CN102675964A - Ink and device - Google Patents
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- CN102675964A CN102675964A CN2012100229420A CN201210022942A CN102675964A CN 102675964 A CN102675964 A CN 102675964A CN 2012100229420 A CN2012100229420 A CN 2012100229420A CN 201210022942 A CN201210022942 A CN 201210022942A CN 102675964 A CN102675964 A CN 102675964A
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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 equipment that contains the printing ink of multiple solids and use this printing ink.
Background technology
Proposition is with the scheme of following conductive ink: through metal powders such as nickel powder, platinum powder, MOX powder are distributed in the solvent, can form wiring, electrode (with reference to patent documentation 1) through ink jet printing etc.The conductor that this conductive ink forms for printing in order to ensure required electroconductibility, requires above-mentioned metal powder, MOX powder etc. stably is distributed in the solvent.
Wherein, The printing ink that contains solids more than 2 kinds such as metallics, metal oxide particle; Kind according to solids is different generally speaking; The physical properties of its particle surface is also different respectively, therefore is easy to by the suitable dispersion agent of the particle surface absorption also kind because of solids different.Therefore, in printing ink, be difficult to disperse the solids more than 2 kinds with a kind of dispersion agent.
Patent documentation 1: TOHKEMY 2006-210301 communique
Summary of the invention
Therefore, in printing ink stably during the multiple solids of dispersed particle Surface Physical different in kind, adopt and add with the method for the multiple dispersion agent of the kind correspondence of every kind of solids etc.But, consider the productivity of the manufacturing cost that comprises printing ink itself etc., hope that the composition of printing ink is simple as far as possible.
The present invention is used to solve above-mentioned problem, and its purpose is to provide a kind of and does one's utmost to suppress to form when becoming complicated, makes the printing ink of the multiple solids stable dispersion that contains and uses the equipment of this printing ink.
For realizing above-mentioned purpose, the printing ink as a mode of the present invention contains: the 1st solids at least; And the staple of mother metal 2nd solids different with above-mentioned the 1st solids; It is characterized in that; At least one side's surface is modified in above-mentioned the 1st solids and the 2nd solids, and electrokinetic potential each other is same polarity, and perhaps separately electrokinetic potential is 0 ± 5mV.
Therefore; Through making surface physical properties between the 1st and the 2nd solids, being that the character at interface of each solids in the printing ink is consistent; Can make the dispersion agent universalization that is easy to be adsorbed onto the 1st, the 2nd solids respectively; So, for example under the situation of identical polar, also can stably disperse multiple solids by a kind of dispersion agent.And, being controlled at the scope of 0 ± 5mV through electrokinetic potential with each solids, can in printing ink, more stably disperse.
And, be characterised in that as the printing ink of a mode of the present invention above-mentioned printing ink is that the viscosity under the normal temperature is the printing ink that the ink jet printing below the 100mPas is used.
So, in the printing ink that viscosity is low at normal temperatures, need recognize interparticle dispersiveness especially, so the present invention is particularly useful.That is, in the ink jet printing of when discharging tiny drop, printing, printing ink itself requires low viscosity, therefore when heavy solids are contained in the printing ink, can worry its deposition etc.But, but between the printing ink stable dispersion solids of above-mentioned formation, the printing ink of therefore preferably using as ink jet printing uses.
And, being characterised in that as the printing 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 that is made up of metal is bigger, and easy the deposition is so the present invention is particularly useful.
And, being characterised in that as the printing 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 printing ink of the proterties of blended solids, can make the character unanimity at the interface of each solids through suitable the present invention, so the present invention is particularly useful.
And, be characterised in that as the printing ink of a mode of the present invention at least one side's surface is modified the surface through modifying with each mother metal kinds of materials in above-mentioned the 1st solids and the 2nd solids.
So, in the 1st solids and the 2nd solids blended printing ink, through modifying and each mother metal kinds of materials, can be with giving each particle with each mother metal different traits.
And, be characterised in that as the printing ink of a mode of the present invention above-mentioned kinds of materials is an organic polymer material.
