JP2014106204A - Preparation condition evaluation device for conductive paste - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a preparation condition evaluation device for conductive paste capable of efficiently compounding two or more kinds of paste with high reliability by utilizing a combinatorial technique.SOLUTION: There is provided a preparation condition evaluation device for conductive paste including: a sampling part which uses the compounding ratio of two or more kinds of paste sample for forming conductive paste as at least one parameter, and samples the two or more kinds of paste sample at a plurality of compounding ratios at a predetermined sampling position while changing the parameter in a plurality of ways; a pressure mixing part which prepares a conductive paste by mixing the two or more kinds of sampled paste sample under a pressure condition; a burning part which forms a plurality of burnt bodies by burning the plurality of prepared conductive pastes; an electric conductivity measurement part which measures electric conductivity of the plurality of burnt bodies; and an evaluation part which evaluates preparation conditions of the plurality of conductive pastes from the compounding ratios and measurement results of the electric conductivity.

Description

  The present invention relates to a preparation condition evaluation apparatus for conductive paste. More specifically, the present invention relates to an evaluation apparatus that evaluates the preparation conditions of a conductive paste used to form a conductive substance such as an electrode.

  Conventionally, a conductive paste has been widely used as an IC circuit forming material, an electrode forming material, a resistor forming material, a conductive adhesive, an electromagnetic wave shielding material and the like used for manufacturing battery members and electronic devices. By supplying such a conductive paste to the surface of a substrate or the like by a technique such as printing and baking, a conductive film having a predetermined function and characteristics can be obtained. In recent years, along with improvements in performance and quality of battery members and electronic devices, it has been required to strictly control the characteristics such as the electrical conductivity or resistivity of the conductive film obtained after firing for this conductive paste. ing. For example, in the case of a conductive paste for electrode formation, the electrical conductivity of the conductive film obtained by firing is set to a predetermined value for each target product or for each use site of the paste. The electrical conductivity is also required to have an accuracy of about ± 0.01 Ω · cm, for example.

  In general, the conductive paste is prepared by dispersing conductive particles having functions and characteristics according to the purpose in a solvent together with a binder. For example, conductive particles are selected according to desired electrical conductivity or resistivity (hereinafter, unless otherwise specified, “electrical conductivity or resistivity” is simply referred to as “electrical conductivity”). The conductive particles are used alone or in combination of two or more kinds of conductive particles. It is possible to adjust the characteristics such as electrical conductivity of the conductive paste by selecting conductive particles and mixing a binder and a solvent each time. In many cases, a paste having a desired performance is obtained by preparing several types of basic conductive pastes with known properties.

  The blending ratio of this basic paste sample (that is, an individual paste-like sample before blending for preparing a desired conductive paste; the same shall apply hereinafter) is usually through, for example, the following procedure. It is determined. That is, first, a plurality of basic paste samples are mixed in several combinations and kneaded with a roller to prepare a plurality of conductive pastes. Next, this conductive paste is printed on a substrate and baked to produce a plurality of conductive films. Then, by evaluating the characteristics of the produced conductive film to determine whether it has the desired characteristics, the blending ratio of the paste sample that is the most suitable for realizing the characteristics is determined. Here, the prepared conductive paste may be greatly affected by its characteristics due to slight differences in raw material production conditions and paste production methods. Therefore, the preparation of the blending ratio of the conductive paste as described above is an essential process that is performed once a day, for example. And the determination of the blending ratio of this conductive paste is carried out by almost all steps manually.

Japanese Patent Laid-Open No. 2002-033283 Special table 2003-53370 gazette JP 2001-219052 A JP 2003-083855 A JP 2008-246328 A Patent No. 4009712 JP 2003-215069 A

  By the way, in the field of organic materials represented by pharmaceuticals and the like, combinatorial techniques have been utilized for the purpose of exhaustive search for medicinal ingredients and the like. In recent years, in the fields of inorganic solid materials and metal materials, it has been proposed to use a combinatorial technique as a technique for searching for new materials (see, for example, Patent Documents 1 to 5). By adopting combinatorial methods also in the fields of inorganic solid materials and metal materials, a comprehensive search for material compositions that express unique functions from combinations of raw materials in various components and various quantitative ratios can be performed in a short time, and It is possible to do this automatically.

  However, the conductive paste can be, for example, a highly viscous suspension having a viscosity of 3 to 2000 Pa · s at 25 ° C., and the conductive particles contained in the paste settle down over time to be in a suspended state. Therefore, it is relatively difficult to automatically perform sampling with few errors by using a combinatorial method. Above all, for such a highly viscous sample, it has been very difficult to uniformly mix the sample after sampling. Therefore, when the paste sample is blended at a ratio different from the target blending ratio due to sampling error or when uniform mixing is not realized, the electrical conductivity etc. It was necessary to measure the characteristics, and there was a possibility that correct evaluation could not be performed. On the other hand, in order to automatically perform sampling with few errors, for example, the sampling rate is reduced sufficiently, or the sampling amount is monitored by a plurality of functions such as a weigh scale during sampling, and the sampling amount is corrected on the spot. It was necessary to do so, and even the combinatorial method had to take time.

  On the other hand, the method of determining the basic paste sample mixing ratio by hand requires a long time for the work, and also increases the waste loss because the sample is prepared in a certain amount. There was a problem that should be improved. Another problem is that human error is unavoidable because each work is carried out manually. In order to suppress such an error, it was necessary to perform a longer and careful work. Therefore, since the number of conditions that can be practically evaluated is limited, there is a problem that the range in which the characteristics of the obtained conductive film can be managed becomes relatively rough.

  The present invention has been created to solve the above-described conventional problems, and the object of the present invention is to shorten the preparation conditions of a conductive paste formed by blending two or more types of paste samples. It is an object of the present invention to provide an apparatus for evaluating preparation conditions for conductive paste that can be accurately evaluated over time.

  The conductive paste preparation condition evaluation apparatus disclosed herein (hereinafter sometimes simply referred to as “evaluation apparatus”) is an apparatus for evaluating the preparation conditions of a conductive paste for producing a conductive substance. It is. Such an evaluation apparatus uses, as at least one parameter, a blending ratio of two or more types of paste samples for constituting a conductive paste, and changes the parameters in a plurality of ways so that the two or more types of paste samples are blended into the plurality of blends. A sampling unit for sampling at a predetermined sampling position at a rate; a pressure mixing unit for preparing a conductive paste by mixing two or more sampled paste samples under pressure; and a plurality of the prepared plurality A firing part for firing a conductive paste to form a plurality of fired bodies, an electrical conductivity measuring part for measuring electrical conductivity of the fired bodies, and a blending ratio and a measurement result of the electrical conductivity. From the relationship, an evaluation unit that evaluates the preparation conditions of the plurality of conductive pastes is provided.

In the sampling unit, according to a combinatorial method, the blending ratio of the paste sample which is a constituent material of the conductive paste is set as at least one parameter, and the conductive paste having various compositions is blended by changing this parameter. However, this type of conductive paste, that is, a paste sample, has a very high viscosity. For example, uniform mixing by a non-contact method is extremely difficult. In addition, although mixing by a contact method, for example, mechanical stirring using a mixing device or the like, uniform mixing is possible, for example, in this case, the number of mixing devices corresponding to the number of paste samples blended It is necessary to sample a paste sample in an amount suitable for such a mixing device, and it is not preferable in terms of equipment and disposal loss of the paste sample.
On the other hand, according to the preparation condition evaluation apparatus disclosed here, two or more kinds of sampled paste samples are mixed in a pressure mixing unit under pressure conditions. In other words, non-contact and uniform mixing is possible by applying pressure to a highly viscous paste sample. Therefore, a homogeneous conductive paste can be prepared, and the preparation conditions can be evaluated with higher accuracy. Moreover, since non-contact mixing is possible, it is not necessary to newly prepare or wash a stirring device or the like for each blending, and it is possible to suppress the waste loss of the paste sample. Furthermore, it is possible to mix a plurality of paste samples at a time. Therefore, the preparation conditions of the conductive paste can be evaluated efficiently.

In a preferred embodiment of the conductive paste preparation condition evaluation apparatus disclosed herein, the paste sample includes conductive particles, a binder, and a solvent, and has a viscosity at 25 ° C. and 10 rpm of 3 Pa · s to 2000 Pa ·. It is characterized by being s.
The composition of the paste sample used to prepare the conductive paste varies, and there are low viscosity to high viscosity. The preparation condition evaluation apparatus disclosed here is preferable because the effect can be exerted without any limitation by applying it to a paste sample having a relatively high viscosity in the range as described above. The viscosity of the paste sample may be 3 Pa · s or more, depending on the application, for example, 10 Pa · s or more, particularly 50 Pa · s or more, and further 100 Pa · s or more. Although the upper limit of the viscosity of the paste sample cannot be generally stated, it can be set to about 2000 Pa · s or less as an approximate guide.

In a preferred aspect of the conductive paste preparation condition evaluation apparatus disclosed herein, the sampling unit is configured to be capable of preparing each of the plurality of conductive pastes in an amount of 10 g or less.
According to such a configuration, since the sample of highly viscous paste to be sampled can be mixed in a non-contact manner, for example, even when the amount of one conductive paste to be prepared is as small as 10 g or less, it is sufficiently accurate. The preparation conditions can be evaluated well. More specifically, such a conductive paste can be prepared in an amount of 1 g or less, for example. In addition, even if the conductive paste is a highly viscous paste, it is sufficient to prepare only the amount necessary for testing and analysis without considering strict sampling accuracy, and the waste loss of the conductive paste can be reduced. it can.

In a preferred embodiment of the conductive paste preparation condition evaluation apparatus disclosed herein, the pressure mixing unit is characterized by mixing under a pressure condition of 0.05 MPa to 1 MPa.
According to such a configuration, more uniform mixing can be realized in the pressure mixing unit, and variations in the characteristics and the like of the prepared conductive paste, and thus the fired body obtained by firing can be reduced.

