JP4911349B2 - Method for forming composite metal oxide film - Google Patents

Description

The present invention relates to the formation how double if the metal oxide film.

For example, Patent Document 1 (Japanese Patent Laid-Open No. 9-309705) describes a technique of using composite metal oxide nanoparticles as a dielectric material. Fine particles having such a nanoscale particle size have a very small particle size and high surface activity, and therefore exhibit properties different from the original physical properties of the compound. In particular, it is known that firing is possible at a low temperature of about 300 ° C. to 400 ° C. Therefore, application to a capacitor-embedded substrate in which a capacitor is integrally incorporated in an insulator such as a resin constituting the circuit board is expected.
JP-A-9-309705

  However, nanoparticles are extremely strong in interaction and have the property of being easily aggregated, so that they are difficult to handle, and there are no examples of application to the formation of components on a high-density LSI substrate.

  As a simple method for obtaining such composite metal oxide nanoparticles, there is a method using a coprecipitation method. In this method, a coprecipitate is produced by reacting a plurality of types of metal salts constituting a composite metal oxide with a precipitant in a liquid phase, and the obtained coprecipitate is baked to obtain a target compound. Is the way to get.

  Therefore, by using this coprecipitation method, a solution in which a metal salt and a precipitating agent are mixed just before use is applied to a substrate in a desired pattern shape, and the coprecipitate generated on the substrate is baked. It is conceivable to form a composite metal oxide film on the substrate.

  However, since the reaction between the metal salt and the precipitating agent proceeds between mixing and application to the substrate, the coprecipitate aggregates and precipitates when the solution is concentrated at high concentration, and dispersion stability Will get worse. On the other hand, if the concentration of the solution is low in order to improve the dispersion stability, it is necessary to repeatedly apply in order to obtain a composite metal oxide film having a desired thickness, resulting in a reduction in production efficiency.

  An object of the present invention is to provide a method suitable for forming a high-density pattern using two types of liquid agents that start reaction upon mixing.

  In addition, the code | symbol with the parenthesis attached | subjected to each element shown below is only the illustration of the element, and does not limit each element.

  According to the first aspect of the present invention, a method of forming a pattern on a substrate (10) using an ink jet type droplet discharge device (1) having a first nozzle (6A) and a second nozzle (6B). The first liquid discharging step (S11) for discharging the first liquid (L1) from the first nozzle (6A) and landing on the substrate (10), and the first liquid from the second nozzle (6B). A second liquid discharge step (S12) for discharging the second liquid (L2) that reacts with (L1) and landing at the same position as the landing position of the first liquid (L1) in the first liquid discharge step (S11); A pattern forming method is provided.

  In the pattern forming method of the present invention, the first liquid (L1) and the second liquid (L2) are mixed at the time of landing on the substrate (10), and then the reaction starts. Therefore, for example, in the case of obtaining a thick film, there is no problem that the coprecipitate aggregates and precipitates before application, and dispersion stability deteriorates by mixing two liquids having a high concentration in advance. Furthermore, by mixing and using two low-concentration liquids in order to ensure dispersion stability, it is possible to avoid the problem that the number of coatings increases and the production efficiency decreases. When the interval between mixing the two liquids (L1, L2) and using them is long, it is necessary to store them at an extremely low temperature so that the reaction does not proceed, or to lower the two liquids in a low concentration. However, in the present invention, since the two liquids (L1, L2) are not mixed until just before landing on the base material (10), there is no storage cost. In addition, when a thick film is desired, a high concentration liquid can be used according to the purpose. Furthermore, since the ink jet method is used to land the liquid on the substrate (10), the appropriate amount of liquid and the landing position can be precisely controlled. Therefore, the first liquid (L1) and the second liquid (L2) can be landed at the same position with high accuracy, and a high-density pattern can be formed.

  In the pattern forming method of the present invention, the surface treatment step (S10) for treating the landing surface on which the first liquid (L1) and the second liquid (L2) land on the substrate (10) is replaced with a first liquid discharge step ( It may be included before S11) and the second liquid discharge step (S12). Thereby, the contact angle between the treated substrate (10) and the landed liquids (L1, L2) is controlled, or the reaction between the first liquid (L1) and the second liquid (L2) is activated. You can make it.

