CN1745194A - Method of forming a conductive metal region on a substrate - Google Patents

Abstract

There is disclosed a method of forming a conductive metal region on a substrate, comprising depositing on the substrate a solution of a metal ion, and depositing on the substrate a solution of a reducing agent, such that the metal ion and the reducing agent react together in a reaction solution to form a conductive metal region on the substrate.

Description

In substrate, form the method for conductive metal region

Technical field

The present invention relates in substrate, form the field of conductive metal region.

Background technology

In substrate, form conductive metal region, particularly can many industrial application be arranged according to the technology that pattern forms conductive metal region.A kind of important use according to predetermined layout, forms pattern with metal level, thereby is electrically connected different parts and electrical means in the above for making printed circuit board (PCB).Other application comprises that pole line (aerial) and antenna are as being present in antenna in mobile telephone, radio frequency (RFID), means of identification, the smart card, being used for contact that battery and power supply supply with, being used for flat screen technology contact array, the electrode that is used for biology and electrochemical sensor, smart fabric and the decorative characteristics of (liquid-crystal display, light emission polymkeric substance show or the like).

During these were used at great majority, metallic region must or be conducted electricity sometimes basically, and expectation has the specific conductivity of high level.

People are known to be used for preparing conductive metal region in substrate method comprises that ink jet printing contains the step of the liquid of metal nanoparticle.Heat chemical composition and the evaporating solvent of printed liquid then to condense liquid.Thereby nano particle is in contact with one another and conducts electricity.Yet these materials do not have the specific conductivity near the reguline metal specific conductivity.Heating steps is not only inconvenient, and has stoped this technology is used for low-melting plastic-substrates.

A kind of example of this technology is open in " Metallisations by Direct-Write InkjetPrinting ", it is proposed on NCPV Program Review Meeting, Lakewood Colorado 14-17October 2001, by C.Curtis etc.Digital ink jet printing technology is used for the pattern of type metal organic decomposition printing ink, its use or do not use nanoparticle additives.For depositing silver, organometallic compound is dissolved in a kind of organic solvent as silver (hexafluoroacetylacetone hydrochlorate) (1, the 5-cyclooctadiene), silver-colored particle is added to wherein, thus the enough little ink jet printing head aperture of avoiding stopping up the 10-50 micron of this silver particle.Ink-jet printer by number control applies printing ink then, and it runs through substrate ink deposition pattern.Heat the pattern that printing ink forms nano particle then, it is electrically connected to reach by remaining silver compound to a certain degree provides most specific conductivity.This technology provides specific conductivity good silver zone.But this technology is used to prepare that the copper zone is but very complicated, and it need be operated under inert environments, and resulting copper film has resistivity, and it is than basic long-pending copper metal difference several magnitude.Although this technology provides a kind of mode easily to come the metal level of preparation formation pattern in substrate, it needs not convenient annealing steps, and specific conductivity and the basic long-pending approaching layer of conductivity metal are not provided.

A kind of known specific conductivity that is used to provide is an electroless plating with the basic technology of amassing the approaching metal level of conductivity metal.Electroless plating is a kind of solution chemistry coating technology, and it is used for basadly applying the conducting metal coat existing a lot of year, and it can be flats or with it shaping.Substrate is immersed in a series of baths.Resulting conductive metal layer can be shaped, perhaps make it to go through the thickness that follow-up electrodeposition technology increases conductive layer.A kind of important technology of commercialization is so-called " plated-through-hole " technology, for follow-up plating, by electroless plating techniques, with the boring in its printed circuit board (PCB) that is used for metallizing above 30 years.

The common instance of electroless plating is as follows.At first, at 68 ± 2 ℃ with plastic-substrates etching in chromic acid/concentrated vitriol is bathed.Thereby, guarantee that copper is adsorbed onto on the plastic-substrates well on the surface of microscopically etching plastic-substrates.Secondly, at about 50 ℃, in a kind of bath that comprises about 30% concentrated hydrochloric acid, the sexavalent chrome material on the plastic-substrates is stayed in neutralization arbitrarily.Then plastic-substrates is joined during the third bathes, add a kind of activator to wherein prepare plastic-substrates surface, with at the next procedure absorbing catalyst.At room temperature, the third bath is typically about 30% concentrated hydrochloric acid.

Then, plastic-substrates is immersed in the 4th kind of bath, it comprises the dilute solution of palladium colloid and pink salt.This glue is deposited on the frosting, thus in follow-up plating step the deposition of catalytic copper.This bath comprises a high proportion of pink salt, about 30% concentrated hydrochloric acid and operation at room temperature.The 5th kind of bath that plastic-substrates immerses wherein comprises promotor, and the palladium of its activation adsorption improves sedimentary speed and homogeneity.Accelerator bath comprises about 30% concentrated hydrochloric acid.

At last, the plastic-substrates after the activation immersed comprise that it is able to catalysis by the palladium colloid in the 6th kind of bath of plating bath on plastic-substrates, and make copper be deposited on to be coated with on the zone of plastic-substrates of catalyzer.Plating bath comprises mantoquita, as the sodium hydroxide of the formaldehyde of reductive agent and activation formaldehyde.Must be very carefully the composition of plating bath be carried out temperature control, for some commercial compositions, 45 ± 2 ℃ temperature suits.Plating can't take place in lower temperature.In higher temperature, the spontaneous generation of plating, and the copper in bathing is separated out.Because so the mixing solutions instability is must be with mantoquita, formaldehyde and sodium hydroxide separate storage.

The electroless copper deposition is used extensively, and has the significant advantage of preparation high-conductive metal layer.The specific conductivity of resulting metal level is usually near the corresponding basic specific conductivity of amassing metal.

Yet main drawback is for when plating is a kind of bath process, and the whole surface of substrate will be applied with metal usually.This technology itself does not make metal deposition become pattern, and in above-mentioned many application it is all had needs.

This technology also has several other restrictions.At first, this technology relative complex often needs 6 kinds of baths, thereby only suitable being used in the professional production factory.Slight error in the composition or depart from optimum temps and can cause most of copper spontaneous depositions in the plating bath, the waste chemical substance.In addition, the metal ion in the refuse is deleterious for environment, therefore needs expensive waste treatment operation.The palladium (volatility of palladium price) of high price causes the further expensive and economic uncertainty in the catalysis operation.

Several methods that prepare the metal level that forms pattern by electroless plating are disclosed.May the simplest technology be to form metal level, then mask is applied to the metal level part that to be retained, use etching reagent to remove remaining metal level.This technology is wasted metal, is required great effort, has reproducibility restriction and product component quality malleable.

A kind of replacement scheme that provides the metal part according to pattern uses additional base part to attach it to a kind of device, with the support metal parts for by the several assemblies of stamped metal then.Developed this idea as inlaying moulded known this technology, target is to reduce the quantity of different parts and reduces manufacturing cost.In inlaying moulded, metal parts is supported in the injection moulding machine, then around metal parts, molded this part.

Recently, after deliberation comprise the many of plating and injection injection molding (multi-and singleshot-moulding) technology.First parts are injected into plastics, then by above-mentioned electroless plating metal deposition.The part that plating is crossed is placed in second mold then, forms rest parts around the part that plating is crossed.

Another kind of research is the plastics of two kinds of different gradess of injection moulding fusion, a kind of plating in the electroless plating operation easily, a kind of being not easy.These parts of manufacturing in separately molded, plating only makes the plastics of the first estate be able to plating then.Although very effective, this technology is very expensive, thereby is unsuitable for using in low-cost mode.