In a preferred aspect of the conductive paste preparation condition evaluation apparatus disclosed herein, the electrical conductivity measurement unit is configured to be able to simultaneously measure the plurality of fired bodies by a single measurement operation. It is characterized by.
Such an electrical conductivity measuring unit is provided with a plurality of functions for measuring electrical conductivity so that, for example, all electrical conductivities of fired bodies formed at a plurality of sample positions set on the substrate can be measured simultaneously. For example, an apparatus for measuring electrical conductivity is disposed at a position corresponding to each sample position on the substrate. Thereby, the electrical conductivity of a plurality of fired bodies can be measured instantaneously, and the preparation conditions can be evaluated in a shorter time.

In a preferred aspect of the conductive paste preparation condition evaluation apparatus disclosed herein, the pressure mixing unit further includes an ultrasonic wave generation function.
According to such a configuration, the high-viscosity paste sample as described above can be mixed more uniformly and in a shorter time, and the preparation conditions of the conductive paste with higher accuracy can be evaluated.

In a preferred embodiment of the conductive paste preparation condition evaluation apparatus disclosed herein, the electrical conductivity measurement unit is configured to be able to measure the electrical conductivity of the plurality of fired bodies at a high temperature of 500 ° C. or higher. It is characterized by.
The conductive paste can be used in various temperature ranges such as a low temperature region (for example, about −20 ° C.) to a high temperature region of 500 ° C. or higher depending on the application of the fired body. More specifically, for example, a solid oxide fuel cell (SOFC) has a relatively high operating temperature of about 500 ° C. to 1000 ° C. According to the preparation condition evaluation apparatus having such a configuration, the electrical conductivity measurement unit can measure electrical conductivity at a high temperature of 500 ° C. or higher (for example, about 500 ° C. to 1000 ° C.). Thereby, for example, when the use of the fired body is a component of SOFC and it is used at a high temperature of 500 ° C. or higher, the characteristics in the usage situation can be evaluated.

In a preferred embodiment of the conductive paste preparation condition evaluation apparatus disclosed herein, the sampling position is set to a sample position provided on the surface of the substrate, and the pressure mixing unit is a sample on the substrate. All the positions are hermetically sealed at the same time, and the sampled two or more types of paste samples are pressure-mixed.
Since the pressure mixing unit enables non-contact mixing as described above, the sampling position of the paste sample is not limited. Therefore, for example, the paste sample can be directly sampled on the substrate for baking, and the sampled paste sample can be mixed on the substrate all at the same time. Thereby, the disposal loss of a paste sample can be reduced and the preparation conditions of a conductive paste can be evaluated more efficiently.

In a preferable aspect of the conductive paste preparation condition evaluation apparatus disclosed herein, the apparatus further includes a transfer unit, and the sampling position is set in each of a large number of prepared sampling containers. The mixing unit hermetically seals the sampling container, pressurizes and mixes two or more types of paste samples sampled in the sealed sampling container, and the transfer unit is prepared in the sampling container. The conductive paste is transferred to sample positions provided in large numbers on the surface of the substrate.
According to such a configuration, even when a highly viscous paste sample is mixed under pressure under a higher pressure, it is uniform without causing problems such as scattering of the paste sample and the accompanying compositional deviation. Mixing can be performed.

In a preferable aspect of the conductive paste preparation condition evaluation apparatus disclosed herein, the electroconductive paste preparation condition evaluation apparatus further includes a composition analysis unit that performs composition analysis of the plurality of fired bodies. The blending ratio of two or more types of paste samples is corrected based on the result of the composition analysis, and the preparation conditions for the plurality of conductive pastes are evaluated from the relationship between the blending ratio after the correction and the measurement result of the electrical conductivity. It is characterized by doing.
If a conventionally used combinatorial sample preparation device or the like is used as the sampling unit, accurate sampling of a highly viscous paste sample may be difficult depending on the device. A situation may occur in which a paste and a fired body are not obtained. In addition, if the sampling amount is monitored or corrected on the spot in order to improve the sampling accuracy, the sampling time will be lengthened.
According to this structure, it is set as the structure which can perform an electrical conductivity measurement and a composition analysis about the sintered body (for example, electroconductive film) formed. Therefore, even if the blending ratio of the fired body is randomly deviated from the set value, the blending ratio can be corrected based on the actual composition. Therefore, the preparation conditions of the conductive paste can be accurately evaluated based on the actual sampling composition.

In a preferred embodiment of the conductive paste preparation condition evaluation apparatus disclosed herein, the apparatus further comprises a thermal expansion coefficient measurement unit that measures the thermal expansion coefficient of a plurality of fired bodies, and the evaluation unit measures the thermal expansion coefficient. Including the results, the preparation conditions of the plurality of conductive pastes are evaluated.
The conductive paste is typically made of various materials such as ceramic materials, metal materials, and composite materials thereof, and is coated on the substrate to form a laminated structure of conductive films. Used in. For example, in manufacturing such a laminated structure, it is important to manage the coefficient of thermal expansion so that deformation such as warpage does not occur. According to said structure, about the baked product obtained by baking an electroconductive paste, the preparation conditions of an electroconductive paste can be evaluated including a thermal expansion coefficient in addition to the above electrical conductivity. Therefore, it is possible to evaluate the preparation conditions of a conductive paste having more desired characteristics and functions.

  In a preferred embodiment of the conductive paste preparation condition evaluation apparatus disclosed herein, the thermal expansion coefficient measurement unit has a function of measuring the thermal expansion coefficient of the fired body in an oxidizing atmosphere and a reducing atmosphere, and the evaluation unit Calculates the reductive expansion coefficient defined by the following equation (1) from the measurement results of the thermal expansion coefficient in the oxidizing atmosphere and the reducing atmosphere of the fired body, and includes the reductive expansion coefficient of the plurality of conductive pastes. It is characterized by evaluating preparation conditions.

  The reductive expansion coefficient is a value representing the difference in thermal expansion state between the oxidizing atmosphere (for example, the air atmosphere) and the reducing atmosphere as represented by the above formula (1) with reference to the thermal expansion state in the oxidizing atmosphere. . For example, SOFC has a complicated structure in which a plurality of inorganic solid materials are joined in layers, for example, and since the operating temperature is high, if a temperature gradient occurs during start-up and stop, etc. Stress is generated at the interface of the material. In addition, since the SOFC has a reducing atmosphere and the anode has an oxidizing atmosphere with the solid electrolyte membrane sandwiched therebetween, the product can be warped if the reduction expansion coefficient represented by the above formula (1) is large. Therefore, the reduction expansion coefficient is a characteristic that cannot be ignored in the development of SOFC. According to the evaluation apparatus disclosed herein, for example, when the reductive expansion coefficient is an important evaluation index, such as a conductive paste for SOFC applications, the conditions for preparing the conductive paste in consideration of this reductive expansion coefficient Can be evaluated. For example, when the room temperature state (typically 25 ° C.) is used as a reference, the reductive expansion coefficient is represented by a room temperature state of 1, and generally increases as the temperature increases. Such a reduction expansion coefficient is preferably a value close to 1 or a value approximated between materials to be joined.

In a preferred embodiment of the conductive paste preparation condition evaluation apparatus disclosed herein, the thermal expansion coefficient measuring unit is capable of controlling the measurement atmosphere and analyzing the crystal structure in a region from at least room temperature to 1200 ° C. The evaluation unit calculates the reduction expansion coefficient based on a change in lattice constant in the measurement temperature range, and evaluates the preparation conditions of the plurality of conductive pastes including the reduction expansion coefficient. And as this thermal expansion coefficient measurement part, it is set as the preferable aspect that an X-ray diffraction analyzer is included.
In general, the thermal expansion coefficient of an inorganic solid material is measured by a thermomechanical analyzer (TMA) or the like. This measurement method is applied to a very small amount of fired body sample prepared by a combinatorial technique. It is difficult to apply. On the other hand, according to the technique for obtaining the reduction expansion coefficient from the lattice constant obtained by the crystal structure analysis, even a small fired body sample (so-called library-like sample) by the combinatorial technique can be used in an oxidizing atmosphere and a reducing atmosphere. By performing the crystal structure analysis in a predetermined temperature range, it is possible to calculate the reduction expansion coefficient continuously and quickly with high accuracy for a plurality of fired bodies. As such a crystal structure analysis technique, for example, a crystal structure analysis method using an X-ray or a neutron beam is typically known. In the preparation condition evaluation apparatus disclosed here, it is preferable to use a more general-purpose X-ray diffraction analyzer as a function capable of performing the crystal structure analysis.

In a preferred embodiment of the conductive paste preparation condition evaluation apparatus disclosed herein, the baking section sets the baking temperature as at least one parameter, changes the parameter, and fires the plurality of conductive pastes, and evaluates the evaluation. The section is characterized by evaluating the baking temperature parameters as preparation conditions for the plurality of conductive pastes.
According to such a configuration, not only the composition of the fired body sample but also the firing conditions including the firing temperature can be evaluated for the preparation conditions of the conductive paste.

It is the conceptual diagram which showed the structure of the preparation condition evaluation apparatus of the electrically conductive paste which concerns on one Embodiment of this invention. It is the figure which showed an example of the flow at the time of evaluating the preparation conditions of an electrically conductive paste with the preparation condition evaluation apparatus of the electrically conductive paste of this invention. It is the schematic diagram which showed the structure of the pressurization mixing part which concerns on one Embodiment of this invention. It is the schematic diagram which showed the structure of the pressure mixing part which concerns on other embodiment of this invention. It is the schematic diagram which showed the structure of the electrical conductivity measuring apparatus which concerns on one Embodiment of this invention. It is the schematic diagram which showed the structure of the electrical conductivity measuring apparatus which concerns on other embodiment of this invention. It is the figure which showed an example of the electroconductive substance created in the Example.

