CN102675964B - Ink and device - Google Patents
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- CN102675964B CN102675964B CN201210022942.0A CN201210022942A CN102675964B CN 102675964 B CN102675964 B CN 102675964B CN 201210022942 A CN201210022942 A CN 201210022942A CN 102675964 B CN102675964 B CN 102675964B
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Abstract
The invention provides an ink and device, which can greatly prevent composition from becoming complicated and make various solid particles in the ink stably dispersed. The ink contains at least a first solid particle, and a second solid particle formed of a base material of a different main component from that of the first solid particle. The first solid particle and the second solid particle have zeta potentials of the same polarity, or zeta potentials of 0+-5 mV. The first and second solid particles in the ink have the same surface property, specifically the same interface property in the ink. This makes it possible to use a common dispersant suited for adsorption on the first and second solid particles. In this way, more than one kind of solid particle can be stably dispersed using a sole kind of dispersant.
Description
Technical field
The present invention relates to a kind of ink that contains many kinds of solids particle and use the equipment of this ink.
Background technology
Scheme with following conductive ink is proposed: by the metal powder such as nickel powder, platinum powder, metal oxide powder are distributed in solvent, can form wiring, electrode (with reference to patent documentation 1) by ink jet printing etc.The conductor that this conductive ink forms for printing, in order to ensure required electroconductibility, requires above-mentioned metal powder, metal oxide powder etc. to be stably distributed in solvent.
Wherein, the ink that contains two or more solids such as metallics, metal oxide particle, generally according to the kind difference of solids, the physical properties of its particle surface is also different respectively, and the suitable dispersion agent that is therefore easy to be adsorbed by particle surface is also because the kind of solids is different.Therefore, in ink, be difficult to disperse solids of more than two kinds with a kind of dispersion agent.
Patent documentation 1: TOHKEMY 2006-210301 communique
Summary of the invention
Therefore,, when stably the physical properties on dispersed particle surface is different in ink many kinds of solids particle, adopt and add and the method for the multiple dispersion agent that the kind of every kind of solids is corresponding etc.But, consider including the productivity the manufacturing cost of ink itself etc., wish that the composition of ink is as far as possible simple.
The present invention is used for solving above-mentioned problem, and its object is to provide a kind of and does one's utmost to suppress composition when becoming complicated, makes the ink of the particle-stabilised dispersion of many kinds of solids containing and uses the equipment of this ink.
For achieving the above object, as the ink of a mode of the present invention, at least contain: the 1st solids; And the main component of mother metal 2nd solids different with above-mentioned the 1st solids, it is characterized in that, in above-mentioned the 1st solids and the 2nd solids, at least one party's surface is modified, and electrokinetic potential is each other same polarity, or electrokinetic potential is separately 0 ± 5mV.
Therefore, by making surface physical properties between the 1st and the 2nd solids, the character at the interface of the each solids in ink is consistent, can make to be easy to respectively be adsorbed onto the dispersion agent universalization of the 1st, the 2nd solids, so, for example, the in the situation that of identical polar, also can stably disperse many kinds of solids particle by a kind of dispersion agent.And, by the electrokinetic potential of each solids being controlled to the scope of 0 ± 5mV, can in ink, more stably disperse.
And, being characterised in that as the ink of a mode of the present invention, above-mentioned ink is that the viscosity under normal temperature is the ink that the ink jet printing below 100mPas is used.
So, in the ink that viscosity is low at normal temperatures, need to recognize especially interparticle dispersiveness, therefore the present invention is particularly useful.That is, in the ink jet printing of printing in discharging tiny drop, ink itself requires low viscosity, therefore, in the time that heavy solids are contained in ink, can worry its precipitation etc.But, the ink of above-mentioned formation can stable dispersion solids between, the ink of therefore preferably using as ink jet printing uses.
And, being characterised in that as the ink of a mode of the present invention, above-mentioned the 1st solids are metallicss, above-mentioned the 2nd solids are metal oxide particles.
So, the general proportion of solids being made up of metal is larger, easily precipitates, so the present invention is particularly useful.
And, being characterised in that as the ink of a mode of the present invention, above-mentioned the 1st solids are electroconductive particles, above-mentioned the 2nd solids are insulativity particles.
So, in the different ink of the proterties of solids of mixing, can make the character at interface of each solids consistent by being suitable for the present invention, therefore the present invention is particularly useful.
