containing 1000nm.

Appropriate electron donor sensitising agent is in response to triggering salt (or the acid of other light being produced from radiating absorbed photon Agent) chemical transformation.Electron donor sensitising agent should also have absorbed light (that is, photo induced electron transfer) in electron donor sensitising agent The ability of light acid producing agent is reduced afterwards.Therefore, electron donor sensitising agent generally has general from after radiation absorption photon at once Electronics supplies the ability of light acid producing agent.

When solidification (e.g., the solidification of the film of the thin non-aqueous Photocurable composition through applying) extremely fast is needed, Using ultraviolet curing process, under required radiation wavelength, electron donor sensitising agent can have at least 1000 liters-mole^-1cm^-1And it is logical Normal at least 50,000 liters-mole^-1cm^-1Extinction coefficient.

For example, each electron donor sensitising agent typically has at least 0.4V and at most and containing 3V (relative to SCE) or more generally At least 0.8V and at most and containing the oxidation potential of 2V (relative to SCE).

In general, many different classes of compounds can be used as electron donor sensitising agent for various reactants.Can use Electron donor sensitising agent include but is not limited to aromatic compounds, such as naphthalene, 1- methyl naphthalenes, anthracene, 9,10- dimethoxys anthracene, benzene And [a] anthracene, pyrene, phenanthrene, benzo [c] phenanthrene and fluoranthene (fluoranthene).

Other available electron donor sensitising agents on triplet excited state are carbonyls, such as 9- oxygen sulphur xanthone And xanthone.(such as ketocoumarin, such as they have strong supplied for electronic for ketone (including aromatic ketone, such as Fluorenone) and coumarine dye Partly (such as dialkylamino) person) also act as electron donor sensitising agent.It is believed that other appropriate electron donor sensitising agents include Xanthene dye, acridine dye, thiazole dye, thiazine dye, oxazine dye, azine dye, aminoketone dye, porphyrin, aromatics are more Cyclic hydrocarbon, the aminostyryl ketone compounds of contraposition substitution, aminotriaryl methanes, merocyanine element, squarylium cyanine dyes and pyridine Dyestuff.

It is also possible to use the mixture of the electron donor sensitising agent selected from identical or different classification material.

Various available electron donor sensitising agents can be bought from various commercial sources and can be readily ascertained by for this hair In bright.

When deployed, one or more electron donor sensitising agents can by with non-aqueous Photocurable composition gross weight meter at least 0.000001 weight % and at most and containing 5 weight % and typically at least 0.0001 weight % and at most and the amount containing 2 weight % is deposited In non-aqueous Photocurable composition.The precise volume of required electron donor sensitising agent is combined according to overall non-aqueous photocurable Thing, it is intended to purposes and extinction coefficient and changes.

In certain embodiments, electron donor sensitising agent be pyrene, BaP, perylenes or Ben Bing perylenes, its be by with it is non-aqueous can Photocurable composition gross weight meter at least 0.0001 weight % and at most and the amount containing 2 weight % exist.

In some non-aqueous Photocurable compositions of the invention, electron donor sensitising agent can be received by one or more electronics The combination replacement of body sensitising agent and one or more electron donor coinitiators.

Available electron acceptor sensitising agent should be dissolved in non-aqueous Photocurable composition, without will generally disturb sun The functionality of ion ultraviolet curing process, and with the light absorbs at least 150nm and at most and in the wave-length coverage containing 1000nm The ability of (sensitiveness).

Appropriate electron acceptor sensitising agent is in response to the chemical transformation from the absorbed photon initiation salt of radiation.Electronics is received Body sensitising agent should also have electron donor coinitiator after electron acceptor sensitising agent has absorbed light (that is, photo induced electron transfer) (being set forth in hereafter) is oxidized to the ability of radical cation.Therefore, electron acceptor sensitising agent from after radiation absorption photon at once Generally have and connect nucleophobic ability from electron donor coinitiator.

When solidification (e.g., the solidification of the film of the thin composition through applying) extremely fast is needed, using ultraviolet curing process, Under required radiation wavelength, electron acceptor sensitising agent can have at least 1000 liters-mole^-1cm^-1And typically at least 10,000 liters- Mole^-1cm^-1Extinction coefficient.

In general, many different classes of compounds can be used as electron acceptor sensitising agent for various reactants, its limit Condition processed is to meet above-mentioned energy requirement.Available electron acceptor sensitising agent includes but is not limited to cyano group aromatic compounds, such as 1- cyano group naphthalene, 1,4- dicyano naphthalenes, 9,10- dicyanos anthracene, 2,9,10- tricyanos anthracene, 2,6,9,10- four cyano anthracenes；Aromatic acid Acid anhydride and acid imide, such as 1,8- naphthalene dicarboxylic acids, Isosorbide-5-Nitrae, 6,8- naphthalene tetracarboxylic acids, 3,4- perylene dianhydride carboxylic acids and 3,4,9,10- perylene tetracarboxylic acid acid anhydrides Or acid imide；Condensed pyridine salt, such as quinoline, isoquinolin, phenanthridines, acridine and pyralium salt.

Other available electron acceptor sensitising agents on triplet excited state are carbonyls, such as quinone, e.g., electric with drawing Son substitution base (such as chlorine and cyano group) benzene-, naphthalene-, anthracene-quinone.Ketone (including aromatic ketone, such as Fluorenone) and coumarine dye (such as ketone group Cumarin, such as they have the person's (such as pyridine) that hales electronic section) also act as electron acceptor sensitising agent.It is believed that other are appropriate Electron acceptor sensitising agent include xanthene dye, acridine dye, thiazole dye, thiazine dye, oxazine dye, azine dye, ammonia Base ketone dyes, porphyrin, aromatic polycyclic hydrocarbons, aminostyryl assimilation compound, aminotriaryl methanes, the merocyanine of contraposition substitution Element, squarylium cyanine dyes and pyridine dye.Diaryl ketone and other aromatic ketones (such as Fluorenone) are available electron acceptor sensitising agent.

As long as meeting above-mentioned electrochemical requirements, the electron acceptor sensitising agent selected from identical or different classification material is it is also possible to use Mixture.

Various available electron acceptor sensitising agents can be bought from various commercial sources.

Described one or more electron acceptor sensitising agents can by with non-aqueous Photocurable composition gross weight meter at least 0.000001 weight % and at most and containing 5 weight % and typically at least 0.0001 weight % and at most and the amount containing 2 weight % is deposited In non-aqueous Photocurable composition.

It is incorporated in non-aqueous Photocurable composition by by one or more electron donor coinitiators, electron acceptor is photosensitive Effectively, each electron donor coinitiator has at least 0.1V and at most and containing the oxidation of 3V (relative to SCE) to the use height of agent Potential.Therefore, during these electron donor coinitiators should dissolve in non-aqueous Photocurable composition.Can also be by considering other Factor (such as property of bin stability and selected photopolymerization epoxy material, light acid producing agent and electron acceptor sensitising agent) is selected Select electron donor coinitiator.

Available electron donor coinitiator is alkyl aromatic polyethers, aryl-alkyl amino compound, wherein the aryl It is to replace through the electron withdrawing group of one or more including but not limited to carboxylic acid, carboxylate, ketone, aldehyde, sulfonic acid, sulphonic acid ester and itrile groups. For example, dialkyl aryl diamino compounds are applicable, wherein the aryl is the phenyl or naphthyl for being substituted or being unsubstituted (e.g., with the phenyl or naphthyl of one or more electron withdrawing groups as described above), and this two alkyl independently includes 1 to 6 carbon Atom.

Available electron donor coinitiator can be obtained from various commercial sources easily.

In general, described one or more electron donor coinitiators can be by with non-aqueous Photocurable composition gross weight Meter at least 0.001 weight % and at most and containing 10 weight % or more generally at least 0.005 weight % and at most and containing 5 weight % or Even at least 0.01 weight % and at most and the amount containing 2 weight % exist.

As described above, it is all it is described containing it is various must and the non-aqueous Photocurable composition of component optionally can wrap Containing with non-aqueous Photocurable composition gross weight meter at least 0.5 weight % and at most and containing 20 weight % or at least 1 weight % And at most and containing the carbon black being dispersed through of 10 weight % contents.

Some embodiments of non-aqueous Photocurable composition of the invention can include following each component：A () is as described above Photopolymerization epoxy material, (b) light acid producing agent as described above, (c) electron donor sensitising agent as described above, (d) such as The upper described carbon coated metallic particles being dispersed through and any particle dispersants, (e) organic diluent as described above, Such as, organic solvent medium as described above, (f) free redical polymerization material and (g) free radical photo-initiation, wherein：

The photopolymerization epoxy material per molecule has at least two polymerizable epoxy bases,

The smooth acid producing agent Wei Iodonium or sulfonium, and

The carbon coated metallic particles being dispersed through is the tool for such as being measured using dynamic light scattering method as described above There is the carbon coated Argent grain being dispersed through of the median diameter equal to or less than 0.5 μm.

Free radical photocurable chemistry：

In other embodiments, non-aqueous Photocurable composition includes one or more UV-curable components, wherein at least One is for free redical light-cured components and the non-aqueous Photocurable composition can further include free radical photo-initiation To provide free radical during photocuring.