  Hereinafter, preferred embodiments of the present invention will be described. It should be noted that matters other than matters specifically mentioned in the present specification (for example, characteristics of each component constituting the preparation condition evaluation apparatus for conductive paste), matters necessary for the implementation of the present invention (for example, A manufacturing method, an operation method, an operation condition, and the like of each component constituting the evaluation apparatus) can be grasped as a design matter of a person skilled in the art based on the conventional technology in the field. The present invention can be carried out based on the contents disclosed in this specification and common technical knowledge in the field.

FIG. 1 conceptually shows the configuration of a conductive paste preparation condition evaluation apparatus as an embodiment disclosed herein. Moreover, FIG. 2 is a figure which showed an example of the flow at the time of evaluating the preparation conditions of an electrically conductive paste by this evaluation apparatus. The conductive paste evaluation apparatus disclosed herein will be described in detail below along the flow shown in FIG.
The evaluation apparatus 500 is generally composed of a control unit 100, a sample adjustment unit 200, and a measurement unit 300, and main components of the evaluation apparatus 500 are arranged at any one of these parts. . In the example illustrated in FIG. 1, the control unit 100 includes the evaluation unit 40 together with the input unit 10, and the sample adjustment unit 200 includes the sampling unit 20, the pressure mixing unit 22, and the baking unit 24, and the measurement unit 300 includes an electrical conductivity measuring unit 30 and a composition analyzing unit 32. The evaluation apparatus is not limited to such a configuration. For example, the input unit 10 and the evaluation unit 40 are provided in the sample preparation unit 200 and the measurement unit 300, respectively, so that data can be transmitted and received between them. Various modes such as the mode and the firing unit 24 in the sample preparation unit 200 may play a part of the function of the test / analysis unit in the measurement unit 300 may be considered.

The above evaluation apparatus 500 evaluates the blending ratio of the two or more types of paste samples so that the conductive film, which is a fired body obtained by mixing and baking two or more types of paste samples, has a desired function. To do.
The paste sample used here is a paste-like material (including slurry-like and ink-like) that is the basis for constituting a conductive paste, and this paste sample is mixed at an optimum blending ratio. Thus, a conductive paste exhibiting desired functions and characteristics is constructed. The configuration and characteristics of the paste sample are not particularly limited. For example, the paste sample can be configured to be a part of the configuration of the target conductive paste. Such sample paste basically includes conductive particles, a binder, and a solvent. The configuration of such a paste sample will be described below by exemplifying typical ones.

The conductive particles are a substance responsible for the conductivity of a fired body (typically a conductive film) obtained after firing the conductive paste. There is no restriction | limiting in particular about the kind etc. of this electroconductive particle, The various electroconductive particle conventionally used for the target electroconductive paste can be especially used without a restriction | limiting. The target conductive paste may be various conductive pastes for electrode formation, printed circuit, bonding, resistor, anisotropic conductive ink, etc., as an example of such conductive particles, Gold (Au), silver (Ag), copper (Cu), platinum (Pt), palladium (Pd), ruthenium (Ru), rhodium (Rh), iridium (Ir), osmium (Os), nickel (Ni) and Metals such as aluminum (Al) and alloys thereof, carbonaceous materials such as carbon black, LaSrCoFeO ₃ -based oxides (eg LaSrCoFeO ₃ ), LaMnO ₃ -based oxides (eg LaSrGaMgO ₃ ), LaFeO ₃ -based oxides (eg LaSrFeOO) _3), a transition metal perovskite acids represented as LaCoO ₃ type oxide (e.g., LaSrCoO ₃₎ or the like Conductive ceramics typified by the object is illustrated.
There are no strict restrictions on the shape and particle diameter of the particles, and typically, for example, the average particle diameter is selected from a range of several nm to several μm, for example, about 10 nm to 10 μm, depending on the application. Particles having an average particle size can be used. In the present specification, the “average particle size” means an integrated value of 50% in the particle size distribution measured by a particle size distribution measuring apparatus based on the laser scattering / diffraction method in the range where the average particle size is approximately 0.5 μm or more. In the range where the average particle diameter is about 0.5 μm or less, it can be obtained by observation means such as an electron microscope. It can be determined as the particle diameter at an integrated value of 50% in the particle size distribution created based on the equivalent circle diameter of a plurality of particles in the observed image to be observed. Note that there is no strict criticality in the particle size range to which these average particle size calculation methods are applied, and the calculation method can be appropriately selected according to the accuracy of the apparatus to be employed.

As another component of the conductive paste, there is a medium called a vehicle in which the conductive particles are dispersed. Such a medium is typically composed of a binder and a solvent. Any vehicle can be used as long as it can disperse the conductive particles appropriately, and those used in conventional conductor pastes can be used without particular limitation.
Examples of the binder include those based on acrylic resin, epoxy resin, phenol resin, alkyd resin, cellulosic polymer, polyvinyl alcohol, polyvinyl butyral, and the like. Further, a glass frit may be included as a component responsible for the ability of the conductive paste to adhere to the substrate (binder function) or as a component responsible for other functions such as adhesion and durability.

Examples of the solvent include cellulose polymers such as ethyl cellulose, ethylene glycol and diethylene glycol derivatives, high-boiling organic solvents such as toluene, xylene, mineral spirits, butyl carbitol, and terpineol, or combinations of two or more thereof. An organic vehicle can be used.
In addition, the paste sample contains various additives that can give desired properties such as good viscosity and ability to form a coating film (attached film to the base material) to constitute the conductive paste, if necessary. May be. Examples of such additives include surfactants, antifoaming agents, plasticizers, thickeners, antioxidants, dispersants, various photopolymerizable compounds and photopolymerization initiators, polymerization inhibitors, and ceramic groups. Various coupling agents such as silicon-based, titanate-based, and aluminum-based materials for the purpose of improving adhesion to the material can be mentioned.

  The above paste sample can have, for example, the same composition as the intended conductive paste or a composition that is a part thereof. Specifically, for example, when the composition of the paste sample is the same as that of the conductive paste, for example, it is possible to prepare paste samples having two or more kinds of concentrations by appropriately changing the concentration. When the composition of the paste sample is different from that of the conductive paste, for example, the constituents of the target conductive paste can be divided into two or more parts, and two or more types of paste samples including the parts can be prepared.

These paste samples are viscoplastic fluids that exhibit non-Bingham flow and can be adjusted to high viscosity. Such viscosity cannot be uniquely indicated because it depends on the performance of the sampling unit 20 to be used. However, generally, a viscosity of 3 Pa · s or more can be considered, for example, 10 Pa · s or more. it can. In the evaluation apparatus disclosed herein, the viscosity is preferable because the effect can be clearly obtained by applying it to a paste sample having a relatively high viscosity of about 10 Pa · s to 2000 Pa · s. More specifically, the viscosity of the paste sample is preferably about 50 Pa · s to 1500 Pa · s, for example, about 100 Pa · s to 1000 Pa · s.
The viscosity of the conductive paste can be measured with a viscometer or rheometer capable of measuring the viscosity of the viscoplastic fluid. The viscosity in the present specification is a value measured using a Brookfield viscometer of the HBT type under the condition of 10 rpm at 25 ° C.

In the evaluation apparatus 500 of this embodiment, first, as shown in step S <b> 10, the operating conditions of the sampling unit 20, the pressure mixing unit 22, and the baking unit 24 are set in the input unit 10.
As the setting of the sampling unit 20, it is only necessary to input conditions necessary for sample preparation based on a combinatorial technique. For example, the blending ratio of two or more basic paste samples is determined. Such a blending ratio determines the necessary number and a plurality of blending ratios of the necessary composition range so that the necessary number and composition range of conductive paste can be prepared. Here, for example, the blending ratio of one paste sample is set as at least one parameter, and the ratio is continuously or discretely changed, whereby the blending ratio of the remaining paste sample (the total of the remaining basic paste samples is calculated). It may be a blending ratio). When there are a plurality of remaining basic paste samples, their blending ratio can be further set. For example, only the proportion of some paste samples may be changed and the proportion of the remaining part of paste samples may be constant, or the proportion of all paste samples may be changed comprehensively. good. The number of conductive pastes to be prepared (that is, the number of blending ratios and the number of compositions of the conductive paste to be prepared) is not particularly limited, but is preferably 5 or more, for example, 8 or more More preferably. For example, it is possible to use 10 or more types, 30 or more types, and the like.

As the setting of the pressurizing and mixing unit 22, for example, conditions such as the type of equipment for pressurizing and mixing, the applied pressure at the time of mixing, the pressurizing time, and the type of pressurized gas can be set. Such pressure mixing conditions vary depending on the type of pressure mixing, such as when pressure-mixing a plurality of sampled paste samples individually or when several (for example, all) are pressure-mixed together. You may let them. The pressure mixing unit 22 can be provided with a conventionally known stirring function using vibration, ultrasonic waves, or the like, and the conditions for stirring using such vibrations or ultrasonic waves may be set simultaneously.
As setting of the baking part 24, conditions, such as the temperature increase rate in baking, baking temperature, baking time, baking atmosphere, can be set, for example. Such firing conditions may be changed based on a combinatorial method, or may be set to constant conditions for all conductive pastes. Furthermore, in addition to baking of the conductive paste, it may be set to additionally perform a heat cycle.
As the input unit 10, a computer, a personal computer (PC), or the like having a predetermined information input / output function and an arithmetic processing function can be suitably used. The information input in the input unit 10 is sent to the sampling unit 20, the pressure mixing unit 22, and the baking unit 24 of the sample preparation unit 200. Transmission and reception of information (including various signals; the same applies hereinafter) in the evaluation apparatus may be performed by wired communication or wireless communication (hereinafter the same).

  In the sample preparation unit 200, as shown in step S20, based on information such as preparation conditions input in the input unit 10, two or more types of paste samples are collected at a predetermined sampling position at a plurality of blending ratios, As shown in step S22, these sampled paste samples are mixed under pressure to prepare a conductive paste having a plurality of blending ratios (that is, a plurality of compositions) on the substrate. Thereafter, as shown in step S24, the conductive paste on the substrate is fired to form a fired body. The fired body formed by the sample preparation unit 200 becomes a conductor (typically a conductive film) that is an object to be evaluated.

