CN1914353A - Formation of layers on substrates - Google Patents

Abstract

Disclosed is a method of forming, on the surface of a substrate, a first layer which is suitable for activating a second solid-layer-forming chemical reaction thereon, the method comprising the steps of bringing into contact with the substrate a first liquid which forms a first solid layer thereon, the first liquid comprising an activator for the second solid-layer-forming chemical reaction, characterised in that the first liquid is selected so that the first solid layer adheres to the substrate and is permeable to a second liquid that comprises one or more reagents for the second solid-layer-forming chemical reaction. A second solid layer can then be formed on the substrate by bringing into contact with the first solid layer a second liquid comprising one or more reagents for the second solid-layer-forming reaction.

Description

The formation of layers on substrates

Technical field

The present invention relates on base material, form solid layer, especially, but be not limited to, on base material, form conductive metal region by reduction of metal ion.In this manual, the adjective solid about solid layer or solid substrate the time, is meant that material is in solid phase.Solid layer or base material can be plasticity, elastic, resilience, inflexible, gelatinous, permeable or have any other performance that meets the solid phase.

Background technology

Conductive metal region on the base material especially can form the method for conductive metal region according to pattern, and many industrial application are arranged.An important application is to make printed circuit board (PCB), at this moment will make metal level form pattern, to be electrically connected different parts and electric installation according to predetermined layout.Other application comprises that antenna, the radio frequency of antenna such as mobile telephone discriminate electrode, intelligent textile and the decoration parts of the contact array of the contact of equipment (RFID), smart card, battery and power supply, plane screen technology (liquid-crystal display, luminescence polymer indicating meter etc.), biology and electrochemical sensor.

During these are used at great majority, metal area must be conduction and preferably or, necessary in some cases, be high conductivity.

Known with the metal ion reduction method and on matrix, formed conductive metal region.This is the basis of so-called " electrodeless " electrochemical plating, and wherein painting catalyst on base material is immersed in a series of baths then.Wherein there is a bath to comprise the alkali (sodium hydroxide) of metal ion (for example mantoquita), reductive agent (for example formaldehyde) and activation formaldehyde.Metal ion is reduced into conductive metal region in the place that substrate surface has scribbled catalyzer.

In our International Patent Application PCT/GB2004/000358 (WO 2004/068389), we have proposed another kind of infusion method, wherein will be deposited on metal ion and reductive agent together on the base material, preferably use ink jet printing method, and reaction in, form conductive metal region.

In immersion and these two kinds of technology of deposition-based metallization, importantly guarantee to form conducting metal, rather than in solution, form fine metal particle in the place that substrate surface is wanted.In case formed fine metal particle in the solution of metal ion and reductive agent, they will expand rapidly, and metal will fall down and do not stick on the base material.Prepare and to be deposited on needed place and to keep quite difficulty of stable metallization solution.

Painting catalyst or can activated metal during any other material of technology on base material will make the solution metal ion deposition on catalyzer or activator.But, only when activator is bonded on the base material, could play a role effectively; Otherwise, can form fine metal particle or metalation may not take place.

Improvement material and the adhesive a kind of currently known methods of base material are to deposit binding agent and activated material (this paper is referred to as activator) from the teeth outwards, thereby activator is stayed on the surface in printing technology.But, do like this and the binding agent that is not metallized solution is blocked the passage that leads to catalyzer and is difficult to.

Another terms of settlement is that deposition contains the catalyzer of the aggressiveness solvent of dissolving or permeable base substrate, makes activator enter base material.This point is particularly useful to the base material of the impermeable metallization solution of script.But, be difficult to make the metal level of gained to realize good tackiness simultaneously and react with activated metal near activator easily.

US 5751325 is disclosed in the ink jet printing method that forms the high-density image on the base material, wherein will provide to base material to contain permeable films therefrom-formation binding agent, as polyacrylic acid or Polyvinylpyrolidone (PVP); The reductive agent and/or the nuclear that develops are as the printing ink-receiving layer of silver sulfide-nickelous sulfide.Can be to this printing ink-receiving layer the printing ink ink jet printing of the aqueous solution that contains reducible metal salt such as silver salt.

WO 03/021004 is disclosed in the method that forms film porous ceramics-metal composite on the base material, is particularly useful for catalyzer and gas sensor.In one embodiment, the preparation method who is coated with the polyimide plate of nickel by pattern is with propionic acid zirconium, 2 ethyl hexanoic acid aluminium and acid chloride this plate of solution spin coating in tetrahydrofuran (THF), allows solvent evaporates then, forms the layer that contains palladium zirconium white/aluminum oxide.The method of ceramic layer patterning is the UV light that is exposed to by photomask, cleans in the acetone/isopropanol mixture then, to remove the unexposed portion in the coating.350 ℃ of base materials of handling these patternings 2 minutes, make it then to cool down.The method of nickel plating is to be immersed in the electrodeless electroplate liquid.

WO 2004/068918 relates on printed circuit board (PCB) and to form thin silver layer to reduce the loss of skin effect as far as possible.Coated polymeric polyimide particularly on the dielectric substance base material of printed circuit board (PCB), and then coating contains the propionic acid zirconium, preferably also has the solution of acid chloride.This base material of heating formed silver layer thereon by being immersed in the electrodeless silver-colored plating liquor then with dry this coating at least 20 minutes under at least 120 ℃ temperature.

Summary of the invention

According to the present invention, be provided at the method that substrate surface forms the first layer, described the first layer is suitable for activating the chemical reaction of formation second solid layer thereon, this method comprises the following step: allow first liquid contact with base material, make first liquid on base material, form first solid layer, first liquid comprises the activator that activates second solid-layer-formation chemical reaction, it is characterized in that, the selection of first liquid will make first solid layer be bonded on the base material and permeable second liquid, and second liquid comprises one or more reagent for the chemical reaction that forms second solid layer.

The present invention also expands to the method that forms material layer on base material, this method comprises the following step: allow first liquid contact with base material, make first liquid on base material, form first solid layer, first liquid comprises for the activator that forms the reaction of described layers of solid material on base material, and allow first solid layer contact with second liquid, second liquid comprises one or more reagent that confession (second) solid layer forms reaction, wherein the selection of first liquid will make first solid layer be bonded on the base material and permeable second liquid, thereby make second liquid advance first solid layer thoroughly, one or more reagent that second solid layer is formed in the reaction contact with activator, generate (second) layers of solid material with reaction.

According to the present invention, be provided at the method that substrate surface forms first solid layer, first solid layer can activate the chemical reaction that forms second solid layer thereon, this method comprises allows the first liquid contact substrate surface, be bonded in described first solid layer of substrate surface with formation, first liquid and the first layer comprise the activator for described chemical reaction, and permeable second liquid of first solid layer, second liquid comprises one or more reagent for the chemical reaction that forms second solid layer, and wherein the first layer comprises first chemical functionality who is insoluble to second liquid to small part.