And, being characterised in that as the ink of a mode of the present invention, in above-mentioned the 1st solids and the 2nd solids, at least one party's surface is modified surface by modification and the different types of material of each mother metal.
So,, in the ink of the 1st solids and the mixing of the 2nd solids, by modifying and the different types of material of each mother metal, can give each particle by the proterties different with each mother metal.
And, being characterised in that as the ink of a mode of the present invention, above-mentioned different types of material is organic polymer material.
And it is characterized in that, above-mentioned different types of material is carboxymethyl cellulose ammonium.
Therefore, by modify each solid particle surfaces with organic polymer material, can give molecular chain to particle surface, improve the dispersiveness of each solids by being derived from the spatial masking of this molecular chain.And carboxymethyl cellulose ammonium has insulativity, therefore can make the electrokinetic potential of each solid particle surfaces of modifying approach 0mV.
And it is characterized in that, above-mentioned different types of material has electroconductibility.
So, by modify each solid particle surfaces with conductive material, the electroconductibility of ink itself can be improved, by using this ink to print, the conductive pattern with satisfactory electrical conductivity can be formed.
And, being characterised in that as the ink of a mode of the present invention, the surface of above-mentioned the 2nd solids is modified surface by the identical material of main component of the mother metal of modification and above-mentioned the 1st solids.
So,, by side's solids being modified and the identical material of main component of the mother metal of the opposing party's solids, can make the character at interface of each solids consistent.And, modify and do not use and the different types of material of each mother metal, therefore can reduce costs.
And, being characterised in that as a mode ink of the present invention, at least one party in the above-mentioned the 1st and the 2nd solids provides ablution by enforcement and makes the charged processing of particle surface that surface is modified.
So, by ablution being provided and making the charged processing of particle surface, can not change the proterties of each individual particles, only making surface charge unified is same polarity.
And, ink as a mode of the present invention is characterised in that, be same polarity chron making the above-mentioned the 1st and the 2nd solids electrokinetic potential each other, also contain dispersion agent, this dispersion agent has and the 1st and the opposite polarity absorption base of electrokinetic potential of the 2nd solids.
So, while making the electrokinetic potential of each solids be identical polar by above-mentioned the whole bag of tricks, further in ink, contain and have and the 1st and the dispersion agent of the opposite polarity absorption base of electrokinetic potential of the 2nd solids, thereby the static retroaction between dispersion agent, can expect to be derived from the dispersed raising of the spatial masking between dispersion agent.
And, being characterised in that as the ink of a mode of the present invention, above-mentioned dispersion agent is only made up of one.
Therefore, in the ink that contains each solids that surface texture is unified, only just can improve dispersiveness by a kind of dispersion agent, contribute to reduce costs.And, can make ink composition simplify.
And, be characterised in that as the equipment of a mode of the present invention, use above-mentioned ink to carry out pattern printing.
Therefore, the present invention is particularly useful in the conductive pattern printing of equipment.
In addition, as mentioned above, for making the character homogeneity at the interface (surface) between the each solids in ink, example following situation: same material is modified respectively on the each surface to the 1st and the 2nd solids; To modify the surface of the 2nd solids with the identical material of main component of the mother metal of the 1st solids; At least one party in the 1st and the 2nd solids is implemented the ablution of regulation to be provided and to make the charged processing of particle surface.
And, make in the unified situation for same polarity of electrokinetic potential of the 1st in ink, the 2nd solids, make to contain in ink the dispersion agent of the absorption base with electrokinetic potential and their opposite polarities, thereby can improve, this dispersion agent is relatively each the 1st, the adsorptivity of the 2nd solids.So, can make reactive force useful effect between dispersion agent (the absorption base of dispersion agent) in the 1st, the 2nd solids, improve the dispersiveness of the each solids in ink.
According to the present invention, can provide a kind of doing one's utmost to suppress to form when becoming complicated, make the ink of the particle-stabilised dispersion of many kinds of solids containing.
Brief description of the drawings
Fig. 1 is the schematic diagram that represents the formation of the solids that contain in the ink of embodiment.
Fig. 2 is the figure of the modifying method for the solid particle surfaces to the ink shown in Fig. 1 is described.
Fig. 3 is the figure of the method for the dispersed precipitation test of the solids for the ink shown in evaluation map 1 is described.
Fig. 4 is the schematic diagram that represents the formation of the solids that contain in the ink of other embodiments different with the ink of Fig. 1.