  The sampling unit 20 samples a plurality of conductive pastes having different compositions based on a combinatorial technique. Specifically, each paste sample is sampled according to the blending ratio determined by the input unit 10 described above. The paste sample is sampled at a predetermined sampling position. Although this sampling location is not strictly limited, it can typically be a pressurized mixing vessel or a predetermined sample location on the substrate. Essentially, the sampled paste samples are not uniformly mixed as a whole only by the action of dispersion or the like.

The pressure mixing container may be, for example, a pressure resistant container having pressure resistance in a pressure range under pressure mixing conditions (for example, a test tube made of metal such as stainless steel, tempered glass, or reinforced resin, an ampule, or the like. ) Etc. can be considered.
As the substrate, a flat library plate having a predetermined sample arrangement position can be used. Such a substrate may have a smooth entire surface on which the sample is disposed, or may be provided with a depression in accordance with the sample disposition position. There is no particular limitation on the material of the substrate, for example, a material that does not react with the conductive paste, a material that causes a desired reaction with the conductive paste, or the actual use of such a conductive paste. It can be arbitrarily configured from a material to be applied.

  Here, it is preferable that the sampling unit 20 be prepared so that the amount of conductive paste prepared is, for example, 10 g or less (for example, 1 g or less). Although this evaluation apparatus will be described in detail later, even if an error or variation in sampling occurs, the blending ratio can be corrected. Therefore, even if the amount of one conductive paste is as small as 10 g or less. The preparation conditions of the conductive paste can be evaluated with sufficient accuracy. Therefore, only a necessary amount of sampling is prepared without considering strict accuracy control, and the waste loss of the conductive paste can be reduced.

  The sampling unit 20 can be realized, for example, by using various automatic wet sample preparation apparatuses and sampling apparatuses that can perform sampling based on a combinatorial technique. As an automatic wet sample preparation device and a sampling device, a liquid or slurry wet sample can be handled, and a paste sample having the above viscosity can be sampled at 1 g or less (for example, about 10 mg to 1 g). If so, the configuration and the like are not particularly limited, and various types can be used. A preferable example of such an apparatus is one that performs sampling by sucking and discharging a paste sample by a pipette and a syringe pump connected to the pipette. Specifically, for example, a weighing and mixing device and a chemical reaction processing device disclosed in Patent Document 6 can be exemplified.

The pressure mixing unit 22 is configured to prepare a plurality of conductive pastes having different compositions by mixing two or more basic paste samples sampled by the sampling unit under pressure conditions. More specifically, this pressure mixing is performed by placing paste samples, which are not mixed with each other, sampled at a predetermined sample position on the pressure mixing container or the substrate, mainly in a pressurized atmosphere. . For example, by applying compressed air abruptly or by applying pressure to the paste sample as a whole or locally, a flow is generated in the highly viscous paste sample to achieve uniform stirring.
Such pressure mixing is preferably performed in a non-contact manner with respect to the paste sample in order to prevent compositional deviation of the sample. As a device for realizing such non-contact pressure mixing, for example, a device including a compressor such as a blower or a compressor capable of realizing an effective discharge pressure of about 0.05 MPa to 1 MPa is shown as a preferable example. Such a pressure mixing unit 22 may be provided with a mechanism such as a safety valve that releases the pressure when the applied pressure exceeds a predetermined pressure. The air blowing (pressurization) by the compressor may be performed continuously or intermittently (pulsed) by intermittent operation of the compressor. When pressurizing in pulses, for example, the pressure applied between pressurizations may be reduced (released). As an example of the pulsed pressurization, pressurization for about 0.01 seconds to 1 second is performed and the repetition frequency is set to about 0.1 seconds to 10 seconds.

Here, when performing pressure mixing in a pressure mixing container, a pressure mixing part can be comprised by said lid | cover pressure container and a lid member connectable with said compressor etc., for example.
FIG. 3 is a schematic view illustrating the pressure mixing unit 22 for pressure mixing the paste sample 50 sampled in the pressure mixing container (pressure container) 221. Here, the pressurized mixing container 221 has a sufficient capacity (for example, about 3 to 10 times the head space) with respect to the sampling amount of the paste sample 50, for example. The lid member 222 is configured to be able to hermetically seal the pressure vessel 221 and can be connected to the compressor 223 or the like via a pressure tube or the like. Can be pressurized. In the airtight state, for example, a packing (not shown) is disposed on the inner surface of the lid member 222 and in contact with the pressure vessel 221, and the lid member 222 is inserted into the opening of the pressure vessel 221 via the packing. This can be realized by bringing them into contact with each other. For example, the airtight state may be maintained by keeping the lid member 222 pressed against the pressure vessel 221. For example, the lid member 222 that can be attached and detached with one touch. You may make it implement | achieve by mounting | wearing. As the lid member 222 that can be attached and detached with one touch, a snap cap type or a rubber plug type lid member 222 can be used. The lid member 222 may include a connecting portion (not shown) that allows a pressure-resistant tube or the like connected to the compressor 223 to be detachable. Further, the lid member 222 may include a safety valve (not shown) that opens the internal pressure to the outside when the internal pressure of the pressure-resistant container 221 exceeds a predetermined pressure. When pressure mixing is performed in the pressure mixing container 221, the conductive paste 51 obtained by mixing is supplied to a predetermined sample position on the substrate by the transfer means. The transfer means may use the sampling unit 20 described above, or may use a sample supply device that can collect and discharge a sample, which is different from the sampling unit 20 described above.

In addition, when performing pressure mixing on all paste samples sampled on the substrate at the same time, the pressure mixing unit includes, for example, a lid member that covers the upper surface of the substrate with a predetermined space, a pressure tube, and the like. It can be configured by the above-described compressor connected to the lid member.
FIG. 4 is a diagram illustrating the pressure mixing unit 22 that simultaneously presses and mixes all paste samples 50 on the substrate 224. In the example of FIG. 4, for example, the lid member 222 is a bottomless casing having a shape corresponding to the planar shape of the substrate 224. A pressure-resistant tube 225 connected to the compressor 223 and the like is disposed on the upper surface of the lid member 222. On the inner surface of the lid member 222, a packing member (not shown) is disposed in a region in contact with the peripheral edge of the substrate 222. Note that a groove may be provided in the peripheral edge of the substrate 222 and a heat-resistant O-ring (not shown) may be attached. Such a lid member 222 is placed on the substrate 224, and the substrate 224 is fitted inside the lid member 222 by sliding the cover member 222 from the upper side to the lower side while abutting the inner surface of the lid member 222 against the peripheral edge of the substrate 224. When pressure is applied by sending air into the lid member 222 in such a state, the sealing action of the packing member or the O-ring functions to maintain the space formed by the substrate 224 and the lid member 222 at a high pressure. Can do. The lid member 222 may include a safety valve (not shown) that opens the pressure to the outside when the pressure in the space formed by the substrate 224 and the lid member 222 exceeds a predetermined pressure. In addition, a pressure-resistant tube 225 that communicates between the compressor 223 and the lid member 222 is branched in the middle, and is connected to the compressor 223 at a plurality of locations on the lid member 222 (for example, above each sample position on the substrate 224). It may be. Note that the lid member 222 and the substrate 224 are not limited to a form in which airtightness is maintained by fitting as illustrated in FIG. For example, a seal member such as packing is disposed at the opening end of the housing-like lid member 222, and the lid member 222 is brought into contact with the upper surface of the substrate 224 via the seal member and pressed to maintain airtightness. It is also good.

The pressure mixing time cannot be generally described because it depends on the viscosity of the paste sample, the sampling amount, the mode of air discharge, etc., but can be approximately several minutes to several tens of minutes.
Thereby, the sampled paste sample can be uniformly mixed in a non-contact manner.
In addition to the mixing by pressurization as described above, the pressurizing and mixing unit 22 may be additionally provided with another stirring function (not shown) as a means for promoting pressurization and mixing. Examples of such auxiliary agitation functions include a vibration agitation function that imparts vibration, an ultrasonic agitation function that imparts ultrasonic waves, and electromagnetic induction agitation that generates a flow in the conductive particles themselves in the paste sample by electromagnetic induction. Examples include functions. When the electromagnetic induction stirring function is provided, a cooling mechanism such as a water-cooled tube may be provided on the pressurized mixing container or the substrate.
As a result, uniform stirring can be achieved in a shorter time, and a conductive paste with little compositional deviation can be prepared. In addition, such pressure mixing has advantages such as less sample loss and easy maintenance because there is no contact between the paste sample and the mixing device.

The firing unit 24 fires the conductive paste prepared above, and forms a fired body at a predetermined position on the substrate. The firing unit 24 may use various known heating devices. Specific examples of the heating device include a muffle furnace using a high frequency induction coil, a tunnel heating furnace, a laser heating device, a local heating device, and the like. In order to make the firing conditions of all the conductive pastes on the substrate uniform and accurately control the firing atmosphere and firing temperature, it is preferable to use a closed heating device such as a muffle furnace. In addition, it is preferable to employ a tunnel heating furnace or the like because a large number of substrates can be continuously heated and the temperature history of heating is easily changed. Furthermore, when changing the heating conditions of the conductive paste on the same substrate, for example, it is considered to employ a heating device that enables local heating by a laser heating device, a ceramic heating element, or the like. .
The fired bodies having different compositions prepared in this manner can be changed in terms of firing conditions.