Present method is included in easily and forms second solid layer on first solid layer.Therefore this method preferably also comprises and allows second liquid contact first solid layer, to form second solid layer.Second liquid infiltration or advance the first layer thoroughly makes second liquid near to or in contact with activator, generates second solid layer with reaction.

Therefore, in preferred inventive point of the present invention, be provided at the method that substrate surface forms the first and second superimposed layers of solid material, this method comprises allows first liquid contact with substrate surface, be bonded in first solid layer of substrate surface with formation, first liquid and the first layer comprise the activator for the reaction that forms second solid layer, and allow second liquid contact first solid layer, second liquid comprises one or more reagent that generate second solid layer for reaction, permeable second liquid of the first layer wherein, therefore the second liquid porous or see through the first layer, make one or more reagent in described second liquid react the activator that generates second solid layer, and wherein the first layer comprise first chemical functionality who is insoluble to second liquid to small part near to or in contact with confession on the first layer.

In the method for the invention, the method that activator is bonded on the base material is that it is included in (no matter by parcel, fixing or other method) in first solid layer.

When allowing second liquid contact with first solid layer, second liquid sees through first solid layer, thereby makes second liquid can be near the activator in first solid layer.Therefore second solid-layer-formation reaction can take place on substrate surface or near substrate surface, thereby form the second desired layers of solid material on base material.Further, second liquid advances first solid layer thoroughly and can cause second layers of solid material and first solid layer to interweave mutually, thereby improves the tackiness of second layers of solid material and base material by agglutinating first solid layer.

Second layers of solid material should be a conductive metal layer, can be used in the multiple different methods that comprises activator in the first layer and form.These class methods generally all relate to reduction of metal ion, also comprise electrodeless plating, disclosed method as previously mentioned and among the WO 2004/068389.

Because activator is positioned at the layer of substrate surface, second reaction, promptly metallization will preferably occur on the first layer or in the first layer, rather than, for example, in second liquid, form the reaction of metal fine.

Second liquid can be single component or polycomponent form, and they can simultaneously or successively be applied on first solid layer.

The first layer not necessarily directly is bonded in matrix surface: one or more layers media layer can be arranged.And the second layer is not necessarily outermost top layer or final layer also: can also form one or more layers other layer thereon.

Because the first layer comprises first chemical functionality who is insoluble to second liquid to small part, when the second layer contacted and form second solid layer with the first layer, the first layer kept its physical integrity.Its result has just improved the tackiness of second solid layer and substrate surface.First chemical functionality not necessarily is insoluble to second liquid fully, and can reach above-mentioned effect as long as quite just do not dissolve.Therefore, first chemical functionality only need quite be insoluble to second liquid just can keep the first layer when forming second solid layer globality.

Another effect of first chemical functionality is that the first layer is bonded on the base material, so it will be selected according to base material.Tackiness can be improved by chemical bonding, physical bond, mechanics combination or their mixing mechanism.

Preferred second liquid is aqueous, as being discussed below, so preferred first chemical functionality is water insoluble to small part.First chemical functionality can be present in first liquid, also in the first layer, maybe can pass through, for example crosslinked, is formed in the first layer by the intravital reactant of first liquid (promptly may be dissolved in second liquid).Preferred first chemical functionality's right and wrong pottery.Be to improve the tackiness with many organic substrates such as plastic basis material, preferred first chemical functionality is most of at least or be organic and/or silica-based all, comprises the organic and/or silicon materials of at least 50 weight %.First chemical functionality can absorb second liquid and swelling.First chemical functionality who is suitable for comprises polyvinyl butyral acetal (PVB), and the component that it can be used as first liquid is comprised.This make it and comprise plastic basis material such as many base materials of polyester between all have good tackiness.First chemical functionality also can be made of the reaction product of intravital one or more curable monomers of first liquid and/or oligopolymer, for example, as discussed below, comprise Actilane 505 (reactive four functionality polyester acrylic ester oligomer-Actilane are trade marks), DPHA (dipentaerythritol acrylate) and DPGDA (dipropylene glycol diacrylate).This class material can be included in first liquid and at the first layer internal reaction and become to have suitable deliquescent polymkeric substance.This polymer product and many base materials comprise metal, glass, pottery and plastics, all have good tackiness.Therefore, first liquid is included in one or more components that constitute or form first chemical functionality in the first layer.

First liquid generally is the solution form, non-aqueous solution preferably as previously mentioned, but also can be suspensoid or the dispersion form that contains one or more solids or colloidal form component.First liquid comprises solvent or carrier fluid, preferably is non-water.Preferred on-aqueous liquid is discussed below.

Second liquid can be the solution form, the aqueous solution preferably as previously mentioned, but also can be suspensoid or the dispersion form that contains one or more solids or colloidal form component.Second liquid comprises solvent or carrier fluid, and is preferably moisture.

Therefore, preferred first and second liquid comprise different solvents or carrier fluid.

Preferred active agent is a catalyzer, as the palladium of catalytic metal reaction.But activator also can comprise and can activate second solid layer and form chemical reaction but can be consumed or react in this process thereby be not the chemical substance of catalyzer strictly speaking.

Chemical reaction causes forming second solid layer on first solid layer one or more reagent can take place thereby activator also can comprise when contacting with second liquid.

Activator can the precursor forms coating.In this case, present method can comprise another step that one or more precursor agents is chemically converted to activity or catalysis form.For example, the reductant solution in-situ reducing that acid chloride can be coated with subsequently becomes metallic palladium, and the latter can deposit thereon by catalytic metal when being coated with the second suitable liquid.

Preferred the first layer comprise to small part dissolve in or swellable in second chemical functionality of second liquid or permeable second liquid.Second liquid is preferably aqueous, as previously mentioned, so second chemical functionality preferably to small part dissolve in or swellable in water or water permeable.Second chemical functionality can be present in first liquid, also in the first layer, or can be formed in the first layer by the intravital reactant of first liquid.The second suitable chemical functionality is discussed below, and comprises Polyvinylpyrolidone (PVP) (PVP), its water soluble, and be included in wherein as the component of first liquid.The near small part of second chemical functionality is dissolved in or swells in or permeable second liquid, thereby allows liquid solvent to advance first solid layer and contact activation agent thoroughly.First chemical functionality keeps enough globalities to be bonded on the base material and second solid layer, causes " spongy " structure.

First and second chemical functionalities can be the discrete molecule or the group of molecule, also can be or become the part of same molecular.Generally speaking, they are two kinds of discrete binding agents.

First liquid preferably includes has enough rodent solvent so that first liquid can advance wherein thoroughly to base material, thereby improves the tackiness of first solid layer and base material, and therefore also improves the tackiness (by first solid layer) of second solid layer and base material.

First liquid can be curable, as discussed below.