  In the pattern forming method of the present invention, the first liquid discharge step (S11) and the second liquid discharge step (S12) may be performed simultaneously. Or after performing a 1st liquid discharge process (S11) and a 2nd liquid discharge process (S12) with respect to a desired landing position, a 1st liquid discharge process (S11) and a 2nd liquid are changed, changing a landing position. The discharge step (S12) may be repeated. In these cases, the landing of the first liquid (L1) or the second liquid (L2) can be avoided.

  According to the second aspect of the present invention, the composite metal oxide film is formed on the substrate (10) using the ink jet type droplet discharge device (1) having the first nozzle (6A) and the second nozzle (6B). The first liquid (L1) containing a metal salt constituting the composite metal oxide is discharged from the first nozzle (6A) to land on the substrate (10). From the liquid discharge step (S11) and the second nozzle (6B), the second liquid (L2) containing a precipitant that reacts with the metal constituting the composite metal oxide to form a coprecipitate is discharged, The second liquid discharging step (S12) for landing at the same position as the landing position of the first liquid (L1) in the first liquid discharging step (S11), and the first liquid (L1) and the second liquid (L2) The coprecipitate produced by mixing on the substrate (10) is baked, and the coprecipitate is formed on the substrate (10). Forming a composite metal oxide film and a baking step (S13) for generating a film of coupling the metal oxide is provided.

  In the method for forming a composite metal oxide film of the present invention, the first liquid (L1) and the second liquid (L2) are not mixed before use, but are mixed when landing on the substrate (10), and the reaction starts. To do. Therefore, a high-concentration liquid can be used according to the purpose, for example, when a thick film is desired. In addition, since the ink jet system is used to land the liquid on the substrate (10), the mixing ratio of the first liquid (L1) and the second liquid (L2) can be precisely controlled. Therefore, the quality of the film can be stabilized.

  In the method for forming a composite metal oxide film of the present invention, a surface treatment step (S10) for improving the liquid repellency of the landing surface on which the first liquid (L1) and the second liquid (L2) land in the base material (10). May be included before the first liquid discharging step (S11) and the second liquid discharging step (S12). The surface treatment can suppress the wetting and spreading of the first liquid (L1) and the second liquid (L2) to a predetermined amount, so that the first liquid (L1) and the second liquid (L2) are reliably mixed. Can do.

  In the method for forming a composite metal oxide film of the present invention, the first liquid discharge step (S11) and the second liquid discharge step (S12) may be performed simultaneously. Or after performing a 1st liquid discharge process (S11) and a 2nd liquid discharge process (S12) with respect to a desired landing position, a 1st liquid discharge process (S11) and a 2nd liquid are changed, changing a landing position. The discharge step (S12) may be repeated. In these cases, the landing of the first liquid (L1) or the second liquid (L2) can be avoided.

  In the method for forming a composite metal oxide film of the present invention, the composite metal oxide film may be a piezoelectric film constituting a piezoelectric actuator. In this case, it is possible to easily and accurately form a piezoelectric film for a piezoelectric actuator having good characteristics.

  In the method for forming a composite metal oxide film of the present invention, the composite metal oxide may be lead zirconate titanate, and the second liquid (L2) may include a solution in which ammonium sulfate is dissolved in ammonia water. Furthermore, the first liquid (L1) may contain an aqueous block copolymer solution for low-temperature crystallization.

  According to the third aspect of the present invention, a two-component reaction curing type is performed on the substrate (10) using the ink jet type droplet discharge device (1) having the first nozzle (6A) and the second nozzle (6B). A method of applying an adhesive, the first liquid (L1) including one of a main agent and a curing agent constituting a two-component reaction curable adhesive being discharged from a first nozzle (6A), and A first liquid discharging step (S11) for landing on (10), and a second liquid (L2) containing the other of the main agent and the curing agent from the second nozzle (6B), and the first liquid discharging step There is provided a coating method of a two-component reaction curable adhesive comprising a second liquid discharging step (S12) for landing at the same position as the landing position of the first liquid (L1) in (S11).

