CN100577328C - Method for producing surface-treated silver-containing powder and silver paste using surface-treated silver-containing powder - Google Patents
Method for producing surface-treated silver-containing powder and silver paste using surface-treated silver-containing powder Download PDFInfo
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- CN100577328C CN100577328C CN200580040489A CN200580040489A CN100577328C CN 100577328 C CN100577328 C CN 100577328C CN 200580040489 A CN200580040489 A CN 200580040489A CN 200580040489 A CN200580040489 A CN 200580040489A CN 100577328 C CN100577328 C CN 100577328C
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Abstract
Disclosed is a method for producing a surface-treated silver-containing powder wherein a dispersion liquid, which is obtained by dispersing silver or silver compound particles (a) in a solvent together with a surfactant (b) of alkylamine type, alkylamine salt type or phosphate type having a phosphorus content of 0.5-10% by mass, is subjected to vacuum freeze drying for having the surfactant (b) adsorbed on the surfaces of the silver or silver compound particles (a), thereby producing a silver-containing powder (c) whose surface is treated with the surfactant (b). Also disclosed is a silver paste produced by dispersing the surface-treated silver-containing powder (c) in a solvent or in a solvent and a resin.
Description
Technical field
The present invention relates to a kind of manufacture method of surface-treated silver-containing powder, this silver-containing powder is used to be used in the silver-colored paste of electric conductivity in the printed wire that uses in e-machine etc., printing precision excellence.In more detail, relate to and contain the silver-colored paste of surface-treated silver-containing powder as the electroconductive powder composition.
In addition, in the present invention, " surface-treated silver-containing powder " is meant and comprises " surface-treated silver powder " and " surface-treated silver compound powder ".
Background technology
Conductive paste is the paste that contains electrically conductive microparticle in the solid constituent, generally uses in air metals such as non-oxidizing gold, platinum, silver, palladium as conductive particle.All the time, conductive paste roughly is divided into: (1) high temperature burns till the type conductive paste, and it can realize good electrical conductivity by the bond vitrified between the silver-colored particle, but base material is defined to pottery etc.; (2) polymer-type conductive paste, it can extensively be suitable for from glass, epoxy resin seal carving brush substrate to film etc., the contact between the metallic particles that the thermal contraction when solidifying by adhesive brings, thus obtain conducting, thereby resistance ratio is higher.
Use the polymer-type conductive paste, for example form under the situation of conducting channel on supporter at flexible printed base plate, utilize serigraphy etc. to make described polymer-type conductive paste on plastic foils such as PETG, polyimides, form the conducting channel pattern, adhesive in the formed pattern coating film is heating and curing, improve electric conductivity, durability, and guarantee the cementability on the film.
Particularly use the polymer-type conductive paste of silver or silver compound easily to realize stable electric conductivity, thermal conduction characteristic is also good in addition, and therefore, it is used in the formation of various circuits, electronic circuit pattern between electronic unit inside or the electronic unit.
With in the printing process of pattern, be accompanied by the miniaturization of circuit in conducting channel, require to improve printing precision as far as possible, but its precision be subjected to the restriction of conductive particle average grain diameter.Therefore, in order to obtain good printing precision, require to be in conductive particle in the conductive paste and be dispersed to 1 particle and then this 1 particle, promptly be in the state of enhancement of dispersion by the state that resin etc. coats fully.
If the coating of 1 circumgranular resin of enhancement of dispersion etc. is insufficient, particle grain size is thin more, then active increase more, therefore, and the particle aggregation in this conductive paste, perhaps viscosity rises in time easily, sometimes also can gelation under opposite extreme situations.
Like this, good and stably form fine line pattern for precision, need conductive particle stable dispersion to 1 time particle, and on this basis each particle by resin-coating.On the other hand, when the resin-coating around the conductive particle was blocked up, residual resinous principle hindered intergranular electrical conduction between the particle, thereby had and can not obtain good conductive tendency, the particle diameter of used conductive particle is more little, then should be inclined to remarkable more.
Therefore, be used to disperse and the amount of resin of coating conducting particle surface is preferably essential minimum, preferably the amount of resin with less amount makes the dispersiveness of conductive particle, conductive paste become good to tack, the film forming of matrix.
At present, when making paste when conductive particle is dispersed in the resin, in order to improve its dispersiveness, nonionic dispersants such as the oxirane of the oxirane of polyalcohols such as the oxirane of use higher fatty acids or the ester compounds of expoxy propane addition ester compounds, sorbitan and aliphatic acid, sorbitan or expoxy propane addition ester compounds, alkylbenzene or propylene oxide adduct; The oxirane of benzene sulfonamide acid alkali metal salt, higher alcohol sulfate alkali metal salt, phosphate compound, higher fatty acids, higher fatty acids or the anionic species dispersants such as sulfuric ester alkali metal salt of propylene oxide adduct; Various dispersants such as cationic dispersant such as quaternary.
But,, in the method for for example using dispersion machine, mixing roll dispersed electro-conductive particle in resin in the past, can not fully improve the dispersiveness of conductive particle, and can't guarantee the electric conductivity of conductive paste well even use these dispersants.
Particularly using under the situation of silver-colored particle as the silver-colored paste of conductive particle, the true specific gravity of silver-colored particle is 10.5, and silver-colored particle free settling, reassociating property are big, therefore, when using after long preservation, exist and need effort and time taking problem in the dispersion step.The good redispersibility of needs when therefore, needing long preservation stability.
For such problem, carried out following trial: the anion surfactant by using for example organic paint vehicle and being made up of the sulfosuccinate that contains alkyl obtains good dispersiveness and long-time stability (referring to Patent Document 1).But the method for only using patent documentation 1 to be put down in writing can not fully improve the redispersibility of sedimented particle.In addition, under the situation of the line width of conducting channel, be inadequate the printed wire pattern well for precision.
In addition, the amount of resin that is used to disperse does not reduce to essential minimum yet, and is insufficient aspect electric conductivity yet.
On the other hand, in the manufacturing of the dispersion liquid that has used metallic particles, use vacuum freeze-drying method, known have a following method: for example be used for making the manufacturing of electrolytic capacitor with the tantalum powder coating of anode component, in solvent, mix tantalum powder and dispersant, carry out vacuum freeze drying, make the method (referring to Patent Document 2) of tantalum particle surface absorption dispersant.
But, although be metal dispersion equally, still in the manufacturing of the conductive paste that purposes, needed characteristic all differ widely, be not suitable for the example of vacuum freeze drying, for the also not enlightenment of relation of dispersed and electric conductivity.And, there is not the open selection of carrying out dispersant in order to show good electrical conductivity fully yet.
As mentioned above, in order to give full play to the characteristic of polymer-type conductive paste in the past, it is important being suitable for only process for dispersing and selecting the dispersant in this process for dispersing, seeks to realize dispersant, the process for dispersing of the satisfactory electrical conductivity of conductive paste.
Particularly in recent years in order to reduce the resistance of the conducting channel that forms by conductive paste, but inquired into the silver-colored paste of use easy fired, it is by making the very miniaturization of silver-colored particle grain size, perhaps use granular silver oxide, the comprise uncle's fatty acid silver salt graininess silver compound of (tertiary fatty acid silver salt), and make the silver-colored paste can easy fired.In this easy fired type silver paste, under the situation of micronized silver-colored particle, by the heating below 300 ℃, bond vitrified between the adjacent particle reduces the resistance of conducting channel.In addition, under the situation of graininess silver compound, by the heating under the existence of heating below 300 ℃ or reducing agent, silver compound is reduced into argent, bond vitrified between the adjacent silver-colored particle makes the resistance of conducting channel reduce (for example, referring to Patent Document 3).
Traditionally, the polymer-type conductive paste is to add the adhesive be made up of acrylic resin, epoxy resin, polyurethane resin, mylar etc., organic solvent, curing agent, catalyst etc., and spherical or laminar conductive particle disperseed, mixes, the contact between the conductive particle that causes by the cure shrinkage when adhesive solidifies obtains electric conductivity.Therefore, resistance ratio is higher, in addition, has following defective: because variations in temperature etc. cause the aggregation force of cured resin to change, therefore, the easily change thereupon of resistance of the conducting channel that use polymer-type conductive paste forms etc.