Preferred first and second liquid are based on different solvents, as previously mentioned.This permission will be suitable for the formation of the first layer and the bonding of the first layer and base material to first choice of Solvent, and will be suitable for the formation of the second layer to second choice of Solvent.Preferred second solvent is a water.Also preferably first choice of Solvent is wanted and can be partially soluble in or penetrate into base material, as previously mentioned, thus the tackiness of raising the first layer and base material.Therefore, moisture metallization chemistry and non-water first solvent can be used in the different step of Same Way.Preferred first solvent is part or all of non-water.First liquid is curable, as discussed below.

First chemical functionality can be water-fast polyvinyl butyral acetal (PVB) easily.Whenever first chemical functionality is the binding agent polyvinyl butyral acetal and second chemical functionality when being the binding agent Polyvinylpyrolidone (PVP), be easy to determine two kinds of binding agents in first liquid suitable relative content to meet the demands.

As previously mentioned, first liquid can be included in constitute in the first layer or form dissolve in or swellable in one or more components of second chemical functionality of second liquid.A kind of preferred second chemical functionality is water-soluble Polyvinylpyrolidone (PVP) (PVP).The component that PVP can be used as first liquid is included in wherein.Other selection of second chemical functionality comprises polyacrylic acid, polyvinyl acetate, polymine, polyethylene oxide, polyoxyethylene glycol, gelatin or their multipolymer.When second liquid was contacted with first solid layer, soluble constituent will dissolve.For example, Polyvinylpyrolidone (PVP) will dissolve when the aqueous solution with metal ion that can be used to formation conductive metal region on first solid layer and reductive agent contacts.Utilize the Polyvinylpyrolidone (PVP) of maximum about 50 weight % in the gained solid the first layer to obtain good result, suitable consumption depends on other related chemistry, especially first chemical functionality's character.For curable first liquid to be discussed below, first solid layer should comprise about 5 weight %PVP.

Second chemical functionality also can comprise water swellable monomer and/or oligopolymer such as HEMA (methacrylic acid 2-hydroxyl ethyl ester), GMA (glycidyl methacrylate) and NVP (N-vinyl pyrrolidone).Also can with this in the solvent of second liquid swellable or when polymerization other monomer and/or the oligopolymer of swellable.This makes second liquid can advance first solid layer thoroughly, thereby ratio second liquid has higher tackiness when existing only in first solid layer surface and allows approaching more activator.

Second chemical functionality also can comprise and the mixable high boiling solvent of the solvent of second liquid.For example, when second liquid is the aqueous solution, can use NMP (N-Methyl pyrrolidone).This can keep the opening of resulting polymers matrix in first solid layer, makes second liquid can enter and improve the tackiness of second solid layer and first solid layer thoroughly.

First liquid also can comprise little-hole particle-hole membrane structure little to produce.Little-hole particle can be organically (to gather (Polyvinylpyrolidone (PVP)) as PPVP) or inorganic (as silicon-dioxide).

First liquid can solidify because of the volatilization of first solvent or because of curing.

First solid layer can be coated with the most of or whole of whole substrate surface.Perhaps, first solid layer can be formed on the base material according to required pattern.This can realize with several method.For example, can allow first liquid deposit according to pattern, method is especially used ink jet printing method as by required pattern printing.Perhaps, first solid layer can be made pattern again after first liquid has deposited; For example, can carry out selective sclerosing (for example, using mask technique) according to pattern then, and then remove uncured liquid first liquid all over being coated on the base material.

Therefore, if use first liquid harden into first solid layer can make patterning reach activator as keeping soft and flowable liquid deposition impossible degree on base material the time.

First liquid can be with various technology all over being coated in substrate surface, comprise with printing, dip-coating, spraying and spin coating technique, as jet printing, ink jet printing, spin coating, dip-coating, spraying, aerosol sprays and ozone, roller coat, curtain be coated with, silk screen printing, lithography, flexographic printing, intaglio printing and intaglio plate bat printing, or with any other liquid coating technique.First liquid preferably is coated with as single liquid, for example uses the ink jet printing from the single liquid storehouse.

Preferably use sedimentation, for example, print process makes first liquid contact with base material.The preferred deposition method is non-contact process, and is preferably digital, as ink jet printing.

Generally speaking, printing quality and tackiness mainly are controlled by the performance of the first layer of first liquid and formation thereof.Therefore, to a certain extent, the present invention allows the first layer to select and the second layer will be selected according to the required performance of second layers of solid material according to required pattern quality.This can allow to have greater flexibility when designing the first and second suitable aqueous chemicals for application-specific.

Present method can repeat (randomly using the first and second different liquid) to constitute multilayered structure.

Preferred first liquid is curable; That is to say, can experience because of liquid hardening the chemical transformation that preferred consolidation took place.

Use the first curable liquid can make selected this liquid to better than second liquid of the wettability of one or more matrixes.So just can such as fruit from second liquid phase with curable first liquid of carrier fluid (as water) coating the time more accurate patterns is arranged, also have finer feature and better sharpness of border degree.If compare when with different technology activator being applied to the surface with the relatively poor carrier fluid of wetting property, the scared situation in the hemorrhage and edge of curable first liquid is generally less.The raising of wettability allows more accurate patterns because along a line in abutting connection with drop can be bigger spacing deposition (with the technology of ink jet printing and so on), thereby can make narrower line and thinner feature with the liquid of less volume.Use curable first liquid can also make the tackiness of first solid layer and substrate surface better.

Every in hope with ink jet printing with digital when on base material, making pattern, but use solid first liquid that comprises activator to be even more important.Many curable liquids are all in the correct range of viscosities of ink jet printing.

Curable first liquid preferably comprises the pharmaceutical chemicals that one or more can make the reaction of liquid hardening.

In use can polymerization or crosslinked one or more monomers and/or the oligopolymer that hardens and form solid layer thereby preferred curable first liquid comprises.This class monomer and/or oligopolymer can be constituted to the precursor that small part is insoluble to first chemical functionality of second liquid.Preferred resulting polymers forms the matrix that comprises activator.Normal low when only comprising monomer of toxicity that comprises curable first liquid of at least some oligopolymer.

First solid layer can be (no matter whether by solidifying to form) of inflexible, elastic or plasticity.First solid layer needn't harden before coating second liquid fully.

Preferred first liquid irritates in response, for example, and specific band electromagnetic radiation (for example, ultraviolet, indigo plant, microwave, infrared), electron beam or be curable when hot.Therefore, curable first liquid can be the response particular range of wavelengths electromagnetic radiation (for example, UV-light, blue light, infrared light) but the time curable, heat-setting electrocuring etc.This liquid can respond the existence of one or more chemical substances such as moisture and air and is curable.The preferred component chemical medicine of selecting can react when one of irritating more than response.First liquid of at present preferred UV curable.