  In the application method of the two-component reaction curable adhesive of the present invention, the first liquid (L1) and the second liquid (L2) are not mixed before use, and are mixed and cured at the time of landing on the substrate (10). The reaction starts. Therefore, the adhesive does not solidify inside the nozzle, and a cleaning mechanism inside the nozzle is unnecessary. Further, since the first liquid (L1) and the second liquid (L2) can be stored without being mixed, there is no restriction that the first liquid (L1) and the second liquid (L2) must be used up at once. Furthermore, since the ink jet method is used to land the liquid on the substrate (10), the appropriate amount of liquid and the landing position can be precisely controlled. Therefore, the first liquid (L1) and the second liquid (L2) can be landed at the same position with high accuracy, and a high-density adhesive pattern can be formed.

  In the coating method of the two-component reaction curable adhesive of the present invention, a surface treatment step (S10) for radicalizing the landing surfaces of the base material (10) on which the first liquid (L1) and the second liquid (L2) land. May be included before the first liquid discharging step (S11) and the second liquid discharging step (S12). By the surface treatment to be radicalized, the reaction with the adhesive can be activated and the adhesiveness can be enhanced.

  In the two-component reaction curable adhesive coating method of the present invention, the first liquid discharge step (S11) and the second liquid discharge step (S12) may be performed simultaneously. Or after performing a 1st liquid discharge process (S11) and a 2nd liquid discharge process (S12) with respect to a desired landing position, a 1st liquid discharge process (S11) and a 2nd liquid are changed, changing a landing position. The discharge step (S12) may be repeated. In these cases, the landing of the first liquid (L1) or the second liquid (L2) can be avoided.

  Hereinafter, a first embodiment of the present invention will be described in detail with reference to FIGS. 1 to 6 and FIG. 13. In the present embodiment, the present invention is applied to a method of forming a pattern of a composite metal oxide film on a substrate 10 (base material) for a printed wiring board by using the printer device 1 (inkjet droplet discharge device). Is.

  FIG. 1 shows a schematic diagram of a printer apparatus 1 used in the present embodiment. This printer apparatus 1 performs printing by a mechanism similar to a known inkjet printer, and includes a recording unit 2 for performing printing on a substrate 10. The recording unit 2 includes a carriage 4 having two recording heads 3 </ b> A and 3 </ b> B in parallel, and a drive unit 5 including a motor and the like for driving the carriage 4. Although not shown in detail, the carriage 4 is supported on a frame having a guide plate. When the drive unit 5 is driven, the carriage 4 is guided by the guide plate and reciprocates in the direction crossing the substrate 10. A substrate feed unit (not shown) for transporting the substrate 10 is provided below the guide plate.

  The two recording heads 3A and 3B are juxtaposed along the reciprocating direction of the carriage 4 (left and right direction in FIG. 1; arrow direction in the figure). Each of the recording heads 3A and 3B includes droplet discharge nozzles (hereinafter abbreviated as “nozzles”) 6A and 6B for discharging liquid (first liquid L1 and second liquid L2) on the lower surface side. While the carriage 4 reciprocates, the liquid is discharged downward from the nozzles 6A and 6B of the recording heads 3A and 3B, whereby printing on the substrate 10 is performed. Of the two recording heads 3A and 3B, the nozzle provided in one recording head 3A is the first nozzle 6A for ejecting the first liquid L1, and the nozzle provided in the other recording head 3B is the second liquid. It is the 2nd nozzle 6B for injecting L2. There are no particular restrictions on the liquid ejection method, and methods commonly used in ink jet devices, such as the piezo method and the thermal head method, can be applied.

  In each of the recording heads 3A and 3B, liquid supply units 7A and 7B having tanks and the like for supplying the first liquid L1 and the second liquid L2 to the recording heads 3A and 3B are respectively connected via the tubes 8A and 8B. Connected.

  Of the liquids used for printing, the first liquid L1 is an aqueous solution containing a salt of a metal constituting the composite metal oxide. Suitable metal salts include sulfates, nitrates, chloride salts and the like as inorganic salts, and acetates, oxalates, citrates and the like as organic salts. For example, when the target composite metal oxide is lead zirconate titanate (PZT) used as the material of the piezoelectric film, an aqueous solution containing a titanium salt, a zirconium salt, and a lead salt can be used as the first liquid L1.