Described one or more polymerizable compounds there may be to provide free redical polymerization functionality, including ethylene linkage (such as simple function or polyfunctional acrylic ester is (also including methacrylic acid for formula unsaturated polymerizable monomer, oligomer or polymer Ester)).These polymerizable compounds comprising at least one ethylenic unsaturated polymerizable key (part) and they in many Two or more these unsaturated parts can be included in embodiment.The appropriate material of these types contains at least one ethylene linkage Formula unsaturated polymerizable key and with carry out addition (or free radical) polymerization ability.These free redical polymerization materials include Single-, two- or poly- acrylate and methacrylate, including but not limited to methyl acrylate, methyl methacrylate, third Olefin(e) acid ethyl ester, isopropyl methacrylate, the just own ester of acrylic acid, octadecyl acrylate, allyl acrylate, diacrylate glycerine Ester, three glycerol acrylates, ethylene glycol diacrylate, diethyleneglycol diacrylate, TEGDMA, Diacrylate 1,3- propylene glycol esters, dimethacrylate 1,3- propylene glycol esters, diacrylate 1,4- butanediol esters, diacrylate 1, 6- hexylene glycols ester, diacrylic acid pentyl diol ester, neopentyl glycol dimethacrylate, trimethylolpropane trimethacrylate, Trimethacrylate acid 1,2,4- butantriols ester, diacrylate 1,4- cyclohexanediols ester, pentaerythritol triacrylate, pentaerythrite It is tetraacrylate, pentaerythritol tetramethylacrylate, dipentaerythritol acrylate, the acrylate of D-sorbite six, double [1- (2- acryloxies)]-p- ethoxyl phenenyl dimethylmethane, double [1- (3- acryloxy -2- hydroxyls)]-p- third Phenyl dimethylmethane and three-ethoxy-chlorinated isocyanurates trimethyl acrylic ester；Double acrylic acid of the polyethylene glycol The molecular weight of ester and double methyl methacrylate with 200 to (containing) 500, acrylate monomer (such as they are set forth in United States Patent (USP) 4, Person in 652,274 (Bert Xie Er (Boettcher) et al.)) and acrylate oligomer (such as they are set forth in United States Patent (USP) 4, Person in 642,126 (Zha Daer (Zader) et al.)) copolymerizable mixture；And vinyl compound (such as styrene and benzene second Ene derivative), diallyl phthalate, divinyl succinate ester, vinyl hexanediacetate and phthalic acid divinyl Ester.Two kinds can be used if necessary or more than two kinds of mixtures of these free redical polymerization materials.

These materials can be bought from many commercial sources or are obtained using known synthetic method and parent material.

Although the amount of one or more free redical polymerization materials is not particularly limited, its can by with it is non-aqueous can light consolidate Change composition total weight meter at least 10 weight % and at most and containing 90 weight % or typically at least 20 weight % and at most and containing 85 The amount of weight % is stored in non-aqueous Photocurable composition, and can be with the desired combination of the composition through photocuring of gained Optimize based on thing solubility and mechanical intensive property.

One or more free radical photo-initiations can be also stored in non-aqueous Photocurable composition to produce free radical.These Free radical photo-initiation includes any with exposed to photocuring radiation (such as ultraviolet or can for implementing to be used in the present invention See light radiation) after produce at once free radical ability compound.For example, free radical photo-initiation may be selected from triaizine compounds, 9- oxygen sulphur xanthones compound, aroma compounds of resting in peace, carbazole compound, dione compounds, boric acid sulfonium compound, diazo compounds Thing and united imidazole and other compounds that will can be readily appreciated by for those skilled in the art.These compounds it is mixed Compound may be selected from identical or different classification.

Also available is benzophenone cpd (such as benzophenone, benzoylbenzoate, benzoyl benzoic acid first Double (dimethylamino) the hexichol first of ester, 4- phenyl benzophenones, dihydroxy benaophenonel, the benzophenone of acroleic acid esterification, 4,4'- Double (diethylamino) benzophenone of ketone and 4,4'-), anthraquinone compounds and acetophenone compound (such as 2,2'- diethoxybenzenes second Ketone, 2,2'- dibutoxies acetophenone, 2- hydroxy-2-methyls propiophenone, p- tert-butyl group trichloroacetophenone, p- tert-butyl group dichloro Acetophenone, benzophenone, 4- chloro-acetophenones, 4,4'- dimethylamino benzophenones, 4,4'- dichloro benzophenones, 3,3'- bis- The chloro- 4- metaphenoxy acetophenones of methyl -2- methoxy benzophenones, 2,2'- bis-, 2- methyl isophthalic acids-(4- (methyl mercapto) phenyl) -2- Quinoline base propyl- 1- ketone and 2- benzyl -2- dimethylaminos -1- (4- morpholino phenyls)-butyl- 1- ketone).Other availableization of these types Compound is set forth in such as United States Patent (USP) 7,875,416 (Parker (Park) et al.).

Many these free radical photo-initiations can be obtained from various commercial sources.

One or more free radical photo-initiations can be by with non-aqueous Photocurable composition gross weight meter at least 0.3 weight % And at most and containing 10 weight % or typically at least 0.4 weight % and at most and containing 10 weight % or even at least 0.5 weight % and At most and the amount containing 5 weight % is stored in non-aqueous Photocurable composition.

In some these embodiments, non-aqueous Photocurable composition includes one or more free redicals as described above Polymeric material, one or more free radical photo-initiations as described above, the as described above carbon coated Argent grain being dispersed through, Organic solvent medium, wherein acrylate are present in a kind of free redical polymerization component.

Prepare non-aqueous Photocurable composition

To prepare non-aqueous Photocurable composition of the invention, in any suitable manner (including must by various components Need component and component optionally) combination, photocurable group in for example appropriate organic diluent (such as organic solvent medium) Except point useing organic diluent (as described above) as.Therefore, these group technologies as described above can be dispersed through appropriate Carbon coated metallic particles (including particle dispersants as described above) and one or more photocurable components (as described above) Mix in organic diluent.These photocurable components may include UV-curable component and UV light triggers.Or, it is described can Light-cured components may include polymerizable epoxy material and light acid producing agent.

The non-aqueous Photocurable composition of gained can be in having at least 1 centipoise at 25 DEG C and at most and containing 100,000 centipoises The fluid of viscosity, gel or paste.Non-aqueous Photocurable composition can be applied to various substrates and (be set forth in down by conventional method Text) and using various solidification equipments and radiation source at 1 second or at most in 10 minutes or longer time photocuring to tack-free state. While photocuring or before, can be used appropriate drying means to remove any inert organic solvents.

The especially useful inert organic solvents (in addition to those described above) that can be used for this mixing are included (but not Be limited to) acetone, methyl alcohol, ethanol, isopropanol, 1- methoxy-2-propanols (ten thousand promise PM more), dichloromethane and its will not substantially with it is non- The mixture of any reactive component reaction of aqueous Photocurable composition.

Article

Non-aqueous Photocurable composition of the invention can as described above be allocated and is applied to using any appropriate method One or two support-sides (planar side) of any appropriate substrate (being set forth in hereafter).For example, non-aqueous Photocurable composition can (for example) dip-coating, roller coat, funneling coating, spraying, spin coating, ink spraying, photoetching is used to imprint, use flexographic printing element The flexographic printing of (such as flexographic printing plate and flexographic printing sleeve), the lithographic printing using lithographic printing plate and use appropriate print Intaglio plate or the intaglio printing of brush component are so that uniformly or one by one patterning method is applied to any or two support-sides.Use flexographic printing portion The flexographic printing of part is used especially for the pattern of the non-aqueous Photocurable composition for providing predetermined, and the method can be used in lining Multiple identical or different non-aqueous Photocurable composition patterns are provided in one or two support-sides at bottom.These techniques it is more Details is provided below.

The non-aqueous Photocurable composition for being applied can be formed and be dried to conforming layer or be dried to predetermined pattern.Institute Obtain article and " forerunner " article was can be considered before photocuring is carried out as mentioned below.

It is as described in greater detail below, can be made up of any useful material for the substrate of these articles and can be for for example What is be made up of metal material, glass, paper making raw material (paperstock) (any kind of cellulosic material) or ceramics is any suitable When size and dimension indivedual films or thin slice, or it can be the continuous net of material, such as continuous polymer net.

Non-aqueous composition (including non-aqueous Photocurable composition) described above required and component optionally Various amounts, but should be apparent that the amount refers to solution or dispersion liquid containing these components.It should be appreciated, however, that appropriate being applied to Substrate, and optionally dry, and then after photocuring, the amount of various components is not in the non-aqueous composition for being applied Together.Can from the non-aqueous composition being applied to before substrate the information of the amount of component calculate easily remaining component (if (for example) inert organic solvents have been removed) discrete amount and relative quantity.

For example, in through dry non-aqueous composition (including through dry non-aqueous Photocurable composition), through carbon The metallic particles of coating can at least 10 weight % and at most and the amount containing 90 weight % is present, particle dispersants can at least 1 Weight % and at most and the amount containing 30 weight % exist, carbon particle can at most and the amount containing 20 weight % exist, and can light consolidate Change component (being set forth in above, before solidification) can at most and the amount containing 90 weight % exist.

The purposes of non-aqueous Photocurable composition

Non-aqueous Photocurable composition specifically described herein can be used appropriate radiation (including ultraviolet light or Visible-light Irradiation Light or the two) photocuring (or photopolymerization).One or more appropriate light sources can be used for exposure technology.Each forerunner's article can be individually Exposed as single component, or in the alternate embodiment being described below, be included in one or two supports of continuous polymer net The net of the multiple forerunner's articles (comprising multiple photocurable patterns) in some on side is (for example, takeup type continuous polymerization Thing net) continuous polymer net individually can be passed through with required path at continuous polymer Netcom overexposure station or in exposure device When expose.Identical or different non-aqueous Photocurable composition can apply (for example, using flexographic printing) in two branch of substrate On support side, no matter substrate is in single component form or in continuous polymer web form.In many examples, can be used herein Described non-aqueous Photocurable composition forms different conductive golds on the relative support side of substrate (or continuous polymer net) Metal patterns.