And it is characterized in that above-mentioned kinds of materials is a carboxymethyl cellulose ammonium.
Therefore,, can give molecular chain, improve the dispersiveness of each solids through the spatial masking that is derived from this molecular chain particle surface through modifying each solid particle surfaces with organic polymer material.And carboxymethyl cellulose ammonium has insulativity, and the electrokinetic potential of each solid particle surfaces that therefore can make modification is near 0mV.
And it is characterized in that above-mentioned kinds of materials has electroconductibility.
So,, can improve the electroconductibility of printing ink itself, print, can form conductive pattern with satisfactory electrical conductivity through using this printing ink through modifying each solid particle surfaces with conductive material.
And, be characterised in that as the printing ink of a mode of the present invention the surface of above-mentioned the 2nd solids is modified the surface through the staple identical materials of the mother metal of modification and above-mentioned the 1st solids.
So, through side's solids being modified the staple identical materials with the mother metal of the opposing party's solids, can make the character unanimity at the interface of each solids.And, modify and do not use and each mother metal kinds of materials, therefore can reduce cost.
And, be characterised in that as a mode printing ink of the present invention at least one square tube in the above-mentioned the 1st and the 2nd solids is crossed and implemented that ablution is provided and make the charged processing of particle surface and the surface is modified.
So, through 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; Printing ink as a mode of the present invention is characterised in that; Making the above-mentioned the 1st and the 2nd solids electrokinetic potential each other is same polarity chron, also contains dispersion agent, and this dispersion agent has and the opposite polarity absorption base of the electrokinetic potential of the 1st and the 2nd solids.
So; When making the electrokinetic potential of each solids be identical polar through above-mentioned the whole bag of tricks; Further in printing ink, contain and have and the dispersion agent of the opposite polarity absorption base of the electrokinetic potential of the 1st and the 2nd solids; Thereby the static retroaction between dispersion agent, can expect to be derived from the raising of the dispersiveness of the spatial masking between the dispersion agent.
And, be characterised in that as the printing ink of a mode of the present invention above-mentioned dispersion agent only is made up of a kind of.
Therefore, in the printing ink that contains each unified solids of surface texture, only just can improve dispersiveness, help to reduce cost through a kind of dispersion agent.And, printing ink is formed oversimplified.
And, be characterised in that as the equipment of a mode of the present invention, use above-mentioned printing ink to carry out the pattern printing.
Therefore, the present invention is particularly useful in the conductive pattern printing of equipment.
In addition, as stated, for making the character homogeneity at the interface (surface) between each solids in the printing ink, example following situation: same material is modified on each surface to the 1st and the 2nd solids respectively; To modify the surface of the 2nd solids with the staple identical materials of the mother metal of the 1st solids; At least one side 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 the electrokinetic potential of the 1st in the printing ink, the 2nd solids unified under the same polar situation; Make the dispersion agent that contains absorption base in the printing ink, thereby can improve this dispersion agent adsorptivity of each the 1st, the 2nd solids relatively with electrokinetic potential and their opposite polarities.So, can make reactive force useful effect between the dispersion agent (the absorption base of dispersion agent), improve the dispersiveness of each solids in the printing ink in the 1st, the 2nd solids.
According to the present invention, can provide a kind of doing one's utmost to suppress to form when becoming complicated, make the printing ink of the multiple solids stable dispersion that contains.
Description of drawings
Fig. 1 is the synoptic diagram of the formation of the solids that contain in the printing ink of expression embodiment.
Fig. 2 is the figure that is used for explaining to the modifying method of the solid particle surfaces of printing ink shown in Figure 1.
Fig. 3 is the figure of method of precipitation test that is used for explaining the dispersiveness of the solids of estimating printing ink shown in Figure 1.
Fig. 4 is the synoptic diagram of the formation of the solids that contain in the printing ink of expression other embodiments different with the printing ink of Fig. 1.
Fig. 5 is the synoptic diagram of the formation of the solids that contain in the printing ink of expression other embodiments different respectively with the printing ink of Fig. 1 and Fig. 4.