  Thereafter, in the measurement unit 300, as shown in steps S30 to S36, for the fired bodies having different compositions formed as described above, for example, based on information from the control unit 100, a desired function test and analysis are automatically performed. It can be performed. In the case of the evaluation apparatus 500 illustrated in FIG. 1, for example, the measurement unit 300 includes an electrical conductivity measurement unit 30, a composition analysis unit 32, a crystal structure analysis unit 34, and a thermal expansion coefficient measurement unit 36. Measurement and analysis of the electrical conductivity (resistivity), composition, crystallinity, thermal expansion coefficient (or reduction expansion coefficient) and the like of the fired body can be performed. This test and analysis can be performed while transmitting / receiving information to / from the control unit 100 as necessary.

  The electrical conductivity measuring unit 30 can automatically measure the electrical conductivity (resistivity) of the plurality of fired bodies (conductive films) prepared above based on information from the control unit 100, for example. . That is, a plurality of fired bodies (conductive films) sent to the electrical conductivity measuring means 30 are installed at a predetermined measurement position together with, for example, the substrate, and the electrical conductivity (resistivity) of each fired body is measured. Can do. The measurement of electric conductivity can be realized by an apparatus having a function of measuring electric conductivity by, for example, a four-probe method, a two-terminal method, a four-terminal method, or the like. In the measurement of electrical conductivity, a plurality of fired bodies may be measured one by one in order.For example, the electrical conductivity of all the fired bodies formed on the substrate is measured at a time. More preferably.

  In order to measure the electrical conductivity of the plurality of fired bodies at once, for example, the electrical conductivity measurement unit 30 has a plurality of electrical conductivity measurement functions arranged so as to correspond to the sample positions on the substrate. It is shown as a preferred example that the installed electrical conductivity measuring device 301 is used. FIG. 5 is a diagram for conceptually explaining an electrical conductivity measuring device 301 in which a plurality of electrical conductivity measuring functions 302 are arranged (a part of the electrical conductivity measuring function 302 is omitted in FIG. 5). Is shown.) This electrical conductivity measurement function 302 is constituted by, for example, a four-probe probe, so that all samples (fired) formed on the substrate 222 even if the fired body 52 is in the form of a fine thin film or the like. The electrical conductivity of the body 52) can be measured simultaneously and instantaneously. Further, for example, the tips of the four probes in each electric conductivity measuring function 302 are movable in the respective needle axis directions, so that the four-probe method probe is pushed onto the sample (fired body 52). By simply touching, the unevenness of the surface of the sample (fired body 52) and the difference in surface height of each sample can be absorbed by the movement of the probe, and all the samples (fired body 52) can be measured simultaneously and instantaneously. It can be carried out. Specifically, the movement of the tip of the probe 303 is caused by, for example, the probe 303 sliding in the needle axis direction as shown in FIG. 6A or as shown in FIG. 6B. In addition, this can be realized by the minute curvature of the probe 303. Furthermore, the electrical conductivity measuring unit 30 includes a function that enables control of the temperature and measurement atmosphere of a muffle furnace or the like, so that, for example, electrical conductivity can be measured in a high temperature environment. Information on the electrical conductivity measured by the electrical conductivity measurement unit 30 is sent to the evaluation unit 40.

  The composition analysis unit 32 automatically measures the chemical composition of the plurality of fired bodies (conductive films) prepared above based on information from the control unit 100, for example. Analysis of chemical composition is, for example, analysis capable of non-destructive composition analysis of solid inorganic substances such as X-ray fluorescence analyzers having an analysis function by X-ray fluorescence analysis, X-ray photoelectron spectroscopy, secondary ion mass spectrometry, etc. An analysis apparatus or the like based on a technique can be preferably employed. As the fluorescent X-ray analyzer, for example, either an energy dispersion type or a wavelength dispersion type may be used. In composition analysis, for example, a substrate on which a plurality of fired bodies are formed is moved in the horizontal direction so that the fired body to be measured is moved to the measurement position, and all the fired bodies are automatically and sequentially analyzed. May be performed. Note that, depending on the configuration of the composition analysis unit 32 to be used, the composition analysis procedure and method are not limited to this example. The result of the composition analysis in the composition analysis unit 32 is sent to the evaluation unit 40.

  The crystal structure analysis unit 34 can automatically analyze information on the crystal structures of the plurality of fired bodies (conductive films) prepared above based on information from the control unit 100, for example. The analysis of the crystal structure can be suitably realized by using, for example, an X-ray diffraction analyzer having an analysis function by an X-ray diffraction analysis method. In such X-ray diffraction analysis, for example, the substrate on which a plurality of fired bodies are formed is moved in the horizontal direction so that the fired body to be measured is moved to the measurement position. The composition analysis can be performed. Note that, depending on the configuration of the crystal structure analysis unit 34 used, the composition analysis procedure and method are not limited to such examples. The result of the composition analysis in the crystal structure analysis unit 34 is sent to the evaluation unit 40.

  The thermal expansion coefficient measurement unit 36 automatically measures the thermal expansion coefficient or the reduction expansion coefficient of the plurality of fired bodies (conductive films) prepared above based on information from the control unit 100, for example. The thermal expansion coefficient may be either a linear thermal expansion coefficient or a volume thermal expansion coefficient. Such a coefficient of thermal expansion measurement unit 36 can be suitably realized by employing a device having a measurement function based on a precise absolute measurement method such as an optical interference method, an X-ray diffraction method, a telephotometry method, or the like. It is desirable that such measurement can be performed in a predetermined measurement atmosphere within a predetermined temperature range, for example. For example, two types of measurement atmospheres, an oxidizing atmosphere and a reducing atmosphere, are measured, and a thermal expansion coefficient in a desired measurement temperature range from room temperature to about 500 ° C. or more in each measurement atmosphere is measured. It can be calculated in the evaluation unit 40 described later. The reductive expansion coefficient can be calculated by, for example, the above equation (1). For example, when an X-ray diffraction analyzer is employed as the thermal expansion coefficient measuring unit 36, the same X-ray diffraction analyzer may be used as the thermal expansion coefficient measuring unit 36 and the crystal structure analyzing unit 34. . The measurement of the coefficient of thermal expansion by the X-ray diffraction method is to calculate the coefficient of thermal expansion by reading the temperature change of the lattice spacing (ie, lattice constant) of the crystal lattice as the change of the diffraction angle of X-ray. In addition, since the X-ray diffraction method can measure even a very small amount of sample that is difficult to measure with other measurement methods if it is a crystalline sample, the thermal expansion of the fired body produced by such a combinatorial method It is preferable to apply to the measurement of rate. The measurement result of the thermal expansion coefficient in the thermal expansion coefficient measurement unit 36 is sent to the evaluation unit 40.

In the evaluation unit 40, the relationship between the information sent from the measurement unit 300 as described above and the composition of the conductive paste set in the input unit 10 is analyzed, and the conductive paste that can realize a desired function or characteristic is analyzed. The composition can be calculated. Such analysis can be performed using known analysis software. For example, it may be analysis software attached to each test / analysis apparatus.
When the apparatus 500 includes the composition analysis unit 32, the evaluation unit 40 calculates the blending ratio of the actual paste sample based on the result of the composition analysis sent from the composition analysis unit 32. The value may be used for analysis (that is, corrected) instead of the blending ratio set in the input unit 10. This is because in the preparation of the conductive paste, the accuracy of the composition analysis of the conductive paste by the composition analysis unit 32 may be higher than the accuracy of the preparation of the conductive paste by the sample preparation unit 200. . Then, by analyzing the relationship between the corrected conductive paste composition and the function or characteristic tested and analyzed above, a more accurate blending ratio of the conductive paste that can realize the desired function or characteristic. (Or blending range) can be calculated and evaluated.
The introduction of the correction value into the analysis may always be reflected in the evaluation. For example, the difference between the basic paste sample blending ratio set in the input unit 10 and the correction value is set in advance. If it is larger than the threshold value, the blending ratio set in advance in the input unit 10 may be replaced with a correction value for correction.

The information regarding the function (which may be a characteristic) of the fired body sent from the measurement unit 300 includes, for example, the electrical conductivity (resistivity), crystallinity, thermal expansion coefficient, reduction expansion coefficient, and the like of the fired body. Although a threshold is set for each of these functions in advance, a fired body within the range indicated by this threshold is evaluated as “OK”, and a fired body outside the range indicated by this threshold is evaluated as “impossible”. This is exemplified. For example, the evaluation is not limited to two stages “permitted” and “impossible”, but can be performed in more detail by providing a plurality of stages. Then, the evaluation result and the blending ratio of the fired body can be correlated to determine the blending ratio of the conductive paste capable of forming a fired body having more desirable characteristics.
The relationship between the evaluation results of the above functions and the blending ratio of the fired body can be expressed, for example, on a composition map. For example, it is possible to create a map showing the relationship between the glass composition and the contact angle. Thereby, the relationship between the blending ratio of the conductive paste and the function of the fired body achieved by the blending ratio can be visually and clearly evaluated.

Note that the functional evaluation of the fired body can be performed by other various measuring devices that are known or will be developed in the future, without being limited to the test and analysis of the functions exemplified above. Further, a measurement unit in which a plurality of measurement functions are combined into one measurement unit may be provided. Examples of the evaluation and analysis unit for various functions and characteristics provided in the measurement unit 300 include a dielectric constant measurement unit that measures the dielectric constant of a fired body, a laser Raman analysis unit that includes a laser Raman spectrophotometer, and the like. Evaluation of the dielectric constant and molecular structure of each fired body can be taken into consideration in determining the blending ratio.
In addition, a transfer means that can automatically transfer the fired body (sample) together with the substrate can be provided between a plurality of measurement and / or analysis apparatuses provided in the measurement unit 300. Examples of such transfer means include vertical transfer means capable of transferring a transfer object such as a lift and a robot arm in the vertical direction, horizontal transfer means capable of transferring a transfer object such as a roller conveyor and a belt conveyor in the horizontal direction, and transfer. Various well-known transport systems including a control unit that controls the operation of these transfer units based on the movement of the object can be employed. However, since a relatively large space is required for installation of the transfer means that can be automatically transferred, in some cases, such a transfer means is not necessarily automatically (mechanically) implemented, You may make it utilize the transfer by a human hand.
EXAMPLES Examples relating to the present invention will be described below, but the present invention is not intended to be limited to those shown in the following examples.