The silver-colored paste of described easy fired type has remedied these shortcomings, by using this silver paste, also can form electric conductivity favorable conductive circuit on plastic foils such as PET.
But, being used for following silver-colored particulate, the graininess silver compound of micronized sub-micron of easy fired type silver paste, it is reactive high, and is all difficult under dried pulverulence.Particularly graininess silver compound is because the speed of reduction reaction is very fast, thereby must preserve in the low solution such as solvent of water or reproducibility.When particularly dispersion solvent uses alcohols solvent etc., in the dispersion of silver-colored paste, reduce, give birth to bond vitrified between the silver-colored particle with disperseing opposite real estate sometimes.Therefore, need more the particle of these silver and silver compound is dispersed to particle 1 time, coat each particle surface, and stabilisation.
And then, in order in these silver-colored pastes, to obtain high conductivity originally, need the silver-colored particle in the silver-colored paste to keep high content and dispersion well, in addition, also need to carry out described stabilisation by the resin of essential minimum, make the coating thickness attenuation as much as possible of particle surface, thereby, easily make bond vitrified between the adjacent particle by easy fired.Be formed at the filming when blocked up of silver and silver compound particle surface, be difficult to take place bond vitrified between the adjacent particle, the compactedness of silver or silver compound also reduces, therefore, even if can not give play to these easy fired type silver pastes advantage originally that easy fired also can be given satisfactory electrical conductivity.
Therefore, for these easy fired type silver pastes, further importantly satisfy selection, the manufacture method of the dispersant of following requirement simultaneously, described requirement is: the particle of each silver or silver compound passes through to coat and stabilisation, dispersed raising and the electric conductivity raising owing to easy fired.
Patent documentation 1: TOHKEMY 2000-231828 communique
Patent documentation 2: TOHKEMY 2004-006502 communique
Patent documentation 3: TOHKEMY 2003-309337 communique
Summary of the invention
Invent problem to be solved
The object of the present invention is to provide a kind of silver-colored paste, wherein, the silver of nominal particle size or the particle of silver compound are disperseed well, rerum naturas such as viscosity rising do not take place over time, can form the electric conductivity favorable conductive circuit of line width.
In addition, the manufacture method of surface-treated silver-containing powder that the object of the present invention is to provide enforcement indispensable in the manufacturing of this silver paste.
In addition, the object of the present invention is to provide a kind of silver-colored paste, but it is by using the low silver of sintering temperature or the particle of silver compound, but can form easy fired and burn till after have filming of high conductivity.
The method that is used to deal with problems
The invention provides a kind of manufacture method of surface-treated silver-containing powder, it is characterized in that having following drying process: the particle that makes silver or silver compound is that the phosphoric acid ester surfactant of 0.5～10 quality % is distributed to and disperses to carry out vacuum freeze drying with the dispersion liquid that forms in the solvent with alkyl amine or alkylamine salt surfactant or phosphorus containing ratio.
In addition, the invention provides the silver-colored paste that contains described surface-treated silver-containing powder and resin.
The invention effect
The manufacture method of the surface-treated silver-containing powder of the application of the invention, the particle of silver or silver compound disperses with the form of subparticle, and the surface of each particle of silver or silver compound is adsorbed with surfactant, and this particle surface is coated well.
Usually, heavy metallic particles free settling in common processing method as silver, in dispersion machine, easily produce CONCENTRATION DISTRIBUTION, therefore, be difficult to carry out identical processing, but use method of the present invention, after in containing the solvent of surfactant, disperseing, carry out vacuum freeze drying, thus, can be with the more identical treatment conditions Processing Ag or the particle surface of silver compound.
In addition, among the present invention, use the alkylamine or the surfactant of alkylamine salt or the surfactant of the phosphoric acid ester that the phosphorus containing ratio is 0.5～10 quality % to carry out surface treatment, therefore, this surfactant is adsorbed in the particle surface of silver and silver compound extremely well, the dispersed raising.
Such when having handled the silver-containing powder of particle surface when using with surfactant, only by adding solvent or adding resin and solvent mixes and stirs or by simple scatter operation, just can make the silver-colored paste of wide region viscosity.And surface treatment has been carried out by surfactant in the surface of the particle that is formed by silver or silver compound, therefore, the particle that is formed by silver or silver compound is disperseed well in silver-colored paste.In addition, the addition as the resin of dispersant can be suppressed to when disperseing the untreated metal particle still less amount.In addition, owing to do not increase the resin-coating amount of particle surface, thereby can not reduce the electric conductivity when forming conductive paste.And, consequently can improve the cooperation ratio of the particle of silver or silver compound, therefore also effective to the raising of electric conductivity.In addition, the particle of silver or silver compound is distributed in the solvent with resin glue is fine well, therefore can make the silver-colored paste of excellent.
In the existing method that paste viscosity is limited by used dispersal device, the paste viscosity after will disperseing usually to finish is adjusted to the optimum viscosity that is fit to each printing process again.For example, in order to be set at the high viscosity of suitable silk screen print method, must make the solvent evaporates of the paste after the dispersion etc. sometimes, to reduce quantity of solvent.
But, when using surfactants such as alkyl amine, phosphoric acid ester to carry out the surface treatment of aforesaid silver-colored particle, only, just can form paste by forming with solvent and mixed with resin, stirring with paste.Consequently can easily make to have and be used for making the optimal silver powder content of printing process of conducting channel and the silver-colored paste of viscosity.
Long between the resting period after even if silver-colored paste paste of the present invention is made, also easily stablize by the dispersion again of stirring extent, but so long preservation.In addition, can under the state of the surface-treated silver-containing powder by manufacture method manufacturing of the present invention, preserve, and only prepare the silver-colored paste of necessary amounts as required.
Description of drawings
Fig. 1 is used for the illustrative key diagram that silver powder is carried out the surface-treated method with surfactant of the present invention.
Fig. 2 is the figure of an example of the dsc analysis measurement result of the silver powder of expression after the surface treatment of the present invention.
Fig. 3 is the figure of the size distribution of the silver powder after the surface treatment of representing in embodiment 1 and the comparative example 1 to make with volume reference.
Fig. 4 is the figure that the firing time under expression changes 250 ℃ is measured the result of the resistivity of the formed dry coating of conductive paste of making in embodiment 1 and the comparative example 1.
Fig. 5 is the figure of the size distribution of the silver powder after the surface treatment of representing among the embodiment 4 to make with volume reference.
Fig. 6 is the figure of the size distribution of the silver powder after the surface treatment of making among the expression embodiment 5.
Fig. 7 is that expression is used the silver-colored paste made among the embodiment 5, utilized the figure of the section of the thread pattern that serigraphy makes.
Fig. 8 is the figure that is illustrated under 160 ℃ or 250 ℃ the relation between the specific insulation of heat time heating time (firing time) when the thread pattern made from the silver-colored paste of embodiment 5 burnt till and thread pattern.
Symbol description
A: the powder of silver or silver compound (particle);
B: surfactant (molecule);
C: surface-treated silver-containing powder (particle)
The specific embodiment
Below, the present invention will be described in more detail.In addition, " sintering of the particle of silver or silver compound " is meant the material (for example powder, paste) that contains the particle of silver or silver compound by heating in the present invention, thereby makes fusion and bond vitrified between the particle of silver or silver compound.In addition, " burning till of silver-colored paste " be meant by heating silver-colored paste and make resin solidification, the contraction that is contained, thereby make contact between the particle of adjacent silver or silver compound or make the partial melting bonding of contact.In addition, " dispersion " be meant that other is the phenomenon of microgranular distribution mutually in continuous phase.
Particle to silver or silver compound carries out the silver-containing powder that surface treatment obtains according to the present invention by using, and can make the good silver-colored paste of excellent dispersion and electric conductivity.Particularly be suitable for the low silver of sintering temperature or the particle of silver compound, for example under the situation of the silver-colored particle handled of the particle of (the crystallite diameter is little) silver that the particle of the silver of ultramicrofine nominal particle size or silver compound, crystallinity are low or silver compound, silver oxide, can obtain following silver-colored paste: it can burn till (but firing temperature is low) burning till than existing high temperature under the significantly low low temperature of type conductive paste, and can form the line pattern with good electrical conductivity after burning till.