The preferred use need not obviously first liquid of heating.This means that method of the present invention can be used for many base materials, comprise thermosensitive plastic and in WO 03/021004 disclosed will be in the method for 350 ℃ of heating out of use other material.Especially the temperature that is preferably formed the first layer is lower than about 300 ℃ (allowing to use polyimide base material), preferably be lower than about 200 ℃ (allow use polyester base material such as Teonex (Teonex is a trade mark)), more preferably less than about 100 ℃ (allowing to use many thermoplastic matrixes), again more preferably less than about 50 ℃ (allow use low Tg base materials) and may be at room temperature, in order to avoid need heating.Be working (machining) efficiency, heating if desired, is only carried out the short period, generally is shorter than 15 minutes, preferably is shorter than about 2 minutes.

The method that masking-out operation is carried out can be earlier on base material all over being coated with first liquid, apply by pattern then and irritate.

General curable first liquid comprises one or more monomers and/or the oligopolymer that can form polymkeric substance and constitute first chemical functionality.For example, first liquid can comprise the monomer and/or the oligopolymer of reacting generating copolymer and respond above-mentioned one of irritate and causes initiator of polyreaction.For example, can comprise that AIBN (2,2 '-Diisopropyl azodicarboxylate) responds the thermal-initiated polymerization reaction.Generally, initiator produces free radical when response irritates.Can use other curing process, for example initiator produces cationic cationic curing.

Easily, monomer and/or oligopolymer be in the curable field of UV known those or be desired other curable ink of ink jet printing of curable ink.

It is big that preferred curable first liquid comprises some crosslinkable functional group numbers, as 4 or more a plurality of, or even 6 or more a plurality of functional groups' monomer and/or oligopolymer.For example, Actilane505 (Akzo Nobel UV Resins, Manchester, the reactivity four functionality polyester acrylic ester oligomer-Actilane of UK supply are trade marks) be to be suitable for, what also be suitable for has UCB, Dragenbos, six functionality monomer DPHA (dipentaerythritol acrylate) and UCB of Belgium supply, Dragenbos, the reactive diluting monomer DPGDA (dipropylene glycol diacrylate) of Belgium supply.Monomer and/or oligopolymer that these crosslinkables functional group number is many, than from the formed polymkeric substance of the less monomer of functional group's number, degree of crosslinking is higher and can produce and better stronger, the more firm film of base material tackiness.But the ratio of height crosslinkable monomers and/or oligopolymer is too high can to form brittle surface.

When first liquid when being curable, preferably do not comprise in the use and can allow second liquid and the volatile carrier liquid with regard to volatilizing away before the first layer contacts.Therefore, nearly all component of preferred this curable first liquid all stay in first solid layer (though perhaps with chemical transformation form).

Preferably the time of lag between deposition and cure curable liquid is short as far as possible.This can reduce the excessive moistening of base material, and excessive moistening can cause the loss of image definition.Be 20 seconds or shorter time of lag between preferred deposition and the curing.

But first liquid can comprise volatile carrier liquid.In general, in use, wait part or all of volatile carrier liquid (if exist) volatilize or make it to volatilize away after allow second liquid contact again with the first layer.For example, first liquid can comprise water or (preferably) in use can be at second liquid and one or more organic solvents that just vapor away before the first layer contacts.Present method can comprise a time-out in this case, allowing the volatile carrier liquid volatilization, and then applies one or both and irritates (if can execute) and allow second liquid contact with the first layer.

Because activator is also included within first liquid, thus it generally all be wrapped in the first layer, for example, in the matrix by polymer formation.Activator also can be used as the part matrix and is fixed, and method is for example, activator to be included on the molecule that has the reactive group that reacts with monomer or oligomer units.Activator can be inactive at the beginning, and only when first liquid has formed first solid layer, or response is when irritating, or when the component with second liquid contacts, just becomes active.

The present invention is particularly useful in the conductive metal layer that generates as second solid layer.Conductive metal layer is generally formed by reduction of metal ion in the reaction that comprises catalyzer, metal ion and reductive agent.Can use various technology, comprise disclosed method among electrodeless plating and the WO 2004/068389.A kind of reagent of this method, it generally is catalyzer, to be deposited in the first layer of (generally using ink jet printing method) on the base material with method of the present invention, and allow other necessary reagent deposition (with ink jet printing, immersion or other technology) in second liquid (probably in one or more other containers), cause reaction, generate the conductive metal layer that constitutes by second solid layer.

In embodiments of the invention, all second layers be the reaction by metal ion and reductive agent form conductive metal region the time, activator generally all should comprise catalyzer or catalyst precursor, they contain conductive metal salt, the organic acid salt of preferred transition metal, for example, acid chloride or propionic acid palladium.At present preferred activator is an acid chloride, and it is fit to 1～3 weight % with deposit fluid, and the amount that is generally 2 weight % is present in first liquid.Also can be with the another kind of organic acid salt of isocyatic transition metal.Optionally other material comprises other palladium salt for this reason, as salt, title complex or the colloid of Palladous chloride and transition metal, or metallic particles, as brass, aluminium, gold or red copper particle.

Deposition transition metal organic acid salt is to wait 50/50 mixture of weight part Pyranton and methoxypropanol as the suitable solvents of acid chloride.50/50 mixture of parts by weight of toluene such as another kind of solvent is and methoxypropanol.The 2 weight % acid chloride solution of preferably in this solvent, having an appointment.The preferred cosolvent that adds to increase viscosity for ink jet printing.

When activator was catalyzer or catalyst precursor, in order to form conductive metal region on first solid layer, second liquid should be included in the activator activation down can a metal ion that react and the solution of reductive agent.The composition of preferred second liquid can make it can spontaneous reaction, and can only just can react when activator in being present in first solid layer contacts at it.For the activating and reducing agent, second liquid also can comprise alkali/acid.

Metal ion, reductive agent and optional alkali/acid can 2 or 3 independent component solution deposit, they mix on base material, form reaction soln.Other details can be disclosed as PCT/GB2004/000358 (WO 2004/068389).

All second solids-layer-formation chemical reaction will be when reaction is with the formation conductive metal region between metal ion and the reductive agent, activator is not catalyzer or catalyst precursor, and can be one or more metal ions and reductive agent, also have acid/alkali of regulating the pH value when needing.The characteristics of second liquid are just to begin the second layer-formation reaction when second liquid contacts with the first layer.When all activators comprised generally the metal ion that the form with metal-salt or metal complexes (and perhaps also having acid/alkali) exists, second liquid can comprise reductive agent, may also have suitable pH regulator agent, for example under the situation of formaldehyde alkali is arranged.Second liquid also can contain other ion of identical or different metal.When all activators comprised reductive agent (perhaps also having alkali or acid), second liquid was with the preferred package metal ion, and generally the form with metal-salt or metal complexes exists.Second liquid also can comprise other reductive agent identical or different with first reductive agent.Using stronger reductive agent such as DMAB (dimethyamine borane) at the beginning is suitable with time strong reductive agent as formaldehyde then, and this can produce the metal level purer, that electric conductivity is higher.When all activators comprised alkali/acid, second liquid generally comprised metal ion and reductive agent, and randomly also had alkali/acid.