[Embodiment 1]
A conductive paste (so-called resistive paste) having a predetermined resistivity is prepared from two types of paste samples A and B having different electrical conductivities using a conductive paste preparation condition evaluation apparatus described below. Therefore, the blending ratios of paste samples A and B were examined. The conductive paste preparation condition evaluation apparatus used in the present embodiment includes a sampling unit that samples paste samples A and B at a predetermined mixing ratio at a predetermined sampling position on the substrate, and covers all the sampling positions from above the substrate. A pressure mixing unit for preparing a plurality of conductive pastes by mixing samples sampled by simultaneously pressing, a baking unit for baking the prepared conductive paste together with the substrate under predetermined baking conditions, and a plurality of post-baking units An electrical conductivity measurement unit that measures the resistivity (electrical conductivity) of the fired body, a composition analysis unit that performs composition analysis of a plurality of fired bodies, and an evaluation of the blending ratio of paste samples A and B from information received from each part An evaluation unit is provided.

The paste samples A and B are pastes for forming resistors for electronic devices, in which conductive ruthenium oxide (RuO ₂ ) powder and glass powder as a binder are dispersed in terpineol as a solvent. I prepared something. Paste sample A and paste sample B are prepared to have different resistivities in advance by adjusting the composition of RuO ₂ powder and glass powder. When the viscosity of these paste samples A and B was measured, they were 100 Pa · s and 120 Pa · s at 25 ° C. and 10 rpm, respectively.

[Sampling part]
The sampling unit is equipped with an automatic sampling device capable of collecting a plurality of liquid samples by a predetermined amount and placing them at a predetermined sampling position based on a combinatorial method. In this apparatus, a paste sample is sucked and discharged by a pressure control method using a pipette and a syringe pump continuous with the pipette. In this embodiment, the blending ratio of paste samples A and B was used as a parameter, and by changing this parameter at a constant ratio, each sample was sampled so as to have the nine blends shown in Table 1 below. . The pipette is automatically replaced with a new one before sampling a different paste sample.

  In this embodiment, each sample is sampled at a predetermined sample position on the substrate. As the substrate, a substrate made of alumina and having a spherical recess at a predetermined sample position on the surface of the flat substrate was used. In this example, the sample positions are set in a 6 × 6 lattice pattern on the substrate, and the sampled paste samples are discharged in a predetermined order to the predetermined sample positions. As for the paste samples A and B, a predetermined amount of about 10 mg to 100 mg is automatically collected by a pipette and discharged to a predetermined sample position set on the substrate. Thus, it took about 10 minutes to take a sample on the substrate with nine combinations of two types of resistance paste.

[Pressure mixing section]
As shown in FIG. 4, the pressure mixing unit includes a bottomless housing-like lid member 222 that covers the upper surface of the substrate 224 with a space, and a high-pressure pump (Fig. 4) connected to the upper surface of the lid member 222 by a pressure-resistant tube 225. Not shown). The inside of the lid member 222 is coated with polytetrafluoroethylene (PTFE) and is mounted while sliding against the peripheral edge of the substrate 224, and even when the inside of the lid is at a high pressure during pressurization. It is possible to maintain airtightness with 224 and maintain a high pressure state. In the present embodiment, after the lid member 222 is attached to the substrate 224, all the sampling samples 50 on the substrate 224 are mixed simultaneously by applying pressure intermittently for 10 minutes so that the inside of the lid becomes approximately 0.2 MPa. A conductive paste (resistive paste) 51 having nine compositions was prepared. The prepared conductive paste 51 is sent to the firing section together with the substrate.

[Baking part]
As a baking part, the baking furnace which can control all the baking conditions automatically is provided. In this embodiment, nine types of conductive pastes were fired at 800 ° C. together with the substrate in an air atmosphere to obtain resistor samples having nine compositions as a fired body. The obtained resistor sample is sent to the composition analysis unit after air cooling.

[Composition Analysis Department]
As the composition analysis unit, an energy dispersive microscopic X-ray fluorescence analyzer equipped with a substrate holder capable of automatically moving the substrate to a predetermined measurement position is provided. In the present embodiment, the concentration (mass%) of ruthenium (Ru) in the resistor sample was examined using this fluorescent X-ray analyzer. Information on the Ru concentration of each resistor sample is sent to the evaluation unit. For reference, the measurement results of the Ru concentration of each resistor sample are shown in Table 1. The resistor sample for which the composition analysis has been completed is sent to the electrical conductivity (volume resistivity) measuring unit together with the substrate.

[Electric conductivity measurement unit]
As the electrical conductivity measurement unit, a plurality (36 in this case) of electrical conductivity measurement functions 302 are arranged so as to correspond to the sample positions on the substrate as shown in FIG. An electrical conductivity measuring device 301 was used. This electrical conductivity measuring device 301 simultaneously measures the resistivity (electrical conductivity) of all the samples formed on the substrate, even with a minute thin film sample or the like, using a four-probe probe. be able to. In addition, each of the four probes (probes 303) can be independently slid in the direction of the needle axis. By simply pressing the four-probe method probe against the sample, the unevenness of the sample surface and the surface height of each sample Absorbing the difference, the accurate resistivity (electric conductivity) can be measured instantly. Furthermore, the measuring unit is also installed in the muffle furnace, and can measure the electrical conductivity at a high temperature of about 1400 ° C. at the maximum. With this electrical conductivity measuring device, the volume resistivity of the resistor sample at 25 ° C. is measured, and the information is sent to the evaluation section. For reference, the measurement results of the volume resistivity of each resistor sample are shown in Table 1. In the table, the blending ratios of paste sample A and paste sample B are shown in the columns of paste A and paste B, respectively.

[Evaluation Department]
In the evaluation part, the relationship between the composition of the resistor sample (Ru content) and the volume resistivity was obtained from the measurement results sent from the composition analysis part and the electrical conductivity measurement part as described above. Although it is extremely rare for this relationship to show complete linearity due to differences in the lots of RuO ₂ powder and glass powder used in the preparation of the resistance paste, in this embodiment, linearity having a relatively high correlation is exhibited. It was confirmed that That is, a more reliable evaluation can be performed by replacing the blending ratio, which is a setting condition, with a blending ratio calculated after the Ru content (after correction) and evaluating the relationship with the volume resistivity. .
Further, the above measurement results also change delicately under the influence of the weather and the like of the day when the resistance paste preparation conditions are evaluated, and thus preparation for each day is indispensable. From this relationship between the corrected blending ratio and volume resistivity, for example, to prepare a resistance paste having a volume resistivity of 1.20 Ω · cm on this day, paste sample A and paste sample B are prepared as (A) 53 .8: (B) It was found that mixing at a ratio of 46.2 was sufficient.
Table 2 below shows the time required for each process when this evaluation apparatus is used. For reference, Table 2 also shows the time required for evaluating the conventional resistance paste preparation conditions.

  As described above, by using the conductive paste preparation condition evaluation apparatus disclosed here, conventionally, the optimization evaluation of the conductive paste preparation conditions can be performed by film-forming one sample at a time or one sample at a time. It was confirmed that the time required can be greatly shortened by depositing multiple samples at the same time and analyzing or testing multiple samples simultaneously or continuously. In addition, the basic paste used for sample preparation must be used only in an amount that can be prepared with small errors such as weighing and mixing by human hands. According to such an evaluation apparatus, it was possible to produce a sample with a small amount of error even with a small amount, and the loss of disposal could be reduced. Thereby, for example, the enormous test time and cost for optimizing the daily preparation conditions of the conductive paste can be reduced.

In this example, Ru-type resistive pastes are used as the two types of conductive pastes. However, as the conductive pastes, those having different components and compositions of conductive particles may be used. As described above, for example, three or four kinds of conductive pastes may be blended.
Moreover, the evaluation content of the formed multiple types of resistors is not limited to composition analysis and resistivity measurement, and other evaluations may be performed.

[Embodiment 2]
In the present embodiment, the sampled paste sample is mixed (a) with a mixing device by pressure mixing similar to that of the first embodiment, and (b) with a mixing device by general-purpose ultrasonic irradiation. The difference in properties of the obtained conductive paste was evaluated depending on the case.
That is, in the second embodiment, when the (a) pressure mixing device is used for mixing, the same conductive paste preparation condition evaluation device as that in the first embodiment is used. In the mixing section, the paste sample sampled directly on the substrate was pressure-mixed at a time and sent to the firing section, composition analysis section and electrical conductivity measurement section together with the substrate for firing and various analyses.
Moreover, (b) When mixing with an ultrasonic mixing apparatus, the structure of the mixing part and the sampling position was changed from the apparatus of the said Embodiment 1, and others used the same apparatus. That is, (b) when performing ultrasonic mixing, the samples were sequentially sampled in a stainless steel tubular sampling container (φ10 mm × t50 mm) arranged at a predetermined sampling position. An ultrasonic homogenizer was used as the mixing unit, and the sampled paste samples were mixed by irradiating each sampling container with ultrasonic waves for 30 minutes. The mixed paste sample was again supplied in sequence to a predetermined sample position on the substrate similar to that used in Embodiment 1 by using the sampling device again. Thereafter, in the same manner as in (a) above, the entire substrate was sent to the firing section, composition analysis section, and electrical conductivity measurement section for firing and various analyses.

The conductive paste is the same paste sample A and paste sample B as used in the first embodiment, and the blending ratio of the paste samples A and B is (A) 53.8: (B) 46.2. Sampling was performed at a constant. Moreover, the conductive paste of 10 samples was adjusted with each mixing apparatus by mixing with the mixing apparatus from which said (a) (b) differs.
The result of measuring the composition analysis and volume resistivity of the fired body obtained by firing the conductive paste is sent to the evaluation section. The measurement results sent from the composition analysis unit and the electrical conductivity measurement unit to the evaluation unit are shown in Table 3 below.