As the silver-colored particle that uses among the present invention, can use fine silver particle, surface by the metallic particles of silver coating or these mixture.As silver-colored particle, can use grain shape is the silver-colored particle of arbitrary shapes such as spherical, flakey, needle-like, dendroid.The manufacture method of silver particle does not have particular restriction yet, and mechanical crushing method, reducing process, electrolysis, vapor phase method etc. are any.The metallic particles that the surface is coated by silver forms the clad of silver on the surface of the particle that is formed by the metal beyond the silver by methods such as plating.For example, commercially available have a product etc. that coats the copper particle surface with silver.As silver-colored particle, from electric conductivity and cost aspect, preferred spherical silver particles and the flakey silver particle of only forming by silver.
The volume average particle size of spherical silver particles is preferably 0.05～10 μ m, more preferably about 0.05～5 μ m.Under the situation of flakey silver particle, the major diameter of the face of scale is preferably the scope of 0.05～100 μ m.
As silver-colored particle, by making up the particle that two or more volume average particle size varies in size, improve the packed density of silver-colored particle, thereby the electric conductivity of conductive film is improved.
As the silver compound particle, can use the particle of argentiferous organic compounds such as silver oxide and silver aliphatic carboxylate, ester ring type silver carboxylate, aromatic carboxylic acid silver etc.These silver compound particles (graininess silver compound) can use industrial material, can also use the material that obtains by reaction from the aqueous solution that contains silver compound.Particularly when to use average grain diameter be silver compound particle below the 0.5 μ m, the speed of reduction reaction accelerated, and is preferred.Generating average grain diameter by the reaction of silver compound and other compound is silver compound particle below the 0.5 μ m, for example, can alkaline aqueous solutions such as NaOH be added drop-wise to the method manufacturing that makes its reaction obtain silver oxide particle in the silver nitrate aqueous solution by stirring down.
In manufacture method of the present invention, preferably use the following silver or the particle of silver compound, it makes the firing temperature of silver-colored particle fusion bonding can be below 300 ℃ by heating this silver paste when making silver-colored paste.The silver-colored paste of the easy fired type that firing temperature is low like this can directly burn till the line pattern that is formed on for example polyimide film, the PET film.Generally, be dispersed with conductive particle in the conductive paste imperceptibly, the thermal capacitance of conductive paste is low more, and the firing temperature of conductive paste approaches the intrinsic sintering temperature of conductive particle itself.And along with conductive particle disperses and its packed density improves imperceptibly, therefore general high dispersive, it is good that the electric conductivity after burning till becomes more.
And, the silver-colored paste of the surface-treated silver-containing powder that use obtains by manufacture method of the present invention, owing to can reduce resinous principle, the thickness of the resin of the particle of coated with silver or silver compound is thin, therefore burns till fusion easily between the particle of adjacent silver in back or silver compound.Therefore, as being fed into the silver in the surface treatment that utilizes surfactant or the particle of silver compound, when using sintering temperature to be the particle of the silver of the low-temperature sintering type below 300 ℃ or silver compound, even if after utilizing surfactant to carry out surface treatment, also can give full play to its low-temperature sintering originally, can obtain the silver-colored paste of easy fired type, in addition, make and to obtain the good line pattern of electric conductivity after silver-colored paste burns till.
As the low silver-colored particle of sintering temperature, can use volume average particle size is the silver-colored particle of 0.05～10 μ m.The volume average particle size of the silver-colored particle of further preferred use is the silver-colored particle of 0.05～5 μ m.In surface treatment method of the present invention; when in liquid phase, making silver-colored particle or silver compound particle; can be effectively little and active high particle carries out surface treatment to these volume average particle size; and; can be under these particles be dispersed in state in liquid phase when manufactured, directly the particle to silver or silver compound carries out surface treatment in the presence of surfactant.Therefore, handle becoming easily, can give full play to the low particle of these sintering temperatures characteristic originally.As the manufacture method of silver-colored particulate, the reduction precipitation method (Japanese kokai publication hei 11-319538 communique) that uses amines in evaporation (Japanese kokai publication hei 3-34211 communique) in the gas for example, the reduction is arranged.
In addition, as the low silver-colored particle of sintering temperature, can use the low silver-colored particle of crystallization degree.When the crystallization degree of silver particle was low, the crystallite diameter diminished usually.Therefore, diminish, can significantly reduce silver-colored intergranular bond vitrified temperature (sintering temperature) by making the crystallite diameter.For but the firing temperature that makes silver-colored paste is reduced to below 300 ℃, the crystallite diameter is preferably 0.1～20nm, more preferably 0.1～10nm.
In addition, as the low silver-colored particle of sintering temperature or the particle of silver compound, the silver-colored particle that can use the oxidized silver of a part of particle to handle.The silver-colored particle that silver oxide is handled can make by the following method: utilize partial oxidation to handle, make the surface of silver-colored particle be oxidized to the method for silver oxide from silver; And the method etc. that on the surface of silver-colored particle, coat to form the layer of silver oxide.
By the oxidation processes of silver-colored particle surface, the silver of particle surface is oxidized to silver oxide (I), silver oxide (II) etc.In the silver-colored particle that the oxidized silver of particle surface coats, the silver oxide of particle surface can be in silver oxide (I), silver oxide (II) etc. and mix the state that exists.The silver-colored particle that the oxidized silver of these particle surfaces coats is not under existing reducing agent or exist in the reduction reaction under the reducing agent, and the silver oxide on top layer becomes silver, bond vitrified between the adjacent particle under low temperature.The silver-colored particle that the oxidized silver in surface is handled can be according to reduction reaction conditions, i.e. the reducing power of the having or not of heating-up temperature, reducing agent, reducing agent etc. is suitably selected to form, variform silver-colored particle.The volume average particle size of the silver-colored particle that silver oxide is handled is preferably 0.05～10 μ m, more preferably about 0.05～5 μ m.When particularly using average grain diameter to be the particle of 0.05～0.5 μ m, the speed of reduction reaction accelerates, and is preferred.
When use is carried out surface-treated silver particle with silver oxide, be reduced into the oxygen that silver is emitted owing to being accompanied by from silver oxide, circumgranular organic matter is oxidized, can obtain heat release, therefore, can the be reduced effect of apparent firing temperature of silver powder and silver-colored paste.Here, the silver oxide containing ratio that carries out surface-treated silver particle with silver oxide is preferably (silver-colored containing ratio is that 99 quality % are following) more than the 1 quality %, and the silver oxide containing ratio is preferably 5 quality % above (silver-colored containing ratio is that 95 quality % are following) especially.In addition, from making the viewpoint of the easy bond vitrified of silver-colored particle, be desirably in granule interior and have a certain amount of argent, the silver oxide containing ratio is preferably 30 quality % following (silver-colored containing ratio is more than the 70 quality %), and the silver oxide containing ratio is preferably 20 quality % following (silver-colored containing ratio is more than 80 quality) especially.The preferable range of carrying out the silver oxide containing ratio of surface-treated silver particle with silver oxide is 1～30 quality %, and preferred scope is 5～20 quality %.
Silver-colored particle for these silver oxides processing, by being suitable for of the present invention is the surface treatment method of feature with the vacuum freeze drying, can produce the low silver-colored paste of firing temperature with good electrical conductivity, in addition, can also stably preserve these particles with character of very easy reduction when drying.In addition, in the silver-colored paste, silver-colored particle stably disperses with fine particle (1 particle), and therefore, unwanted aggregation in the bond vitrified between the particle in the time of can preventing to be created in reduction does not have the problem of meticulous printing aspect to take place.
(surfactant)
In the present invention, as the surfactant of the surface treatment of the particle that is used for silver or silver compound, the surfactant and the phosphorus containing ratio that can list alkyl amine or alkylamine salt are the surfactant of the phosphoric acid ester of 0.5～10 quality %.