The US4 of Whittaker Corporation, 242,369 disclose the composition and the technology of the ink jet printing that is used for metal or alloy.Tiny, the uniform drop of ink jet inks comprises at least a soluble salt of at least a metal lining.This process limitations is in metal refining on the base metal surfaces more cheap than metal lining.

The US4 of E.L.Du Pont de Nemous and Company, 668,533 disclose use comprises copper particle in small, broken bits or contains activator such as printing ink ink jet printing in substrate of the metal of palladium (II) salt.Substrate with resulting printing is placed in a kind of metal deposition bath then, and it is by above-mentioned electroless plating depositing metal layers.In the ink jet printing stage, the pattern that passes through the drop that applied is determined the pattern that forms by resulting metal level.

AGFA-Gevaert, N.V. US5,751,325 disclose a kind of ink-jet printing process, and it makes and accept material, reducible metal compound, is used for the reductive agent of described metallic compound and the physical growth nuclear (physicaldevelopment nuclei) that described metallic compound catalytic reduction is a metal is produced work relationship.This technology is used for preparing the ink jet printing image of high light intensity but not conductive metal layer.This physical growth nuclear is dispersed in image receiving layer such as the gelatin layer, and it is on substrate.Like this, in gelatin layer, around each physical growth nuclear, metal is formed discrete particle.Discrete particle will not form the conductive region on the electric power.

Print conductive carbon (for example graphite) printing ink or conductive polymers such as PEDOT in substrate, this substrate of metallide is known then.Yet this is a kind of multistage process of complexity.

In substrate, produce conductive polymers by printing polymkeric substance, with this polymkeric substance of permanganate oxidation, to make the polymkeric substance of oxidation react the polypyrrole for preparing conduction with the pyrroles then also be known.Compare with conducting metal, resulting material has very low specific conductivity, thereby can apply follow-up metallide step.This is again a kind of multistage process of complexity.

Summary of the invention

According to a first aspect of the invention, a kind of method that forms conductive metal region in substrate is provided, be included in metal refining solion on the metal, and in substrate, deposit reductant solution, thereby in reaction soln, metal ion and reductive agent one react to form the metallic region of conduction in substrate.

Be not to know which being reflected at taking place between metal ion and the reductive agent very clearly, still, preferably this be reflected on the substrate surface, neighbouring or within promptly take place on the spot, and not at metal ion with before reductive agent contacts with this substrate surface.

The metal of preferred deposition is the metal level of only or topmost in the product.Like this, the present invention can be used for depositing all or most of metal, thereby in finished product, form the metallic region of conduction.

Do not resemble at US5, disclosed method in 751,325 does not need physical growth nuclear here.In reaction soln, metal ion and reductive agent one react, and form the metallic region of conduction in substrate, rather than form discrete tiny metallic particles away from substrate.

Reaction soln must have a kind of composition, thereby makes in substrate, and being formed on the thermodynamics of conductive metal region is favourable.Conductive metal region will be set up in substrate, and catalyzer further makes the conductive metal region growth.

Whether on thermodynamics favourable with depend on the pH that comprises reaction soln and temperature, reductive agent intensity, use the other factors of factor such as the performance of adding component in the easness that this reductive agent metal can be reduced, the influence that can slow down metal ion reductive complexing agent, the reaction soln and those skilled in the art's thorough.

But the composition of reaction soln should not be the sort of composition in the spontaneous formation of entire reaction solution generation metallic particles.If this situation, the fine particle that does not have physical connection to arrive substrate surface the formation or do not have each other to be electrically connected mutually, rather than in substrate, set up conductive metal region.

Deposit solution makes the amount of metal ion and reductive agent measure together with the expectation thickness of conductive metal region in substrate.Make deposition opposite with immersion technology such as conventional electroless plating, the latter is immersed in substrate in the bath that comprises metal ion and reductive agent.Compare with immersing technology, deposition needs the metal ion and the reductive agent of less amount, can cut the waste.In addition, deposition reduces or has avoided adjusting the difficulty of composition and immersion bath temperature.

Can select the composition of reaction soln, thereby so that its enough unstable GOLD FROM PLATING SOLUTION that makes belongs to the spontaneous generation of reaction between ion and the reductive agent to form conductive metal region in substrate.But the instability that reaction soln should not be formed makes at the fine powder of the spontaneous formation conducting metal of entire reaction solution, rather than form conductive metal region in substrate.

The composition that those skilled in the art are easy to conditioned reaction solution comes preparation feedback solution, and it will be in substrate rather than separates out in that entire reaction solution is spontaneous.

Thereby belonging between ion and the reductive agent reaction in GOLD FROM PLATING SOLUTION forms conductive metal region and can activate by activator in substrate.In this case, if not the existence of activator, thereby reaction formation conductive metal region in substrate does not need spontaneous generation between metal ion and the reductive agent.

Can activator be applied to substrate.Activator can be the component of substrate.When initial period, activator can be applied to, preferred deposition is in substrate.

Preferred active agent is a catalyzer, the reaction between its catalytic metal ion and the reductive agent.Suitable catalyzer reduces activation energy and makes spontaneous formation metallic region in substrate.

Preferred activator comprises tiny metallic particles or metal level (it plays catalyzer).This activator can comprise the component of the reaction that forms tiny metallic particles or metal level on the spot; thereby for example can react metal ion or the reductive agent that forms tiny metallic particles or metal level in the reaction soln of metal ion and reductive agent, this metallic particles or metal level are as the catalyzer of follow-up metallization reaction.In this case, it is usually different with the metal of a large amount of conductive metal layers of formation on finished product to comprise the metal of activator.For example, preferred one or more tackiness agents that use, can be with the organic acid salt of transition metal such as acid chloride deposition (preferred ink jet printing), be reduced to palladium on the spot by applying reductive agent (preferably by ink jet printing, but may by being included in any metallization process of submerged in the reductive agent bath) then.The same with reductant solution, by method of the present invention, thereon with the solution deposition of different metal ion such as copper, nickel or silver ions.Preferred resulting reaction soln is autocatalytic, in case promptly its component metals begins deposition, another kind of metal will deposit thereon.Catalyst metal play a part by autocatalytically solution catalyzing metal form thereon, with the beginning depositing operation.

Suitable activator comprises organic acid salt such as the acid chloride or the propionic acid palladium of transition metal.Have been found that acid chloride has good solvent nature, be easy to print by ink-jet technology, thus and dry very fast very high printing quality and the good marginal sharpness of obtaining.Many other palladium salt also suit as Palladous chloride.The preference chain alkyl salt.Alternative activator comprises salt, complex compound or the colloid of transition metal, perhaps the particle of bronze (bronze), aluminium, gold or red metal (copper).

The suitable solvent that is used to deposit the transition metal organic acid salt is 50/50 mixture of Pyranton and methoxypropanol.The organic acid salt of preferred transition metal constitutes the 1-3 weight % of acid chloride, most preferably is 2 weight % of deposit liquid.Can use the concentration of equal value of the another kind of organic acid salt of transition metal.

A kind of replace solvents is 50/50 mixture of toluene and methoxypropanol.In this solvent, preferably by weight, about 2% acid chloride solution.A kind of cosolvent of preferred interpolation increases the viscosity that is used for ink jet printing.

Activator/catalyzer can be second metal different with first metal.Can form second metal by the ion and the reductive agent of deposition second metal in substrate, thereby make second metal ion and reductive agent in reaction soln, one react in substrate, to form conductive metal region.In this case, preferred first metal forms sedimentary a large amount of conducting metal.