  The second liquid is an aqueous solution containing a precipitant. As the precipitating agent, an alkaline substance such as aqueous ammonia can be used, and the pH of the mixed liquid Lm is adjusted to be within a range in which a coprecipitate can be generated when mixed with the first liquid L1.

  In addition, you may add a complexing agent, a pH adjuster, etc. to the 1st liquid L1 as needed. Further, the concentrations of the first liquid L1 and the second liquid L2 may be set appropriately according to the purpose, for example, high when a thick film is desired and low when a thin film is desired.

  The substrate 10 can be a resin plate used for a circuit board. A surface of the substrate 10 on which a pattern is to be formed (landing surface 10A on which the liquid droplets D1 and D2 of the first liquid L1 and the second liquid L2 land) may be subjected to plasma surface treatment with fluorine gas before pattern formation. preferable. By this surface treatment, fluorine groups are added to the pattern forming surface of the substrate 10, so that the liquid repellency can be improved. Therefore, the contact angles of the first liquid L1 and the second liquid L2 are controlled according to the material and surface state of the substrate 10, and the wet spread amount after the droplets D1 and D2 have landed on the surface of the substrate 10 is defined as a predetermined amount. can do.

  In order to form a pattern on the substrate 10 using the printer apparatus 1, first, the first liquid L1 is applied to the tank of the liquid supply unit 7A connected to one recording head 3A (the side including the first nozzle 6A). The tank of the liquid supply unit 7B connected to the other recording head 3B (the side provided with the second nozzle 6B) is filled with the second liquid L2. Next, while the carriage 4 is driven to reciprocate in the direction crossing the substrate 10 by the drive unit 5, the droplets D1 and D2 are ejected from the nozzles 6A and 6B to the positions where the elements are to be formed on the substrate 10, and the first liquid L1 A pattern of the mixed liquid Lm of the second liquid L2 is formed. FIG. 2 illustrates a state in which the pattern of the mixed liquid Lm is formed vertically and horizontally on the substrate 10.

  Here, in one scan of one dot row, droplets D1 and D2 are ejected from both the first nozzle 6A and the second nozzle 6B. FIG. 3 shows a partially enlarged view showing how the pattern of the mixed liquid Lm is formed. The arrows in the drawing indicate relative movement paths of the nozzles 6A and 6B with respect to the substrate 10. The droplet D1 of the first liquid L1 is discharged from the first nozzle 6A (first liquid discharge step), and the same position as the landing position of the droplet D1 of the first liquid L1 on the substrate 10 from the second nozzle 6B. A droplet D2 of the second liquid L2 is discharged (second liquid discharge step) to form one dot. That is, after the first liquid discharge process and the second liquid discharge process are performed on a desired landing position, the first liquid discharge process and the second liquid discharge process are repeated while changing the landing positions. When the scanning of one dot row is completed, the substrate 10 is fed forward by a predetermined amount by the substrate feeding portion, and the next dot row is printed. By repeating this, a pattern in which the droplets D1 of the first liquid L1 and the droplets D2 of the second liquid L2 are overstruck is formed. At this time, the droplet D1 of the first liquid L1 and the droplet D2 of the second liquid L2 landed at the same position are mixed, and the metal salt contained in the first liquid L1 is mixed with the precipitant contained in the second liquid L2. It reacts to form a coprecipitate such as hydroxide.

  In addition, what is necessary is just to adjust the discharge amount of the 1st liquid L1 for every dot, and the 2nd liquid L2 appropriately according to the density | concentration etc. of both liquid L1, L2. In addition, it is preferable that the landing time difference between the first liquid L1 and the second liquid L2 discharged to the same position is as short as possible, but the time difference is within a range in which no adverse effect due to drying of the liquid that has landed first occurs. It is within the allowable range.

  When the pattern formation is completed, moisture contained in the mixed liquid Lm on the substrate 10 is evaporated by vacuum drying. Thereafter, the remaining coprecipitate is heated to produce a composite metal oxide (firing step). In this way, a complex metal oxide film 11 having a predetermined pattern is formed on the substrate 10 (see FIGS. 5 and 6).