(surfactant of alkylamine and alkylamine salt)
As the surfactant that uses among the present invention, can suit to use alkylamine and alkylamine salt.The cationic surfactant of the nonionic surfactant of alkyl amine and alkylamine salt uses also effective respectively separately, but particularly by being used in combination, it is better that dispersiveness becomes, and effect is remarkable.
As the alkyl amine surfactant, preferred polyoxyalkylene alkylamine type surface-active base, further preferred polyoxyethylene alkyl amine type surfactant.Wherein, the material that further preferably has following general formula (1).
(a, b are respectively 1～20 integers, and R represents the alkyl or the alkylaryl of carbon number 8～20.)
On the other hand, as the surfactant of alkylamine salt, the acetate of preferred alkyl amine wherein, further preferably has the material of following general formula (2).
(R-NH
3 +)(CH
3COO
-) (2)
(R represents the alkyl or the alkylaryl of carbon number 8～20.)
In general formula (1) and general formula (2), alkyl as carbon number 8～20, it can be straight chained alkyl, also can be branched alkyl, can list for example octyl group, nonyl, decyl, undecyl, dodecyl, lauryl, myristyl, myristyl, cetyl, cetyl, octadecyl, stearyl, eicosyl etc.As the alkylaryl of carbon number 8～20, can list for example alkyl phenyls such as octyl phenyl, nonyl phenyl, dodecylphenyl.The moieties of alkylaryl can be a straight chained alkyl, also can be branched alkyl.
When being used alone or as a mixture the cationic surfactant of alkyl amine surfactant and alkylamine salt, need according to the kind of the particle of silver or silver compound suitably adjust total combined amount of the surfactant of the particle of silver or silver compound this moment, for example the particle with respect to 100 parts of quality silver or silver compound is preferably 0.01～3.00 mass parts, more preferably 0.05～1.50 mass parts.When total combined amount of surfactant is 0.01 mass parts when above, have to obtain dispersed fully tendency easily.On the other hand, when total combined amount of surfactant is that 3.00 mass parts are when following, the particle surface of silver or silver compound is coated thinly by the organic principle of surfactant, and the contact between the dried particle of acquisition easily that becomes has the tendency that electric conductivity improves.
When the cationic surfactant of the surfactant of alkyl amine and alkylamine salt used simultaneously, the mixed proportion of alkyl amine and alkylamine salt was preferably 1: 20～1: 5 scope.
(phosphoric acid ester surfactant)
The phosphoric acid ester surfactant that uses in the present invention is with the surfactant as principal component such as phosphate monoester or di-phosphate ester, and using the phosphorus containing ratio is the material of 0.5～10 quality %.The phosphoric acid ester surfactant is preferably the phosphate of polyoxyalkylene alkyl, further preferably has the represented chemical constitution of following general formula (3).
(in the general formula (3), R represents the alkyl or the alkylaryl of carbon number 1～20, and n represents 1～20 integer, and x represents 1 or 2 integer).
In formula (3), alkyl as carbon number 1～20, it can be straight chained alkyl, also can be branched alkyl, can list for example methyl, ethyl, propyl group, isopropyl, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl, lauryl, myristyl, myristyl, cetyl, cetyl, octadecyl, stearyl, eicosyl etc.As the alkylaryl of carbon number below 20, can list for example alkyl phenyls such as octyl phenyl, nonyl phenyl, dodecylphenyl.The moieties of alkylaryl can be a straight chained alkyl, also can be branched alkyl.
In addition, the carbon number of preferred R is 1～10, n be 1～10 and carbon number and the n sum of R be 7～15.The weight average molecular weight of phosphoric acid ester surfactant is preferably 100～10,000, and more preferably 150～5000.The content of P (phosphorus) is preferably 0.5～10 quality %, and more preferably 1～7 quality % is preferably 2～6 quality % especially.2～5 quality % more preferably.
In addition, as the phosphoric acid ester surfactant that is used for manufacture method of the present invention, preferred use HLB (hydrophile-lipophile balance, hydrophilic lipophilic balance) is the surfactant more than 10, perhaps adds in the alkali compounds and uses with acid value.
The kind of phosphoric acid ester surfactant and combined amount can suitably be selected according to the kind of silver or silver compound particle.The combined amount of phosphoric acid ester surfactant need suitably be adjusted according to the kind of the particle of silver or silver compound, for example the particle with respect to 100 mass parts silver or silver compound is preferably 0.01～3.00 mass parts, more preferably 0.05～0.50 mass parts.When surfactant is 0.01 mass parts when above, having becomes obtains dispersed fully tendency easily.On the other hand, when surfactant is 3.00 mass parts when following, the surface of the particle of silver or silver compound is coated thinly by the organic principle of surfactant, becomes and obtains contact between the dried particle easily, has the tendency that electric conductivity improves.
(1) dispersion liquid modulating process
In the manufacture method of surface-treated silver-containing powder of the present invention, at first, the modulation dispersion liquid, that is, the particle that makes silver or silver compound is that the phosphoric acid ester surfactant of 0.5～10 quality % is distributed to and disperses with the dispersion liquid that forms in the solvent with alkyl amine or alkylamine salt surfactant or phosphorus containing ratio.
(disperseing to use solvent)
At this,, just be not particularly limited with solvent (decentralized medium) as the dispersion of the particle that is used to disperse silver or silver compound so long as be suitable for dissolving the solvent of described surfactant, for example can list water; Lower alcohol such as ethanol, isopropyl alcohol; The propylene oxide adduct of alkylols such as the ethylene oxide adduct of alkylols such as glycol hexyl ether, diethylene glycol butyl ether, propylene glycol propyl ether etc.These disperse with in the solvent, preferred water.
These dispersions are not limited to the material of enumerating at this with solvent, can separately or mix two or more (for example, making the aqueous solution, mixed solvent) and use when it uses.
(modulator approach of dispersion liquid)
The modulator approach of disperseing the dispersion liquid that forms with described surfactant as the particle of silver or silver compound, can list following method: the particle of silver or silver compound and surfactant are added to disperse, the method for utilizing mixer or dispersion machine that the particle of silver or silver compound is ground into subparticle (1 particle) and mixes with described surfactant with in the solvent.In this case, for example, with the ratio combined silver particle of expectation, disperse, utilize dispersion machine etc. to make silver-colored particle be ground into particle 1 time, and it is distributed to disperse thus, can obtain the dispersion liquid of silver-colored particle with in the solvent with solvent, surfactant.It also is the same replacing silver-colored particle and using the situation of the silver-colored particle of silver compound particle or silver oxide processing.Add to when disperseing to use in the solvent, if will make the powder (dried powder) of silver or silver compound as the particle of the silver of raw material or silver compound, then easy use amount optimization with particles such as silver, in addition, having the advantage that can prevent the composition do not expected to sneak into etc. from raw material in dispersion step, is preferred.
As spendable mixer or dispersion machine, can from known mixer of aftermentioned or dispersion machine, suitably select to use.
When the powder that makes described silver or silver compound was distributed in the dispersion usefulness solvent, preferred described dispersion cooperated silver or silver compound powder with mixed surfactant in the solvent and after it is fully dissolved.Can be as required, by in and surfactant (for example, under the situation of phosphoric acid ester surfactant, utilizing generation phosphate ester salts such as alkali metal) improve this surfactant to disperseing solubility with solvent.When cooperating the back to disperse 0.5～4.0 hour, 2 particles (particle of gathering) in silver powder or the silver compound powder are ground into particle 1 time, and 1 particle of surfactant and silver or silver compound reaches adsorption equilibrium.
In addition, as other dispersion liquid modulator approach, the particle of synthetic silver or silver compound in liquid phase (below, be sometimes referred to as particles such as " " silver) after, from mother liquor, filter particles such as silver, behind the particles such as washing silver, it is distributed to disperses with in the solvent.In the method, expect particles such as moist silver, can suitably set processing such as having or not filtration, washing.
In addition, having synthesized the silver-colored solvent (for example water) of the mother liquor of particle that waits also can directly use with solvent as the dispersion in the dispersion liquid.In this case, can omit the processing of particle such as isolated by filtration silver from mother liquor.In addition, when coexistence in the mother liquor has unwanted composition, the processing of removing this unwanted composition as required.Then, after the dispersion liquid that dispersion forms to particles such as silver adds the surfactant of aequum, carry out freeze drying and handle.When in mother liquor, being added with suitable surfactant, can use it for freeze drying and handle, also can further add surfactant.