Catalytic metal zone or tiny metal-powder can form by following steps, preferably with tackiness agent or to form the chemical formulation of solid layer, one or more (preferably by ink jet printings) in elder generation's metal refining ion, reductive agent or the alkali, deposition is thereon as yet in metal refining ion and the reductive agent any then, alkali.This forms the zone of conductive metal region or tiny metallic particles.

In one embodiment, by ink jet printing (preferably dried/cured/sclerosis on the spot) metal ion (for example palladium) is applied to substrate, immerse in the reductive agent bath then or with substrate, perhaps with reductive agent deposition (for example by ink jet printing) thereon, thereby in substrate, form conductive metal region or tiny metallic particles zone to play catalyzer.Then,,, and in substrate, deposit reductant solution, the suitable metallization by metal refining solion in substrate as in the past.Usually, the metal ion of a large amount of resulting conductive metal regions of formation of deposits is different with the metal ion of formation of deposits catalyzer.In a kind of alternate embodiment, at first reductive agent is applied to substrate, then it is immersed in the solution of metal ion and alkali, perhaps by ink jet printing metal refining ion thereon.

No matter whether need activator, metal ion solution and reductant solution can be stored in the solution or single component solution of multiple different components.

Also can deposit pH and change agent, it typically is acid or alkali, come the activating and reducing agent.Acid/alkali can be stored in to has in metal ion and the reductive agent in arbitrary or both component solution.Alkali can be stored in the different component solutions, its have in metal ion and the reductive agent arbitrary or both.Acid/alkali also can deposit together with activator.Like this, metal ion can be stored in the component solution under can not the pH of spontaneous formation metal.

For example, metal ion, reductive agent and acid/alkali can be stored in three kinds of different component solutions, and it mixes and form reaction soln in substrate.

In another kind of embodiment, metal ion and reductive agent are stored in first component solution, and acid/alkali is stored in second component solution, thereby in substrate first and second component solutions is mixed and form reaction soln.

In another kind of embodiment, single component solution comprises metal ion, reductive agent and acid/alkali.

Usually the solution that preferably has the least possible component, thus minimize the complicacy of depositing operation.Yet, thereby in that reaction soln is stable inadequately when being used for selected depositing operation safely, the component of reaction soln is separated into a plurality of component solutions makes reaction soln by more stable component solution preparation.

When using activator, this method is preferably included in before the deposition component solution, and activator is deposited on suprabasil step.More preferably, arbitrary in metal refining ion or the reductive agent in substrate or both before, the deposition activator.Therefore, activator is positioned in the substrate, thereby helps forming in substrate conductive metal region, rather than forms the fine particle of conducting metal in entire reaction solution.

Activator preferably is stored in the activator solution.Preferably, the solvent that is used for activator solution basically or anhydrous fully.Thereby preferably before one or more component solution form layers of deposition, make solvent evaporate basically or dissipation.This minimizing or stoped the diffusion of activator away from substrate, otherwise may cause excessively forming not at suprabasil conductive metal region.Usually, one or more component solutions deposition thereon before, need to make to several minutes in several seconds volatile constituent dissipation to be typically about 30 seconds time.

Randomly, the activator liquid deposition thereon before, this substrate of pre-treatment.This causes the very fast of activator liquid dried and diffusion seldom, and obtains thinner line.For example, at 350 ℃, use fan heater with Melinex substrate (Melinex is trade mark) heating 4 seconds.

Preferably, activator is stored in and comprises that the promotion activator adheres in the solution of suprabasil chemical ingredients such as polymkeric substance.Suitable tackifier are retained in activator on the surface of substrate, thereby when the another kind of component solution of deposition, activator can not washed in the reaction soln.The suitable polymer blend tackifier comprise polyvinylpyrrolidone and polyvinyl butyral acetal.

At this, as preferably, activator be stored in basically or complete anhydrous solution in, this activator can be stored in the solvent of selecting according to substrate characteristics.Preferably, selective solvent to be partly dissolving substrate, thereby makes activator permeate this substrate and strengthen the adhesion to substrate of the conductive metal region that obtains.Like this, preferably in metal refining ion and reductive agent arbitrary or both before, activator is stored in the solution.But this solvent must be able to not be corrosive very much, otherwise, not only will damage substrate, and substrate will expand, and activator will be penetrated in the substrate too dark, thereby make its surface in substrate no longer exist enough amounts to activate the deposition of conductive metal ion reliably.

Before the deposition activator, but the pre-treatment substrate, thus improve adhesive power.For example, as known in the conventional electroless plating operation, substrate can be immersed in the water base oxidizing solution.Before catalyst deposit, this method also comprises preparation reagent (preparation reqgent) is deposited in the substrate as the solvent or the water base oxidizing solution of etching substrate.

Activator solution can comprise one or more in metal ion, reductive agent or the alkali/acid.

The component solution that comprises metal ion also can comprise complexing agent.Complexing agent such as EDTA connect metal ion, slow down or stop metal ion to be reduced agent reductive speed.Therefore, complexing agent can stop the spontaneous formation of metal in comprising the component solution of metal ion.

Between depositional stage or as sedimentary result, can deposit the solution of one-component, perhaps can deposit the various ingredients solution that mixes.If metal ion deposits in the different time with reductive agent, it can arbitrary sequential aggradation.When deposition various ingredients solution, it can deposit in order or simultaneously.Preferably deposit various ingredients solution in order, before one or more other component solutions deposit, make the built-up section of single solution or solution or all become dry, solidify or sclerosis thereon.We have found that this operation can make conductive metal region adhere in the substrate better, and can improve the quality of pattern.

At this, at one or more other component solutions (after this being " second liquid ") thus deposition beginning conductive metal region forms before the reaction thereon, make the solution (may form) (after this being " first liquid ") that comprises the activator that is used for conductive metal region formation reaction divide or all exsiccation in base upper portion by multiple solution, solidify or sclerosis, thereby form first solid layer, at this, first liquid comprises a kind of activator that second solid layer forms chemical reaction that is used for, thereby select first liquid that the solid layer of winning is adhered in the substrate, and it is that second liquid institute is porous, and this second liquid comprises that one or more are used for the reagent that second solid layer forms chemical reaction.

Like this, rely on its be included in first solid layer (no matter be by catch, fixing, or alternate manner) in activator is adhered in the substrate.

When making second liquid with the contact of first solid layer, second liquid infiltration, first solid layer makes second liquid that activator is entered in first solid layer.Therefore, second solid layer forms that reaction can occur on the substrate, contiguous substrate or in substrate, and (second) (conducting metal) solid layer of preparation expectation in substrate.In addition, second liquid infiltration can cause (second) solid layer of material to mix with first solid layer in first solid layer, thereby by adherent first solid layer, strengthens the adhesive power of (second) (conducting metal) solid layer and substrate.

When activator is positioned at when layer on the substrate surface, have precedence over the tiny metallic particles of formation in second liquid, will on the first layer, metallize.

First liquid needn't one be decided to be solution.Its a kind of or various ingredients can be solid, colloid etc.

Preferably, first liquid is included in insoluble first chemical functional group (chemical funtionality) in second solvent.

Also preferred first liquid is included in partly soluble at least second chemical functional group in second solvent.The near small part of a kind of like this second chemical functional group is dissolved in second solvent, makes second solvent permeate first solid layer and contact activation agent.The sufficiently complete that first chemical functional group keeps, thus adhere on the substrate and second solid layer.

This method can comprise that another is converted into one or more reagent the step of activation or catalysis form.For example acid chloride can be reduced on the spot, form metallic palladium by the follow-up reductant solution that applies, when applying second liquid, but the deposition of its catalysis metal on it.

First liquid can comprise second chemical functional group, and it can expand in second solvent or absorb second solvent.