Fig. 6 is the synoptic diagram of the formation of the solids that contain in the printing ink of expression another other embodiments different respectively with the printing ink of Fig. 1, Fig. 4 and Fig. 5.
Fig. 7 is the figure that schematically shows the effect of the dispersion agent that contains in the printing ink shown in Figure 6.
Fig. 8 is the decomposition diagram of sensor element of substrate of conductive pattern that had the ink printing that uses embodiment.
Embodiment
Following according to the description of drawings embodiment.
As shown in Figure 1, the printing ink 5 that embodiment relates to is the mother metal of staples mainly contain (a plurality of) the 1st solids 1, to(for) the butyl carbitol acetate equal solvent and the inkjet printing ink of solids 1 different (a plurality of) the 2nd solids 2, tackiness agent, a kind of dispersion agent.
The printing ink 5 that ink jet printing is used is in order suitably to discharge the drop of this printing ink from the small nozzle of ink gun, for example the viscosity under the normal temperature (25 ℃) is at least below the 100mPas, preferred 20mPas constitutes followingly.The adjustment of the viscosity of printing ink 5 is through the content of increase and decrease tackiness agent, suitably the tackiness agent that is suitable for of change and solvent types wait and realize.
Wherein, As shown in Figure 1; In the printing ink 5 of this embodiment, solids 1 are by the staple (particle main part) that constitutes mother metal as for example platinum (Pt) the particle 1a of metallics, and solids 2 are by the for example ZIRCONIUM DIOXIDE 99.5 (ZrO as metal oxide particle
2) particle 2a constitutes the staple of mother metal.Further, same material is modified on each surface (each surface of platinum particles 1a and ZIRCONIUM DIOXIDE 99.5 particle 2a) of these solids 1,2 respectively, carried out surface-treated.
Particularly, as shown in Figure 1, modify respectively on each surface of solids 1,2 and the carboxymethyl cellulose ammonium (NH of the staple different kinds material of mother metal
4-CMC), form decorative layer 3.In printing ink 5, unified solids 1, the Surface Physical character between 2, the i.e. character (homogeneity) at the interface of each solids 1,2 in this printing ink 5.
So, the electrokinetic potential each other (interface electrokinetic potential) of the solids 1,2 in the printing ink 5 becomes same polarity, and this current potential itself also becomes identical, can realize being prone to respectively the universalization by the dispersion agent of solids 1,2 absorption.Promptly; For example through making the a kind of dispersion agent that contains absorption base in the printing ink 5 with electrokinetic potential and solids 1,2 opposite polarities; Can be acted on solids 1,2 effectively by the electric reactive force between the dispersion agent (the absorption base of dispersion agent) of solids 1,2 difference absorption well thereby can make, can improve the dispersiveness of each solids 1,2 in the printing ink 5.Therefore, in printing ink 5, can do one's utmost to suppress to form when becoming complicated, solids 1,2 are stably disperseed in this printing ink.
The decorative layer 3 on the surface of solids 1,2 can be modified each surface of solids 1,2 through carrying out the processing of Fig. 2 example.As shown in Figure 2, at first will add to and dissolve NH as the ZIRCONIUM DIOXIDE 99.5 particle 2a of the pulverulence of the staple of the mother metal of the object of modifying
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 the jar mill in the lump, for example stir/disaggregating treatment with 5 hours (5hr).Then, the slurries in the jar mill (outstanding absurd creature) are moved in the container such as beaker,, moisture is evaporated from slurries for example in one evening of drying machine inner drying that is warmed to 40 ℃, thus as shown in Figure 1, can obtain on ZIRCONIUM DIOXIDE 99.5 particle 2a, to have formed NH
4The 2nd solids 2 of the decorative layer 3 of-CMC.And, when this modification processing is carried out at platinum powder end (platinum particles 1a), can obtain the 1st solids 1.