  As shown in Table 3, (a) a fired body obtained by mixing with a pressure mixing device has a higher volume resistivity and composition than a fired body obtained by mixing with (b) an ultrasonic mixing device. It was found that the variation was significantly reduced in both cases. That is, according to the conductive paste preparation condition evaluation apparatus provided with (a) a pressure mixing device as a mixing unit, it is possible to mix a highly viscous paste sample more uniformly, and the conductive paste preparation conditions are more It was confirmed that it can be evaluated with high accuracy.

[Embodiment 3]
In this embodiment, a paste sample A and a paste sample B are used in the same manner as in the above embodiment 2, using the conductive paste preparation condition evaluation apparatus provided with the mixing device (a) by pressure mixing as in the above embodiment 2. The conductive paste was prepared with the blending ratio of paste samples A and B being constant at (A) 53.8: (B) 46.2. In mixing the conductive paste, the pressure conditions of the pressure mixing were changed as shown in Table 4 below, and 10 samples of the conductive paste were prepared under each pressure condition.
From the result of measuring the volume resistivity of the fired body obtained by firing the conductive paste, the standard deviation (10 samples) of the volume resistivity under each pressure condition was determined and shown in Table 4 below.

  As shown in Table 4, when the pressure condition is 2 MPa, the pressure is too high, so it is necessary to prepare a more robust pressure mixing device. However, in the range where the pressure condition is 1 MPa or less, compared with mixing by ultrasonic irradiation. It was confirmed that uniform and non-uniform mixing was possible. In particular, it was found that uniform mixing without variation can be performed when the pressure condition is in the range of 0.01 MPa to 1 MPa.

[Embodiment 4]
Using the conductive paste preparation condition evaluation apparatus described below, it has predetermined characteristics (electric conductivity, crystal structure, reduction expansion coefficient) from two types of paste samples C and D having different electric conductivities. The blending ratio of paste samples C and D for preparing the conductive paste was examined. The conductive paste preparation condition evaluation apparatus used in Embodiment 4 changed the pressure mixing unit from the apparatus in Embodiment 1 above, reset the sampling position, and otherwise used the same apparatus.

[Sampling part]
The sampling unit is equipped with an automatic sampling device capable of collecting a plurality of liquid samples by a predetermined amount and placing them at a predetermined sampling position based on a combinatorial method. In this apparatus, a paste sample is sucked and discharged by a pressure control method using a pipette and a syringe pump continuous with the pipette. In this embodiment, the blending ratio of paste samples C and D was used as a parameter, and by changing this parameter at a constant ratio, each sample was sampled so as to have the nine blends shown in Table 5 below. .

As the paste samples C and D, a paste for electrode formation in the solid oxide fuel cell, the paste C includes LaSrCoFeO ₃ as the conductive oxide, the paste D LaSrTiFeO ₃ as conductive oxide In addition, a glass powder as a binder and dispersed in terpineol as a solvent were used. Paste sample C and paste sample D are prepared in advance with different electrical conductivities. When the viscosity of these paste samples C and D was measured, they were 130 Pa · s and 150 Pa · s, respectively.
In this embodiment, stainless steel tubular ampules (φ10 mm × t50 mm) arranged at a predetermined sampling position are used as a pressure resistant container, and the paste samples C and D are sequentially sampled in the container. As for the paste samples C and D, a predetermined amount of about 50 mg to 100 mg is automatically collected by a pipette and discharged into a predetermined sampling container. Thus, it took about 10 minutes to collect samples from the two types of resistance pastes in the sampling container in nine combinations.

[Pressure mixing section]
As the pressure mixing unit, a pressure mixing device having a configuration similar to that shown in FIG. 3 was used. That is, the inside of the container 221 is automatically hermetically sealed by pressing the PTFE lid member 222 against the opening of the pressure container 221. The lid member 222 is provided with a connecting portion (not shown) that can be connected to the pressure-resistant tube 225 connected to the compressor 223, and the connecting portion and the pressure-resistant tube 225 can be connected with one touch. In this embodiment, after the pressure vessel 221 was covered, the sample paste 50 sampled in the vessel was mixed by intermittently pressurizing the inside of the vessel to 0.5 MPa for 1 minute. Nine kinds of sampling samples were sequentially pressure-mixed one by one to prepare nine kinds of conductive paste 51.

  A predetermined amount of the prepared conductive paste was again collected by an automatic sampling device of the sampling unit, and discharged to a predetermined sample position on the substrate, thereby arranging the conductive paste on the substrate. As the substrate, a substrate made of 8 mol% yttria-stabilized zirconia (8YSZ) and having a spherical recess at a predetermined sample position on the surface of the flat substrate was used. In this example, sample positions are set in a 6 × 6 grid on the substrate, and the collected prepared conductive paste is ejected to the predetermined sample positions in a predetermined order. About 50 mg each of the conductive paste was automatically collected with a pipette and discharged to a predetermined sample position set on the substrate. Thereafter, the conductive paste is sent to the firing section together with the substrate.

[Baking part]
As a baking part, the baking furnace which can control all the baking conditions automatically is provided. In this embodiment, nine types of conductive paste were fired at 1000 ° C. in the air atmosphere together with the substrate, thereby obtaining electrode film samples having nine types of compositions as a fired body. The obtained fired body is air-cooled and then sent to the reduction expansion coefficient measurement unit. FIG. 7 shows a part of the electrode film sample produced on the substrate. FIG. 7 shows the state of the electrode film sample formed in one row among the sample positions provided in a 6 × 6 row grid pattern on the substrate.

[Reduction expansion coefficient measurement unit]
The reduction expansion coefficient measurement unit includes a substrate holder that can automatically move the substrate to a predetermined measurement position, and an X-ray that can continuously perform X-ray diffraction analysis of a plurality of electrode film samples under desired atmospheric conditions. A diffraction analyzer is provided. In this embodiment, this X-ray diffractometer measures the data related to the unit crystal lattice size (that is, the crystal lattice constants a, b, c) of the electrode film sample at room temperature and 1273 K, and uses it for the evaluation unit. In the feeding and evaluation section, the volumetric thermal expansion coefficient from room temperature to 1273K was determined from the volume change of the unit cell calculated from these values. In addition, the size of the unit crystal lattice of the above electrode film sample is obtained in both the oxidizing (atmospheric) atmosphere and the reducing atmosphere, and the thermal expansion in the reducing atmosphere is based on the thermal expansion volume in the oxidizing (atmospheric) atmosphere. The degree of increase in volume was determined as the reduction expansion coefficient. That is, this reduction expansion coefficient is expressed by the above formula (1). For reference, the reduction expansion coefficient obtained for each electrode film sample is shown in Table 5 below. The electrode film sample that has been subjected to the X-ray diffraction analysis is sent to the electrical conductivity measuring unit together with the substrate.

[Electric conductivity measurement unit]
As the electrical conductivity measuring unit, the same electrical conductivity measuring device as that used in the first embodiment is provided. In this embodiment, the high-temperature electrical conductivity of the electrode film sample at 800 ° C. was measured by such an electrical conductivity measurement device, and the information was sent to the evaluation unit. For reference, the measurement results of the high temperature electrical conductivity of each electrode film sample are shown in Table 5 below. In the table, the blending ratios of the conductive paste C and the conductive paste D in the electrode film sample are shown in the columns of paste C and paste D, respectively.

[Evaluation Department]
As described above, from the measurement results sent from the electrical conductivity measurement unit and the reduction expansion coefficient measurement unit, the relationship between the composition of the electrode film sample and the high temperature electrical conductivity and the reduction expansion coefficient was determined.
The relationship between the composition of the electrode film sample and the high-temperature electrical conductivity rarely shows perfect linearity due to the difference in lot of each material powder used for the preparation of the conductive paste, but in this embodiment, It was confirmed that the linearity was relatively correlated. That is, according to this conductive paste preparation condition evaluation apparatus, it was confirmed that a high-viscosity paste sample was sampled at a desired blending ratio and uniformly mixed.
Moreover, the reduction expansion coefficient was calculated from the lattice constant data sent from the reduction expansion coefficient measurement unit, and the relationship between the reduction expansion coefficient and the high temperature conductivity was obtained. As the characteristics of the electrode film, it is preferable that the electrical conductivity at high temperature is high, but it is preferable that the reduction expansion coefficient is small. From the results in Table 5, for example, in order to prepare a conductive paste having a high-temperature conductivity of 100 S / cm or more and a reduction expansion coefficient of 0.1% or less, paste C and paste D are obtained by (C) 50: (D) It has been found that mixing at a ratio of 50 is sufficient. In addition, there is an exponential correlation between the composition of the electrode film sample and the reduction expansion coefficient, and the preparation conditions of the paste for the purpose of producing an electrode film having a desired reduction expansion coefficient can be evaluated. Was also confirmed.

Further, the above measurement results also change delicately under the influence of the weather and the like on the day of conducting the evaluation of the preparation conditions of the conductive paste, so that the preparation for each day is indispensable. From this relationship between the corrected blending ratio and the high temperature conductivity, for example, in order to prepare a resistance paste having a high temperature conductivity of 120 S / cm on this day, paste sample C and paste sample D are (C) 55 :( D) It has been found that mixing at a ratio of 45 is sufficient.
As described above, the time required for each step when this evaluation apparatus is used is shown in Table 6 below. For reference, Table 6 also shows the time required for evaluating the conditions for preparing a conductive paste by a conventional manual operation.