First and second chemical functional groups can be different molecules or molecular radical or can be or become the part of same molecular.Usually, it is two kinds of different tackiness agents.

First chemical functional group only need insufficient dissolving in second solvent, thereby is kept perfectly when forming second solid layer.Preferred first solvent also has enough corrodibility to substrate, thereby makes the first layer allow first liquid infiltration wherein, increases the adhesive power of first solid layer and substrate, thereby also increases the adhesive power (by first solid layer) of second solid layer and substrate.

The preferred first and second solvent differences.This allows to select to be suitable for to form the first layer and the first layer is adhered to suprabasil first solvent, selects to be suitable for second solvent that forms the second layer simultaneously.Preferred second solvent is a water.Also preferred first solvent of selecting is partly dissolved substrate or penetrates in the substrate, improves the adhesive power of the first layer and substrate.Like this, moisture metallization chemistry and anhydrous first solvent can be used in the different step of same technology.Preferably, first solvent is partly or completely anhydrous.

Like this, first liquid can comprise one or more second chemical functional groups, and it is solvable in second solvent, and as polyvinylpyrrolidone, it is solvable in water.Surrogate comprises polyacrylic acid, polyvinyl acetate (PVA), polymine, polyethylene oxide, polyoxyethylene glycol, gel or its multipolymer.When second liquid begins to contact with first solid layer, the soluble constituent solubilized.For example, when the aqueous solution with metal ion and reductive agent contacts, thereby polyvinylpyrrolidone will dissolve on first solid layer and form conductive metal region.By weight, in resulting solid layer, about 5% polyvinylpyrrolidone suits.

(perhaps and) as an alternative, second chemical functional group can comprise can water swellable monomer and/or oligopolymer such as HEMA (2-hydroxyethyl methylacrylate), GMA (glyceral methacrylate) or NVP (positive vinyl pyrrolidone).Other monomer and/or oligopolymer himself can expand in the solvent of second liquid and/or when using polymkeric substance to substitute, it is inflatable.This makes second liquid infiltration in first solid layer, improves adhesive power and with comparing on the surface that exists only in first solid layer, makes to enter more activator.

(perhaps and) as an alternative, second chemical functional group can comprise can with the second liquid solvent blended high boiling solvent.For example, when second when liquid aqueous, can use NMP (positive methyl-2-pyrrolidone).This makes that resulting polymeric matrix keeps opening wide in first solid layer, thereby allows second liquid infiltration and improved the adhesive power of second solid layer and first solid layer.Replace solvents comprises ethylene glycol, glycol ether or glycerine.

(perhaps and) as an alternative, first liquid comprises microporous particles, thereby makes microporous membrane structure.Organic (for example PPVP gathers (polyvinylpyrrolidone)) of microporous particles or inorganic (for example silicon-dioxide).

As the result of first solvent evaporation, the first liquid solidifiable.

Can repeat this technology (the first and second different liquid of optional use), thereby set up multilayered structure.

Preferred first liquid is curable, that is to say, as the result of liquid hardening, preferred consolidation, can go through a kind of chemical transformation.

Select the first curable liquid that it is had in one or more substrates with second liquid phase than the wettability that improves.If by applying curable first liquid phase ratio with second liquid phase carrier (for example water) together, this reaches more accurate and accurate patterns together, it has tiny feature and better marginal sharpness.If with using the carrier with poorer wettability, by different technology activator is applied to the surface and compares, the first curable liquid still less runs off and sprouts wings (feathering) usually.When along line, during a good distance off deposition successive liquid dot (by for example ink-jet printing technology), the wettability that improves gives more accurate and accurate patterns, the liquid volume that its permission will be used still less, thereby make the line that is produced is narrower and feature is more tiny.

Use comprises the first curable liquid particularly important of activator, uses ink jet printing with a kind of material of digital drafting in substrate in this expectation.Many curable liquids are in by the correct range of viscosities of ink jet printing.

The preferred first curable liquid comprises one or more component chemical medicines, and it can go through a kind of reaction that causes liquid hardening.

The preferred first curable liquid comprises monomer and/or oligopolymer, its polymerizable and/or crosslinked use, thereby sclerosis and formation solid layer.Preferred resulting polymer formation comprises the matrix of activator.If only comprise that with it monomer compares, comprise that first liquid at least some oligopolymer, curable has lower toxicity usually.

First solid layer is hard, flexible or plastic (no matter whether it is by solidifying to form).Preferably before applying second liquid, it needn't finish sclerosis.

As to stimulating as electromagnetic radiation, electron beam or the hot response of specific band (for example ultraviolet ray, blueness, microwave, infrared rays), preferred first liquid is curable.Like this, the first curable liquid can be owing to particular range of wavelengths (for example uv-radiation, blue light, ir radiation) but electromagnetic radiation and curable, thermal curable electrocuring etc.This liquid can solidify owing to the existence of one or more chemical substances such as moisture or air.Preferably, the component composition of selection is gone through a kind of a kind of reaction that responds in the above-mentioned stimulation.

Usually, the first curable liquid comprises one or more monomers and/or oligopolymer, and it can form polymkeric substance, and constitutes first chemical functional group.For example, reaction forms the monomer and/or the oligopolymer of polymkeric substance, and a kind of a kind of initiator of polyreaction that starts in the above-mentioned stimulation of response.For example can comprise that AIBN (2,2 '-Diisopropyl azodicarboxylate) causes the polyreaction of response heat.Usually, the initiator response stimulates the generation free radical.It is possible using response to stimulate and producing cationic initiator.

Preferred monomers and/or oligopolymer are known monomer in the curable field of UV and/or oligopolymer, perhaps are plan other curable ink as the ink jet printing of curable ink.

Delay between preferred deposition and the cure curable liquid is short as far as possible.This reduces the excessively wetting of substrate, and it causes the sharpness of image very low.Preferred deposition and solidify between delay be 20 seconds or still less.

Preferred curable first liquid comprises that some have very high quantity, as four or more, perhaps even the monomer and/or the oligopolymer of six or how crosslinkable functional group.For example, (it is by AKZO Nobel UV Resins to Actilane505, Manchester, reactive four functional polyester origoester acrylates of UK supply) suit, DPHA (six vinylformic acid, two seasons penta 4 ester) also suits, it is by UCB, six functional monomers that Dragenbos, Belgium provide.Together by having the polymer phase ratio that monomer seldom, crosslinkable functionality forms, these crosslinking degrees with the monomer of very high quantity crosslinkable functionality and/or oligopolymer are higher, and provide substrate is had better adhesive power, more solid, firmer film.But too a high proportion of high crosslinkable monomers and/or oligopolymer will form brittle surface.

When activator is also included within first liquid, for example usually it is captured in the basic intravital the first layer by polymer formation.Activator also can be fixed as the part of matrix, for example by comprise activator on the molecule with the reactive group that reacts with monomer or oligomer units.At first, activator can be inert, in case first liquid has formed first solid layer, or the response stimulation, perhaps when contacting, the component with second liquid just will become active.

At this, second solid layer formation chemical reaction is the reaction between metal ion and the reductive agent, thereby forms conductive metal region, and activator can be one or more in metal ion, reductive agent and (choosing wantonly) acid or the alkali.Second liquid will be so to form reaction so that begin the second layer when second liquid contacts with the first layer.When activator comprises metal ion, is generally metal-salt or metal complex when (perhaps also having alkali), second liquid can comprise reductive agent and (optional) acid/alkali.Second liquid also can comprise the additional ions of identical or different metal.When activator comprises reductive agent (perhaps also having acid/alkali), preferred second liquid will comprise metal ion, be generally metal-salt or metal complex.Second liquid also can comprise reductive agent.When activator comprised alkali, second liquid generally included metal ion and reductive agent and optional, also comprises acid/alkali.