And the solids 1,2 in the printing ink 5 dispersed as shown in Figure 3 can be estimated through precipitation test.Specifically as shown in Figure 3, the printing ink of evaluation object is put in the graduated cylinder with cover, begin the timing that constantly begins from initial (0hr).When the time process, solids component (composition of suspension liquid) deposition, it is transparent that supernatant liquid becomes, and therefore after x hour (xhr), confirms the height of the bottom surface of printing ink till the upper space that comprises supernatant liquid from graduated cylinder, obtains whole quantity of ink A.Further, this time inscribe, the height till confirming from the upper surface (bottom surface of supernatant liquid) of precipitated solid composition to the upper surface of supernatant liquid is obtained supernatant liquid amount B.
Like this, through detecting the shared ratio (B/A) of supernatant liquid amount B, thereby can quantitatively obtain the dispersiveness of the solids component (solids 1,2) in the printing ink with respect to the whole quantity of ink A after x hour.That is, in printing ink, when the dispersiveness of solids 1,2 was low, it is many that the ratio that supernatant liquid amount B occupies becomes, and on the other hand, when solids 1,2 dispersed higher, the ratio that supernatant liquid amount B occupies tails off.In addition, this precipitation test is also applicable to the evaluation of the dispersiveness of the solids in the printing ink 6,7,8 of following Fig. 4～shown in Figure 7.
And, in Fig. 1, example will be as the NH of organic polymer material
4-CMC modifies the mode of solids 1,2 (platinum particles 1a, ZIRCONIUM DIOXIDE 99.5 particle 2a) respectively, but the material of modifying can suitably be selected.For example, dry in this way back then also can be with NH as the solid remaining material
4Organic polymer material beyond the-CMC is selected as the material of modifying usefulness.And, also alternative above-mentioned NH with electrical insulating property
4-CMC for example selects conductive material.For example; When conductive material is modified platinum particles 1a and ZIRCONIUM DIOXIDE 99.5 2a respectively; Electroconductibility is also given dielectric ZIRCONIUM DIOXIDE 99.5 particle 2a, and the printing ink that therefore contains more electroconductive particle through use carries out ink jet printing, thereby can form the conductive pattern with good electrical conductivity.
And, each solids is being modified in the mode of same material, can make the dispersion agent in the printing ink is a kind.In other words, when improving particle surface, can freely select the material modified, therefore can the kind of the dispersion agent on the surface that is adsorbed onto various solids be become change arbitrarily.And, be a kind through making dispersion agent, can simplify printing ink and form, can reduce cost.
And; In above-mentioned Fig. 1 and following Fig. 4～Fig. 7; As the staple of the mother metal of each solids, example platinum particles 1a, ZIRCONIUM DIOXIDE 99.5 particle 2a, but also can suitably select these and modify the particle of staple of mother metal of the object of (or clean processing of Fig. 6, Fig. 7).For example, the above-mentioned platinum particles of instead and select metallicss such as iridium (Ir) particle, palladium (Pd) particle, and also instead ZIRCONIUM DIOXIDE 99.5 particle 2a selective oxidation aluminium (Al for example
2O
3) metal oxide particle such as particle.
Wherein, use what material as the particle of the staple of mother metal, the material of the preferred substrate that is printed object (base material) of considering to form printed patterns etc. is selected.When the substrate that is printed object (base material) for example is made up of the ceramic substrate that comprises aluminum oxide etc.,, thereby can make the substrate that is printed object and the thermal expansivity of printed patterns etc. approximate as the particle selection aluminium oxide particles of the staple of above-mentioned mother metal.Mechanical strain that so, can suppress to be applied to because of influences such as temperature variation by substrate etc.Equally, when the ceramic substrate that contains the ZIRCONIUM DIOXIDE 99.5 particle is when being printed the substrate of object, but in printing ink, to contain with the ZIRCONIUM DIOXIDE 99.5 particle be the solids etc. of the staple of mother metal to example.
Fig. 4 representes the printing ink 6 that ink jet printing that other embodiments relate to is used.Printing ink 6 is as shown in Figure 4, mainly contains: through 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 99.5 particle 2a; To the effective a kind of dispersion agent of platinum; Tackiness agent.The surface portion ground of the 2nd solids 12 is modified the platinum of material (staple of the mother metal) same material of conduct and the 1st solids 11.