Fig. 5 is the schematic diagram that represents the formation of the solids that contain in the ink of other different embodiments respectively with the ink of Fig. 1 and Fig. 4.
Fig. 6 is the schematic diagram that represents the formation of the solids that contain in the ink of different another other embodiments respectively with the ink of Fig. 1, Fig. 4 and Fig. 5.
Fig. 7 is the figure that schematically shows the effect of the dispersion agent containing in the ink shown in Fig. 6.
Fig. 8 be have use embodiment ink printing the decomposition diagram of sensor element of substrate of conductive pattern.
Embodiment
Embodiment is below described with reference to the accompanying drawings.
As shown in Figure 1, the ink 5 that embodiment relates to is mainly to contain main component different with solids 1 (multiple) the 2nd solids 2, the tackiness agent of (multiple) the 1st solids 1, mother metal, the inkjet printing ink of a kind of dispersion agent for butyl carbitol acetate equal solvent.
The ink 5 that ink jet printing is used is in order suitably to discharge the drop of this ink from the small nozzle of ink gun, and for example, viscosity under normal temperature (25 DEG C) is at least following, the preferred 20mPas of 100mPas and forms below.The content of the adjustment of the viscosity of ink 5 by increase and decrease tackiness agent, the kind etc. that suitably changes applicable tackiness agent and solvent realize.
Wherein, as shown in Figure 1, in the ink 5 of present embodiment, solids 1 are made up of the main component (particle main part) of mother metal for example platinum (Pt) the particle 1a as metallics, and solids 2 are by for example zirconium dioxide (ZrO as metal oxide particle
2) particle 2a forms the main component of mother metal.Further, same material is modified respectively on the each surface (each surface of platinum particles 1a and zirconium dioxide particle 2a) to these solids 1,2, carries out surface modification.
Particularly, as shown in Figure 1, modify respectively on each surface of solids 1,2 and carboxymethyl cellulose ammonium (the NH of the main component different kinds material of mother metal
4-CMC), form decorative layer 3.In ink 5, the surperficial physical properties between unified solids 1,2, the i.e. character (homogeneity) at the interface of the each solids 1,2 in this ink 5.
So, the electrokinetic potential each other (interface electrokinetic potential) of the solids 1,2 in ink 5 becomes same polarity, and this current potential itself also becomes identical, can realize respectively easily by the universalization of the dispersion agent of solids 1,2 absorption.; for example, by the a kind of dispersion agent that makes to contain the absorption base with electrokinetic potential and solids 1,2 opposite polarities in ink 5; thereby the electric reactive force between the dispersion agent (the absorption base of dispersion agent) that can make to be adsorbed well respectively by solids 1,2 acts on solids 1,2 effectively, can improve the dispersiveness of the each solids 1,2 in ink 5.Therefore, in ink 5, can do one's utmost to suppress to form when becoming complicated, solids 1,2 are stably disperseed in this ink.
The surperficial decorative layer 3 of solids 1,2, by carrying out the processing of Fig. 2 example, can be modified each surface of solids 1,2.As shown in Figure 2, first, using the zirconium dioxide particle 2a of pulverulence as the main component of the mother metal of the object of modifying, add to and dissolved NH
4in the water of-CMC.
Then, to having added the NH of above-mentioned Zirconium dioxide powder
4the solution of-CMC and jade join in jar mill in the lump, for example, with 5 hours (5hr) stir/disaggregating treatment.Then, the slurries in jar mill (being suspended thing) are moved in the containers such as beaker, for example, in one evening of drying machine inner drying that is warmed to 40 DEG C, moisture is evaporated from slurries, thereby as shown in Figure 1, can obtain on zirconium dioxide particle 2a and form NH
4the 2nd solids 2 of the decorative layer 3 of-CMC.And, when platinum powder end (platinum particles 1a) carried out to this modification processing, can obtain the 1st solids 1.
And the dispersiveness of the solids 1,2 in ink 5 as shown in Figure 3, can be evaluated by precipitation test.Specifically as shown in Figure 3, the ink of evaluation object is put in graduated cylinder with cover, started the timing starting from initial (0hr) moment.When time process, solids component (composition of suspension liquid) precipitation, it is transparent that supernatant liquid becomes, therefore after x hour (xhr), confirm the bottom surface of ink from graduated cylinder till comprise the height of the upper space of supernatant liquid, obtain whole quantity of ink A.Further, this time inscribe, confirm from the upper surface (bottom surface of supernatant liquid) of solids component of precipitation till the height of the upper surface of supernatant liquid is obtained supernatant liquid amount B.