Metal ion can be the especially ion of magnesium-yttrium-transition metal of any conducting metal.Preferred conducting metal comprises the alloy of red copper, nickel, silver, gold, cobalt, platinum metals or 2 kinds or multiple these materials.Conducting metal can comprise non-metallic element, and for example, conducting metal can be a nickelous phosphate.

Metal ion generally exists with the form of salt, for example blue vitriol.Metal ion also can title complex such as EDTA (ethylenediamine tetraacetic acid (EDTA)) or prussiate existence.

The example that is suitable for reductive agent is formaldehyde, glucose or other aldehyde of great majority, or sodium hypophosphite, or Glyoxylic acid hydrate or DMAB (dimethyamine borane).

Preferred first liquid deposits on the base material with ink jet printing method.Second liquid can be with ink jet printing or other deposition techniques on the first layer.When all first liquid and/or the first layer that is generated will be made pattern, second liquid can deposit by identical patterns.

Because ink-jet printing process generally is numerically controlled, so can make different patterns with same equipment on different substrate materials.This point is even more important for production single products, tailor-made product or a series of special product differentiated.

Randomly, deposit activator liquid after base material will preheat again thereon.This makes dry rapidly and less the sprawling of activator liquid, obtains thinner line thus.For example, Melinex (Melinex is a trade mark) polyester will be with hot air gun 350 ℃ of 4 seconds of air heating.

Base material can be selected from many possibilities, comprises plastics, pottery, natural materials, fabric etc.At second solid layer is in the embodiment of conducting metal, and the base material that is suitable for comprises, for example, and slice plastic and fabric.Base material may be to have electrical element such as conductor, semi-conductor, resistance, electric capacity, inductance on it, or optical material, as the material of liquid crystal, luminescence polymer or the like.As previously mentioned, method of the present invention needn't relate to tangible heating, therefore compares to disclosed method among WO03/021004 and the WO 2004/068918, applicable to more base materials, comprises thermosensitive plastic.Present method can comprise with next step: preferably deposit one or more described electrical elements with ink jet printing method on base material, form conductive metal region then on the gained base material.

Equally, present method also can be included in and deposit electrical element on the gained conductive metal region to constitute another step of equipment complex.Described another deposition step also can carry out with ink-jet printing technology.

The present invention is specially adapted to the battery printing.In the method that forms battery on the base material can be: on base material, form 2 different conductive metal region with method of the present invention, use ionogen (can be ink jet printing) to connect this two zones then, form electrochemical cell with electrolytic process.Many electrochemical cells can electric serial or parallel connection, thereby increases obtainable voltage and/or electric current.The invention still further relates to method of the present invention and on base material, form 2 different conductive metal region, use ionogen (can be ink jet printing) to connect this 2 districts then, thereby form the method for battery with electrolytic process.The present invention also expands to the battery that forms with described method.

Therefore method of the present invention can be as the stage of making in the electric product.Be particularly useful for making the electric product that comprises complex pattern, as comprise the indicating meter of complicated pixel pattern.Other application comprises the antenna of making auto radio, mobile telephone and/or satellite navigation system; Radio shielding equipment; The edge connector of circuit card, contact and female contact; Radio frequency identifiers (RFID identifier); The conductive traces of printed circuit board (PCB) comprises flexible printed circuit board; Smart fabric, as comprise those of circuit; Decoration parts; Vehicles windshield well heater; The parts of battery and/or fuel cell; Ceramic component; Transformer and induction power supply, especially microminiaturized form; Safety equipment; Printed circuit board component is as electric capacity and conductor; Touch the membrane type keyboard, especially their electrical contact; Disposable low-cost electronic products; The disposable indicating meter of electroluminescent; Biosensor, mechanics sensor, chemistry and electrochemical sensor.

Present method also can be applicable to produce in the circuit electrical connection between 2 elements.

Present method can comprise that also another step is as follows: form another layer metal level on the conductive metal region that is made of the second layer, for example with electrolysis or electrodeless electrochemical plating or immersion metallization.

When wanting ink jet printing first liquid and/or second liquid, each liquid should satisfy the specific requirement of ink jet inks aspect viscosity, surface tension, electroconductibility, pH value, filtration, particle size and stability to aging.In one or more component solutions, can add one or more wetting agents to reduce volatilization.These desired specific performance values all are different for different ink-jet technologies, and for specific application, those skilled in the art is easy to design the suitable component solution that satisfies these performances.

The present invention also expands to the goods of making according to the present invention.

According to another inventive point of the present invention, provide and be applicable to that activation forms the activator liquid of (second) solid layer on base material, this liquid comprises the activator that is applicable to activation second solid layer formation chemical reaction, and to choose and make the activator liquid curing and be bonded on the base material, form (first) solid layer of permeable second liquid, second liquid comprises one or more reagent that the time can react by the activator activation and form second solid layer.

The present invention also provides the activator liquid that is applicable to first solid layer that is generated as the formation of activation second solid layer on base material, this liquid comprises the activator of the chemical reaction that is applicable to activation formation second solid layer, and the characteristics of this liquid are: when in use being applied on the matrix, activator liquid solidifies and is bonded on the base material, form first solid layer of permeable second liquid, second liquid comprises when being subjected to the activator activation can react one or more reagent that generate second solid layer, and this activator liquid is included in the interior formation of the first layer or is formed up to one or more reagent that small part is dissolved in first chemical functionality of second liquid.

The invention still further relates to activator liquid and the combination that is suitable for second liquid.

As previously mentioned, the preferred feature of layer-formation activator solution is relevant with the preferred feature of first liquid and second liquid discussed above.

In the following example, also to further describe the present invention by explanation.All percentage ratios all are meant weight percentage in these embodiments, except as otherwise noted.

Embodiment 1

On the base material of multiple differing materials, form the conductive copper zone with following method.

Prepare activator solution composed as follows:

％

Acid chloride 2.0

Pyranton 47.5

Methoxypropanol 47.5

Polyvinyl butyral acetal (PVB) 1.6

Polyvinylpyrolidone (PVP) (PVP) 1.4

Acid chloride exists as activator (catalyzer).Pyranton and methoxypropanol with etc. weight ratio mix, just to adhere to the solvent on the matrix before the reaction soln that is enough to soon acid chloride is discussed that obtains volatility below adding.But its rate of volatilization be enough to make activator solution ink jet printing expediently slowly again.

The polyvinyl butyral acetal (PVB) that plays first chemical functionality effect is water-fast, and its existence is in order to help activator to be bonded on the base material.Molecular weight is 15,000～25, and the polyvinyl butyral acetal between 000 is suitable for, and BN18 level for example can be available from Wacker.