Wavelength and at least 1mJ/cm with least 184.5nm to (containing) 700nm can be used²And at most and containing 1000mJ/ cm²Or more generally at least 1mJ/cm²And at most and containing 800mJ/cm²Intensity UV or visible radiation realize that desired light is consolidated Change.

When non-aqueous Photocurable composition is evenly applied into appropriate substrate, the uniform drying layer of gained can By the exposing radiation " image conversion " through the appropriate light shield (shield assemblies) with required pattern or optionally exposure (or figure Case), and be then used by appropriate dissolving or disperse the material of non-photocuring " development " solution suitably remove it is uncrosslinked (not Solidification) Photocurable composition.These features or step can be carried out in the two of substrate (relative) support-sides.Except this it Outward, identical or different light is visually needed to use to cover on through forming multiple patterns in dry layer.

More specifically, can be used method as mentioned below formed on appropriate substrate one or more it is non-aqueous can light The predetermined pattern of solidification composition filling.

The appropriate substrate (being also referred to as in the related art " receiving unit ") that can be used to provide forerunner's article can be by any Appropriate material is constituted, as long as the material does not suppress the purpose of non-aqueous Photocurable composition.For example, available substrate can Formed by the material for including but is not limited to following：Polymeric membrane, metal, paper making raw material, hard or flexible glass (it is unprocessed or Processed via such as carbon tetrafluoride plasma, hydrophobicity fluorine or siloxanes waterproof material), silicon or ceramic wafers, fabric and its Combination (laminate of such as various films or the laminate of paper and film), its restrictive condition can be appropriate method be formed on it is non- The conforming layer or pattern of aqueous Photocurable composition and then radiate with its at least one receive (support) surface on formation Uniform cured layer or one or more through photocuring pattern.Substrate can be transparent, translucent or light tight and hard or flexibility.Perhaps More available substrate is transparent and with least 90% comprehensive transmissivity, and these transparent substrates can also be flexibility, such as continuous Polymeric web.

Substrate can include one or more supplemental polymerics or non-polymeric layers or one or more are applying non-aqueous photocurable group The pattern of the other materials applied before compound.For example, the support of any one or two (plane) surfaces of substrate can be the bottom of for example, by Enamelled coating treatment or electrically or mechanically treatment (as being granulated) improve non-aqueous photocurable group to assign the surface " receiving surface " Compound is with gained through photocurable layers or the adhesion through photocuring pattern.Adhesion coating can be arranged with response to stimulating on substrate (for example, the stimulation can be thermal activation, activating solvent or chemical activation) provides various properties and the adhesion coating can be useed as and connect Receive layer.

In certain embodiments, substrate can include the indivedual receiving layers as receiving surface being arranged on substrate, described Receiving layer and substrate can be made up of the material (such as appropriate polymeric material) for highly receiving non-aqueous Photocurable composition.When When being measured at 25 DEG C, these receiving layers can have at least 0.05 μm and at most and containing 10 μm or typically at least 0.05 μm and at most and Containing 3 μm of dry thickness.

Can be by exposed to such as such as United States Patent (USP) 5,492,730 (Barabbas (Balaba) et al.) and 5,527,562 (bars Draw bar et al.) and Patent Application Publication 2009/0076217 (Ge Mansi (Gommans) et al.) described in corona put Electricity, mechanical wear, flame treatment or oxygen plasma or by coating various polymeric membranes (such as poly- (vinylidene chloride)) or aromatics The support-side of polysiloxanes treatment substrate (particularly polymeric substrates).

For formed in the appropriate backing material of forerunner's article of continuous net include but is not limited to metal film or paper tinsel, It is metal film (e.g., the metal film on conductive polymerized film), flexible glass, semiconductive organic or inorganic film on polymer, organic Or the laminate of two or more layers of inorganic dielectric film or these materials.For example, available continuous net substrate can be wrapped Include polymeric membrane (such as poly- (PETP) film, poly- (polyethylene naphthalate) film, polyimide film, polycarbonate membrane, Polyacrylate film, polystyrene film, polyolefin film and PA membrane), metal foil (such as aluminium foil, cellulose paper or through resin apply Cover or through the paper of vitreous coating), cardboard web and metalizing polymeric films.

Especially useful substrate is (to benzene two through surface treatment as described above or without surface treatment as described above by poly- Formic acid second diester), the transparent polyester film that constitutes of poly- (polyethylene naphthalate), makrolon or poly- (vinylidene chloride).

In certain embodiments, first polymer latex and second polymer latex can be mixed, warp is formed on substrate Dry priming coat is with the patterning materials with the fine rule formed using non-aqueous Photocurable composition of adhering.Described first Polymer latex can include first polymer and first surface activating agent causes that the coating that dries of the first polymer latex has There is at least 50% surface polarity.The second polymer latex can cause institute comprising second polymer and second surface activating agent The coating that dries for stating second polymer latex has the surface polarity for being less than or equal to 27%.In addition, the mixture Drying coating can have at least 15% and at most and containing 50% surface polarity.

At least one of described first and second polymer specifically described herein comprising containing at least in part derived from (methyl) glycidyl acrylate (represent glycidyl acrylate, GMA or the two) repetition The polyvinyl of unit, and in most embodiments, first and second polymer it is each at least in part derived from (methyl) glycidyl acrylate.Additionally, at least one of the first polymer and second polymer are crosslinkable, And can be such as during the drying or various heat treatments of substrate for example in being coated to appropriate support member post-crosslinking.

Especially useful first polymer is have glycidyl functional base derived from one or more at least in part The polyvinyl of ethylenic unsaturated polymerizable monomer, such as glycidyl acrylate and methyl propenoic acid glycidyl Ester.Therefore, the first polymer can be the homopolymers derived from (methyl) glycidyl acrylate, but it is more likely to spread out It is conigenous the copolymer of (methyl) glycidyl acrylate and one or more other ethylenic unsaturated polymerizable monomers.Term " glycidyl " refers to containing being connected to 1 to 4 alkyl of carbon atom (line style or branched alkane that can be also further substituted with Base) (such as methyl, ethyl, isopropyl and the tert-butyl group) oxirane ring group.

The first polymer is especially so that one or more (methyl) glycidyl acrylates and one or more (methyl) Alkyl acrylate combined polymerization mode is designed and obtained, wherein the ester alkyl has at least 2 carbon atoms, including but not limited to third Olefin(e) acid ethyl ester, EMA, n-butyl acrylate, n-BMA, cyclohexyl acrylate, methacrylic acid Cyclohexyl, lauryl acrylate, lauryl methacrylate, allyl methacrylate, hydroxyethyl methacrylate, acrylic acid Other persons that hydroxyl ethyl ester and those skilled in the art will be readily appreciated by.Especially useful co-monomer is (methyl) alkyl acrylate Ester, wherein the ester alkyl has at least 4 carbon atoms, the including but not limited to positive fourth of n-butyl acrylate, methacrylic acid Ester, the just own ester of acrylic acid, the just own ester of methacrylic acid and cyclohexyl methacrylate.

The second polymer latex (can be stated comprising one or more second polymers and one or more second surface activating agents In hereafter) so that the coating that dries of the second polymer latex has less than or equal to 28% or less than or equal to 27% Surface polarity.

Especially useful second polymer is have glycidyl functional base derived from one or more at least in part The polyvinyl of ethylenic unsaturated polymerizable monomer, such as (methyl) glycidyl acrylate, such as acrylic acid shrink Glyceride and GMA, as described above for described in first polymer.Therefore, the second polymer can be Homopolymers derived from (methyl) glycidyl acrylate or derived from (methyl) glycidyl acrylate and one or more The copolymer of other ethylenic unsaturated polymerizable monomers.Term " glycidyl " is defined in above.

The second polymer is single particularly by making one or more (methyl) glycidyl acrylates be total to one or more Body (such as one or more (methyl) alkyl acrylates) combined polymerization design is obtained, wherein the ester alkyl has at least 2 carbon atoms, Including but not limited to ethyl acrylate, EMA, n-butyl acrylate, n-BMA, acrylic acid Cyclohexyl, cyclohexyl methacrylate, lauryl acrylate, lauryl methacrylate, allyl methacrylate, methyl-prop Other persons that olefin(e) acid hydroxyl ethyl ester, hydroxy-ethyl acrylate and those skilled in the art will be readily appreciated by.Especially useful common list Body is (methyl) alkyl acrylate, wherein the ester alkyl has at least 4 carbon atoms, such as n-butyl acrylate, metering system Sour N-butyl, the just own ester of acrylic acid, the just own ester of methacrylic acid and cyclohexyl methacrylate.

The first polymer latex includes one or more first surface activating agents, and it is respectively mersolates, wherein The alkyl has at least 10 carbon atoms.For example, the first surface activating agent can be alpha-olefin (C₁₄-C₁₆) sodium sulfonate, or The first surface activating agent can be by R-CH₂- CH=CH-CH₂- S (=O)₂O^-Na⁺(wherein R is C to the compound of expression₁₀、C₁₁ Or C₁₂Alkyl) or these have be C₁₀To C₁₂The mixture of the compound of the different R groups of any one in alkyl.One kind is available The commercially available prod containing first surface activating agent be Luo DekaA246L (can for example from Luo Diya (Rhodia) Obtain).The mixture of these first surface activating agents can be used if necessary.