Like this, by detecting the shared ratio (B/A) of supernatant liquid amount B with respect to the whole quantity of ink A after x hour, thereby can quantitatively obtain the dispersiveness of the solids component (solids 1,2) in ink.That is, in ink, in the time that the dispersiveness of solids 1,2 is lower, it is many that the ratio that supernatant liquid amount B occupies becomes, and on the other hand, in the time that the dispersiveness of solids 1,2 is higher, the ratio that supernatant liquid amount B occupies tails off.In addition, this precipitation test is also applicable to the dispersed evaluation of the solids in the ink 6,7,8 shown in following Fig. 4～Fig. 7.
And, in Fig. 1, example using the NH as organic polymer material
4-CMC modifies respectively the mode of solids 1,2 (platinum particles 1a, zirconium dioxide particle 2a), but the material of modifying can suitably be selected.For example, dry in this way after as the remaining material of solid, also can be by NH
4organic polymer material beyond-CMC is selected as the material of modifying use.And, the also alternative above-mentioned NH with electrical insulating property
4-CMC, for example, select conductive material.For example, when conductive material is modified respectively to platinum particles 1a and zirconium dioxide 2a, electroconductibility is also given dielectric zirconium dioxide particle 2a, and the ink that therefore contains more electroconductive particle by use carries out ink jet printing, thereby can form the conductive pattern with good electroconductibility.
And in to the mode of each solids modification same material, can make the dispersion agent in ink is a kind.In other words, in the time of improving particle surface, can freely select the material of modification, therefore the kind of the surperficial dispersion agent that is adsorbed onto various solids can be become to change arbitrarily.And, be a kind by making dispersion agent, can simplify ink composition, can reduce cost.
And, in above-mentioned Fig. 1 and following Fig. 4～Fig. 7, as the main component of the mother metal of each solids, example platinum particles 1a, zirconium dioxide particle 2a, but also can suitably select these to modify the particle of the main component of the mother metal of the object of (or clean processing of Fig. 6, Fig. 7).For example, can replace above-mentioned platinum particles and select the metallics such as iridium (Ir) particle, palladium (Pd) particle, and also can replace for example selective oxidation aluminium (Al of zirconium dioxide particle 2a
2o
3) metal oxide particle such as particle.
Wherein, use any material as the particle of the main component of mother metal, preferably consider that the material etc. of the substrate that is printed object (base material) that forms printed patterns is selected.In the time being printed the substrate (base material) of object and for example being formed by the ceramic substrate that comprises aluminum oxide etc., as the particle selection aluminium oxide particles of the main component of above-mentioned mother metal, thereby it is approximate to make to be printed the substrate of object and the thermal expansivity of printed patterns etc.So, can suppress mechanical strain of being applied to because of impacts such as temperature variation by substrate etc.Equally, when the ceramic substrate that contains zirconium dioxide particle is while being printed the substrate of object, can example in ink, contain solids of the main component taking zirconium dioxide particle as mother metal etc.
Fig. 4 represents the ink 6 that ink jet printing that other embodiments relate to is used.Ink 6 as shown in Figure 4, mainly contains: by integrant the 1st solids 11 of platinum particles 1a self; The 2nd solids 12 of decorative layer 1b have been formed on the surface of zirconium dioxide particle 2a; To the effective a kind of dispersion agent of platinum; Tackiness agent.The surface of the 2nd solids 12 is partly modified to the platinum of material (main component of the mother metal) same material of conduct and the 1st solids 11.
This decorative layer 1b is for example by formation such as infusion methods.Particularly, last as the silicon dioxide powder of carrier to dropping in the platinic acid aqueous solution of the aqueous solution as catalyst metal salts, make moisture evaporation drying, further, heat-treat with 500 DEG C of left and right, thereby make the platinum (1b) as catalyst metal separate out (carrying) from the surface of the zirconium dioxide 2a as carrier.
So, make the 2nd solids 12 of surface modification and the 1st solids 11 that entirety consists of platinum particles 1a by platinum, the physical properties homogeneity of particle surface, accompany with it, also homogeneity of the character at the interface in ink 6 (value, its polarity of for example electrokinetic potential become identical).So, the effective a kind of dispersion agent of platinum, containing in the many kinds of solids particle ink 6 of (containing the metal oxide particles such as zirconium dioxide particle), becomes effective dispersion agent relatively.Therefore, though ink 6 is better simply formations, can solids 11,12 are stably disperseed in this ink.