This decorative layer 1b is for example through formation such as infusion methods.Particularly; In as the platinic acid aqueous solution of the aqueous solution of catalyst metal salts, drop into last as the silicon dioxide powder of carrier; Make moisture evaporation dry; With about 500 ℃, heat-treat further, thereby make platinum (1b) separate out (carrying) from surface as the ZIRCONIUM DIOXIDE 99.5 2a of carrier as catalyst metal.
So; Make the 2nd solids 12, and whole the 1st solids 11 that constitute through platinum particles 1a of surface-treated through platinum; The physical properties homogeneity of particle surface is accompanied with it, also homogeneity of the character at the interface in the printing ink 6 (for example the value of electrokinetic potential, its polarity become identical).So, the effective a kind of dispersion agent of platinum becomes effective dispersion agent in containing the multiple solids printing ink 6 of (containing metal oxide particles such as ZIRCONIUM DIOXIDE 99.5 particle) relatively.Therefore, though printing ink 6 is better simply formations, can solids 11,12 are stably disperseed in this printing ink.
Other embodiments of the further example of Fig. 5.As shown in Figure 5, the printing ink 7 that the ink jet printing that this 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 99.5 particle 2a surface; To the effective a kind of dispersion agent of platinum; Tackiness agent.On the surface of the 2nd solids 22, as to modify the 2nd solid particle surfaces whole with the platinum of material (staple of the mother metal) same material of the 1st solids 11.
This modified layer 1c for example forms through further implementing platinum plating etc. on the ZIRCONIUM DIOXIDE 99.5 particle of having separated out platinum at particle surface.The 2nd solids 22 are through further implementing platinum plating to the ZIRCONIUM DIOXIDE 99.5 particle of having separated out platinum on the surface, at the whole formation in the surface of the 2nd solids 22 decorative layer 1c.So, the same with printing ink 5 shown in Figure 4, the effective a kind of dispersion agent of platinum becomes effective dispersion agent in the printing ink that contains multiple solids 7 relatively.Therefore, in the printing ink 7 of this embodiment, can do one's utmost to suppress to form when becoming complicated, solids 11,22 effectively are distributed in this printing ink.
And; In Fig. 4, printing ink 6,7 shown in Figure 5; Example to the mode of metal oxide particle finishing metallic substance such as ZIRCONIUM DIOXIDE 99.5 particle 2a; But also can not modify the surface of ZIRCONIUM DIOXIDE 99.5 particle 2a, and, make the surperficial homogeneity of each solids the finishing metal oxide materials of metallics 1a.And, can suitably select the method for modifying to the material of reply particle surface modification.
For example in Fig. 4, Fig. 5, as method to particle surface modified metal material (platinum), example infusion method, gold-plated processing, but when the modified metal material, vapor deposition, sputters etc. such as also applicable PVD, CVD.On the other hand, as method to particle surface modifying metallic oxide material, applicable sputter, vapor deposition, infusion method etc.
In addition, as the method for modifying, but the whole surface of applying solid particle also can be carried by the part of solid particle surfaces.That is,, the surface texture homogeneity is got final product through modifying solid particle surfaces.
The printing ink 8 that the ink jet printing that another other embodiments of Fig. 6 and Fig. 7 example relate to is used.Like Fig. 6, shown in Figure 7, the printing ink 8 of this embodiment mainly contains: the 1st solids 11 that self are made up of platinum particles 1a; Handle the 2nd solids 32 of ZIRCONIUM DIOXIDE 99.5 particle 2a with ablution; 1 kind of dispersion agent (constituting its a plurality of particles) 9; Tackiness agent.Wherein, above-mentioned the 2nd solids 32 forward direction particle surface in covering printing ink provides ablution, implements to make the processing of the charged 32a of this particle surface.