The Polyvinylpyrolidone (PVP) (PVP) that plays second chemical functionality effect is water miscible, so can be dissolved in the moisture metallization solution of discussing below.K30 level Polyvinylpyrolidone (PVP) is derived from International Speciality Products.The molecular weight of this polymkeric substance is 60,000～70,000.

The viscosity of activator solution is 3.85cps, and surface tension is 30.5dyn/cm.

For preparing above-mentioned activator solution, prepare polyvinyl butyral acetal is that concentration is 30% solution in 50/50 the mixed solvent in diacetone and methoxypropanol weight ratio.In 2～3 hours, in identical solvent mixture, make 3% acid chloride solution with the sonication method.Mix these two solution then and add more homogeneous solvent mixture, make cumulative volume reach above specific ratio.Then the gained fluid is filtered 1 μ m GF-B glass fibre funnel available from Whatman.Visible sometimes a little settling on filter paper.

Deposition

Use the XJ128-200 print head, with ink jet printing method, deposit activator solution by following standard on the base material of multiple differing materials, described print head with the activator solution bottoming, is used for activator solution is ejected on the base material earlier available from Xaar then.Can regulate resolving power off the net for specific base material.For being easy to moistening base material, 250 point/inches (dpi) are suitable.For very difficult moistening base material, can guarantee moistening fully with 1000dpi.

The XJ128-200 print head sprays the 80pL drop with the injection frequency of 1～2kHz and the jet length of 1～2mm.

After spraying activator solution, in order to form first solid layer on base material, allow or manage to make typographic activator solution drying, for example, with the infrared heater that just in time is positioned at the base material top, the temperature of substrate surface is no more than about 50 ℃.Also can under the condition that does not heat fully, make the activator solution drying of printing.All when using Infrared heaters, be generally time of drying 30 seconds.

Metallization

Then on base material exsiccant activator solution (constituting first solid layer) go up coating metal solution.The method of coating metal solution can be that base material is immersed in traditional electrodeless bath.But in the present embodiment, metallization solution is sedimentary with ink jet printing method.

Metallization solution is by following 3 component solution A, and B and C form.

Solution A

％

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 source, is Cu here ²⁺Having sodium sulfate is for stabilization copper sulfate.EDTA forms the coordination agent of protective barrier around cupric ion, as does not have it, and said composition solution can be precipitated out immediately.The trimethyl carbinol is the cosolvent that reduces surface tension and increase wettability.

Solution B

％

Formaldehyde solution (aqueous solution of 37 weight %) 0.22

Sodium formiate 3.71

Water 91.07

The trimethyl carbinol 5.00

Formaldehyde exists as reductive agent.

Solution C

％

Sodium hydroxide 1.74

Water 93.26

The trimethyl carbinol 5.00

The effect of sodium hydroxide is activating and reducing agent when solution makes up.

Rock solution A, B and C filter 1 μ m GF-B glass fibre funnel available from Whatman then.The viscosity of each solution is all less than 3cps.

Then, 3 component solution A independently, B and C respectively ink jet printing to the exsiccant activator.Respectively these 3 solution equal-volumes be printed onto same position on the matrix, but spread over equably on the whole print surface area of base material, 3 solution original positions are combined into reaction soln.Use these solution of 64ID3 print head ink jet printing available from Ink Jet Technology.All contact injection fluidic parts all are ceramic on the print head, so this print head is particularly suitable for printing very alkalescence or tart liquid.Be injected under the 5kHz and carry out.Selection is applied to the potential waveform on the piezoquartz print head, and making liquid droplets is 137pL.

Allow reaction soln keep contacting up to the copper that deposits suitable thickness with base material.General at room temperature need be less than just producing suitable copper layer in 5 minutes.

Have been found that with the infrared heating base material and can form the copper district quickly.But,, to guarantee that importantly surface temperature is no more than 50 ℃ for avoiding the base material warpage to many kinds of plastic basis materials.

At last, wipe or the flush away matrix on any excessive solution or dry salt, obtain copper plating district corresponding to ink jet printing the copper-plated samples of activator pattern.

The result

With this technology the copper ink jet printing to the following base material and the cohesive strength between observational measurement conductive metal deposition district and the base material.

The base material tackiness

Vinylformic acid is good

Polystyrene is good

Polyethylene is bad to good, depends on rank

The delrin polyacetal homopolymer is bad

Hostaform or Ultraform Copolyacetal are bad

ABS (acrylonitrile/butadiene/styrene) is good

U-PVC is good

Silicon rubber is bad

(Delrin is the trade mark of E.I.Du Pont Company.Hostaform is the trade mark of Hoechst.Ultraform is the trade mark of BASF.)

Present embodiment shows, the electroconductibility in printed conductive metal district and base metal approaching.

The metal level that has proved 0.3～3 μ m depends on used concrete chemistry.Repeating print can be used to constitute thicker layer, as the layer of needed 15～20 μ m of antenna applications.

Embodiment 2

Present embodiment is similar to embodiment 1 substantially, but replaces independent solution A and B with the single solution of metal ion that is designated as solution A B and reductive agent.Solution A B's is composed as follows:

％

Copper sulfate 1.63

Sodium sulfate 3.21

EDTA disodium salt 0.60

Formaldehyde solution (the 37 weight % aqueous solution) 0.22

Sodium formiate 3.71

Water 85.63

The trimethyl carbinol 5.00

Allow solution A B filter 1 μ m GF-B glass fibre funnel available from Whatman.

As described in embodiment 1, deposit, start from the ink jet printing of activator solution, suspend then, make the solvent evaporates of catalyst solution.Then, use the 64ID3 ink jet printing head in isopyknic solution A B of substrate surface ink jet printing and solution C (as described in embodiment 1).

The same with the front, on base material, form the conductive copper district.

Embodiment 3

Present embodiment is similar to embodiment 1 and 2 substantially, but with the solution A among the single solution replacement embodiment 1 that contains the second reaction reagent that is necessary, solution A B and C among B and C and the embodiment 2.

Single solution composed as follows:

％

Enplate 872A 24.09

Enplate 872B 24.09

Enplate 872C 8.03

Water 13.29

Ethylene glycol 20

The trimethyl carbinol 5

Surfadone LP-100 0.5

PEG-1500 5

Enplate 872A sulfur acid copper.Enplate 872B contains prussiate coordination agent and formaldehyde.Enplate 872C contains sodium hydroxide.(Enplate is a trade mark).Enplate 872A, B and C can and be commonly used for electrodeless copper-plated component solution available from Enthone-OMI.There is the also effect of landing low surface tension in ethylene glycol as wetting agent.The trimethyl carbinol is the cosolvent that reduces surface tension and increase wettability.Surfadone LP-100 is the wetting agent with surfactant properties.PEG-1500 plays the wetting agent effect.

By forming the above solution of preparation, filter 1 μ m GF-B glass fibre funnel then available from Whatman.Viscosity is 9.8cps, and surface tension is 30.0dyn/cm.Solution is stable in a few hours and can be as one-component solution by ink jet printing.