Other embodiments of the further example of Fig. 5.As shown in Figure 5, the ink 7 that the ink jet printing that present embodiment relates to is used mainly contains: with integrant the 1st solids 11 of platinum particles 1a; The 2nd solids 22 of decorative layer 1c have been formed on zirconium dioxide particle 2a surface; To the effective a kind of dispersion agent of platinum; Tackiness agent.On the surface of the 2nd solids 22, as modifying the 2nd solid particle surfaces entirety with the platinum of material (main component of the mother metal) same material of the 1st solids 11.
This modified layer 1c, for example, further implement platinum plating etc. and form by having separated out at particle surface on the zirconium dioxide particle of platinum.The 2nd solids 22, by the zirconium dioxide particle of having separated out platinum on surface is further implemented to platinum plating, form decorative layer 1c at the surface integral of the 2nd solids 22.So, the same with the ink 5 shown in Fig. 4, the effective a kind of dispersion agent of platinum becomes effective dispersion agent in the ink 7 that contains many kinds of solids particle relatively.Therefore, in the ink 7 of present embodiment, can do one's utmost to suppress to form when becoming complicated, solids 11,22 are effectively distributed in this ink.
And, in the ink 6,7 shown in Fig. 4, Fig. 5, example the mode to metal oxide particle finishing metallic substance such as zirconium dioxide particle 2a, but also can not modify the surface of zirconium dioxide particle 2a, and finishing metal oxide materials to metallics 1a makes the surperficial homogeneity of each solids.And the material that can modify reply particle surface, suitably selects the method for modifying.
For example, in Fig. 4, Fig. 5, as the method to particle surface modified metal material (platinum), example infusion method, gold-plated processing, but in the time of modified metal material, also evaporation, the sputter etc. such as applicable PVD, CVD.On the other hand, as the method to particle surface modifying metallic oxide material, applicable sputter, evaporation, infusion method etc.
In addition, as the method for modifying, can the whole surface of applying solid particle, also can be carried by a part for solid particle surfaces.,, by modifying solid particle surfaces, make surface texture homogeneity.
The ink 8 that the ink jet printing that another other embodiments of Fig. 6 and Fig. 7 example relate to is used.As shown in Figure 6, Figure 7, the ink 8 of present embodiment mainly contains: the 1st solids 11 that self are made up of platinum particles 1a; Process the 2nd solids 32 of zirconium dioxide particle 2a with ablution; 1 kind of dispersion agent (forming its multiple particles) 9; Tackiness agent.Wherein, above-mentioned the 2nd solids 32 provide ablution covering forward direction particle surface in ink, implement to make the processing of the charged 32a of this particle surface.
Particularly, as shown in Figure 6, Figure 7, in ink 8, in the time that the electrokinetic potential of the 1st solids 11 is for example straight polarity, for making the electrokinetic potential of the 2nd solids 32 also become straight polarity (homopolarity), select ablution and make the surface charging of the 2nd solids 32.For example comprise the basic solutions such as acidic solution, sodium hydroxide such as hydrochloric acid etc. as ablution.
Wherein, as shown in Figure 7, making the electrokinetic potential unification of the solids 11,32 in ink 8 is same polarity (for example straight polarity), the dispersion agent 9 of the absorption base for example, with electrokinetic potential and their opposite polarities (negative polarity) is contained in ink, thereby can improve, this dispersion agent 9 is relatively each the 1st, the adsorptivity of the 2nd solids.In addition, identical with the ink 5,6,7 shown in Fig. 1, Fig. 4, Fig. 5, in the ink 8 shown in Fig. 7, by having improved in the electrical resistance reactive force between the dispersion agent of the adsorptivity to each solids, each solids the interparticle spatial masking 10 that is derived from the base that mixes (not shown) in the dispersion agent of absorption conscientiously, can improve the dispersiveness of the each solids in ink 8.In addition, dispersion agent 9 is made up of absorption base and the base that mixes, and this absorption base is adsorbed onto the surface of each solids.
And, the ink the 5,6,7, the 8th of Fig. 1 and Fig. 4～Fig. 7 example, the ink that the ink jet printing that need to make small drop discharge from nozzle is used, therefore be for example the low viscosity ink formation below 20mPas as the viscosity under normal temperature, but as mentioned above, between each solids, stably disperse, so for example without the precipitation etc. of worrying heavy solids, can be well for ink jet printing.