  The flow of processing in the first embodiment described above is represented by the flowchart of FIG. That is, after performing a plasma surface treatment (surface treatment step: S10) with fluorine gas on the substrate 10, the first liquid L1 is discharged from the first nozzle 6A, and the substrate 10 is landed on the surface-treated surface. (First liquid discharge step: S11). Next, the second liquid L2 that reacts with the first liquid L1 is discharged from the second nozzle 6B and landed at the same position as the landing position of the first liquid L1 in the first liquid discharging step S11 (second liquid discharging step). : S12). Finally, moisture contained in the mixed liquid Lm in which the first liquid L1 and the second liquid L2 are mixed on the substrate 10 is evaporated by vacuum drying, and the remaining coprecipitate is heated to generate a composite metal oxide. (Sintering step: S13).

  As described above, according to the present embodiment, the droplet D1 of the first liquid L1 and the droplet D2 of the second liquid L2 are mixed when landing on the substrate 10, and the droplets D1 and D2 land on the substrate 10. Since the reaction starts from the above, problems due to mixing the two liquids L1 and L2 before use can be avoided.

  That is, when the first liquid L1 and the second liquid L2 are mixed in advance, the reaction between the metal salt and the precipitating agent progresses between the mixing and the application on the substrate 10, so that the mixing and application are performed. It is necessary to make the time to the shortest possible. However, in the present embodiment, since there is no pre-mixing step, it is not necessary to consider the time from mixing to coating, and the manufacturing process can be simplified. In addition, for example, when the first liquid L1 and the second liquid L2 are mixed in advance to obtain a thick film, the coprecipitate aggregates and precipitates when the concentration of the mixed solution is high, resulting in poor dispersion stability. was there. On the other hand, when the concentration of the solution is low in order to improve the dispersion stability, there is a problem that it is necessary to repeatedly apply the solution, and the production efficiency is lowered. However, in the present embodiment, since the first liquid L1 and the second liquid L2 are not mixed in advance, a solution having an appropriate concentration can be adjusted and used according to the purpose.

  In addition, by reacting the metal salt contained in the first liquid L1 and the precipitant contained in the second liquid L2 on the substrate 10, there is no time for agglomeration of the reactant particles, and nanoscale fine particles Can be formed. Since the fine particles can be sufficiently fired at a low temperature, they are suitable for forming a dielectric element on a substrate made of a material having low heat resistance such as a resin.

  Further, since the ink jet method is used, it is possible to finely control the appropriate amount of liquid and the landing position, and the first liquid L1 and the second liquid L2 can be landed at the same position with high accuracy. Therefore, it is advantageous for forming a high-density pattern. Further, since the mixing ratio of the first liquid L1 and the second liquid L2 can be precisely controlled, the quality of the film 11 can be stabilized.

  Further, in one scan of one dot row, the droplets D1 and D2 are ejected from both the first nozzle 6A and the second nozzle 6B so that the landing time difference between the droplets D1 and D2 hardly occurs. Therefore, the first liquid L1 or the second liquid L2 that has landed on the substrate 10 can be prevented from being decomposed alone.

  Further, before performing printing by the printer apparatus 1, a plasma surface treatment process using fluorine gas is performed on the landing surface 10A on which the droplets D1 and D2 of the first liquid L1 and the second liquid L2 land on the substrate 10. In addition, the liquid repellency of the landing surface 10A can be improved, and the wetting and spreading of the first liquid L1 and the second liquid L2 can be suppressed to a predetermined amount. Thereby, the 1st liquid L1 and the 2nd liquid L2 can be mixed reliably.

  If a piezoelectric material such as lead zirconate titanate (PZT) is selected as the target composite metal oxide, a piezoelectric film for a piezoelectric actuator having good characteristics can be easily and accurately formed.

Hereinafter, reference examples of the present invention will be described with reference to FIGS. 7 to 10 and FIG. 13. In this reference example , the present invention is applied to a method of forming a pattern of an adhesive 12 for bonding an electronic component on a substrate 10 for a printed wiring board using the printer device 1. In addition, the same code | symbol is attached | subjected to the structure similar to 1st Embodiment, and description is abbreviate | omitted.