Particularly, like Fig. 6, shown in Figure 7, in printing ink 8, when the electrokinetic potential of the 1st solids 11 for example is straight polarity,, selects ablution and make the surface charging of the 2nd solids 32 for the electrokinetic potential that makes the 2nd solids 32 also becomes straight polarity (homopolarity).For example comprise basic solns such as acidic solution, sodium hydroxide such as hydrochloric acid etc. as ablution.
Wherein, As shown in Figure 7; Make the electrokinetic potential unification of the solids 11,32 in the printing ink 8 be same polarity (for example straight polarity); The dispersion agent 9 of the absorption base with electrokinetic potential and their opposite polarities (for example negative polarity) is contained in the printing ink, thereby can improves this dispersion agent 9 adsorptivity of each the 1st, the 2nd solids relatively.In addition; Identical with Fig. 1, Fig. 4, printing ink 5,6,7 shown in Figure 5; In printing ink shown in Figure 78; Through having improved, can improve the dispersiveness of each solids in the printing ink 8 to being derived from the interparticle spatial masking 10 of the base (not shown) that mixes in the electric property reactive force between the dispersion agent of the adsorptivity of each solids, each solids conscientiously in the dispersion agent of absorption.In addition, dispersion agent 9 is made up of the absorption base and the base that mixes, and this absorption base is adsorbed onto the surface of each solids.
And; The printing ink the 5,6,7, the 8th of Fig. 1 and Fig. 4～Fig. 7 example, the printing ink that the ink jet printing that small drop is discharged from nozzle is used; Therefore be the low viscosity ink formation below the 20mPas for example, but as stated, stably disperse between each solids as the viscosity under the normal temperature; So for example need not deposition of worrying heavy solids etc., can be used for ink jet printing well.
Then; An example as the equipment that printing ink of the present invention is applied to the conductive pattern printing; For any ink jet printing with the printing ink 5,6,7,8 through Fig. 1 and Fig. 4～shown in Figure 7 the sensor element of substrate of conductive pattern, describe with reference to Fig. 8.As shown in Figure 8, this sensor element 20 is with gas sensor element main body 20a and well heater 20b lamination and the gas sensor element that constitutes at least.
Well heater 20b has the 1st matrix 27 and the 2nd matrix 25, and resistance heater 26.Resistance heater 26 is that main body constitutes with platinum etc., and the 1st matrix 27 and the 2nd matrix 25 are made up of the ceramic sintered bodies that with the aluminum oxide is main body respectively.Resistance heater 26 is clamped in respectively between orthogonal the 1st matrix 27 and the 2nd matrix 25.
And resistance heater 26 has: heat generating part 26b, form the shape of crawling, and generate heat through energising; The a pair of heating wires 26a of portion, an end separately is connected to heat generating 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 separately is through 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 usefulness with external circuit.
On the other hand, equipment component main body 20a has concentration detecting unit (concentration detecting unit substrate) 24 and resist 35.Concentration detecting unit 24 has orthogonal solid electrolyte substrate 33, as the 1st electrode pattern 36 and the 2nd electrode pattern 34 of conductive pattern.Solid electrolyte substrate 33 for example is to have added yttrium oxide (Y as stablizer
2O
3) or the ZIRCONIUM DIOXIDE 99.5 (ZrO of quicklime (CaO)
2) be the solid electrolyte body that the oxygen concentration cell of formations such as sintered compact is used.In addition, solid electrolyte substrate (solid electrolyte body) 33 also can be by LaGaO
3Be formations such as sintered compact.
To on one of the solid electrolyte substrate 33 of (fire before) before the sintering and another interarea, use Fig. 1, Fig. 4～printing ink shown in Figure 7, the 1st electrode pattern 36 and the 2nd electrode pattern 34 with inkjet direction respectively by the pattern printing.Wherein, in sensor element 20, after the printing of this pattern, the 1st electrode pattern 36 and the 2nd electrode pattern 34 and above-mentioned solid electrolyte substrate 33 at least are for example to surpass 1100 ℃ temperature simultaneously by high-temperature firing.