Then, as an example of equipment that ink of the present invention is applied to conductive pattern printing, for the sensor element of substrate of conductive pattern that there is any one ink jet printing by the ink 5,6,7,8 shown in Fig. 1 and Fig. 4～Fig. 7, describe with reference to Fig. 8.As shown in Figure 8, this sensor element 20 is at least by gas sensor element main body 20a and well heater 20b lamination and the gas sensor element forming.
Well heater 20b has the 1st matrix 27 and the 2nd matrix 25 and resistance heater 26.Resistance heater 26 forms taking platinum etc. as main body, and the 1st matrix 27 and the 2nd matrix 25 are made up of the ceramic sintered bodies taking aluminum oxide as main body respectively.Resistance heater 26 is clamped in respectively between the 1st matrix 27 and the 2nd matrix 25 of rectangle.
And resistance heater 26 has: heating part 26b, form the shape of crawling, generate heat by switching on; The a pair of heating wires 26a of portion, an end is separately connected to heating part 26b, and extends along the length direction of the 1st matrix 27 and the 2nd matrix 25.The a pair of heating wires 26a of portion the other end is separately by connecting 2 through hole 25a of the 2nd matrix 25, be connected respectively to a pair of well heater energising terminal 25b of the outside terminal connection that is connected use with external circuit.
On the other hand, equipment component main body 20a has concentration detecting unit (concentration detecting unit substrate) 24 and protective layer 35.Concentration detecting unit 24 has the solid electrolyte substrate 33 of rectangle, the 1st electrode pattern 36 and the 2nd electrode pattern 34 as conductive pattern.Solid electrolyte substrate 33 for example, has added yttrium oxide (Y as stablizer
2o
3) or the zirconium dioxide (ZrO of calcium oxide (CaO)
2) be the solid electrolyte body that the oxygen concentration cell of the formations such as sintered compact is used.In addition, solid electrolyte substrate (solid electrolyte body) 33 also can be by LaGaO
3be the formations such as sintered compact.
On one of solid electrolyte substrate 33 to (before firing) before sintering and another interarea, use the ink shown in Fig. 1, Fig. 4～Fig. 7, the 1st electrode pattern 36 and the 2nd electrode pattern 34 are printed by pattern respectively with inkjet direction.Wherein, in sensor element 20, after the printing of this pattern, at least the 1st electrode pattern 36 and the 2nd electrode pattern 34 and above-mentioned solid electrolyte substrate 33, for example, to exceed the temperature of 1100 DEG C simultaneously by high-temperature firing.
Now, although the 1st electrode pattern 36 and the 2nd electrode pattern 34 are heated with the high temperature that exceedes 1100 DEG C, but as mentioned above, ink by the particle-stabilised dispersion of many kinds of solids that makes to contain is as the material of pattern printing use, excessive sintering can be suppressed, thereby decline and the broken string of the conduction property of pattern self can be suppressed.And, be suitable for the NH shown in Fig. 1 at this
4when the decorative layer 3 of-CMC system has been modified the ink 5 of the 1st, the 2nd solids 1,2 and has been carried out pattern printing, in the time of the above-mentioned high-temperature firing that exceedes 1100 DEG C, NH
4the disappearance of simultaneously burning of the decorative layer 3 of-CMC system and dispersion agent 9, thus make the platinum particles 1a exposing surface as the main component of the mother metal of the 1st solids 1, obtain conductive pattern.
In addition, in this 1st electrode pattern 36 and the 2nd electrode pattern 34, the 1st electrode part 36b and the 2nd electrode part 34b with solid electrolyte substrate 33 interlock formation test sections (not shown), clamp solid electrolyte substrate 33 and be arranged on position respect to one another.
The 2nd electrode pattern 36 has the 1st 36a of electrode cable portion, and its length direction from the 1st electrode part 36b to solid electrolyte substrate 33 extends.On the other hand, the 2nd electrode pattern 34 has the 2nd 34a of electrode cable portion, and its length direction from the 2nd electrode part 34b to solid electrolyte substrate 33 extends.In addition; protective layer 35 and solid electrolyte substrate 33 between clamp lamination on the position of the 2nd electrode pattern 34, there is electrode protecting layer 35b for preventing the poisoning Porous shape of the 2nd electrode part 34b and the enhanced protection layer 35a for the protection of solid electrolyte substrate 33.