Adopt this method,, thereby can suppress agglomeration of particles such as silver, and can obtain silver-colored particle and disperse the dispersion liquid that forms with surfactant because the particles such as silver that generate are 1 particles in the liquid phase.In this case, needn't be used for 2 particles of silver etc. are ground into the use mixer of 1 particle or the processing of dispersion machine, even the degree gentleness that stirs, mixes also can obtain particle such as silver and be dispersed in the dispersity of disperseing with the expectation in the solvent with the form of 1 particle.
The dispersion liquid of the particles such as silver that contain surfactant that make by the dispersion liquid manufacture method shown in the above example carries out freeze drying in subsequent processing handles.The scope of the solid component concentration in the dispersion liquid of the particles such as silver when carrying out freeze drying is preferably 0.5～80 quality %, is preferably 1～50 quality % especially.
In the present invention, under the situation of using the phosphoric acid ester surfactant, as the result who uses, preferred dispersion liquid becomes acid condition (for example pH1～3), when using alkylamine or alkylamine salt surfactant, preferred dispersion liquid becomes alkali condition (for example pH12～14).Thus,, produce interfacial electric double layer, obtain dispersion stabilization on the surface of particles such as silver by surfactant.In addition, phosphoric acid ester and alkylamine or alkylamine salt, the opposite charge during its hydrophilic group partial ionization, thereby preferably select a class surfactant to use according to the symbol of the surface charge of particles such as silver, so that repulsive force works between particle.
For example, under the situation of the silver-colored particle that the oxidized silver in surface is handled, the surfactant of preferred alkyl amine or alkylamine salt, the silver-colored paste that is obtained by this combination have thixotropy excellence, characteristics that loading is big.In addition, under the situation of fine silver particle (the silver-colored particle that the not oxidized silver in surface is handled), the surfactant of preferably phosphoric acid ester class by the silver-colored paste that this combination obtains, has the characteristics of the excellent dispersion in adhesive resin.
(2) drying process
With in the solvent, the particle of silver or silver compound is removed the dispersion solvent by vacuum freeze-drying method from this dispersion liquid after fully disperseing in the presence of the surfactant in described dispersion.
In manufacture method of the present invention, seasoning is used vacuum freeze drying, thereby the preferred use freezing solvent easily of selecting from above-mentioned solvent.In order to carry out vacuum freeze drying, if consider that the cooling capacity of common obtainable device is to about-40 ℃, then can select its freezing point for the dispersion solvent more than-40 ℃, can reduce implementation cost like this, so preferred.
In the employed vacuum freeze-drying method of manufacture method of the present invention, be basically the dispersion liquid freezing under low-temperature condition only distillation remove described dispersion solvent.In this process, surfactant can stripping to disperseing with in the solvent and lose, therefore, the surfactant that is added almost all remains in the silver or silver compound powder after the processing.As shown in Figure 1, in dispersion liquid, surfactant b part is present in the near surface of the particle a of silver or silver compound, when implementing only to remove the vacuum freeze drying of disperseing the usefulness solvent, be adsorbed in the possibility height that the state on surface of the particle a of silver or silver compound takes out equably with this surfactant b, and, can be as utilizing usual method except that vacuum freeze drying when desolvating, assemble between the particle a of silver or silver compound, the surface-treated particle c when removing, can be described as extremely effectively processing method.So, whole surfaces that after vacuum freeze drying, also remain in the particle a of silver or silver compound of the surfactant b that uses in the dispersion liquid, yield provides well by the particle c of surfactant b surface-treated silver or silver compound, therefore, grasp the effect of surfactant and the relation of use amount easily.In addition, carry out optimization easily, thereby can prevent that the addition of surfactant from becoming superfluous use amount.
The molecule of surfactant b is adsorbed in the surface of the particle a of silver or silver compound with the end of hydrophilic group side, so the end of hydrophobic group side is towards the outside of particle.Thus, be improved with the compatibility of adhesive resin, the dispersiveness of the particle c of surface-treated silver or silver compound is improved.In addition, the gathering between the particle is suppressed, and can continue to be dispersed into the state of 1 particle.
Vacuum freeze drying can make with the following method: precooling to the dispersion under atmospheric pressure of described dispersion liquid is used below the freezing point of solvent, again with the pressure control vacuum forced down with the steam of solvent than the dispersion under the freezing point and carry out vacuum freeze drying, thus, can from the solid mixture of freezing state, make the molecules sublimated of disperseing in theory with solvent.
For example, make water as under the situation of dispersion with the dispersion liquid (dispersion liquid that comprises particle, water and the surfactant of silver or silver compound) of solvent, under atmospheric pressure below the precooling to 0 ℃, again vacuum degree control is become to be no more than in theory the vapour pressure 4.5mmHg of 0 ℃ of following water (=600Pa) get final product.If consider the easiness of rate of drying, control, then preferably be controlled to be 1mmHg following after, be warming up to the fusing point (freezing point) under this vapour pressure.
So, in utilizing the drying means of vacuum freeze drying, owing to make dispersion with solvent distillation evaporation, dried particles in a vacuum, thereby the dry contraction that causes is minimum, survivable tissue, structure.In addition, do not exist as heated-air drying liquid components such as for example water in the sample at high temperature owing to the dry phenomenon that moves, being to carry out low temperature drying under the freezing state of solid, thereby almost not having composition localized concentrations, composition localized variation, distortion, is preferred.
(3) manufacturing of silver-colored paste
Make conductive paste (silver-colored paste) in order to use by the surface-treated silver-containing powder of manufacture method manufacturing of the present invention, silver-containing powder (powder of silver or silver compound) after aforementioned surfaces handled and solvent or adhesive resin and solvent mix, and use the suitable dispersion machine dispersion silver or the powder of silver compound.
The solvent that uses in the manufacturing of silver-colored paste of the present invention can list methyl alcohol, ethanol, normal propyl alcohol, phenmethylol, terpineol alcohols such as (Terpineol); Ketones such as acetone, MEK, cyclohexanone, isophorone, acetylacetone,2,4-pentanedione; N, dinethylformamide, N, amide-types such as N-dimethylacetylamide; Ethers such as oxolane, diox, methyl cellosolve, diethylene glycol dimethyl ether, BC; Ester classes such as methyl acetate, ethyl acetate, diethyl carbonate, TXIB (1-isopropyl-2,2-dimethyl trimethylene diisobutyrate), acetic acid carbitol, acetic acid BC; Sulfoxide such as methyl-sulfoxide, sulfolane and sulfone class; Carrene, chloroform, carbon tetrachloride, 1,1, aliphatic halogenated hydrocarbons such as 2-trichloroethanes; The fragrant same clans such as benzene, toluene, ortho-xylene, paraxylene, meta-xylene, monochlor-benzene, dichlorobenzene etc.
These solvents are not limited to the material enumerated at this, can be used alone or in mixture of two or more during use.
The powder that is carried out surface-treated silver or silver compound by method of the present invention can be used as the silver-colored paste of coating on the base material under the state in being distributed to aforementioned solvents, preferably further add adhesive resin and the dispersion stabilization of silver or silver compound is improved, and improve cementability, thereby as silver-colored paste to matrix.
Adhesive resin as can be used in the silver-colored paste of the present invention can be used alone or in mixture of two or more following resin: acrylic resin, butyral resin, polyvinyl alcohol resin, acetal resin, phenolic resins, urea resin, acetate emulsion, polyurethane resin, mylar, polyvinyl acetate resin, epoxy resin, melamine resin, alkyd resins, nitrocellulose resin, natural resin.
The preferred per 100 mass parts surface-treated silver-containing powders of the use amount of aforementioned adhesion agent resin are the scope of 0.01～30 mass parts, are preferably the scope of 0.01～10 mass parts especially.
In addition, the use amount of solvent can suitably be selected use amount according to coating process, printing process and different.