At this moment; Though the 1st electrode pattern 36 and the 2nd electrode pattern 34 are heated with the high temperature above 1100 ℃; But as stated; Printing ink through making the multiple solids stable dispersion that contains can suppress the over-drastic sintering, thereby can suppress the decline and the broken string of the conduction property of pattern self as the material of pattern printing usefulness.And, be suitable for NH shown in Figure 1 at this
4The decorative layer 3 of-CMC system has been modified the printing ink 5 of the 1st, the 2nd solids 1,2 and has been carried out pattern when printing, above-mentioned when surpassing 1100 ℃ high-temperature firing, and NH
4The disappearance of burn simultaneously of the decorative layer 3 of-CMC system and dispersion agent 9, thus make the platinum particles 1a exposing surface as the staple of the mother metal of the 1st solids 1, acquisition 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 are arranged on the position respect to one another.
The 2nd electrode pattern 36 has the 1st 36a of electrode cable portion, and it extends to the length direction of solid electrolyte substrate 33 from the 1st electrode part 36b.On the other hand, the 2nd electrode pattern 34 has the 2nd 34a of electrode cable portion, and it extends to the length direction of solid electrolyte substrate 33 from the 2nd electrode part 34b.In addition; Resist 35 and solid electrolyte substrate 33 between lamination on the position of clamping the 2nd electrode pattern 34, have the electrode protecting layer 35b of the porous matter shape that is used to prevent that the 2nd electrode part 34b poisons and be used to protect the enhanced protection layer 35a of solid electrolyte substrate 33.
The end of the 1st 36a of electrode cable portion is by the through hole 33b that is arranged on solid electrolyte substrate 33 and be arranged on the through hole 35d on the resist 35, is connected to signal and takes out with one among the terminal 35f.And the end of the 2nd 34a of electrode cable portion is by the through hole 35e that is arranged on resist 35, is connected to signal and takes out with among the terminal 35f another.The sensor element 20 that constitutes like this can be measured oxygen concn through the concentration cell effect of concentration detecting unit 24, also can be used as air-fuel ratio sensor etc. and is suitable for.
As stated; In sensor element shown in Figure 8 20; Be suitable for the printing ink that the ink jet printing of the dispersiveness between the multiple solids improved Fig. 1 and Fig. 4～shown in Figure 7 is used, on the substrate of pottery system, form conductive pattern, therefore can improve the reliability of electrical connection of element internal.
When especially using Fig. 4,6,7 pairs the 1st electrode patterns 36 of printing ink shown in Figure 5 and the 2nd electrode pattern 34 to carry out the pattern printing; Platinum is also modified on the dielectric ZIRCONIUM DIOXIDE 99.5 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 constitutes of sintered compact by ZIRCONIUM DIOXIDE 99.5; Use and contain printing ink 5,6,7, the 8 formation printed patterns (the 1st electrode pattern 36 and the 2nd electrode pattern 34) as the solids of the staple of mother metal, thereby can make the thermal expansivity of printed patterns and the solid electrolyte that is printed object approximate with ZIRCONIUM DIOXIDE 99.5 particle 2a.So, when 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 Figure 8), therefore can suppress to fire the back deflection etc. takes place.
Below clear specifically embodiment, but the invention is not restricted to this embodiment, in the scope that does not break away from its purport, can carry out various changes.For example, in the printing ink 5,6,7,8 of Fig. 1 and Fig. 4～shown in Figure 7, example contain the 1st and the printing ink of the 2 two kind of solids, but contain 3 kinds, 4 kinds ... In the printing ink of above multiple solids, also applicable certainly the present invention.Promptly; Through each surface of the solids of all kinds being modified same material respectively, will being modified the 2nd, the 3rd, the 4th with the staple identical materials of the mother metal of the 1st solids ... Each surface of solids or to the 1st, the 2nd, the 3rd, the 4th ... At least one side in the 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 ...) when solids electrokinetic potential separately is 0 ± 5mV; For example can be following method etc.: select to wait according to the mensuration result of the electrokinetic potential of preparation property test the specific material of the value of having judged the electrokinetic potential in the printing ink in advance, the material that this is specific be modified the surface of solids.Wherein, the electrokinetic potential that why makes each solids is 0 ± 5mV, for example is to consider fluctuation on the 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; Electrokinetic potential through making each solids in the printing ink is near 0mV; Can suppress the absorption that the electric charge between solids causes; Through making dispersion agent be present in solid particle surfaces, can make dispersion agent as the screen between solids (spatial masking), thereby can multiple solids stably be distributed in the printing ink.