The adhesive 12 used in this reference example is, for example, a two-component curable epoxy adhesive, and is cured by a chemical reaction between the main agent composed of an epoxy resin and a curing agent. It is. The printer device 1 used in this reference example has the same configuration as that used in the first embodiment. Of the liquids used for printing, the first liquid L1 contains a main agent that constitutes the two-component reaction curable adhesive 12, and the second liquid constitutes the two-component reaction curable adhesive 12. It contains a curing agent. The substrate 10 can be a resin plate used for a circuit board. The surface of the substrate 10 on which the pattern is to be formed is preferably subjected to plasma surface treatment with oxygen before the pattern is formed. By this surface treatment, the pattern forming surface of the substrate 10 is radicalized, and the reaction with the adhesive 12 can be activated.

  In order to apply the adhesive 12 on the substrate 10 using the printer device 1, first, the first tank is connected to the tank of the liquid supply unit 7A connected to one of the recording heads 3A (the side having the first nozzle 6A). The liquid L1 (main agent) is filled in the tank of the liquid supply unit 7B connected to the other recording head 3B (side having the second nozzle 6B) with the second liquid L2 (curing agent). Next, as in the first embodiment, while the carriage 4 is driven to reciprocate in the direction crossing the substrate 10 by the drive unit 5, the droplets D1, D6 and 6B are mounted on the substrate 10 from the nozzles 6A and 6B. D2 is discharged. In this way, a pattern of the adhesive 12 is formed in which the droplet D1 of the first liquid L1 and the droplet D2 of the second liquid L2 are overlaid (see FIGS. 7 and 8). 7 and 8 exemplify how the pattern of the adhesive 12 is formed in a frame shape along the periphery of the electronic component 13 at the mounting position of the electronic component 13 on the substrate 10.

  At this time, as in the first embodiment, droplets D1 and D2 are ejected from both the first nozzle 6A and the second nozzle 6B in one scan of one dot row. That is, the droplet D1 of the first liquid L1 is discharged from the first nozzle 6A (first liquid discharge step), and the same position as the landing position of the droplet D1 of the first liquid L1 on the substrate 10 from the second nozzle 6B. Then, a droplet D2 of the second liquid L2 is discharged (second liquid discharge step) to form one dot. In other words, after the first liquid discharge process and the second liquid discharge process are performed on a desired landing position, the first liquid discharge process and the second liquid discharge process are repeated while changing the landing positions. When the scanning of one dot row is completed, the substrate 10 is fed forward by a predetermined amount by the substrate feeding portion, and the next dot row is printed. By repeating this, an element pattern in which the droplet D1 of the first liquid L1 and the droplet D2 of the second liquid L2 are overlaid is formed. Then, the curing reaction starts when the droplet D1 of the first liquid L1 and the droplet D2 of the second liquid L2 landed at the same position are mixed.

  When the pattern formation is completed, the electronic component 13 is placed on the application position of the adhesive 12 (see FIGS. 9 and 10). Then, the adhesive 12 is completely cured at room temperature or by heating, and the electronic component 13 is fixed to the substrate 10.

The flow of processing in this reference example described above is represented by the flowchart of FIG. That is, after plasma surface treatment with oxygen (surface treatment step: S10) is performed on the substrate 10, the first liquid L1 is discharged from the first nozzle 6A to land on the surface of the substrate 10 on which the surface treatment has been performed. (First liquid discharge step: S11). Next, the second liquid L2 that reacts with the first liquid L1 is discharged from the second nozzle 6B and landed at the same position as the landing position of the first liquid L1 in the first liquid discharging step S11 (second liquid discharging step). : S12). In this reference example , instead of the firing step S13, the electronic component 13 is stacked on the landing positions of the first liquid and the second liquid, and the adhesive 12 is cured by heating at room temperature or by heating the electronic component 13 to the substrate 10. A process of fixing to the top is performed.