At this, first liquid is curable, and preferably it does not comprise volatile vehicle, and this carrier, is evaporated with before the first layer contacts at second liquid in use.Thereby all basically components of this curable first liquid keep (though perhaps being the form of chemical transformation) in first solid layer.

But first liquid can comprise volatile vehicle.Usually, in use, begin with before the first layer contact some of this volatile vehicle or be evaporated or all evaporated at second liquid.For example, first liquid can comprise one or more in water or (preferably) organic solvent, and it before second liquid is with the first layer contact, is evaporated in use.This method can comprise once intermittently, thereby makes that before in applying stimulations (if appropriate) and making second liquid and the first layer contacts one or both, volatile vehicle evaporates.

Preferably by ink jet printing with first liquid deposition in substrate.Preferably by ink jet printing with second liquid deposition on the first layer.When making first liquid and/or resulting the first layer form pattern, second liquid can be according to identical pattern deposition.

Before deposition, component solution can be mixed by stock solution.Just before deposition, can mix.For example, before deposition, unstable components solution can be mixed by the stock solution that comprises the component solution component.More particularly, just before deposition, not only comprise metal ion but also comprise that the component solution of reductive agent can be mixed by the independent stock solution of metal ion and reductive agent.This makes unsettled solution deposition in substrate.

Usually preferred elder generation is deposited on (with the form of metal ion solution, reductive agent or activator solution) in the substrate with the component of reaction, for component, makes it dry, solidifies or sclerosis, thereby form solid layer in substrate.The reaction other component subsequently with deposited in liquid form (with one the step or multistep) on solid layer.

Current preferable methods relates to the initial deposition of activator such as acid chloride, and it is drying, curing or sclerosis on the spot, thereby forms solid layer on substrate surface.Optional with DMAB (dimethylamine borane) processing acid chloride, thus palladium ion is reduced to metallic palladium.Metal ion solution such as copper sulfate, reductive agent such as formaldehyde (regulating pH with alkali) are blended in the single solution easily, it is deposited on the metallic palladium layer.

Preferably, activator is deposited in the substrate with pattern, thereby causes forming the conductive metal region of one or more patternings.Component solution can be deposited on according to identical pattern on the activator, perhaps is more typically in the whole substrate.

Also can be by forming pattern with pattern deposition component solution.When the specific distribution that does not have pattern that activator is deposited on whole substrate was regional, this was suitable especially.

Preferably carry out the pattern deposition by ink jet printing.Preferably with the activator solution ink jet printing.As select or and, one or more component solutions of ink-jet printable.Also can use other for example sputter of deposition technique.

Compare with conventional electroless plating operation, can use ink jet printing provide a kind of faster, have the technology of step still less.Compare with the major equipment that conventional electroless plating operation needs, ink-jet printing apparatus may be more cheap, and compare its easier transportation with the immersion bath that is used for conventional electroless plating operation.Ink jet printing allows the deposition of very careful controlled liq volume, and metal ion that permission will be deposited and the metering of the precise chemical structure of reductive agent cut the waste.For example, when metal ion is a copper sulfate, when reductive agent was formaldehyde, reaction product was sodium sulfate and sodium formiate, and it is easy to processedly fall.Like this, can deposit the metal ion and the reductive agent of stoichiometric amount basically.But, but the preferred excessive reductive agent of deposition rate metal ion, thus consume all basically metal ions, reduce or avoid containing the refuse of metal.Unnecessary reductive agent can be washed off.

Another benefit of ink jet printing is that it is digital sequence of control, allows to use identical device to apply different patterns.For disposable products, tailor-made product, perhaps a series of products that can unique identification, this particularly important that seems.

In addition, ink jet printing is a kind of contactless operation, and this method can be used for frangible substrate.

Use successive or drip (drop-on-demand) ink-jet printing technology as required such as binary or grating continous inkjet and piezoelectricity drips as required or heat is dripped ink-jet technology as required and can be realized ink jet printing.For example the US patent 5,463, and 416 disclose the method that ink-jet printer is dripped in a kind of operation as required.

When using acid or alkali, preferred ink jet printing head comprises stupalith, thereby makes the liquid that contains acid or alkali only contact the stupalith in the ink jet printing head.

Multiple will be by the solution of ink jet printing the time when having, can perhaps then deposit simultaneously or in of short duration extensions by different spray nozzles in the identical ink gun or nozzle in a row by the ink gun that separates.

Metal ion can be the ion of arbitrary conducting metal.Preferred conducting metal comprises copper, nickel, silver, gold, cobalt, platinum metals, perhaps the alloy of two or more in these materials.Conducting metal can comprise non-metallic element, and for example conducting metal can be nickel phosphorus.

Metal ion is generally the form of salt.Copper sulfate for example.As selection, metal ion can be present in complexing agent such as EDTA (ethylenediamine tetraacetic acid (EDTA)) or the prussiate.

Suitable reductive agent example is formaldehyde, glucose or most of other aldehyde, sodium hypophosphite, Glyoxylic acid hydrate, hydrazine or dimethylamine borane.Wen He reductive agent can be used for being easy to the reductive metal ion as gold or silver-colored relatively, is difficult for the reductive metal ion and needs strong reductant.Reductive agent should be too not strong, otherwise metallic particles will be away from substrate surface sporadic nucleation.

Can heat substrate and/or reaction soln, thereby beginning and/or acceleration conducting metal are in suprabasil deposition process.For example, the infrared light from Infrared heaters can incide on the reaction soln.

Suitable substrate comprises sheet of plastic material and fiber.This substrate can be the material that has electric elements thereon, as conduction, semi-conductor, resistance, electric capacity, induction or optical material such as liquid crystal, luminescence polymer or the like.This method can be included in the step of one or more described electric elements of deposition in the substrate, preferably before forming conductive metal region in the resulting substrate, is undertaken by the ink jet printing deposition.

Similarly, this method also can be included in the step that deposits electric device, complex structure device on the resulting conductive metal region.Use ink-jet printing technology also can carry out described another deposition step.

Like this, in making electric product, can be with this method as a stage.It suits to be used in manufacturing especially and relates to the electric equipment products of responsible pattern as in the indicating meter that comprises the complex pattern pixel.Other application comprises makes pole line or the antenna that is used for auto radio, mobile telephone and/or satellite navigation system; Radio-frequency shielding fence; The edge connector, contact and the bus connector that are used for circuit card; RFID tag (RFID label); Be used for the strip conductor of printed circuit board (PCB), it comprises flexible printed circuit board; As comprise the smart fabric of circuit card; Ornament; The vehicle windscreen well heater, the parts of battery and/or fuel cell; Ceramic component; Transmodulator and electric induction power source are in particular for the form of miniaturization; Security device; Printed circuit board component such as electric capacity and inducer; Diaphragm type keyboard, particularly their electrical contact; Accessible low-cost electronic product; Electroluminescent, accessible indicating meter; Biosensor, mechanical pick-up device, chemistry and electrochemical sensor.

Preferred conductive metal region form layers.The component of preferred selective reaction solution, thus make this layer adhere on the substrate surface.Can repeat this method, another kind of metal ion and reductive agent on conductive metal region in the deposit solution, thus form thicker conductive metal layer.Different metal ions can be used for second or the successive layer, thereby construct a kind of material that comprises the layer of multiple different metal.Can construct the product that comprises the multilayer different metal by this way, it comprises such product, and this product is included in alternative layer in two or more different metals.Comprise the component solution of metal ion mixture by deposition, perhaps comprise that by deposition different metal ionic various ingredients solution can construct alloy.