The second polymer latex includes one or more second surface activating agents, and it is respectively with least 3 epoxy second The alkyl phenol ammonium sulfate of alkane unit.For example, the second surface activating agent can be the ammonium salt of sulfuric acid polyethoxy nonyl phenol, Or the second surface activating agent can be by R'- phenyl-(O-CH₂CH₂)_n- S (=O) O₂ ^-NH₄ ⁺Represent, wherein R' is C₈To C₁₂Hydrocarbon Base and n are at least 3 and at most and containing 10, or n is more likely at least 3 and at most and containing 6.The available second surface that contains of one kind is lived Property agent commercially available prod for many pecks of sieve thisCO-436 (can be obtained for example) from Luo Diya.If necessary may be used Use the mixture of these second surface activating agents.

The first polymer latex and each usable emulsion polymerization of second polymer latex are prepared or as grain emulsion The aqueous liquid dispersion of polymerizate is obtained.

Available substrate can have according to by the required dry thickness depending on the final use of its article for being formed.For example, lining Bottom dry thickness (comprising all treatment and auxiliary layer) can be at least 0.001mm and at most and containing 10mm, and especially with regard to transparent polymeric For film, substrate dry thickness can be at least 0.008mm and at most and containing 0.2mm.

Substrate for preparing article specifically described herein can take various forms, such as (e.g.) any size or shape Other thin slice and continuous net (such as, it is adaptable to the continuous net of the transparent polymeric substrate of takeup type operation, including transparent polyester net) are provided. These continuous polymer nets are divided into or are formed to can be used to form identical or different indivedual first, second Hes through photocuring pattern Extra section.

After non-aqueous Photocurable composition is applied, can be by adversely influenceing remaining component or prematurely causing light The drying of solidification or prebake program remove any inert organic solvents of organic diluent.Available drying condition can be for as little as Room temperature, 5 seconds are persistently short to and at most and containing a few hours, depending on manufacturing process.In most of techniques (winding as mentioned below Formula technique) in, drying condition can be to remove inert organic solvents at least with least 5 seconds at sufficiently high temperature 90%.

Any applied uniform non-aqueous Photocurable composition layer can have at least 0.1 μm and at most and containing 10 μm or Typically at least 0.2 μm and at most and containing 1 μm of dry thickness, and most preferably dry thickness can be intended to purposes according to gained is uniform through photocurable layers Typically there is customization, the layer conforming layer identical about with the non-aqueous Photocurable composition of non-photocuring to do thickness.This is one equal Even layer can be applied to two (relative) support-sides of substrate, and the conforming layer can have identical or different chemical composition or dry thickness.

Any the applied pattern of non-aqueous Photocurable composition can be comprising having at least 0.2 μm and at most and contain 100 μm or typically at least 5 μm and at most and (or the other shapes, including circular or not of the grid containing 10 μm of averagely dry line wide Regular mesh structure), and most preferably dry width can be customized according to the uniform purposes that be intended to through photocurable layers of gained, the pattern typically has There is size substantially with non-photocuring grid lines identical through photocuring and the grid lines of conduction.

Therefore, the present invention can be used to provide comprising substrate and conforming layer or be combined comprising non-aqueous photocurable of the invention The article of the pattern of thing, wherein these articles can be considered " forerunner " article, it is meant that they are generally before photocuring shape first Into article.In after the non-aqueous Photocurable composition of photocuring, forerunner's article is now considered as middle (through photocuring) article.

In certain embodiments, the identical or different non-aqueous Photocurable composition can put in a suitable approach Forming " duplex coating (duplex) " or bilateral forerunner's article on two support-sides (plane surface) of substrate, and it is each apply it is non- Aqueous Photocurable composition can be in identical or different conforming layer or predetermined pattern form.

In many examples, using the relief component derived from flexographic printing plate predecessor (as elastic relief component is (soft Version printing part)) in apply in one or two (relative) support-sides of substrate (for example, be in takeup type continuous net) it is non-aqueous can light The pattern of solidification composition filling, many of which component is known in the art and some can for example with CyrillicIt is soft Version photo polymer plate (Flexographic Photopolymer Plates) is bought and with Fu Lakesa from Du Pont (DuPont) (Flexcel) the soft version plates of SR and NX (Flexographic plates) and direct soft version plate (the Flexcel Direct of Fu Lakesa Flexographic plates) bought from Eastman Kodak Co (Eastman Kodak Company).

Especially useful elastic relief component be derived from flexographic printing plate predecessor and flexographic printing sleeve predecessor, its The relief component of " printing " or the appropriate pattern of applying can be respectively used for offer through appropriate image conversion (and optionally being processed).

For example, available elastic relief component can include one or more elastic layers with or without substrate, wherein can Relief image is produced using appropriate imaging device.

For example, being counted at least from the superiors' embossed surface with the relief layer for constituting the superiors' embossed surface and with relative 50 μm of average relief image depth (pattern height) or the elasticity generally with least 100 μm of average relief image depth are floated Convex assembly (for example, flexographic printing element) can for example such as United States Patent (USP) 7,799,504 (Jeff Wadlow (Zwadlo) et al.) and 8, Exposed by imaging described in 142,987 (Ali (Ali) et al.) and Patent Application Publication 2012/0237871 (Jeff Wadlow) Elastic photopolymerizable layer in photoelasticity relief component predecessor (such as flexographic printing element predecessor) is obtained.These elasticity can light Polymer layer can be by appropriate mask images (mask image) image conversion providing elastic relief component (for example, flexographic printing Plate or flexographic printing sleeve).In certain embodiments, comprising embossed pattern relief layer can be disposed at as described Ali et al. specially On appropriate substrate described in profit.Other available materials and the image forming method for providing elastic relief image (including development) is also set forth in described Ali et al. patent.Relief layer (and flexographic printing element) can it is different with provide it is non-aqueous can The different pattern of Photocurable composition is to the identical or relative support side of substrate.

In other embodiments, such as such as United States Patent (USP) 5,719,009 (model (Fan)), 5,798,202 (Ke Xina (Cushner) et al.), 5,804,353 (Ke Xina et al.), 6,090,529 (Ge Bate (Gelbart)), 6,159,659 (lattice Bart), 6,511,784 (Xi Le (Hiller) et al.), 7,811,744 (Fei Gefu (Figov)), 7,947,426 (Fei Gefu etc. People), 8,114,572 (blue Delhis (Landry)-Ke Quan (Coltrain) et al.), 8,153,347 (Wei Leisi (Veres) etc. People), 8,187,793 (Rigens (Regan) et al.) and Patent Application Publication 2002/0136969 (uncommon strangle et al.), 2003/0129530 (thunder nonyl Bark (Leinenback) et al.), 2003/0136285 (Te Sa (Telser) et al.), 2003/ Described in 0180636 (bank adds (Kanga) et al.) and 2012/0240802 (blue Delhi-Ke Quan et al.), using or do not use one Body formula mask, from can the elastomer relief component predecessor of direct (or excision) laser engraving elastic relief component is provided.Can be It is obtained through the relief component of direct engraving in the case of without the solvent treatment or development required for photopolymerization elastomeric material.

When using elastic relief component, non-aqueous Photocurable composition can be applied to elasticity in a suitable approach floating The superiors' embossed surface (raised surface) in convex assembly.This applying can be used appropriate device to realize and wish as little as possible It is coated on the side of relief recess (sloping portion) or recessed.Anilox roll system or other roller application systems can be used (especially It is low volume anilox roll, less than 2,500,000,000 cu μ ms/square inch (63.5 hundred million cu μ ms/square centimeter)) and related sharpener (skive knives).Can by control viscosity or thickness or select appropriate bringing device realize most preferably measuring it is non-aqueous can light Solidification composition filling is in the superiors' embossed surface.

For example, non-aqueous Photocurable composition can be formulated with least 1cps (centipoise) coated for this and extremely It is many and containing 5000cps or at least 1cps is at most and the viscosity containing 1500cps.Non-aqueous Photocurable composition on relief image Thickness be generally limited to be transferred to easily substrate, but during applying will not too much and flow through it is recessed in elastic relief group The edge of part it is enough.

Therefore, can be each to obtain with a certain amount of non-aqueous Photocurable composition of charging to ink system from reticulate pattern or other rollers Printing forerunner article (in conforming layer or pattern).In one embodiment, the first roller can be used with by non-aqueous photocurable group Compound is transferred to metering roll or anilox roll from " ink " disk or metering system.The non-aqueous Photocurable composition is general through meter Amount when it is transferred into plate cylinder from anilox roll with when realizing uniform thickness.When the substrate in continuous net passes through takeup type Processing system from plate cylinder move on to impression cylinder when, impression cylinder is applied pressure to non-aqueous Photocurable composition Image is transferred to the plate cylinder of substrate from elastic relief component.

Applying the superiors embossed surface (or the table of projection of the non-aqueous Photocurable composition to elastic relief component Face) after, at least 25 weight % for removing any inert organic solvents are formed more with the superiors' embossed surface of relief image Viscous deposit can be useful.This removal of inert organic solvents can be realized in any method, for example, being sprayed using hot-air Machine, evaporates at room temperature, or in an oven in heating under high temperature, or other sides for removing solvent known in the art Method.