The activator solution described in the above embodiment 1 according to the pattern ink jet printing.In minibreak (30 seconds kinds) with after allowing the solvent evaporates in the activator solution, but with ink jet printing method with above-mentioned single component solution deposition on the zone of activator solution in the ink jet printing on the whole printing area of base material or.Therefore on substrate surface, just form copper layer according to pattern.

Perhaps, also can by will be printing element be immersed in traditional electrodeless method metallization and implement metallization in bathing.Can be immersed in printing element in reductive agent bathes,, soak in the bath of cupric ion, reductive agent and alkali then so that acid chloride is reduced to palladium.Perhaps, also can utilize the metallization of suitable prescription to bathe, the base material that has printed directly be soaked in the bath of into cupric ion, reductive agent and alkali.

The curable active agent layer of embodiment 4-

According to the formulation label shown in the following table 1 is the curable catalyst formulation of UV of ALF 116 and AF 117.From the known used monomer of the association area of UV curable inkjet and initiator have good curing performance and with the tackiness of plastic basis material.These initial formula contain the carrier of some solution as palladium acetate catalyst, are using available from Xaar, and the XJ500/180 ink jet printing head of UK allows these solvent evaporates to fall after prescription is applied to Melinex (Melinex is a trade mark) polyester base material surface.Apply UV light then and make ink solidification, UV causes solidification process, monomer and oligopolymer component generation polymerization in this process.

The curable catalyst formulation of UV

(numeral is weight %)

Material	ALF 116	ALF 117
			Acid chloride	1.25	0.94
PVP K30	-	2.5
			Pyranton	24.38	23.28
Methoxypropanol	24.37	23.28
			Actilane 505	5	5
DPHA	1.5	1.5
			Irgacure 1700	3.25	3.25
Irgacure 819	1.25	1.25
			DPGDA	39	39

Table 1

PVP K30 is ISP, Tadworth, the Polyvinylpyrolidone (PVP) of a kind of grade of UK supply.Actilane 505 is Akzo Nobel UV Resins, Manchester, the reactivity four functionality polyester acrylic ester oligomers of UK supply.DPHA is a dipentaerythritol acrylate, and is a kind of by UCB, Dragenbos, six functionality monomer of Belgium supply.Igracure819 and Igracure 1700 are Ciba Speciality ChemicaIs, Macclesfield, and the UV light trigger-Irgacure of UK supply is a trade mark.DPGDA is a dipropylene glycol diacrylate, by UCB, and Drogenbos, the reactive diluting monomer of Belgium supply.

PVP constitutes water-soluble second chemical functionality.Monomer and oligopolymer, i.e. Actilane 505, DPHA and DPGDA, reacting generating copolymer constitutes water-fast first chemical functionality.

ALF 116 solidifies good (linear velocity is 40m/min), obtains the toughness film of scrape resistant.But, (Enthone 872A, Enthone 872B and Enthone 872C are Enthone Ltdof Working when coating copper layer on film forms solution (being made up of Enthone 872A (30 weight %), Enthone 872B (30 weight %), Enthone 872C (10 weight %), the trimethyl carbinol (5 weight %), ethylene glycol (20 weight %) and polyethylene glycol 1500 (5 weight %)), the copper plating bath of UK supply) time, but there is not the copper deposition.We believe that this is the smooth impermeable surface owing to cured film, and catalyst seal has been advanced plastic layer for it and prevention contacts with copper layer-formation solution.

On the contrary, ALF 117 comprises on a small quantity (5 weight % of dry film) Polyvinylpyrolidone (PVP), the purpose that adds it in the prescription is that its can be dissolved out from cured layer when adding moisture copper layer-formations solution subsequently, or swelling or maintenance permeability, thereby exposes catalytic sites.

The same with ALF 116, under the speed of 40m/min, also solidify finely, and copper deposition (calculated value is 100nm/min) is arranged specifically.

60 ℃ of bakings 24 hours, make base material material have good scratch resistance, the scratch resistance of the optimum catalyst known to copper layer and the plastic substrate Direct Bonding being filled a prescription with us is the same good.

This work shows that in order to keep activity of such catalysts water-soluble, the water-swellable that must have certain form maybe can make second liquid advance other method of the first layer thoroughly.Prepare 3 new prescriptions that label is ALF 120, ALF 121 and ALF 124, such as following table 2 summary.Wherein each prescription all is the modification of ALF 117 in the table 1.

The curable catalyst formulation of UV-

(numeral is weight %)

	ALF 120	ALF 121	ALF 124
				Acid chloride	2	2	2
DPGDA	76	48	48
				DPHA	3	3	3
Actilane 505	10	10	10
				Irgacure 1700	6.5	6.5	6.5
Irgacure 819	2.5	2.5	2.5
				Pyranton	-	12.75	14
Methoxypropanol	-	12.75	14
				PVP K30	-	2.5	-

Table 2

DPGDA is a dipropylene glycol diacrylate, is by UCB, Drogenbos, the reactive diluent monomer of Belgium supply.

With the Fusion UV 500W lamp (Fusion is a trade mark) that the H bulb is housed with 10m/min once by coming curing inks.After the curing, earlier with DMAB (dimethyamine borane) solution, then form solution-treated printing ink with copper-layer, the composition that copper-layer forms solution is Enthone 872A (30 weight %), Enthone 872B (30 weight %), Enthone 872C (10 weight %), uncle's butanone (5 weight %), ethylene glycol (20 weight %) and polyethylene glycol 1500 (5 weight %) (Enthone 872A, Enthone 872B and Enthone 872C are Enthone Ltdof Working, the copper plating bath of UK supply).No copper deposition on ALF 120 and ALF 124.But on ALF 121, deposited layer of even copper layer.Find that this copper layer has good electrical conductivity and the tackiness good with base.Because no copper deposition on ALF 120 or ALF 124, this just proves further that the PVP material is the principal element that keeps catalyst activity, and this takes place by water-soluble mechanism set forth above probably.

Further then modification ALF 121 is to obtain having in the ink jet printing printing ink of good deposition properties.Two kinds of printing ink that are designated as ALF 125 and ALF 126b are shown in the following table 3.

Can spray the UV ink formulations

(numeral is weight %)

	ALF 125	ALF 126b
			Acid chloride	2	2
Irgacure 1700	3.25	3.25
			Irgacure 819	1.25	1.25
DPGDA	61	48
			DPHA	-	3
Actilane 505	-	10
			Pyranton	15	15
Methoxypropanol	15	15
			PVP K30	2.5	2.5
Viscosity, cPs (25 ℃)	9.59	11.2

Table 3

With XaarJet 128-200 print head (can be available from Xaar of Cambridge, England), ALF 125 and ALF 126b show good ink jet printing and the both provides the second best in quality copper deposition.But when making thickness greater than the thicker copper sample of 200nm, ALF 125 bubbles manyly than ALF 126b easily.