This method is a kind of preferably to be applied as a step or a multistep of making in the RFID tag (RFID).The RFID label can send and/or accept to discern the information that arrives/come from the RFID label detector.This method is applicable to inductance and condenser coupling label, and it can be active (promptly comprising internal electric source) or passive (not comprising internal electric source).Such label generally includes microprocessor (generally including certain storer) and conductive antenna.

Operation A, B or among the C one or more that the present invention extends to below using are made the method for RFID label, also extend to the RFID label of one or more manufacturings among operation A, B below using or the C.

In operation A,, in substrate, form the antenna of conducting metal by the method for first aspect.Preferred this antenna is the concentric ring of conducting metal.This technology is applicable to makes active or passive RFID tags.The present invention also extends to the method by first aspect, by in substrate, forming conductive metal region, and with its structure as pole line, and in substrate, form the method (being used for any application) of pole line.

In process B, with the method for first aspect, by in substrate, forming the zone of two different conducting metals, and by electrolytical mode (can with its ink jet printing) electrolysis connects this two zones, thereby the formation electrochemical cell, in substrate, to form battery.But serial or parallel connection is electrically connected a plurality of electrochemical cells, can obtain voltage and/or electric current thereby increase.The present invention also extends to the method with first aspect, by forming the zone of two different conducting metals in substrate, and connects this two zones by electrolytical mode (can with its ink jet printing) electrolysis, with the method for formation battery.The present invention also extends to the battery that forms by described method.

In operation C, microplate is applied to substrate, use the method for first aspect present invention then, in substrate, form one or more conductive metal regions, thereby be electrically connected to one or more electrical contacts of microplate.The present invention also extends to the method for preparing electronic installation (being not only the EFID label), and it comprises microplate is applied to substrate, then by the method for first aspect present invention, forms the step of one or more conductive metal regions in substrate.The present invention also extends to the electronic installation of preparation by this method.

Preferred this operation comprises measures the microplate position, then according to the position of measured microplate, obtains the step (after microplate being applied to substrate) that is electrically connected thereby form conductive metal region.This has such advantage, and the position that applies microplate can change in certain permission limit, and this limit has reduced cost than big with method known, that microplate is set.

This operation also is included in and applies thereon before the microplate, forms conductive metal region in substrate, thereby is used as the step of the heat absorber (heat sink) of microplate.Also preferred this method is included in and applies before the microplate, deposits the step (perhaps by ink jet printing) of thermally conductive material (being generally heat-conductive bonding agent) on heat absorber.

In above-mentioned operation A, B and C, preferably in substrate, form the zone of conducting metal by ink jet printing.

The method of making the RFID label can comprise the step of ink jet printing substrate, and antenna, battery, heat absorber and/or wafer are deposited in this substrate.

The method of making the RFID label can be included on the sedimentary parts step of the tectum of ink jet printing material or protective layer (as polymer layer).

The method of making the RFID label has the advantage simple with respect to known technology, that cost is low.

One or more component solutions will satisfy the specific needs of ink jet inks aspect viscosity, surface tension, electric conductivity, pH, filtration, size of particles and stability to aging.Wetting agent can be added in one or more component solutions, thereby reduce evaporation.For different ink-jet technologies, the particular value of needed these performances is different, and for concrete application, those skilled in the art are easy to design and satisfy component solution these performances, suitable.

This method also comprises by known metallide technology, and other electrolytic etching of metal is electroplated onto step on the conductive metal region.This method also comprises by known electroless plating and immerses operation, with other the step of metal deposition to the conductive metal region.

As selection, can in substrate, form the conducting metal of q.s, it does not need further the step that immerses other metal of operation plating by known electrolysis or electroless plating.

According to a second aspect of the invention, provide a kind of workpiece that comprises substrate, described substrate comprises the conductive metal region according to the method preparation of first embodiment.

Preferred conductive metal region is a layer.

According to a third aspect of the invention we, provide the reaction between a kind of activated metal ion and the reductive agent, thereby form the method for conductive metal region, it comprises that the organic acid salt with transition metal is used as activator.

The organic acid salt of many transition metal has good solvent solubility, be easy to by the ink-jet technology printing, and exsiccant is very fast, thereby very high printing quality and good marginal sharpness are provided.The organic acid salt of preferred transition metal is an acid chloride, and it has above-mentioned performance, and also has the advantage of can reasonable price making a big purchase in large quantities.Surrogate comprises propionic acid palladium, butyric acid palladium etc., perhaps transition metal other alkanoate of palladium particularly.

During use, by the method for first aspect, the organic acid salt of transition metal is reduced to metallic particles or metal level, it is catalytic deposition metal (being preferably different metals) thereon.

Preferably use the polymer deposition activator, thereby catalyzer is adhered in the substrate.

Preferably activator is added in the substrate, and conductive metal region is formed in the substrate as layer.

Also preferably contain the solution of activator, activator is added in the substrate by ink jet printing.

The detailed description of example embodiment

Activator solution below the preparation:

Activator solution

Weight %

Acid chloride 2.0

Pyranton 47.7

Methoxypropanol 47.7

Polyvinyl butyral acetal 1.6

Potassium hydroxide 1.0

Acid chloride exists as activator.Before adding following reaction soln, thereby mix Pyranton and methoxypropanol to obtain a kind of ratio that enough makes acid chloride adhere to suprabasil solvent soon of evaporating.But the speed of evaporation is enough slow, so that this activator solution of ink jet printing easily.The having of polyvinyl butyral acetal helps catalyzer and adheres in the substrate.Polyvinyl butyral acetal with molecular weight between 15,000 and 25,000 suits, as the gradeBN18 that can buy from Wacker.Potassium hydroxide exists as alkali, activates reductive agent described below.

In order to prepare top activator solution, by weight, the polyvinyl butyral acetal solution of preparation 30% in 50/50 mixture of Pyranton and methoxypropanol.In identical solvent mixture, use supersound process to reach 2-3 hour and prepare 3% acid chloride solution.In addition, in identical solvent mixture, the potassium hydroxide solution of preparation 10%.Then these three kinds of solution are mixed, add how identical solvent mixture, thereby the suitable cumulative volume of preparation obtains aforementioned proportion.Resulting liquid is palm fibre-orange, translucent liquid, then with its by can buy from Whatman, 1 micron GF-B glass fibre filters.On filter paper, can see slight deposition sometimes.

The activator solution that is obtained has the viscosity of 3.91cPs and the surface tension of 31.5dynes/cm.

Also prepare following three kinds of component solutions:

Solution A

Weight %

Copper sulfate 1.63

Sodium sulfate 3.21

EDTA, disodium salt 0.60

Water 89.56

The trimethyl carbinol 5.00

Copper sulfate is metal ion, is Cu at this ²⁺, the source.The existence of sodium sulfate is in order to stablize copper sulfate.EDTA is a kind of complexing agent, and it forms protectiveness around cupric ion barrier does not have EDTA, and the solution of this composition will precipitate immediately separates out.The trimethyl carbinol is a kind of cosolvent, and it reduces surface tension and improves degree of wetting.

Solution B

Weight %

Formaldehyde solution (by weight, in water 37%) 0.22

Sodium formiate 3.71

Water 91.07

The trimethyl carbinol 5.00

Formaldehyde exists as reductive agent.

Solution C

Weight %

Sodium hydroxide 1.74

Water 93.26

The trimethyl carbinol 5.00

The function of sodium hydroxide is when solution mixes, the activating and reducing agent.