When the non-aqueous photopolymerisable compositions in forerunner's article are in grid lines or other shapes of conforming layer or predetermined figure Case on substrate (in one or two support-sides of substrate) when, you can with as described above from appropriate light source such as fluorescent lamp or The appropriate radiation of LED with provide on substrate through photocurable layers or one or more through photocuring pattern.For example, photocuring Can be by using the wavelength (λ with least 190nm and at most and containing 700nm_max) and at least 1,000 microwatts/cm²And at most and Containing 80,000 microwatts/cm²Intensity UV- visible radiations realize.Radiating system for producing this to radiate can be by being for example in 1 To 50 one or more ultraviolet lamps of discharge lamp form, for example, xenon, metal halide, metal arc are (e.g., with from several millimeters To about 10 required operating pressures of atmospheric pressure it is low, in or high-pressure mercury vapour discharge lamp) composition.The lamp can be included can be saturating Be incident upon few 190nm and at most and containing 700nm or typically at least 240nm and at most and the light of the wavelength containing 450nm shell.It is described Lamp housing can be made up of quartzy (such as Si Bei sections Qu Xi (spectrocil) or pyrex (Pyrex)).Can be used to provide ultraviolet The typical lamp of beta radiation is (for example) middle pressure mercury arc, such as GE H3T7 arcs and Hanover (Hanovia) 450W arc lamps.Can be used each The combination for planting lamp carries out photocuring, and part or all can be operated in inert atmosphere in the lamp.When using UV lamp, irradiation May be designed as being enough to realize within 1 to 20 seconds in a continuous process in the radiation flux on substrate (or the layer or pattern for being applied) (for example being operated with takeup type) non-aqueous Photocurable composition that sufficiently rapidly photocuring is applied.

Can have 350nm or bigger peak emission wavelength for the LED radiation device in photocuring.LED matrix can be wrapped Containing two kinds or more than the two kinds of component with the different peak emission wavelengths more than or equal to 350nm.With 350nm Or bigger peak emission wavelength and the commercial embodiments of the LED matrix with ultraviolet-light emitting diode (UV-LED) are for can be from The NCCU-033 that Ya chemical companies (Nichia Corporation) obtain.

This obtains comprising substrate (for example, individual flakes or continuous net) and has thereon to derive for the radiation of forerunner's article From in one or two support-sides of substrate non-aqueous Photocurable composition through photocurable layers or one or more through photocuring figure The intermediate items of any one in case.

The intermediate items of gained can be used in some applications in this format, but in most embodiments, the intermediate Product are after further treatment that with uniformly through photocurable layers or through being incorporated to conducting metal on photocuring pattern, it is respectively included with being use In the carbon coated metallic particles of " crystal seed " material for for example further applying conducting metal using electroless metal plating program.Example Such as, as described above without electric " crystal seed " carbon coated metallic particles may include can by electroless-plating copper, platinum, palladium or it is other such as The silver of metal hereinafter described, palladium or platinum grain.

A kind of useful method is (for example, according to mentioned above in printing station using the multiple flexographic printing plates in stacking It is obtained), wherein each stacking has its own plate cylinder to print respective substrates using each flexographic printing version, or can make With the stacking of printed panel printing some of (in one or two support-sides) in continuous polymer net.It is described identical or different Non-aqueous Photocurable composition can be used multiple flexographic printing plate " printing " or be applied to this substrate (identical or relative support side On).

In other embodiments, center press roller can be with the single pressing roller one on squeegee pressure machine frame Rise and use.With substrate (or receiving unit) enter squeegee pressure machine frame, its contacted with pressing roller and with it is non-aqueous can light Solidification composition filling prints appropriate pattern.Or, can be used printing station arrangement to drive on a horizontal and by common line shaft member Online flexography process.The printing station can be coupled to exposure station, cutting station, folder and other equipment for after-treatments.Institute The technical staff in category field can be used the information that can be obtained in the art to judge other applicable equipment with station easily Configuration.For example, circular (in-the-round) imaging process described in WO 2013/063084 (golden (Jin) et al.).

The carbon coated metallic particles being dispersed through can be contained through photocuring with described by specifically described herein at once The intermediate items of pattern be soaked in water base electroless metal plating body lotion or solution, or can be only by intermediate items (for example, in rolling Continuous net) together with the pattern storage through photocuring for being used in the time after a while.

For example, each intermediate items can be made and be incorporated to through the metal phase in the carbon coated metallic particles in photocuring pattern Same or different electroless-plating metal contact.In most embodiments, however, electroless-plating metal be with for be dispersed in through The different metal of the metal in carbon coated metallic particles in the pattern of photocuring.

Now can be used will likely be without electric " plating " in any metal on carbon coated metallic particles, but in most of realities In applying example, electroless-plating metal can for such as copper (II), silver-colored (I), golden (IV), palladium (II), platinum (II), nickel (II), chromium (II) and Its combination.Copper (II), silver-colored (I) and nickel (II) are the electroless-plating metal for being particularly suitable for carbon coated silver, copper or palladium particle.

Described one or more electroless-plating metals can be by least 0.01 weight % in terms of total solution weight and at most and containing 20 The amount of weight % is stored in water base electroless-plating body lotion or solution.

Known temperature and time condition can be used carries out electroless-plating, because these conditions are various textbooks and science It is known in document.It is known that in water base electroless-plating solution comprising various additives (such as metal chelating agent or stabilization Agent).Up time and temperature change are changing metal electroless-plating thickness or metal electroless-plating sedimentation rate.

A kind of available water base electroless-plating solution or body lotion are that can be plated without electrolytic copper (II) as reducing agent comprising formaldehyde Body lotion.Ethylenediamine tetra-acetic acid (EDTA) or its salt can exist in copper complexing agent.For example, copper electroless-plating can at room temperature according to institute Needing sedimentation rate and rate of deposition and plating metal thickness carries out the several seconds at most a few hours.

Other available water base electroless-plating solutions or body lotion include silver-colored (I) and EDTA and sodium tartrate, silver (I) and ammonia and Glucose, copper (II) and EDTA and dimethyamine borane, copper (II) and citrate and hypophosphites, nickel (II) and lactic acid, second Acid is water base with hypophosphites and other industrial standards, and without electrobath liquid or solution, (e.g., Ma Lveli (Mallory) et al. is without electric Plating：General principle and application (Electroless Plating:Fundamentals and Applications) institute in 1990 Those stated).

There is provided conductive with a support-side of substrate or one or more parts of relative support side in electroless-plating program After metal pattern, products obtained therefrom article and usable distilled water or deionization can be removed from water base electroless-plating body lotion or solution Water or another group water solution wash to remove the electroless-plating chemicals of any residual.Now, the metal through electroless-plating is general Be stabilization and can be used for its be intended to purpose with formed it is various with required conducting metal grid lines or conductive metal connector (or BUS connectors or electrode) conductive articles.

In certain embodiments, products obtained therefrom article can be such as [0048] of such as US 2014/0071356 (Petrarch) Described in water at room temperature or as WO 2013/169345 (Luo Makelisinan (Ramakrishnan) et al.) [0027] Described in rinsed or washed at a temperature of less than 70 DEG C with deionized water.

To change through the metallic surface of electroless-plating for vision or durability reason, various post processings can be used, Including electroplating surface again at least another (3rd or more) metal (such as nickel or silver) in (this program has on the metal through electroless-plating When referred to as " coat "), or foundation be enough to change surface color and scattering nature without reducing through (second) metal of electroless-plating The metal oxide of electric conductivity, metal sulfide or metal selenide layer.According to the various cladding programs for methods described In metal, it may be necessary to in water base seed metal catalyst solution another seed metal catalyst treatment through electroless-plating Metal promoting additional metal to deposit.

Additionally, can be used identical or different condition sequentially to carry out repeatedly water base electroless metal plating liquor processing.Can also be suitable In the case of in room temperature or less than 70 DEG C at a temperature of continuously washed or rinsing step.

In addition, can be used identical or different electroless-plating metal and the identical or different electroless-plating condition sequentially repeatedly to carry out Electroless-plating program.

Some details suitable for carrying out the method and apparatus of some embodiments of the present invention are set forth in such as US2014/ In 0071356 (as described above) and WO 2013/169345 (as described above).Suitable for especially being led with method for winding manufacture Other details of the manufacture system of electric article are provided in WO2014/070131 (on October 29th, 2012 by Petrarch and gold Application) in.

Can be used to carrying out equipment of the invention and steps characteristic another system be set forth in U.S. Serial No 14/146,867 ( On January 3rd, 2014 is applied by Xiao Folei (Shifley)) in.

In a certain method one or more conductive articles can be provided using non-aqueous Photocurable composition of the invention. [example is set forth in above continuous net of the method including offer transparent substrates, and can be in particular poly- (PETP) Continuous net].

Methods described is additionally included at least Part I of the continuous net of transparent substrates and is formed comprising photocurable component The non-aqueous Photocurable composition (as described herein) of the carbon coated metallic particles being dispersed through as described above Photocurable pattern.Then photocuring photocurable pattern is formed through the pattern of photocuring with the Part I of continuous net, The pattern through photocuring includes the carbon coated metallic particles (as described above) being dispersed through and is catalyzed as seed metal Agent site.This can then use conducting metal (as described above) electroless-plating to the Part I of continuous net through the pattern of photocuring On.

The method can be further included：

Using identical or different non-aqueous Photocurable composition continuous net one or more different from Part I Formed as described above one or more times again in other parts, photocuring and electroless-plating feature.In this way, can be in substrate Identical or different support-side on formed multiple through photocuring and the pattern of electroless-plating.The composition of gained conductive pattern, pattern Or conductance can be identical, or their any or all these feature can be all different (such as being needed according to client predetermined).