If surface-treated silver-containing powder of the present invention as raw material, when needs silver paste, as long as use solvent or solvent and adhesive resin and simple dispersion treatment such as stir, just can be made silver-colored paste fast.That is, soon carry out simple stirring operation with the interpolation solvent or with interpolation solvent and interpolation adhesive before the printing, thereby can obtain good silver-colored paste, therefore, do not need to be used to modulate a large amount of auxiliary equipment of paste in the printing equipment.But,, can use following dispersal device to carry out dispersion treatment in order to disperse more reliably.
As spendable dispersal device, can list two roller roller mills, three roller roller mills, ball mill, puddle mixer, pebble mill, roll grinding machine (tron mill), sand milling, Szegvari grater, quick runner formula disperser, high speed stone crusher, high-speed impact grinder, kneading machine, homogenizer, ultrasonic dispersing machine etc., can carry out mixing, dispersion by using these devices.
Finished the mixing and silver-colored paste that disperses composition as pasty state, can by known coating process commonly used or print process be printed onto on the dielectric film or heat on the insulated substrate and to it and form conducting channel.
Silver-colored paste of the present invention can form the coating thing by various coating processes.Can be by known roller coat cloth method for example etc., scrape coating, blade coating, rod coating, extrusion coated, airblade coating, extrusion coated, dip coated, reverse roll coating, transferring roller coating, intaglio plate coating, kiss-coating, curtain coating coating, spraying etc. by air knife specifically, formation is coated with thing on matrix.In addition, can also be suitable for various printing processes.In the method that also exists in the print process as optimum viscosity zone the intaglio printing is in the method in lower viscosity zone and the optimum viscosity zone is in the high viscosity zone as serigraphy.Stencil printing method, gravure process, lithographic process etc. can be used specifically, can on matrix, the size that thing is printed as regulation will be coated with.
The material of the matrix during as coating or printing for example can list PETG (PET film), polyimide film (PI film) or tellite (green sheet) (inorganic substrate).Behind pattern that on these films silver-colored paste is printed as regulation and dry printed article, processing also can be heating and curing.
In addition, the thickness of printed article is different because of print process, but the thickness during printed article dry is preferably the scope of 1～30 μ m, is preferably the thickness of 1～15 μ m especially.After the printed article drying,, can carry out compression process or calendering processing that matrix does not produce remarkable deformation extent for the resistance (volume resistance) that improves per unit volume.
With the coating thing that obtains thus for example about 160 ℃ dry about 5 minutes down, then carry out the curing of adhesive resin by about 250 ℃ heat treatment step.Can obtain the conducting channel that various electronic circuit boards are used thus.
When particularly using the oxidized silver-colored silver-colored particle of handling in silver oxide particulate or surface as silver or silver compound particle; when handling generation curing by aforementioned hot; be reduced into silver by silver oxide; can make surfactant, resin oxidation on every side by the oxygen of following reduction reaction to emit, produce heat.Consequently can under the heat treatment of comparing lower temperature (for example 160～200 ℃) with the situation of using the fine silver particle, make bond vitrified between the silver-colored particle that the silver oxide reduction forms.Therefore, when can reducing coating or printing, the silver-colored paste that the silver-colored particle that uses silver oxide particle or silver oxide to handle makes, therefore, the matrix of formation such as PET, PI, other plastics is particularly suitable for the stable on heating requirement of matrix material.
Shown in Fig. 2: the low sintering silver powder (the little silver powder of crystallite diameter that silver oxide is handled) that utilizes surfactant to carry out the silver powder after the surface treatment and use silver oxide to handle that uses that low sintering silver powder (silver powder that the crystallite diameter is little) makes is made utilizes surfactant to carry out the result of the differential thermal analysis (dsc analysis) of the silver powder after the surface treatment.
Among the dsc analysis result (being represented by dotted lines among Fig. 2) of the silver powder after the surface treatment of the present invention that the silver powder that use crystallite diameter is little is made, the endothermic peak of the fusion of expression silver powder appears at 215 ℃.Therefore this expression carries out fusion because the crystallite diameter of silver powder is little under than low in the past temperature.
In addition, the dsc analysis result of the silver powder after the surface treatment of the present invention that the silver powder that uses silver oxide to handle is made (represents with solid line among Fig. 2.) in, the endothermic peak of the fusion of expression silver powder appears at 215 ℃, and exothermic peak occurs at 134 ℃.This exothermic peak can be thought that the silver oxide of this silver powder decomposes and emits oxygen and the carbon component of the surfactant on surface is carried out oxidation and exothermic reaction has taken place.
Embodiment
Below, be described more specifically the present invention with embodiment, but the present invention is not limited to the scope of these embodiment.In addition, assay method such as rerum natura is as described below.
(1) thickness: thickness is to use film thickness gauge K402B (Anritsu Corp. manufacturing) to measure.
(2) specific insulation: specific insulation is to use the low-resistivity meter Rolester EP (Mitsubishi Chemical's (strain) manufacturing) of four terminal mensurations to measure.Try to achieve specific insulation from the thickness of the conductive film of sample.In addition, specific insulation is by for example with 8.8 * 10
-6Ω cm is recited as the method for " 8.8E-06 Ω cm " and represents.
In addition, surfactant A and the B that uses in the present embodiment is following material.
(surfactant A)
Use surfactant D isperbyk-111 (BYK-Chemie Japan KK manufacturing), it is that the phosphate monoester of 2.7 quality % is that principal component, weight average molecular weight are 2800 with P (phosphorus) content value, the utilization potassium hydroxide of amount of its sour composition described surfactant that neutralizes that can neutralize is fully made 10 quality % aqueous surfactant solutions.
(surfactant B)
Use a surfactant, it is that P (phosphorus) content value is that polyoxyalkylene alkyl phosphate, the weight average molecular weight of 4.4 quality % is 1750, HLB is 12, the utilization potassium hydroxide of amount of its sour composition described surfactant that neutralizes that can neutralize is fully made 10 quality % aqueous surfactant solutions.
(surfactant C)
5g as the 10 quality % aqueous solution of the coconut amine acetic acid esters of alkylamine salt cationic surfactant, the 0.5g 10 quality % aqueous solution as the polyoxyethylene coconut oil alkyl ether amine of alkylamine surfactant, is mixed and uses with this weight ratio.
(embodiment 1)
(crystallite diameter＜10nm), the 2.5g plastic bottle of putting into 250cc as the zirconium oxide bead of the water of solvent and 400g diameter 2mm as the 10 quality % aqueous solution of the surfactant A of surfactant, 50g mixes the silver powder FHD that Mitsui Metal Co., Ltd.'s (strain) of 50g medium particle diameter 0.3 μ m is made, use whirler (ball mill) mixing 4 hours, and obtained the dispersion liquid (a1) of silver powder.
Dispersion liquid (a1) 100g of this silver powder is put into the square position that the bottom surface is of a size of 200mmL * 150mmW, after the precooling drying, carry out vacuum freezedrying." DFM-05AS " that frozen vacuum dryer uses Japanese vacuum (strain) to make.The dispersion liquid (a1) of the silver powder of precooling is placed on the shelf that is cooled to approximately-40 ℃ in advance, after 20 hours, obtains surface treatment thing (b1) 50g of the silver powder of loose spongy dry thing shape with vacuum 7～10Pa vacuum freezedrying.The size distribution of the silver-colored particle of this moment is shown with volume reference in Fig. 3.Volume average particle size is 0.6 μ m.Then, with surface treatment thing (b1) 50g of silver powder, (solid constituent=2.5g) and the 2.7g acetic acid carbitol plastic bottle of putting into 250cc mixes as acrylic resin " #15-78 " (eastern Rong Huacheng (strain) manufacturing) 5.6g of adhesive resin, use oscillator (paint mixing unit) to mix and stirred 0.5 hour, obtain silver-colored paste B-1.This silver paste can not cause that viscosity in time rises, assembles, and is stable.With this paste B-1, form the printed patterns of the size of 50mm * 80mm with live width 50 μ m on the PI film, the serigraphy that obtains thick 10 μ m is filmed.It is following dry 5 minutes at 150 ℃ that this printing is filmed.After this, put into the kiln roasting 60 minutes of 160 ℃ and 250 ℃, use the microscopic examination printed state, the result has formed flawless favorable conductive circuit pattern.Carry out the full pattern printing of thick 50 μ m again, after carrying out drying equally, burning till, measure the volume resistance of dry coating.