The end of the 1st 36a of electrode cable portion, by being arranged on the through hole 33b of solid electrolyte substrate 33 and being arranged on the through hole 35d on protective layer 35, is connected to signal and takes out with one in terminal 35f.And the end of the 2nd 34a of electrode cable portion is by the through hole 35e that is arranged on protective layer 35, is connected to signal and takes out with another in terminal 35f.The sensor element 20 forming like this can be measured oxygen concn by the concentration cell effect of concentration detecting unit 24, also can be used as air-fuel ratio sensor etc. and is suitable for.
As mentioned above, in the sensor element 20 shown in Fig. 8, be suitable for the ink that the ink jet printing of the interparticle dispersiveness of many kinds of solids having improved shown in Fig. 1 and Fig. 4～Fig. 7 is used, on the substrate of pottery system, form conductive pattern, therefore can improve the reliability of electrical connection of element internal.
Especially while using 6,7 pairs of the 1st electrode patterns 36 of the ink shown in Fig. 4, Fig. 5 and the 2nd electrode pattern 34 to carry out pattern printing, platinum is also modified on dielectric zirconium dioxide particle 2a, give electroconductibility, therefore, in the conductive pattern of pattern printing, can further improve its electroconductibility.
And, in sensor element 20, be on the solid electrolyte body (solid electrolyte substrate 33) that forms of sintered compact by zirconium dioxide, the ink 5,6,7,8 that use contains taking zirconium dioxide particle 2a as the solids of the main component of mother metal forms printed patterns (the 1st electrode pattern 36 and the 2nd electrode pattern 34), thereby can make printed patterns and the thermal expansivity of the solid electrolyte that is printed object be similar to.So, in the time of high-temperature firing, can suppress to be applied to the mechanically stressed etc. of printed patterns and solid electrolyte body (concentration detecting unit 24 shown in Fig. 8), therefore can suppress to fire rear generation deflection etc.
Below understand specifically embodiment, but the invention is not restricted to this embodiment, in the scope that does not depart from its purport, can carry out various changes.For example, in the ink 5,6,7,8 shown in Fig. 1 and Fig. 4～Fig. 7, example contain the 1st and the ink of the 2 two kind of solids, but contain 3 kinds, 4 kinds ... in the ink of above many kinds of solids particle, also applicable the present invention certainly.; modify respectively same material, will modify the 2nd, the 3rd, the 4th with the identical material of main component of the mother metal of the 1st solids by each surface of the solids to all kinds ... each surface of solids or to the 1st, the 2nd, the 3rd, the 4th ... at least one party in solids provides ablution etc., can realize the homogeneity of each solid particle surfaces.
And, make the the 1st, the 2nd the (the 3rd, the 4th ...) solids electrokinetic potential is separately while being 0 ± 5mV, can be for example following methods etc.: select to have judged in advance according to the measurement result of the electrokinetic potential of preparation property test etc. the specific material of the value of the electrokinetic potential in ink, this specific material is modified to the surface of solids.Wherein, the electrokinetic potential that why makes each solids is 0 ± 5mV, for example, be to consider fluctuation in mensuration etc., and intention is eliminated the skew (making electrokinetic potential as target value is 0mV) of the electric charge of each solids as far as possible.Therefore, approach 0mV by the electrokinetic potential that makes the each solids in ink, can suppress the absorption that the electric charge between solids causes, by making dispersion agent be present in solid particle surfaces, can make dispersion agent as the shield between solids (spatial masking), thereby can be distributed in ink particle-stabilised many kinds of solids.
And in Fig. 8, example form the mode of printed patterns to carrying the cell substrate of sensor element etc., but for example in the pattern printing of semi-conductor associated components etc., also applicable ink of the present invention.In addition, " equipment " recorded in claims, except the exemplified gas sensor of Fig. 8, is also equivalent to semiconductor substrate etc.
Claims (21)
1. an ink, at least contains: the 1st solids; And the main component of mother metal 2nd solids different with above-mentioned the 1st solids, it is characterized in that,
In above-mentioned the 1st solids and the 2nd solids, at least one party's surface is modified,
Electrokinetic potential is each other same polarity, or electrokinetic potential is separately 0 ± 5mV.
2. ink according to claim 1, is characterized in that, above-mentioned ink is that the viscosity under normal temperature is the ink that the ink jet printing below 100mPas is used.
3. ink according to claim 1 and 2, is characterized in that, above-mentioned the 1st solids are metallicss, and above-mentioned the 2nd solids are metal oxide particles.