Therefore, methods described can be used to provide multiple forerunner's articles, including：

Non-aqueous Photocurable composition is applied to the Part I of continuous net first by using flexographic printing element The first photocurable pattern is formed on part,

The continuous net including the first photocurable pattern is set to advance to approach exposing radiation, and thus in Part I It is upper to form first through photocuring pattern,

Identical or different non-aqueous Photocurable composition to the second of continuous net is applied by using flexographic printing element Part forms the second photocurable pattern on the Part II,

The continuous net including the second photocurable pattern is set to advance to approach exposing radiation, and thus in Part II It is upper to form second through photocuring pattern,

Optionally, using identical or different non-aqueous Photocurable composition and identical or different flexographic printing element with class Like method formed on one or more other parts out of the ordinary of continuous net one or more other through photocuring pattern, and

The continuous nets for including multiple through photocuring pattern are rolled, or at once using continuous net for further place Reason, such as electroless-plating.

Therefore, methods described can be further included：

Multiple conductive articles are formed from including multiple continuous nets through photocuring pattern, and

By individual conductive article be assembled into identical or different individual device (e.g., identical or different touch screen display or Device).

The method may also include：

Multiple in electroless-plating continuous net are through photocuring pattern each forming multiple conductive articles, the multiple conduction Article can be assembled into identical or different individual device by identical or different user.Described device can for Touch screen or it is other also Including appropriate controller, shell and the display equipment for any kind of required software through internet communication.Or, Described device can be this Touch screen or the sub-component of other display equipments.

In certain embodiments, methods described can be used to manufacture includes the device of Touch screen, and methods described includes：

One or more individual conductive articles are assembled into crust of the device to form Touch screen region,

Described one or more individual conductive articles respectively include comprising electroless-plating to derived from it is of the invention it is non-aqueous can The conductive pattern through the conducting metal on photocuring pattern of Photocurable composition.

Be can be formulated into comprising conducting metal grid lines, conducting metal according to using available product article obtained in the present invention The Capacitive touch screen sensor of the appropriate pattern of connector (electrical lead or BUS connectors).For example, can be by printed book The non-aqueous Photocurable composition of invention is predetermined pattern, then as described above with printed by appropriate metal electroless-plating Pattern, forms the pattern of conducting metal grid lines and conductive metal connector.

The present invention provides at least following examples and it is combined, but as those skilled in the art will be from religion of the invention Show, other combinations of feature are considered as belonging to the present invention：

1. a kind of containing with the warp in organic diluent of the non-aqueous composition gross weight meter at least amount of 10 weight % The non-aqueous composition of scattered carbon coated metallic particles, the carbon coated metallic particles being dispersed through have be equal to Or the median diameter less than 0.6 μm, and be with least 2,000 and at most and containing 100,000 weight average molecular weight (M_w) and Particle dispersants dispersion containing nitrogenous unit, the median diameter is measured using dynamic light scattering method,

2., such as the non-aqueous composition of embodiment 1, it contains the carbon coated Argent grain being dispersed through or the warp being dispersed through The mixing of both the copper particle or the carbon coated Argent grain being dispersed through of carbon coating and the carbon coated copper particle being dispersed through Thing.

3. as embodiment 1 or 2 non-aqueous composition, wherein the particle dispersants with it is described be dispersed through it is carbon coated The weight ratio of metallic particles be at least 1:100 and at most and containing 30:100.

4. such as the non-aqueous composition of any one of embodiment 1 to 3, wherein the carbon coated metal being dispersed through Grain is by with non-aqueous composition gross weight meter at least 15 weight % and at most and the amount containing 70 weight % is present.

5. such as the non-aqueous composition of any one of embodiment 1 to 4, wherein the particle dispersants have at least 2,000 And at most and containing 50,000 M_w。

6., such as the non-aqueous composition of any one of embodiment 1 to 5, it further contains with non-aqueous composition gross weight Meter at most and the amount containing 20 weight % the carbon black being dispersed through.

7. such as the non-aqueous composition of any one of embodiment 1 to 6, wherein the particle dispersants are to contain ester units Organic polymer.

8. such as the non-aqueous composition of any one of embodiment 1 to 7, wherein the particle dispersants are containing selected from least A kind of organic polymer of following classification (i) to the unit of (iv)：

(i) pyridine unit；

(ii) imines unit；

(iii) acid imide unit；With

(iv) amine unit.

9. such as the non-aqueous composition of any one of embodiment 1 to 8, wherein the carbon coated metal being dispersed through Grain is by with non-aqueous composition gross weight meter at least 15 weight % and at most and being dispersed through of existing of the concentration containing 60 weight % Carbon coated Argent grain, and the carbon coated Argent grain being dispersed through have as measured using dynamic light scattering method Median diameter less than 0.5 μm.

10. such as the non-aqueous composition of any one of embodiment 1 to 9, wherein the organic diluent is to contain 2- ethoxies Base ethanol, 2- (2- methoxy ethoxies) ethanol, 2- (2- ethoxy ethoxies) ethanol, 1- methoxy-2-propanols, 4- heptanone, 3- heptanone, 2-HEPTANONE, cyclopentanone, cyclohexanone, diethyl carbonate, 2-ethoxyethyl acetate, butyric acid N- butyl esters and methyl lactate At least one of organic solvent medium.

The non-aqueous composition of 11. such as any one of embodiments 1 to 10, it is non-aqueous Photocurable composition, and it enters One step contains photocurable component and UV light triggers optionally.

12. as embodiment 11 non-aqueous composition, wherein the photocurable component be UV-curable component.

13. as embodiment 11 or 12 non-aqueous composition, wherein the photocurable component be through it is acid catalyzed can light Curing component and the non-aqueous composition further contain light acid producing agent.

The non-aqueous composition of 14. such as any one of embodiments 11 to 13, wherein the photocurable component is phtotpolymerizable Close epoxy material.

The non-aqueous composition of 15. such as any one of embodiments 11 to 14, wherein the photocurable component is per molecule Photopolymerization epoxy material with least two polymerizable epoxy bases, and the smooth acid producing agent Wei Iodonium or sulfonium compound.

16. as embodiment 11 or 12 non-aqueous composition, wherein the photocurable component be free redical photocuring Component, and the non-aqueous composition further contains free radical photo-initiation.

17. as embodiment 16 non-aqueous composition, wherein the photocurable component include acrylate.

18. a kind of have such as any one of embodiment 1 to 18 including substrate and in one or two support-sides of substrate The drying layer of non-aqueous composition dries the article of any one in pattern.

19. as embodiment 18 article, wherein the substrate be continuous polymer net.

20. as embodiment 18 article, wherein the substrate include metal, glass, paper making raw material or ceramics.

21. as embodiment 18 or 19 article, wherein the substrate is to include the continuous net of polyester.

The article of 22. such as any one of embodiments 18,19 or 21, wherein the substrate is continuous polymer net and described non- Waterborne compositions are arranged in two support-sides of the substrate in multiple patterns.

23. it is a kind of have derived from such as embodiment 11 to 17 including substrate and in one or two support-sides of substrate in times The non-aqueous composition of one through Photocurable composition drying layer or dry the article of any one in pattern.

24. as embodiment 23 article, wherein the substrate be continuous polymer net.

25. as embodiment 23 or 24 article, wherein the composition through photocuring be in one or more patterns arrangement In in one or two support-sides of substrate.

The article of one or more embodiments in 26. such as embodiment 23 to 25, wherein the substrate is continuous polymer net With the composition through photocuring it is arranged in two support-sides of the substrate in multiple patterns.

The article of 27. such as any one of embodiments 23 to 26, wherein continuous net of the substrate for polyester.

A kind of 28. methods for providing forerunner's article, methods described includes：

The continuous net of transparent substrates is provided,

One or more are formed derived from strictly according to the facts on one or more parts at least one support-side of the continuous net Apply the photocurable pattern of the non-aqueous Photocurable composition of any one of example 11 to 17.

29. as embodiment 28 method, it is further included：

Photocuring one or more photocurable patterns form one or more through light with one or more parts of continuous net The pattern of solidification, it is described one or more through photocuring pattern respectively include as seed metal catalyst site the warp being dispersed through The metallic particles of carbon coating, and

With described in conducting metal electroless-plating one or more through the pattern each of photocuring to one or more parts of continuous net On.

30 as embodiment 29 method, it is further included：

Formed in some of continuous net using identical or different non-aqueous Photocurable composition, photocuring With electroless-plating feature repeatedly, the multiple part is identical or different.

The method of 31. such as any one of embodiments 28 to 30, it is for providing multiple forerunner's articles, methods described bag Include：

Non-aqueous Photocurable composition is applied to continuous net one or two by using one or more flexographic printing elements Some in individual support-side to form multiple photocurable patterns over the plurality of portions,

The continuous net for including multiple photocurable patterns is advanced to approach exposing radiation, and be consequently formed multiple warps The pattern of photocuring, and

Roll the continuous net for including multiple patterns through photocuring.

The method of 32. such as any one of embodiments 28 to 31, wherein the substrate is continuous polycondensation net.

33. as embodiment 32 method, wherein the substrate is the continuous polycondensation for including poly- (PETP) Net.

A kind of 34. methods for forming multiple conductive patterns on substrate, methods described includes：

Offer includes substrate and is arranged in one or two support-sides of substrate multiple including as seed metal catalyst The carbon coated metallic particles being dispersed through the pattern through photocuring forerunner's article,

The multiple pattern through photocuring is non-as defined in any one of embodiment 11 to 17 by one or more Aqueous Photocurable composition is provided, and

Electroless-plating it is the multiple through the pattern each of photocuring forming multiple conductive patterns.

A kind of 35. methods for forming multiple electronic installations, methods described includes：

Offer includes substrate and arranges multiple carbon coated including what is be dispersed through in one or two support-sides of substrate The article of the pattern through electroless-plating and through photocuring of metallic particles,

The multiple is any one of such as embodiment 1 to 17 by one or more through electroless-plating and through the pattern of photocuring Defined non-aqueous Photocurable composition is provided, and

Multiple conductive articles are formed through electroless-plating and through the pattern of photocuring by the multiple, and

The multiple conductive articles are manufactured to form multiple electronic installations.