Agitation of solutions A, B and C are then by filtering from 1 micron the GF-B glass fibre that Whatman buys.Each solution all has the viscosity less than 3cPs.

Deposition

At first, by ink jet printing deposition activator.XJ128-200 print head with activator solution perfusion Xaar is ejected into activator solution in the substrate with it then.Regulate resolution down web to adapt to specific substrate.For wetting easily substrate, use 250 point/inches (dpi).For wetting inconvenient substrate, thereby use 100dpi to guarantee complete wetting.

The XJ128-200 print head penetrates the drop of 80pL.The ink-jet frequency is used the jet length of 1-2mm between 1-2KHz.

With the activator ink jet printing is multiple pattern such as solid block, fine rule, yarn fabric, tartan design, standard ink jet inks printing test pattern.

After spraying activator solution, the Infrared heaters that use is arranged on directly over the substrate is come the activator solution of dry printing.In some tests, do not use any extra heating, make the catalyst solution of printing dry under atmospheric condition.

When using Infrared heaters, find 30 seconds be enough time of drying.

Then, with three kinds of independent component solution A, B and C ink jet printing on the exsiccant activator.Respectively these three kinds of solution are printed onto on the position identical in the substrate with identical volume, and cross the whole printable zone of substrate equably, thereby form reaction soln on the spot.Use can come this solution of ink jet printing from the 64ID3 print head that Ink Jet Technology buys.Contact is pottery with all parts of this print head of injected liquid, so this head is specially adapted to print strong basicity or tart liquid.When 5KHz, spray.Selection is applied to the potential waveform of piezoelectricity print head, thereby causes penetrating the drop of 137PL.

From the teeth outwards, make the activator reduction form the palladium particle, its catalysis is the formation of copper metallic region thereon.In case copper begins deposition, this reaction is autocatalytic.

Make that reaction soln keeps contacting with substrate, up to depositing suitable copper thickness.Usually, at room temperature, need be less than preparing suitable copper layer in 5 minutes.

Find, by using the infrared radiation heating substrate, can very fast low formation copper zone.But,,, guarantee that it is important that surface temperature is not elevated to more than 50 degrees centigrade for avoiding substrate deformation for the plastic-substrates of many types.

At last, any too much solution or the salt of exsiccation are wiped or washed off from substrate, obtain copper-plated samples, at this, copper facing zone is corresponding with pattern, wherein ink jet printing activator.

The result

By this technology, in copper ink jet printing substrate below, the adhesion strength between sedimentary conductive metal region of observational measurement and the substrate.

The base material adhesive power

Vinylformic acid is good

Polystyrene is good

Polyethylene according to rank from the difference to good

The delrin polyacetal homopolymer is poor

Hostaform or Ultraform Copolyacetal are poor

ABS (acrylonitrile-butadiene-styrene (ABS)) is good

U-PVC is good

Silicon rubber is poor

(Delrin is the trade mark of DuPont.Hostaform is the trade mark of Hoechst.Ultraform is the trade mark of BASF)

As a result of, the printing of conductive metal region that we are verified, this conductive metal region has the specific conductivity near the reguline metal specific conductivity.

Depend on employed concrete chemical process, the metal level between the verified 0.3-3 micron.Repeating print to be used to construct thicker layer, as the layer of the needed 15-20 micron of pole line/antenna applications.

Embodiment with 2 component solutions

In this embodiment, the component solution that is called as solution A B had both comprised metal ion, comprised reductive agent again.

Solution A B

Weight %

Copper sulfate 1.63

Sodium sulfate 3.21

EDTA, disodium salt 0.60

Formaldehyde solution (by weight, in water 37%) 0.22

Sodium formiate 3.71

Water 85.63

The trimethyl carbinol 5.00

By 1 micron the GF-B glass fibre filtering solution AB that can buy from Whatman.

Equally deposit with the front, begin with the ink jet printing of catalyst solution, time-delay subsequently for a moment, the activator solution solvent evaporation.Then, use the 64ID3 ink jet printing head, with isopyknic solution A B and solution C ink jet printing on the surface of substrate.

The same with the front, in substrate, form the conductive copper zone.

Embodiment with 1 component solution

Select the single solution that preparation is following as another kind.It can stablize several hrs, so can be with it as the ink jet printing of single component solution.

Weight %

Enplate872A 24.09

Enplate872B 24.09

Enplate872C 8.03

Water 13.29

Ethylene glycol 20

The trimethyl carbinol 5

Surfadone?LP-100 0.5

PEG-1500 5

Above-mentioned solution is by its component preparation, then by filtering from 1 micron the GF-B glass fibre that Whatman buys.Viscosity is 9.8cPs, and surface tension is 30.0dynes/cm.

Enplate872A sulfur acid copper.Enplate872B contains prussiate complexing agent and formaldehyde.Enplate872C contains sodium hydroxide.(Enplate is a kind of trade mark).Enplate872A, B and C can buy from Enthone-OMI, are generally used for the component solution of electroless copper.Ethylene glycol exists as wetting agent, and the effect of landing low surface tension.The trimethyl carbinol is for reducing the cosolvent of surface tension and increase degree of wetting.Surfadone LP-100 is the wetting agent with surfactant performance.PEG-1500 is as wetting agent.

With above-mentioned catalyst solution according to the pattern ink jet printing.At of short duration time-out (30 seconds) afterwards, make and solvent evaporation in the activator solution, perhaps run through the whole printable zone of substrate, perhaps, deposit above-mentioned solution on the regional top of ink jet printing activator solution by ink jet printing.Like this, the copper layer is formed on the surface of substrate according to pattern.

Substitute activator solution

Can be with the surrogate of following activator solution as the activator solution that provides among the top embodiment.

Weight %

Acid chloride 2.0

Pyranton 47.5

Methoxypropanol 47.5

Polyvinyl butyral acetal 1.6

Polyvinylpyrrolidone 1.4

This activator solution has the viscosity of 3.85cPs, the surface tension of 30.5dynes/cm.

The polyvinylpyrrolidone of K30 level derives from International SpecialityProducts.This polymkeric substance has the molecular weight between 60,000 and 70,000, and is found the formation of quickening conductive metal region, but with using polyvinyl butyral acetal to compare, brings less repeatably result.

Claims (62)

1. method that in substrate, forms conductive metal region, be included in metal refining solion in the substrate, in substrate, deposit reductant solution,, thereby in substrate, form conductive metal region in reaction soln so that metal ion and reductive agent one react.

2. according to the process of claim 1 wherein that the conducting metal that forms is formed in the whole or most of metals that form conductive metal region in the finished product in substrate.

3. according to the method for claim 1 or claim 2, wherein pH change agent also is deposited in the substrate, thus the activating and reducing agent.

4. according to method arbitrary in the aforementioned claim, the composition of selective reaction solution wherein, so that it is enough unstable, make GOLD FROM PLATING SOLUTION belong to the spontaneous generation of reaction between ion and the reductive agent in substrate, to form conductive metal region, but not unstable, but at the fine powder of the spontaneous formation conducting metal of entire reaction solution in substrate, not forming conductive metal region.

5. according to method arbitrary in the aforementioned claim, wherein the solution of metal ion solution and reductive agent is stored in the multiple isolating component solution.

6. according to the method for claim 5, wherein various ingredients solution deposits according to the order of sequence.

7. according to the method for claim 5 or claim 6, wherein, before one or more other component solution deposits therein, allow built-up section or complete drying, curing or the sclerosis of single solution or solution.