As described above, according to this reference example , the first liquid L1 containing the main agent and the second liquid L2 containing the curing agent are mixed when landing on the substrate 10, and the droplets D1 and D2 land on the substrate 10. Therefore, the disadvantage of mixing the two liquids L1 and L2 before use can be avoided to the maximum. That is, in the case where the main agent and the curing agent are mixed in advance, the curing reaction also proceeds between the mixing and application on the substrate 10. For this reason, it is necessary to provide a cleaning mechanism so that the adhesive 12 does not solidify inside the droplet discharge nozzle and clogging occurs, or there is a restriction that the liquid once mixed must be used up once. is there. However, in the method of this reference example , the main agent and the curing agent are separated in the droplet discharge device, and since it does not solidify, maintenance is easy and there is no need to use up the liquid. , Process restrictions can be reduced.

  In addition, since the ink jet method is adopted, it is possible to control the precise application position required when an electronic component is bonded onto the substrate.

  Hereinafter, the present invention will be described in more detail with reference to an example (Example 1) for forming a composite metal oxide film.

(1) Preparation of the first liquid Titanium salt aqueous solution obtained by mixing 6 ml of 50% hydrogen peroxide water as a complexing agent in 24 ml of 1 mol / L titanium nitrate aqueous solution 50% as a complexing agent in 24 ml of 1 mol / L zirconyl nitrate aqueous solution An aqueous zirconyl salt solution mixed with 6 ml of hydrogen peroxide water and 48 ml of a 1 mol / L lead nitrate aqueous solution were prepared. The above three aqueous solutions were mixed to prepare a metal salt mixed solution. Furthermore, for low temperature crystallization, 30 ml of 10 g of block copolymer EO ₂₀ -PO ₇₀ -EO ₂₀ (BASF's Pluronic (registered trademark) P123) made of ethylene oxide (EO) and propylene oxide (PO) was dissolved in water. A block copolymer aqueous solution was prepared. The metal salt mixed solution and the block copolymer aqueous solution were mixed to form a first solution.

(2) Preparation of second liquid As a precipitant, 3 g of ammonium sulfate was dissolved in 50 ml of 3 mol / L ammonia water to prepare a second liquid.

(3) Base material A multilayer printed board mainly composed of a polyimide resin was used as the base material, and the surface of the base material was surface-treated by plasma treatment using a fluorine-based gas.

(4) Formation of Composite Metal Oxide Film An ink jet type droplet discharge apparatus having the configuration described in the above embodiment was prepared. The tank is filled with the first liquid and the second liquid prepared in the above (1) and (2), the landing time difference between the first liquid and the second liquid is 0 s, and the ratio of the appropriate liquid is the first liquid: second liquid = Pattern formation was performed at 1: 1. Thereafter, the pattern of the coprecipitate formed was vacuum-dried at 100 ° C. for 8 hours to remove excess solvent and temporarily fix the coprecipitate to the substrate surface. After drying, the pattern of the coprecipitate was heated and fired at about 300 ° C. for 60 minutes to obtain a metal composite oxide pattern. Note that, due to the presence of the block copolymer P123, a perovskite phase was generated by low-temperature firing.

Below, the reference example ( reference example 2) regarding the coating method of a two-component reaction hardening type adhesive agent is demonstrated.

(1) Material The first liquid was AP-209A manufactured by Toagosei Co., Ltd., which is the main component of the epoxy two-component curable adhesive. Moreover, Toagosei Co., Ltd. AP-209B which is a hardening | curing agent was used as the 2nd liquid. As a base material, a substrate mainly made of an epoxy resin was used, and the surface of the base material was surface-treated by a plasma treatment using oxygen.

(2) Adhesion of electronic component to base material An ink jet type droplet discharge device having the configuration described in the above embodiment was prepared. The tank is filled with the first liquid (main agent) and the second liquid (curing agent) described in (1), the landing time difference between the first liquid and the second liquid is 0 s, and the ratio of the appropriate liquid is the first liquid: An adhesive pattern was formed at the fixing position of the electronic component with 2 liquid = 2: 1. Thereafter, an electronic component was placed on the formed adhesive pattern and temporarily cured at 30 ° C. for 60 minutes. Thereafter, the adhesive was completely cured at room temperature or by heating, and the electronic component was bonded onto the substrate.

  Although the present invention has been specifically described above, the present invention is not limited thereto, and can be improved and changed within the scope of the claims. For example, in the first embodiment, all of the metal salt as a raw material is included in the first liquid L1, but a metal salt that does not react with the precipitant alone may be included in the second liquid. Absent.