After the drying, the volume resistance of stove after 60 minutes of putting into 160 ℃ and 250 ℃ is shown as 2.9E-03 Ω cm and 6.7E-06 Ω cm respectively.In addition, in stove, the volume resistance of dry coating descends in time.The minimizing of the volume resistance when furnace temperature shown in Fig. 4 is 250 ℃.
(embodiment 2)
Except the surfactant among the embodiment 1 being changed into surfactant B,, obtain dispersion liquid (a2) 105g of silver powder and surface treatment thing (b2) 50g of silver powder by method similarly to Example 1.The average volume particle diameter of this surface treatment thing is 0.6 μ m, and the particle diameter that demonstrates similarly to Example 1 distributes.
Then, operation obtains 58.3g silver paste B-2 similarly to Example 1.This silver paste can not cause that viscosity in time rises, assembles, and is stable.The mask that use is formed with the printed patterns of 50 μ m live width conducting channels carries out serigraphy, obtains printing similarly to Example 1 and films.Carry out the full pattern printing of 50 μ m thickness more similarly to Example 1, measure the volume resistance of stove after 60 minutes of putting into 160 ℃ and 250 ℃ after the drying, the result is shown as 1.7E-02 Ω cm and 1.5E-05 Ω cm respectively.
(embodiment 3)
Except the silver powder Ag C-G that the silver powder FHD among the embodiment 2 is changed into FUKUDA METAL's paper tinsel powder (strain) manufacturing,, obtain dispersion liquid (a3) 105g of silver powder and surface treatment thing (b3) 50g of silver powder by method similarly to Example 2.The volume average particle size of the silver-colored particle of this moment is 0.2 μ m, demonstrates the narrow size distribution of distribution range.
Then, by method similarly to Example 1, obtain 58.3g silver paste B-3.This silver paste can not cause that viscosity in time rises, assembles, and is stable.Use the mask that is formed with printed patterns similarly to Example 1, carry out serigraphy, obtain printing and film.Carry out the full pattern printing of 50 μ m thickness more similarly to Example 1, measure the volume resistance of stove after 60 minutes of putting into 160 ℃ and 250 ℃ after the drying, the result is shown as 4.5E-05 Ω cm and 2.5E-05 Ω cm respectively.
(embodiment 4)
Except the silver powder FHD among the embodiment 2 being changed into the silver powder Ag that handle with 10% silver oxide on its surface
2Beyond the OFHD,, obtain dispersion liquid (a4) 105g of the silver powder that silver oxide handles and surface treatment thing (b4) 50g of the silver powder that silver oxide is handled by method similarly to Example 2.The size distribution of the silver-colored particle of this moment is shown with volume reference among Fig. 5.Volume average particle size is 0.7 μ m, demonstrates the narrow size distribution of distribution range.
Then, by method similarly to Example 1, obtain 58.3g silver paste B-4.This silver paste can not cause that viscosity in time rises, and is stable.Use the mask that is formed with printed patterns similarly to Example 1, carry out serigraphy, obtain printing and film.Carry out the full pattern printing of 50 μ m thickness more similarly to Example 1, should print dried coating film 5 minutes at 150 ℃.Then, be determined at the volume resistance of the dry coating in the stove of 160 ℃ and 250 ℃.
After the drying, the volume resistance of stove after 60 minutes of putting into 160 ℃ and 250 ℃ is shown as 9.8E-05 Ω cm and 1.5E-05 Ω cm respectively.
(embodiment 5)
(plastic bottle that crystallite diameter＜10nm), surfactant C (5g is as the 10 quality % aqueous solution of the coconut amine acetic acid esters of alkylamine salt cationic surfactant, the 0.5g 10 quality % aqueous solution as the polyoxyethylene coconut oil alkyl ether amine of alkylamine surfactant), 50g put into 250cc as the zirconium oxide bead of the water of solvent and 400g diameter 2mm mixes the silver powder FHD that 10% silver oxide that Mitsui Metal Co., Ltd.'s (strain) of 50g medium particle diameter 0.3 μ m is made is handled, use whirler (ball mill) mixing 4 hours, and obtained silver-colored paste (a5).
Dispersion liquid (a5) 100g of this silver powder is put into the square position that the bottom surface is of a size of 200mmL * 150mmW, after the precooling drying, carry out vacuum freezedrying." DFM-05AS " that frozen vacuum dryer uses Japanese vacuum (strain) to make.The dispersion liquid (a5) of the silver powder of precooling is placed on the shelf that is cooled to approximately-40 ℃ in advance, after 20 hours, obtains surface treatment thing (b5) 50g of the silver powder of loose spongy dry thing shape with vacuum 7～10Pa vacuum freezedrying.The size distribution of the surface-treated silver particle of this moment shown in Figure 6.
Then, surface treatment thing (b5) 50g with silver powder, the solvent composition of the mixture of polyol component " BARNOC DE-140-70 " (big Japanese ink chemical industry (strain) make) and " BARNOC DB 980 " (big Japanese ink chemical industry (strain) is made) and isocyanuric acid ester prepolymer composition " BARNOC DB 980K " (big Japanese ink chemical industry (strain) manufacturing) is replaced to the adhesive resin 4.17g that the acetic acid carbitol obtains (solid constituent=2.5g), and the plastic bottle that acetic acid carbitol 4.2g puts into 250cc mixes, use oscillator (paint mixing unit), mix and stirred 0.5 hour, obtain silver-colored paste B-5.Use this silver paste B-5 on the PI film, to form the rectangle of 50mm * 80mm and the printed patterns of line/blank=40 μ m/40 μ m, obtain serigraphy and film.The average thickness that rectangular printing is filmed is 12 μ m.On the other hand, measure the distribution of the thickness in the printed patterns with laser microscope (VK-9500 Keyence Corporation manufacturing).Its section is shown in Fig. 7.At this, the situation of silk screen version is 640 orders, line footpath 15 μ m, calendering thick 22 μ m, the thick 10 μ m of emulsion.The mean value of the peak height of printed patterns is 11.9 μ m.
At 150 ℃ with rectangular printing dried coating film 5 minutes.After the drying, measure the specific insulation of stove after 60 minutes put into 160 ℃ and 250 ℃, the result demonstrates 3.7E-05 Ω cm and 7.5E-06 Ω cm respectively.In addition, in stove, the volume resistance of dry coating descends in time.The minimizing of the volume resistance when furnace temperature shown in Fig. 8 is 160 ℃ and 250 ℃.
(comparative example 1)
Replace the surfactant among the embodiment 1, use 0.5g acrylic compounds surfactant D isperbyk-2001 (BYK-Chemie Japan KK manufacturing), it has the di-phosphate ester that the P content value is 0.4 quality % in composition, weight average molecular weight is 2500, in addition, by method similarly to Example 1, obtain dispersion liquid (a6) 105g of silver powder and surface treatment thing (b6) 50g of silver powder.The particle diameter distribution of this surface treatment thing is shown with volume reference in Fig. 3.Then, use silver-colored paste B6, use the mask that is formed with printed patterns similarly to Example 1, carry out serigraphy, the result causes obstruction in the part of mask, can not carry out the printing of fine rule.In addition, carry out the full pattern printing of 50 μ m thickness similarly to Example 1, should print dried coating film 5 minutes at 150 ℃.After this, measure the volume resistance of the dry coating of stove after 60 minutes put into 160 ℃ and 250 ℃.
After the drying, the volume resistance of stove after 60 minutes of putting into 160 ℃ and 250 ℃ is shown as 2.5E+01 Ω cm and 2.2E-05 Ω cm respectively.In addition, in stove, the volume resistance of dry coating descends in time.The minimizing of the volume resistance when Fig. 4 illustrates furnace temperature and is 250 ℃.