4. ink according to claim 1 and 2, is characterized in that, above-mentioned the 1st solids are electroconductive particles, and above-mentioned the 2nd solids are insulativity particles.
5. ink according to claim 3, is characterized in that, above-mentioned the 1st solids are electroconductive particles, and above-mentioned the 2nd solids are insulativity particles.
6. ink according to claim 1 and 2, is characterized in that, in above-mentioned the 1st solids and the 2nd solids, at least one party's surface is modified surface by modification and the different types of material of each mother metal.
7. ink according to claim 3, is characterized in that, in above-mentioned the 1st solids and the 2nd solids, at least one party's surface is modified surface by modification and the different types of material of each mother metal.
8. ink according to claim 6, is characterized in that, above-mentioned different types of material is organic polymer material.
9. ink according to claim 7, is characterized in that, above-mentioned different types of material is organic polymer material.
10. ink according to claim 8, is characterized in that, above-mentioned different types of material is carboxymethyl cellulose ammonium.
11. ink according to claim 9, is characterized in that, above-mentioned different types of material is carboxymethyl cellulose ammonium.
12. ink according to claim 8, is characterized in that, above-mentioned different types of material has electroconductibility.
13. ink according to claim 9, is characterized in that, above-mentioned different types of material has electroconductibility.
14. ink according to claim 1 and 2, is characterized in that, the surface of above-mentioned the 2nd solids is modified surface by the identical material of main component of the mother metal of modification and above-mentioned the 1st solids.
15. ink according to claim 3, is characterized in that, the surface of above-mentioned the 2nd solids is modified surface by the identical material of main component of the mother metal of modification and above-mentioned the 1st solids.
16. ink according to claim 1 and 2, is characterized in that, at least one party in the above-mentioned the 1st and the 2nd solids provides ablution by enforcement and makes the charged processing of particle surface that surface is modified.
17. ink according to claim 3, is characterized in that, at least one party in the above-mentioned the 1st and the 2nd solids provides ablution by enforcement and makes the charged processing of particle surface that surface is modified.
18. ink according to claim 1 and 2, it is characterized in that, be same polarity chron making the above-mentioned the 1st and the 2nd solids electrokinetic potential each other, also contain dispersion agent, this dispersion agent has and the 1st and the opposite polarity absorption base of electrokinetic potential of the 2nd solids.
19. ink according to claim 3, is characterized in that, are same polarity chron making the above-mentioned the 1st and the 2nd solids electrokinetic potential each other, also contain dispersion agent, and this dispersion agent has and the 1st and the opposite polarity absorption base of electrokinetic potential of the 2nd solids.
20. ink according to claim 18, is characterized in that, above-mentioned dispersion agent is only made up of one.
21. ink according to claim 19, is characterized in that, above-mentioned dispersion agent is only made up of one.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-020629 | 2011-02-02 | ||
| JP2011020629 | 2011-02-02 | ||
| JP2012004055A JP5689081B2 (en) | 2011-02-02 | 2012-01-12 | Ink and device |
| JP2012-004055 | 2012-01-12 |
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| Publication Number | Publication Date |
|---|---|
| CN102675964A CN102675964A (en) | 2012-09-19 |
| CN102675964B true CN102675964B (en) | 2014-09-03 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN201210022942.0A Expired - Fee Related CN102675964B (en) | 2011-02-02 | 2012-02-02 | Ink and device |
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| CN (1) | CN102675964B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101138908A (en) * | 2007-10-24 | 2008-03-12 | 北大方正集团有限公司 | Negative pressure generating device, method and ink-jet printer |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7893138B2 (en) * | 2003-03-14 | 2011-02-22 | Eastman Chemical Company | Low molecular weight carboxyalkylcellulose esters and their use as low viscosity binders and modifiers in coating compositions |
| JP4799881B2 (en) * | 2004-12-27 | 2011-10-26 | 三井金属鉱業株式会社 | Conductive ink |
| US8187500B2 (en) * | 2008-10-17 | 2012-05-29 | The Board Of Trustees Of The University Of Illinois | Biphasic inks |
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| CN101138908A (en) * | 2007-10-24 | 2008-03-12 | 北大方正集团有限公司 | Negative pressure generating device, method and ink-jet printer |
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| Title |
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| JP特开2006-210301A 2006.08.10 |
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| CN102675964A (en) | 2012-09-19 |
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