Following instance is provided to illustrate implementation of the invention, but is not intended to be limiting in any manner.

Following dispersant filler test is used to judge to be suitable to the carbon coated Argent grain of dispersion in implementation of the invention Particle dispersants.This test can be similarly used for judging that the metallic particles for suitably disperseing other carbon coated is (such as carbon coated Copper particle and carbon coated platinum grain) available particle dispersants.

Initial dispersion agent filler test (0.5 weight % carbon coated Argent grain)：

Using carbon coated Argent grain, the particle of testing using a small amount of carbon coated Argent grain and excess disperses (weight of particle dispersants is 10 with the ratio of the weight of carbon coated Argent grain for agent (" dispersant "):1) come carry out this survey Examination.Dispersant needed for 2.5g to 47.5g 1- methoxy-2-propanol (Sigma-Aldrich is added by with stirring (Sigma-Aldrich) dispersant solution) is formed until dispersant is completely dissolved, 5 weight % is obtained and is tested the molten of dispersant Liquid.Then, with stirring by 0.02g carbon coated Argent grain (Sen Kesi (NovaCentrix), Ag-25-ST3 are cut down in promise, The specific average grain diameters of 25nm, Jane Austen (Austin) TX) dispersant of the weight % of 4g 5 that is added in 20ml vials is molten Liquid.Gained non-aqueous composition respectively uses ultrasonic probe system (Wei Bula-celo (Vibra-Cell) at ambient temperature VC600, supersonic speed ＆ Materials Co., Ltd (Sonics＆Materials, Inc.)) process 2 minutes and then visually rank sedimentation. This is carried out by estimating observation after allowing suspension to stand 24 hours under room temperature (20 DEG C).Hereinafter grading scale is used to assess The sedimentation of the carbon coated Argent grain being dispersed through：

5=clear solutions, settle completely；

4=light gray solution, almost settles completely；

3=fascia cinereas wide are located at black suspension top, and part settles；

The narrow fascia cinereas of 2=are located at black suspension top, and some are locally settled but less than grading " 3 "；With

1=black suspensions are without apparent settlement.

The result of dispersant filler test is summarized below in Table I.

Table I

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

=styrene-maleic anhydride copolymer

PVP=poly- (pyrrole pyridine ketone)

Sedimentation is then provided in selection Table I and is rated 3 or smaller dispersant for another wheel test, but it is carbon coated Argent grain concentration it is higher, concentrated dispersant test is as follows.

Concentrated dispersant test (50 weight % carbon coated Argent grain)：

This assessment is designed to dispersant and carbon coated Argent grain weight ratio (4 or 5 weights of the assessment with much less Amount % dispersants and carbon coated Argent grain weight %) concentration composite in dispersant.Its median particle is only characterized, because Excessively concentrated for it and cannot visually rank settling behavior.Size distribution derived from light scattering measurement is by showing non-aqueous group The big agglomerated thing degree in suspension is contained in compound to provide the good instruction of particle dispersants (dispersant) effect.

Dispersant needed for 2.5g is added to 47.5g 1- methoxy-2-propanols until dispersant is completely molten by with stirring The solution that 5 weight % test dispersant is obtained to provide dispersant solution for solution.Then, it is with stirring that 8g is carbon coated Argent grain (Sen Kesi Ag-25-ST3 are cut down in promise, and 25nm determines average grain diameter, Jane Austen TX) is added to 60ml bottles of (LDPE, from receiving synthetic fibre (Nalgene) obtain) in the weight % dispersant solutions of 8g 5.Ultrasonic probe system (Wei is used under environment temperature (20 DEG C) Bradley-celo VC600, supersonic speed ＆ Materials Co., Ltd) non-aqueous composition 2 to 4 minutes obtained by treatment.About 0.2g is removed to hang Supernatant liquid and nanometer-ZS (" ZEN ") device measuring median particle diameters and it is expressed as using Malvern ElWin Sietas wise man by dynamic light scattering Dv (50%).All sized datas are based on volume weighting distribution and equivalent spherical diameter model.Result is shown in following table In II.

Table II

* TLTM=" excessive and " ZEN " device measuring cannot be used "

The dispersant for being identified as testing 2-2 to 2-17 that the result explanation being shown in Table II is assessed can effectively disperse Carbon coated Argent grain with ideally small median diameter (being equal to or less than 0.6 μm) and therefore for of the invention non-aqueous The embodiment of property composition.

Non-aqueous Photocurable composition (the carbon coated Argent grain that 21 weight % are dispersed through)：

Adjusted using each particle dispersants (dispersant) being shown in lower Table III and the carbon coated Argent grain being dispersed through With non-aqueous Photocurable composition, and these non-aqueous Photocurable compositions are respectively used to manufacture conductive articles.

2.5g dispersants are added to 47.5g 1- methoxy-2-propanols until dispersant is completely dissolved shape by with stirring The solution of dispersant needed for 5 weight % is obtained into dispersant solution.Then, it is adjoint to stir 8g carbon coated Argent grain (Sen Kesi Ag-25-ST3 are cut down in promise, and 25nm determines average grain diameter, Jane Austen TX) is added to 60ml bottles (LDPE is obtained from synthetic fibre is received) The interior weight % dispersant solutions of 8g 5.Under environment temperature (20 DEG C) with ultrasonic probe system (Wei Bula-celo VC600, Supersonic speed ＆ Materials Co., Ltd) non-aqueous composition 4 minutes obtained by treatment.

The solution of photocurable component is prepared by mixing following components：27.33 weight % epoxy acrylates CN153 (6.02g, Sartomer), 18.82 weight % PEG diacrylates (4.15g, M_nIt is 250, in Sigma-Order Very), 4.04 weight % PEG diacrylates (0.89g, M_nBe 575, Sigma-Aldrich), 20.62 weight % Tetramethylol methane tetraacrylate (4.55g, Sartomer), 1.52 weight % triarylsulfonium salts six being mixed in 50% propylene carbonate Fluorophosphate (0.34g, Sigma-Aldrich), 1.52 weight % triarylsulfonium salts six being mixed in 50% propylene carbonate Fluorine antimonate (0.34g, Sigma-Aldrich), 4.55 weight % free radical photo-initiation hydroxycyclohexylphenylketones (1.0g, Sigma-Aldrich), 2.32 weight % free radical photo-initiation methyl -4'- (methyl mercapto) -2- morpholinyl phenylpropyl alcohols Ketone (0.51g, Sigma-Aldrich), 0.002 weight %9- Fluorenones (0.0004g, Sigma-Aldrich), 3.81 weights Amount %4- (dimethylamino) ethyl benzoate (0.84g, Sigma-Aldrich) and 15.42 weight %1- methoxy-2-propanols (3.4g, Sigma-Aldrich).

The sample (22.04g) of this photocurable component solution is added to stirring contains carbon coated Argent grain The non-aqueous composition of (16g).Be then used by with rotor-stator probe (PRO science Co., Ltd (PRO Scientific, Inc. the desk-top homogenizers of PRO 300D)) mix 5 minutes each non-aqueous Photocurable composition with 10,000rpm operations, together When cause that non-aqueous Photocurable composition is cooled down.

Remove about 0.2g suspension and Malvern ElWin Sietas wise man's nanometer-ZS (" ZEN ") equipment is used by dynamic light scattering Measurement median particle diameter is simultaneously expressed as Dv (50%).All sized datas are to be with volume weighting distribution and equivalent spherical diameter model Basis.Result is shown in lower Table III.

Take out non-aqueous Photocurable composition (being also considered as " ink ") about 2g samples be placed in narrow vial with Sedimentation and clarification after assessing 24 hours to about 7 days.The non-aqueous Photocurable composition top of gained black is located at after 24 hours The clear band of colourless fluids indicate to be unable to maintain that carbon coated Argent grain suspends.There is precipitum without clarification in bottle bottom Indicate through the suspension of partially stabilized carbon coated Argent grain.The result of these assessments is shown in lower Table III.

Table III

TLTM=is excessive and cannot measure

PVP=poly- (pyrrole pyridine ketone)

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

The non-aqueous Photocurable composition of * Comp=contrastives

Be shown in Table III result explanation only the present invention definition particle dispersants (dispersant) provide it is non-aqueous can light The appropriate small median diameter of the carbon coated Argent grain being dispersed through in solidification composition filling.In addition, the present invention is non-aqueous Property Photocurable composition allotment and during use do not show sedimentation or precipitum.

Article invention example：Non-aqueous Photocurable composition is in the purposes for providing patterned articles

Present example confirms non-aqueous Photocurable composition of the invention, and in manufacturing, have on appropriate substrate can light The purposes of forerunner's article of cured pattern.

Non-aqueous Photocurable composition (as mentioned below) of the invention, the soft version are printed using flexographic printing element Printing unit has using Kodak square luminous point (Kodak Square Spot) laser technology with 12,800dpi's to have used Before commercially available Kodak Fu Lakesa (Kodak Flexcel) NX flexographic printing plates of the mask imaging of the predetermined pattern of resolution ratio write-in Drive the sample of thing (Eastman Kodak Co).The known conditions UV proposed by these flexographic printing elements is exposed using manufacturer And treatment (development) described flexographic printing plate predecessor.Gained flexographic printing plate is 1.14mm thickness (including PET film).For fixing Flexographic printing plate to block letter roller backing adhesive tape for 20 mils (0.051cm) are thick, Shaw (Shore) A hardness is 55 1120 shellfishes heat (1120Beige) adhesive tape (3M companies).Gained relief image design in flexographic printing element includes having on top Embossed surface has 7 μm of lattices of the fine rule of width.