(comparative example 2)
Replace the surfactant among the embodiment 1, use Hitenol NF13 (the DAI-ICHI KOGYO SEIYAKU CO. of 0.5g as highly purified emulsifying dispersant, LTD. produce), in addition, by method similarly to Example 1, obtain dispersion liquid (a7) 105g of silver powder and surface treatment thing (b7) 50g of silver powder.The volume average particle size of this surface treatment thing is 1.5 μ m, and demonstrating maximum particle diameter is the particle diameter distribution of 35 μ m.Then, similarly to Example 1, use the silver-colored paste B6 of made, and use the mask that is formed with printed patterns to carry out serigraphy, the result causes obstruction in the part of mask, can not carry out the printing of fine rule.
(comparative example 3)
Replace the surfactant among the embodiment 1, use the special carboxylic acid type high molecular surfactant of 0.5g Poise 520 (Kao Corporation manufacturings), in addition, by method similarly to Example 1, obtain dispersion liquid (a8) 105g of silver powder and surface treatment thing (b8) 50g of silver powder.The volume average particle size of this surface treatment thing is 0.9 μ m, and demonstrating maximum particle diameter is the particle diameter distribution of 24 μ m.Then, similarly to Example 1, use the silver-colored paste B 7 of made, use the mask that is formed with printed patterns to carry out serigraphy, the result causes obstruction in the part of mask, can not carry out the printing of fine rule.
The silver powder and the surfactant that use in above embodiment and the comparative example are summarized in table 1.In addition, the value of the specific insulation when burning till 60 minutes respectively for 160 ℃ and 250 ℃ and serigraphy precision, serigraphy adaptability are summarized in table 2.
At this, estimate serigraphy precision, serigraphy adaptability in order to following standard.
(serigraphy precision)
With zero, * judging whether can be with the conducting channel pattern of serigraphy zero defect ground printing live width 50 μ m.
(serigraphy adaptability)
Use the silk screen of 400 orders, line footpath, 18 μ m to carry out serigraphy, with zero, * judge whether not have with stopping up and print.
Table 1
| The silver powder of using | The surfactant that uses | |
| |
FHD | A |
| Embodiment 2 | | B |
| Embodiment | ||
| 3 | AgC-G | B |
| Embodiment 4 | Surface oxidation silver is handled | B |
| Embodiment | ||
| 5 | Surface oxidation silver is handled FHD | C |
| Comparative example 1 | FHD | Disperbyk-2001 |
| Comparative example 2 | FHD | Hitenol NF |
| Comparative example 3 | FHD | Poise 520 |
Table 2
From table 1, table 2 as can be known, when using the phosphorus containing ratio is that the surfactant mixture of the surfactant of phosphoric acid ester of 0.5～10 quality % or alkyl amine and alkylamine salt is when making conductive paste (silver-colored paste), can make the conductive paste with good dispersiveness, this conductive paste can not cause obstruction at the mask that is used for printing 30 μ m fine rules.In addition, by the relation of the decentralization of the silver-colored particle in table 2 and Fig. 3, the silver-colored paste shown in Figure 4 and volume resistance as can be known, for the dispersity of silver-colored paste, obtain the closeest filling and electric conductivity uprises easilier when assembling when silver-colored paste disperses.
In addition, these conductive pastes when using the little silver powder of particle diameter, by forming line pattern by easy fired, can be realized good electrical conductivity under the situation of the silver powder of using the oxidized silver in surface to handle.
Utilizability on the industry
According to the present invention, can provide a kind of silver-colored paste, wherein, the silver of nominal particle size or the particle of silver compound are disperseed well, the physical property such as viscosity rise do not occur over time, can form the good conducting channel of electric conductivity of line width, therefore, industrially useful.
Claims (7)
1. the manufacture method of a surface-treated silver-containing powder, it is characterized in that having following operation: the particle that makes silver or silver compound is that the phosphate ester surfactants of 0.5～10 quality % is distributed to and disperses to carry out vacuum freeze drying with the dispersion liquid that forms in the solvent with alkylamine or alkylamine salt surfactant or phosphorus containing ratio.
2. the manufacture method of surface-treated silver-containing powder according to claim 1, it has following operation: in order to modulate described dispersion liquid, in the presence of described surfactant, the particle of silver or silver compound is distributed to described dispersion with in the solvent.
3. the manufacture method of surface-treated silver-containing powder according to claim 2 when the described dispersion liquid of modulation, is the powder of silver or silver compound as the silver of raw material or the particle of silver compound.
4. the manufacture method of surface-treated silver-containing powder according to claim 1, it has following operation: in order to modulate described dispersion liquid, the particle of synthetic silver or silver compound in liquid phase, take out the synthetic particle that obtains by filtering, before the particle drying of this taking-up, be distributed to described dispersion with in the solvent, in this dispersion liquid, add described surfactant then.
5. the manufacture method of surface-treated silver-containing powder according to claim 1, the volume average particle size of the particle of described silver or silver compound are the scope of 0.05～10 μ m.
6. the manufacture method of surface-treated silver-containing powder according to claim 1, the particle of described silver or silver compound are the silver-colored particles that the oxidized silver in surface coats, and its silver oxide containing ratio is 1～30 quality %.
7. silver-colored paste, its resulting surface-treated silver-containing powder of manufacture method that contains each described surface-treated silver-containing powder of with good grounds claim 1～6 is as principal component.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2004343880 | 2004-11-29 | ||
| JP343880/2004 | 2004-11-29 | ||
| JP257667/2005 | 2005-09-06 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101065203A CN101065203A (en) | 2007-10-31 |
| CN100577328C true CN100577328C (en) | 2010-01-06 |
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| CN200580040489A Expired - Fee Related CN100577328C (en) | 2004-11-29 | 2005-11-25 | Method for producing surface-treated silver-containing powder and silver paste using surface-treated silver-containing powder |
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Cited By (1)
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| TWI567756B (en) * | 2014-03-17 | 2017-01-21 | 常寶公司 | A conductive paste composition for forming conductive thin film on a flexible substrate and a method for producing the same |
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| US10272490B2 (en) | 2014-09-29 | 2019-04-30 | Dowa Electronics Materials Co., Ltd. | Silver powder, method for producing same, and hydrophilic conductive paste |
| WO2016080528A1 (en) * | 2014-11-21 | 2016-05-26 | 日清エンジニアリング株式会社 | Fine silver particle |
| CN105618734B (en) * | 2016-01-12 | 2018-03-06 | 昆明理工大学 | A kind of method of the modified sheeted silver powder in surface |
| KR102061720B1 (en) * | 2017-10-31 | 2020-01-02 | 엘에스니꼬동제련 주식회사 | Surface-treated silver powder and method for producing the same |
| KR102149488B1 (en) * | 2017-12-21 | 2020-08-28 | 엘에스니꼬동제련 주식회사 | Electrode Paste For Solar Cell's Electrode And Solar Cell |
| CN112420238A (en) * | 2020-11-09 | 2021-02-26 | 无锡晶睿光电新材料有限公司 | Laser conductive silver paste for touch screen and preparation method thereof |
| CN112759952A (en) * | 2020-12-25 | 2021-05-07 | 浙江苏生元福珠宝有限公司 | Oily sintered silver paste and preparation method thereof |
| CN115762848A (en) * | 2022-11-09 | 2023-03-07 | 宁夏中色新材料有限公司 | Heterojunction low-temperature silver paste and preparation method thereof |
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| CN86102617A (en) * | 1985-04-17 | 1987-01-07 | 约翰森·马思公司 | Silver-filled glass metallizing pastes |
| CN1190423A (en) * | 1995-07-10 | 1998-08-12 | 美国3M公司 | Adhesive containing electrically conductive agent |
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| CN86102617A (en) * | 1985-04-17 | 1987-01-07 | 约翰森·马思公司 | Silver-filled glass metallizing pastes |
| CN1190423A (en) * | 1995-07-10 | 1998-08-12 | 美国3M公司 | Adhesive containing electrically conductive agent |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| TWI567756B (en) * | 2014-03-17 | 2017-01-21 | 常寶公司 | A conductive paste composition for forming conductive thin film on a flexible substrate and a method for producing the same |
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| CN101065203A (en) | 2007-10-31 |
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