And in Fig. 8, example the cell substrate that carries sensor element etc. is formed the mode of printed patterns, but for example in the pattern printing of semi-conductor associated components etc., also applicable printing ink of the present invention.In addition, " equipment " put down in writing in claims also is equivalent to semiconductor substrate etc. except the gas sensor of example shown in Figure 8.
Claims (13)
1. a printing ink contains: the 1st solids at least; And the staple of mother metal 2nd solids different with above-mentioned the 1st solids, it is characterized in that,
At least one side's surface is modified in above-mentioned the 1st solids and the 2nd solids,
Electrokinetic potential each other is same polarity, and perhaps separately electrokinetic potential is 0 ± 5mV.
2. printing ink according to claim 1 is characterized in that, above-mentioned printing ink is that the viscosity under the normal temperature is the printing ink that the ink jet printing below the 100mPas is used.
3. printing 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. according to any described printing ink of claim 1 to 3, it is characterized in that above-mentioned the 1st solids are electroconductive particles, above-mentioned the 2nd solids are insulativity particles.
5. according to any described printing ink of claim 1 to 4, it is characterized in that at least one side's surface is modified the surface through modifying with each mother metal kinds of materials in above-mentioned the 1st solids and the 2nd solids.
6. printing ink according to claim 5 is characterized in that above-mentioned kinds of materials is an organic polymer material.
7. printing ink according to claim 6 is characterized in that above-mentioned kinds of materials is a carboxymethyl cellulose ammonium.
8. printing ink according to claim 6 is characterized in that above-mentioned kinds of materials has electroconductibility.
9. according to any described printing ink of claim 1 to 4, it is characterized in that the surface of above-mentioned the 2nd solids is modified the surface through the staple identical materials of the mother metal of modification and above-mentioned the 1st solids.
10. according to any described printing ink of claim 1 to 4, it is characterized in that at least one square tube in the above-mentioned the 1st and the 2nd solids is crossed and implemented that ablution is provided and make the charged processing of particle surface and the surface is modified.
11. any described printing ink according to claim 1 to 10; It is characterized in that; Making the above-mentioned the 1st and the 2nd solids electrokinetic potential each other is same polarity chron, also contains dispersion agent, and this dispersion agent has and the opposite polarity absorption base of the electrokinetic potential of the 1st and the 2nd solids.
12. printing ink according to claim 11 is characterized in that, above-mentioned dispersion agent only is made up of a kind of.
13. an equipment uses any described printing ink of claim 1 to 12 to carry out the pattern printing.
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 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102675964A true CN102675964A (en) | 2012-09-19 |
| CN102675964B 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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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040180993A1 (en) * | 2003-03-14 | 2004-09-16 | Shelton Michael Charles | Low molecular weight carboxyalkylcellulose esters and their use as low viscosity binders and modifiers in coating compositions |
| JP2006210301A (en) * | 2004-12-27 | 2006-08-10 | Mitsui Mining & Smelting Co Ltd | Conductive ink |
| 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 |
| US20100096596A1 (en) * | 2008-10-17 | 2010-04-22 | Lewis Jennifer A | Biphasic inks |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040180993A1 (en) * | 2003-03-14 | 2004-09-16 | Shelton Michael Charles | Low molecular weight carboxyalkylcellulose esters and their use as low viscosity binders and modifiers in coating compositions |
| JP2006210301A (en) * | 2004-12-27 | 2006-08-10 | Mitsui Mining & Smelting Co Ltd | Conductive ink |
| 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 |
| US20100096596A1 (en) * | 2008-10-17 | 2010-04-22 | Lewis Jennifer A | Biphasic inks |
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| CN102675964B (en) | 2014-09-03 |
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