Using patterning flexographic printing element (as mentioned below), the desk-top testing of printed machine of soft version pattern is used " IGT F1 printabilitys tester (IGT F1 Printability Tester) " (IGT test systems Co., Ltd (IGT Testing Systems Inc.), Arlington mountain villa (Arlington Heights), IL), this hair in upper Table III will be set forth in Bright non-aqueous Photocurable composition 3-1 (Inv) is printed onto PET [poly- (PETP) film [Merrill Lynch's KnicksST505, Du Pont Supreme Being people film (DuPont Teijin Films)] on substrate.For apply it is non-aqueous can light consolidate Changing composition has the 1.3BCMI and 1803lpi for such as determining by IGT test systems to the anilox roll system of flexographic printing element Value.At ambient temperature printing figure is made using the print speed printing speed of the reticulate pattern power, the print force of 10N and 0.20m/s of 20N Case.The pattern that lattice from by described flexographic printing element prints obtains average line width printed on substrate Degree.

These operations obtain the article of the pattern being printed in comprising non-aqueous Photocurable composition on PET substrate.

(Fusion) 300WPI medium pressure mercury lamps are contained with UV between 190 to the radiation wavelength between 1500nm good fortune using offer Each non-aqueous Photocurable composition printed patterns of radiation exposure, approximate light exposure is 298mJ/cm², figure is respectively printed with photocuring Case.Use the warp of Olympus (Olympus) BH-2 light microscopes measurement cured pattern in transmiting and reflecting both of which Printing and the average line width of photocuring.

This working example confirms that non-aqueous Photocurable composition can be successfully used to provide on appropriate substrate with not Forerunner's article of photocuring pattern, forerunner's article so that can be used for provide have through photocuring pattern intermediate items.

Invention example：Non-aqueous Photocurable composition is in the purposes for providing conductive articles

Article comprising the pattern through photocuring mentioned above can be used as intermediate items for further operation.Specifically Ground is said, by accommodating En PalaiteIn 35 in the beaker of Cu-406 electroless-plating solutions (happy to think (Enthone)) DEG C immersion intermediate items the intermediate items is undergone electroless-plating copper, then distilled water flushing and with nitrogen dry, There is the product article of the conductive pattern being arranged on PET substrate to be formed.

The present invention is described in detail referring especially to particularly preferred embodiment of the invention, but it should be apparent that can be in essence of the invention Changed and changed in god and scope.

Claims

1. a kind of non-aqueous composition, it is included with the non-aqueous composition gross weight meter at least amount of 10 weight % in having The carbon coated metallic particles being dispersed through in machine diluent, the carbon coated metallic particles being dispersed through have be equal to Or the median diameter less than 0.6 μm, and with least 2,000 and at most and containing 100,000 weight average molecular weight (M_w) and wrap Particle dispersants dispersion containing nitrogenous unit, the median diameter is measured using dynamic light scattering method,

Wherein, when the non-aqueous composition contains at most and containing the carbon coated metal being dispersed through described in 25 weight % During grain, it is not presented visual sedimentation when 20 DEG C of sedimentations for carrying out at least 24 hours are tested.

2. non-aqueous composition according to claim 1, it includes the carbon coated Argent grain that is dispersed through or is dispersed through Carbon coated copper particle or the carbon coated Argent grain being dispersed through and the carbon coated copper particle that is dispersed through both Mixture.

3. non-aqueous composition according to claim 1, wherein the particle dispersants with it is described be dispersed through applied through carbon The weight ratio of the metallic particles for covering is at least 1:100 and at most and containing 30:100.

4. non-aqueous composition according to claim 1, wherein the carbon coated metallic particles that is dispersed through be with With the non-aqueous composition gross weight meter at least 15 weight % and at most and the amount containing 70 weight % is present.

5. non-aqueous composition according to claim 1, wherein the particle dispersants have at least 2,000 and at most and Containing 50,000 M_w。

6. non-aqueous composition according to claim 1, it is further included with the non-aqueous composition gross weight meter At most and the amount containing 20 weight % the carbon black being dispersed through.

7. non-aqueous composition according to claim 1, wherein the particle dispersants are organic poly- comprising ester units Compound.

8. non-aqueous composition according to claim 1, wherein the particle dispersants are comprising selected from following classification (i) The organic polymer of at least unit of a classification in (iv)：

(i) pyridine unit；

(ii) imines unit；

(iii) acid imide unit；With

(iv) amine unit.

9. non-aqueous composition according to claim 1, wherein the carbon coated metallic particles that is dispersed through be with With the non-aqueous composition gross weight meter at least 15 weight % and at most and the concentration containing 60 weight % being dispersed through of existing Carbon coated Argent grain, and the carbon coated Argent grain being dispersed through have such as using dynamic light scattering method measure it is small In 0.5 μm of median diameter.

10. non-aqueous composition according to claim 1, wherein the organic diluent be comprising cellosolvo, 2- (2- methoxy ethoxies) ethanol, 2- (2- ethoxy ethoxies) ethanol, 1- methoxy-2-propanols, 4- heptanone, 3- heptanone, At least one in 2-HEPTANONE, cyclopentanone, cyclohexanone, diethyl carbonate, 2-ethoxyethyl acetate, butyric acid N-butyl and methyl lactate The organic solvent medium of person.

11. non-aqueous compositions according to claim 1, it is non-aqueous Photocurable composition, and it is further included Photocurable component and UV light triggers optionally.

12. non-aqueous compositions according to claim 11, wherein the photocurable component is UV-curable component.

13. non-aqueous compositions according to claim 11, wherein the photocurable component be through it is acid catalyzed can light Curing component and the non-aqueous composition further include light acid producing agent.

14. non-aqueous compositions according to claim 13, wherein the photocurable component is photopolymerization epoxy material Material.

15. non-aqueous compositions according to claim 14, wherein the photocurable component is per molecule having at least Two photopolymerization epoxy materials of polymerizable epoxy base, and the smooth acid producing agent Wei Iodonium or sulfonium compound.

16. non-aqueous compositions according to claim 11, wherein the photocurable component is free redical photocuring Component, and the non-aqueous composition further includes free radical photo-initiation.

17. non-aqueous compositions according to claim 16, wherein the photocurable component includes acrylate.

A kind of 18. articles, it includes substrate and has according to claim 1 or 11 in one or two support-sides of the substrate The drying layer of described non-aqueous composition dries pattern.

19. articles according to claim 18, wherein the substrate is continuous polymer net.

20. articles according to claim 18, wherein the substrate includes metal, glass, paper making raw material or ceramics.

21. articles according to claim 18, wherein the substrate is the continuous net comprising polyester.

22. articles according to claim 18, wherein the substrate is continuous polymer net and the non-aqueous composition It is to be arranged in two support-sides of the substrate in multiple patterns.

A kind of 23. articles, its include substrate and in one or two support-sides of the substrate have derived from according to right will Ask the non-aqueous composition described in 11 through Photocurable composition drying layer or dry pattern.

24. articles according to claim 23, wherein the substrate is continuous polymer net.

25. articles according to claim 23, wherein the composition through photocuring is arranged in one or more patterns In in one or two support-sides of the substrate.

26. articles according to claim 23, wherein the substrate is continuous polymer net and the group through photocuring Compound is arranged in two support-sides of the substrate in multiple patterns.

27. articles according to claim 23, wherein continuous net of the substrate for polyester.

The continuous net of transparent substrates is provided,

One or more are formed derived from according to right on one or more parts at least one support-side of the continuous net It is required that the photocurable pattern of the non-aqueous composition described in 11.

29. methods according to claim 28, it is further included：

One or more photocurable patterns described in photocuring with one or more parts described in the continuous net formed one or Multiple pattern through photocuring, it is described one or more through the pattern of photocuring respectively comprising the warp as seed metal catalyst site Scattered carbon coated metallic particles, and

With described on one or more parts described in continuous net described in conducting metal electroless-plating one or more through photocuring Pattern each.

30. methods according to claim 29, it is further included：

Implement the formation, the light of feature in some of the continuous net using identical or different non-aqueous composition Repeatedly, the multiple part is identical or different for solidification and electroless-plating.

31. methods according to claim 28, it is that, for providing multiple forerunner's articles, methods described is included：

The non-aqueous composition is applied to one or two of the continuous net by using one or more flexographic printing elements Some in support-side and form multiple photocurable patterns over the plurality of portions,

The continuous net comprising the multiple photocurable pattern is advanced to approach exposing radiation, and be consequently formed multiple warps The pattern of photocuring, and

Roll the continuous net comprising the multiple pattern through photocuring.

32. methods according to claim 28, wherein the substrate is continuous polycondensation net.

33. methods according to claim 32, wherein the substrate is comprising the continuous of poly- (PETP) Polyester webs.

Forerunner's article is provided, forerunner's article arranges multiple bags comprising substrate and in one or two support-sides of the substrate The pattern through photocuring as the carbon coated metallic particles being dispersed through of seed metal catalyst is included,

The multiple pattern through photocuring is provided from one or more non-aqueous compositions according to claim 11, and

A kind of 35. methods for forming multiple electronic installations, methods described is included：

There is provided comprising substrate and arrange multiple carbon coated including what is be dispersed through in one or two support-sides of the substrate The article of the pattern through electroless-plating and through photocuring of metallic particles,

The multiple is from one or more non-aqueous combinations according to claim 1 through electroless plating and through the pattern of photocuring Thing is provided, and

Multiple conductive articles are formed through electroless-plating and through the pattern of photocuring from the multiple, and