  As described above, by using the conductive paste preparation condition evaluation apparatus disclosed here, conventionally, the optimization evaluation of the conductive paste preparation conditions can be performed by film-forming one sample at a time or one sample at a time. Where time was spent, multiple samples were deposited simultaneously, and multiple samples were analyzed or tested simultaneously or continuously, so the time required could be greatly reduced. It was confirmed that the measurement of the reduction expansion coefficient can be performed with high accuracy even with a very small sample by using an X-ray diffraction analyzer. In addition, the basic paste used for sample preparation has conventionally had to be prepared in a certain amount in order to minimize errors such as weighing and mixing by human hands, resulting in a large amount of waste loss. According to such an evaluation apparatus, it was possible to produce a sample with a small amount of error even with a small amount, and the loss of disposal could be reduced. Thereby, for example, the enormous test time and cost for optimizing the daily preparation conditions of the conductive paste can be reduced.

[Embodiment 5]
In this embodiment, the sampled paste sample is mixed (a) with a mixing apparatus using pressure mixing similar to that in the above-described embodiment 4, and (b) ultrasonic waves that are generally employed conventionally. The difference in the properties of the obtained conductive paste was evaluated when it was mixed with a mixing device by irradiation.
That is, in this Embodiment 5, when mixing with the (a) pressurization mixing apparatus, the same conductive paste preparation condition evaluation apparatus as the said Embodiment 1 was used. In the mixing part, paste samples sampled directly on the substrate were pressure-mixed at once and sent to the firing part, electrical conductivity measurement part and reduction expansion coefficient measurement part together with the substrate for firing and various analyses.
Moreover, (b) When mixing with an ultrasonic mixing apparatus, the structure of the mixing part and the sampling position was changed from the apparatus of the said Embodiment 1, and others used the same apparatus. That is, (b) when performing ultrasonic mixing, the samples were sequentially sampled in a stainless steel tubular sampling container (φ10 mm × t50 mm) arranged at a predetermined sampling position. An ultrasonic homogenizer was used as the mixing unit, and the sampled paste samples were mixed by irradiating each sampling container with ultrasonic waves for XX minutes. The mixed paste sample was again supplied in sequence to a predetermined sample position on the substrate similar to that used in Embodiment 1 by using the sampling device again. Thereafter, in the same manner as in the above (a), the whole substrate was sent to the firing part electrical conductivity measurement part and the reduction expansion coefficient measurement part, and subjected to firing and various analyses.

Note that the conductive paste is sampled by using the same paste sample C and paste sample D as those used in Embodiment 4 above, with the blending ratio of the paste samples C and D being constant at (C) 70: (D) 30. Went. Moreover, the conductive paste of 10 samples was adjusted with each mixing apparatus by mixing with the mixing apparatus from which said (a) (b) differs.
The result of measuring the electrical conductivity (high temperature conductivity) at 800 ° C. and the reduction expansion coefficient of the fired body obtained by firing the conductive paste is sent to the evaluation section. The measurement results sent from the electrical conductivity measurement unit and the reduction expansion coefficient measurement unit to the evaluation unit are shown in Table 7 below.

  As shown in Table 7, (a) the fired body obtained by mixing with the pressure mixing device is more electrically conductive and reduced than the fired body obtained by mixing with the (b) ultrasonic mixing device. It was found that the variation in the expansion rate can be greatly reduced. That is, according to the conductive paste preparation condition evaluation apparatus provided with (a) a pressure mixing device as a mixing unit, it is possible to mix a highly viscous paste sample more uniformly, and the conductive paste preparation conditions are more It was confirmed that it can be evaluated with high accuracy.

As mentioned above, although this invention was demonstrated by the preferred embodiment, such description is not a limitation matter and can be variously modified | changed naturally. For example, the evaluation object of the conductive paste preparation condition evaluation apparatus disclosed herein is not limited to the SOFC electrode material and the resistance material of the electronic device as exemplified above. Applicable to evaluation of preparation conditions for electrode paste and conductive adhesive for printed wiring in electro-mechanical systems (MEMS) and multilayer ceramic capacitors (MLCC) Can do. Further, in this evaluation apparatus, the conductive particles contained in the conductive paste to be evaluated are not limited to the above RuO ₂ or transition metal perovskite type oxides, and the conductive particles composed of various other components It can be applied to a conductive paste containing particles. Moreover, it is not limited to mix | blending two types as a conductive paste, For example, you may make it evaluate the mixing | blending ratio of three types or four or more types of conductive paste. In order to evaluate the formed conductive film, it goes without saying that other tests, analysis or evaluation units other than the analysis unit specifically disclosed above may be provided.

DESCRIPTION OF SYMBOLS 10 Input part 20 Sampling part 22 Pressurization mixing part 24 Firing part 30 Electrical conductivity measurement part 32 Composition analysis part 34 Crystal structure analysis part 36 Thermal expansion coefficient measurement part 40 Evaluation part 50 Paste sample 51 Conductive paste 52 Firing body 100 Control 200 Sample preparation unit 221 Pressurized mixing vessel (pressure vessel)
222 Lid member 223 Compressor
224 Substrate 225 Pressure tube 300 Measuring unit 301 Conductivity measuring device 302, 302a, 302b Conductivity measuring function 303 Probe 500 Preparation condition evaluation device for conductive paste

Claims (15)

An apparatus for evaluating preparation conditions of a conductive paste for producing a conductive substance,
A blending ratio of two or more types of paste samples for constituting a conductive paste is set as at least one parameter, and the parameters are changed in a plurality of ways, and the two or more types of paste samples are sampled at a plurality of blending ratios. A sampling unit to collect at a position;
A pressure mixing section for preparing a conductive paste by mixing two or more sampled paste samples under pressure conditions;
A fired portion for firing the prepared plurality of conductive pastes to form a plurality of fired bodies;
An electrical conductivity measurement unit for measuring electrical conductivity of the plurality of fired bodies;
From the relationship between the blending ratio and the measurement result of the electrical conductivity, an evaluation unit for evaluating the preparation conditions of the plurality of conductive pastes,
A preparation condition evaluation apparatus for conductive paste, comprising: The paste sample includes conductive particles, a binder, and a solvent,
2. The conductive paste preparation condition evaluation apparatus according to claim 1, wherein the viscosity at 25 ° C. and 10 rpm is 3 Pa · s to 2000 Pa · s.   The said sampling part is a preparation condition evaluation apparatus of the electrically conductive paste of Claim 1 or 2 comprised so that preparation of each of these some electrically conductive pastes in the quantity of 10 g or less is possible.   The said pressure mixing part is a preparation condition evaluation apparatus of the electrically conductive paste of any one of Claims 1-3 mixed on the pressurization conditions of 0.05 Mpa-1 Mpa.   The said electrical conductivity measurement part is preparation of the electrically conductive paste of any one of Claims 1-4 comprised so that the measurement with respect to these several sintered compact can be measured simultaneously by one measurement operation. Condition evaluation device.   The said pressure mixing part is a preparation condition evaluation apparatus of the electrically conductive paste of any one of Claims 1-5 further provided with the ultrasonic wave generation | occurrence | production function.   The said electrical conductivity measurement part is preparation of the electrically conductive paste of any one of Claims 1-6 comprised so that the electrical conductivity of these baking bodies can be measured at high temperature of 500 degreeC or more. Condition evaluation device. The sampling position is set to a sample position provided in large numbers on the surface of the substrate,
8. The pressure mixing unit according to any one of claims 1 to 7, wherein the sample positions on the substrate are all hermetically sealed at the same time, and the two or more kinds of sampled paste samples are pressure-mixed. The preparation conditions evaluation apparatus of the electroconductive paste of description. In addition, with a transfer unit,
The sampling position is set in each of a large number of sampling containers prepared,
The pressure mixing unit hermetically seals the sampling container, pressurizes and mixes two or more types of paste samples sampled in the sealed sampling container,
The said transfer part transfers the electrically conductive paste prepared in this sampling container to the sample position provided in large numbers on the surface of the board | substrate, The preparation conditions of the electrically conductive paste of any one of Claims 1-7 Evaluation device. Furthermore, a composition analysis unit that performs composition analysis of the plurality of fired bodies is provided,
In the evaluation unit, for each of the fired bodies, the blending ratio of the two or more types of paste samples is corrected based on the result of the composition analysis, and the relationship between the blending ratio after the correction and the measurement result of the electrical conductivity is corrected. The preparation condition evaluation apparatus of the conductive paste according to any one of claims 1 to 9, wherein the preparation conditions of the plurality of conductive pastes are evaluated. Furthermore, a thermal expansion coefficient measuring unit for measuring the thermal expansion coefficient of a plurality of fired bodies is provided,
The said evaluation part is a preparation condition evaluation apparatus of the conductive paste of any one of Claims 1-10 which evaluates the preparation conditions of these conductive paste including the measurement result of the said thermal expansion coefficient. The thermal expansion coefficient measuring unit has a function of measuring the thermal expansion coefficient of the fired body in an oxidizing atmosphere and a reducing atmosphere,
The evaluation unit calculates the following formula (1) from the measurement result of the coefficient of thermal expansion of the fired body in an oxidizing atmosphere and a reducing atmosphere:
While calculating the reduction expansion coefficient defined by
The conductive paste preparation condition evaluation apparatus according to claim 11, wherein the preparation conditions of the plurality of conductive pastes including the reduction expansion coefficient are evaluated. The coefficient of thermal expansion measurement unit is capable of controlling the measurement atmosphere and analyzing the crystal structure in the region from at least room temperature to 1200 ° C,
The conductivity evaluation unit according to claim 12, wherein the evaluation unit calculates the reduction expansion coefficient based on a change in lattice constant in a measurement temperature range, and evaluates the preparation conditions of the plurality of conductive pastes including the reduction expansion coefficient. For evaluating the preparation conditions of adhesive paste.   The said thermal expansion coefficient measurement part is a preparation condition evaluation apparatus of the conductive paste of any one of Claims 11-13 containing an X-ray diffraction analyzer. The firing part has a firing temperature as at least one parameter, changes the parameter, and fires the plurality of conductive pastes,
The said evaluation part is a preparation condition evaluation apparatus of the conductive paste of any one of Claims 1-14 evaluated including the parameter of the said baking temperature as preparation conditions of these electroconductive paste.