Think that this is because ALF 126b contains the material (Actilane 505 is four functionality, and DPHA is six functionality) of higher functionality, so degree of crosslinking is higher and so and formation and better stronger, the more firm film of base material tackiness.

Based on these results, also think and as HEMA (methacrylic acid 2-hydroxyl ethyl ester), GMA (glycidyl methacrylate) or NVP (n-vinyl pyrrolidone), to replace PVP with the monomer of water-swellable.Perhaps, also can use the high boiling solvent miscible,, keep the open and permission of UV-cured layer to be seen through by copper solutions as NMP (n-methyl-2-pyrrolidone), ethylene glycol, glycol ether or glycerine with water.Perhaps also can as silicon-dioxide (inorganic) or PPVP (poly-Polyvinylpyrolidone (PVP)) particle (organically), make little-hole membrane structure with little-hole particle.

Embodiment 5

With following method depositing electrically conductive copper layer on Melinex (Melinex is a trade mark) polyester base material.

Prepare the curable catalyst ink of UV-composed as follows.

Material	Function	Form weight %
			Acid chloride	Metal-salt	2
Dipropylene glycol diacrylate (DPGDA)	The UV curable materials	30.5
			Actilane 505	The UV curable materials	10
Dipentaerythritol acrylate (DPHA)	The UV curable materials	3
			Irgacure 1700	Light trigger	3.25
Irgacure 819	Light trigger	1.25
			Pyranton (DAA)	Solvent	47.5
Polyvinylpyrolidone (PVP) (PVP) K30	Polymkeric substance	2.5

Use available from Xaar, the XJ500/180 print head of UK is coated on this printing ink on the base material with ink jet printing method, drying, be exposed to then in the UV light and be cured, as described in embodiment 4, form the first layer.

Base material and institute's agglutinating the first layer are immersed in the reductive agent bath that comprises 1.6% dimethyamine borane (DMAB)/water,, activate this catalyzer thus so that acid chloride is reduced to metallic palladium.

Then base material is immersed in the copper body lotion composed as follows:

	Form weight %
		Enplate 872A	10.71
Enplate 872B	10.71
		Enplate 872C	3.57
Water	75

Standard among Enplate solution such as the embodiment 3, and comprise cupric ion, reductive agent and alkali causes the palladium-catalytic reduction of copper, and therefore depositing electrically conductive copper layer on base material.

Claims (31)

1. form the method for first solid layer at substrate surface, this solid layer can activate the chemical reaction that forms second solid layer thereon, this method comprises allows the first liquid contact substrate surface, be bonded in described first solid layer of substrate surface with formation, described first liquid and the first layer comprise activator and permeable second liquid of first solid layer that described chemical reaction is used, described second liquid comprises one or more reagent that the chemical reaction that forms second solid layer is used, and wherein the first layer comprises first chemical functionality who is insoluble to second liquid to small part.

2. according to the method for claim 1, also comprise and allow second liquid contact first solid layer, to form second solid layer.

3. according to the method for claim 2, wherein second solid layer comprises conductive metal layer.

4. according to the method for claim 1,2 or 3, wherein activator is a kind of catalyzer or catalyst precursor.

5. according to the method for claim 1,2 or 3, wherein activator comprises one or more reagent, forms second solid layer thereby chemical reaction takes place when contacting with second liquid described reagent on first solid layer.

6. according to any one method in the aforementioned claim, wherein the first layer also comprise to small part dissolve in or swellable in second chemical functionality of second liquid or permeable second liquid.

7. according to the method for claim 6, wherein said second chemical functionality comprises one or more among Polyvinylpyrolidone (PVP), HEMA (2-hydroxyethyl methacrylate), GMA (glycidyl methacrylate) and the NVP (N-vinyl pyrrolidone).

8. according to the method for claim 6 or 7, wherein said second chemical functionality comprises the high boiling solvent miscible with the solvent of second liquid, and it makes the resulting polymers matrix keep open in first solid layer, thereby allows second liquid to see through.

9. according to any one method in the aforementioned claim, wherein first liquid is enough to make first liquid to advance base material thoroughly to the aggressiveness of base material, thereby improves the tackiness of first solid layer and base material.

10. according to any one method in the aforementioned claim, wherein first chemical functionality at least mainly is organic and/or silica-based functionality.

11. according to any one method in the aforementioned claim, wherein the first layer forms being lower than under about 300 ℃ temperature.

12. according to any one method in the aforementioned claim, wherein first liquid is part or all of non-water.

13. according to any one method in the aforementioned claim, wherein second liquid is aqueous.

14. according to any one method in the aforementioned claim, wherein first liquid comprises little-hole particle and first solid layer comprises little-hole membrane structure.

15. according to any one method in the aforementioned claim, wherein first liquid is deposited on the base material according to pattern.

16. according to the method for claim 15, wherein first liquid is deposited on the base material with ink jet printing method.

17., wherein first liquid is coated on and also uses the masking process coated pattern on the base material according to the method for doing what one in the claim 1～15.

18., wherein will repeat this technology to constitute multilayered structure according to any one method in the aforementioned claim.

19. according to any one method in the aforementioned claim, wherein first liquid is curable, preferably UV is curable.

20. according to the method for claim 19, thereby comprise in use can polymerization and/or the monomer and/or the oligopolymer of crosslinked first solid layer that hardens and form for wherein curable first liquid.

21. according to the method for claim 20, wherein resulting polymers forms the matrix that comprises activator.

22. according to any one method in the aforementioned claim, wherein first solid layer is rigidity, elasticity or plasticity.

23., wherein before the first liquid completely solidified, allow second liquid contact with first liquid according to any one method in the aforementioned claim.

24. according to any one method in the aforementioned claim, wherein activator comprises the organic acid salt of transition metal.

25. according to the method for claim 24, wherein activator comprises acid chloride.

26. according to any one method in the aforementioned claim, the chemical reaction that wherein forms second solid layer is the reaction between metal ion and the reductive agent, forming conductive metal region, and activator can be one or more metal ions, reductive agent or alkali.

27., be used for producing battery according to any one method in the aforementioned claim.

28., be used for producing on the circuit electrical connection between two parts according to any one method in the claim 1～26.

29. the goods of making according to the method for any one in the aforementioned claim.

30. be adapted on the base material producing the activator liquid of first solid layer of the formation that is used to activate second solid layer, this liquid comprises the activator that is suitable for activating the chemical reaction that forms second solid layer, and this liquid is when being used for being applied on the base material, activator liquid solidifies and adheres on the base material, form first solid layer of porous second liquid, second liquid is included in when being activated the agent activation can react one or more reagent that generate second solid layer, and described activator liquid is included in the interior formation of the first layer or is formed up to one or more reagent that small part dissolves in first chemical functionality of second liquid.

31. according to claim 30 and activator liquid suitable second liquid combination.