8. according to method arbitrary in the aforementioned claim, wherein GOLD FROM PLATING SOLUTION belongs to reaction between ion and the reductive agent, form conductive metal region in substrate and activates by activator.

9. method according to Claim 8, wherein activator is second conducting metal that is different from first metal.

10. method according to Claim 8, wherein ion and the reductive agent by deposition second metal in substrate forms second metal, so that second metal ion and reductive agent one react in reaction soln, thereby forms conductive metal region from the teeth outwards.

11. arbitrary method according to Claim 8-10 wherein is applied to activator in the substrate.

12. arbitrary method according to Claim 8-11, wherein activator is a catalyzer.

13. according to being subordinated to claim 5 or being subordinated to the method for claim 8-12 of arbitrary claim of claim 5, when depending on that claim 5 or arbitrary claim depend at that time, wherein metal ion, reductive agent and pH change agent are stored in three kinds of different component solutions, it mixes in substrate, and forms reaction soln.

14. according to being subordinated to claim 5 or being subordinated to the method for claim 8-12 of arbitrary claim of claim 5, wherein metal ion and reductive agent are stored in first component solution, pH changes agent and is stored in second component solution, so that first and second component solutions mix, and form reaction soln in substrate.

15. according to being subordinated to claim 5 or being subordinated to the method for claim 8-12 of arbitrary claim of claim 5, wherein metal ion, reductive agent and pH change agent and are stored in the single solution.

16. arbitrary method according to Claim 8-15, wherein this method is included in before the deposition component solution, the step of deposited catalyst in substrate.

17. according to the method for claim 16, wherein arbitrary or before both are deposited in the substrate in metal ion or reductive agent, the deposition activator.

18. arbitrary method according to Claim 8-17, wherein activator is stored in the activator solution.

19. according to the method for claim 18, the solvent that wherein is used for activator solution basically or anhydrous fully.

20., wherein before one or more component solutions of deposition, solvent is evaporated or dissipation basically according to the method for claim 18 or claim 19.

21. according to method arbitrary among the claim 18-20, wherein activator is stored in to contain and promotes that activator adheres in the solution of suprabasil chemical composition.

22. arbitrary method according to Claim 8-21, wherein activator is the organic acid salt of transition metal.

23. according to method arbitrary among the claim 18-22, wherein activator is stored in the solvent through selecting, makes activator can permeate substrate and improves the adhesive power of resulting conductive metal region and substrate thereby this solvent is partly dissolved substrate.

24., wherein depositing activator with before improving adhesive power, the pre-treatment substrate according to the method for claim 23.

25. according to method arbitrary among the claim 18-24, wherein activator solution comprises that metal ion, reductive agent or pH change one or more in the agent.

26., also comprise complexing agent comprising the component solution of metal ion according to method arbitrary among the claim 5-25.

27. arbitrary method according to Claim 8-26, wherein activator is deposited in the substrate with pattern, thereby causes forming the conductive metal region of one or more patternings.

28. according to the method for claim 27, wherein on activator, one or more component solutions are with identical pattern deposition.

29. according to method arbitrary among the claim 5-28, wherein by forming pattern with pattern deposition component solution.

30., wherein carry out deposition with pattern by ink jet printing according to method arbitrary in the aforementioned claim.

31. according to the method for claim 30, wherein with activator solution and one or more component solution ink jet printings.

32., wherein deposit the metal ion and the reductive agent of stoichiometry basically according to the method for claim 31.

33., wherein with respect to metal ion, deposit excessive reductive agent, so that consume whole basically metal ions according to the method for claim 31.

34. according to method arbitrary among the claim 30-35, wherein reaction soln or component solution comprise acid or alkali, wherein ink jet printing head comprises stupalith, only contacts stupalith in the ink jet printing head so that contain the liquid of acid or alkali.

35. according to method arbitrary in the aforementioned claim, wherein conducting metal is selected from copper, nickel, silver, gold, cobalt, platinum metals, perhaps two or more alloy in these materials.

36. according to method arbitrary among the claim 1-34, wherein conducting metal comprises non-metallic element.

37. according to method arbitrary in the aforementioned claim, wherein metal ion is the form of salt.

38. according to method arbitrary among the claim 1-37, wherein metal ion is present in the complex compound.

39. according to method arbitrary in the aforementioned claim, wherein deposit the metal ion of multiple metal, thereby form the conductive metal alloy zone.

40. according to method arbitrary in the aforementioned claim, wherein heat substrate and/or reaction soln, thereby beginning and/or acceleration conducting metal are in suprabasil deposition process.

41. according to method arbitrary in the aforementioned claim, wherein substrate is for having the material of electric device thereon.

42. the method according to claim 41 comprises: before forming conductive metal region in the resulting substrate, one or more described electric devices are deposited on suprabasil step.

43., comprise that another is deposited on electric device on the resulting conductive metal region, thereby the step of complex structure device according to method arbitrary in the aforementioned claim.

44., wherein repeat this method, another metal ion and reductive agent in the solution are deposited on conductive metal region, thereby form thicker conductive metal layer according to method arbitrary in the aforementioned claim.

45., wherein different metal ions is used for second or the successive layer, thereby constructs a kind of material that comprises multiple different metal layer according to the method for claim 44.

46. according to method arbitrary in the aforementioned claim, wherein the solution deposition that will comprise the metal ion mixture perhaps will comprise different metal ionic various ingredients solution deposition in substrate in substrate, to form alloy.

47. according to method arbitrary in the aforementioned claim, wherein at first the component of reaction is deposited in the substrate, dry, solidify or sclerosis, thus in substrate, form solid layer, subsequently one or more other component fluids is deposited on this solid layer.

48. according to the method for claim 47, wherein at first activator is deposited in the substrate, drying, curing or sclerosis are to form solid layer.

49. according to the method for claim 48, wherein, preferably mix, be deposited on the solid layer that comprises activator subsequently with reductant solution and metal ion solution.

50. a method of making RFID tag wherein by the method for arbitrary aforementioned claim, is deposited on conductive metal region in the substrate.Operation A, B or among the C one or more that the present invention extends to below using are made the method for RFID label, also extend to operation A, B below using or the RFID label of one or more manufacturings among the C.

51. according to the method for claim 50, wherein conductive metal region comprises antenna.

52. method according to claim 50 or 51, wherein use method arbitrary among the claim 1-46, by in substrate, forming two different conductive metal regions, and connect this two zones by electrolytical mode electrolysis, thereby the formation electrochemical cell forms battery in substrate.

53., wherein come arbitrary in the conductive metal deposition or both by ink jet printing metal ion and reductive agent according to the method for claim 52.

54., wherein come deposition electrolyte by ink jet printing according to the method for claim 52 or claim 53.

55. according to method arbitrary among the claim 50-54, wherein conductive metal region comprises one or more electrical contacts of microplate.

56. goods that comprise substrate, this substrate comprise the conductive metal region according to method preparation arbitrary among the claim 1-55.

57. the reaction between catalytic metal ion and the reductive agent, thus the method for conductive metal region formed, and this method comprises that organic acid salt with transition metal is as catalyzer.

58. according to the method for claim 57, wherein transition metal is a palladium.

59. according to the method for claim 57 or 58, wherein organic acid salt is acetate, propionic salt or butyrates.

60. according to method arbitrary among the claim 57-59, wherein catalyzer deposits together with polymkeric substance, thereby catalyzer is adhered in the substrate.

61. the method according to arbitrary among the claim 57-60 wherein is applied to catalyzer in the substrate, and conductive metal region is formed in the substrate as layer.

62. according to method arbitrary among the claim 57-61, wherein the solution that contains catalyzer by ink jet printing adds catalyzer in the substrate to.