  In the above embodiment, both the first liquid L1 and the second liquid L2 are ejected from both the nozzles 6A and 6B in one scan, but the procedure for superimposing the first liquid L1 and the second liquid L2 is performed. It is not limited to this. For example, as shown in FIGS. 11 and 12, one dot row is scanned twice by the carriage 4, and the first liquid L1 droplet D1 is ejected during the first scanning (first liquid ejection step). During the second scan, the droplet D2 of the second liquid L2 may be ejected in the same position as the droplet D1 landed the first time (second liquid ejection step). Alternatively, when the carriage 4 moves forward, the droplet of the first liquid L1 is discharged (first liquid discharge step), and when returning, the first liquid L1 droplet D1 is discharged at the same position as the landing position. The droplet D2 of the two liquid L2 may be discharged (second liquid discharge step). Further, the discharge order of the first liquid L1 and the second liquid L2 may be reversed. However, it is desirable that the allowable range of the landing time difference be determined in consideration of the influence of concentration change due to evaporation of the solvent from the previously landed droplets.

The combination of the first liquid and the second liquid is not limited to the above embodiment. For example, when the purpose is to form a ferromagnetic film (ferrite plating) on a substrate, an oxidizing solution (NaNO ₂ ) and a reaction solution (FeCl ₂ + MCl ₂ ) can be combined. For the purpose of forming a film with a reaction curable paint, a repair agent, or a resin, a main agent and a curing agent may be combined. When the purpose is to form a coating film with an inorganic coating agent such as a glass coating agent, the main agent and catalyst can be combined, and when the purpose is to form a heat insulating resin layer by foam curing, the main agent and the curing agent can be combined. Combinations can be used.

  The scope of application of the present invention is not limited to a two-component mixed system. For example, when the present invention is applied to a three-liquid mixing system, an ink jet type droplet discharge device is provided with another droplet discharge nozzle in addition to two droplet discharge nozzles. Three liquid droplets may be ejected and landed at the same positions as the landing positions of the first and second liquid droplets. Furthermore, even in a mixed system of four or more liquids, the number of droplet discharge nozzles is similarly increased by the number of necessary liquids, and the droplets from these droplet discharge nozzles are the same as the landing positions of the first liquid and the second liquid. Just land at the position.

  Furthermore, the present invention can also be applied when forming a thick film. For example, the first liquid and the second liquid are discharged and reacted on the substrate to form a coprecipitate pattern and vacuum dried. Thereafter, the first liquid and the second liquid are again discharged onto the formed pattern to form a coprecipitate pattern, and vacuum drying is repeated, whereby a thick film can be formed. . In this case, the first layer is formed on the surface-treated substrate, while the second and subsequent layers are formed on the coprecipitate pattern already formed. Therefore, it is necessary to adjust the concentration of the solution to be used when forming the first layer and when forming the second and subsequent layers. The resulting thick film can be used as a piezoelectric film for an inkjet head, for example.

  Furthermore, since the present invention can precisely control the droplet amount and the landing position by the ink jet type droplet discharge device, for example, as shown in FIG. 14, it includes a thick portion T1 and a small portion T2. The present invention can also be applied when forming such a film 30. For example, the thick portion T1 and the small portion T2 can be formed by changing the number of times the coprecipitate pattern is further formed on the coprecipitate pattern as described above for each landing position. Also, the thick portion T1 and the small portion T2 can be formed by changing the droplet amount for each landing position.

It is the schematic of the printer apparatus used by each said embodiment. It is a top view which shows the mode in the middle of forming the pattern of the liquid mixture of the 1st liquid and the 2nd liquid on the board | substrate in 1st Embodiment vertically and horizontally. FIG. 3 is an enlarged view within a chain line circle in FIG. 2. It is IV-IV sectional drawing of FIG. It is a top view which shows a mode that the pattern of the composite metal oxide film was formed vertically and horizontally on the board | substrate. It is a partial expanded sectional view of the pattern of a board | substrate and a composite metal oxide film. It is a top view which shows a mode in the middle of the pattern of the adhesive agent being formed in the vertical and horizontal on a board | substrate in a reference example . It is an enlarged view in the chain line circle of FIG. It is a top view which shows a mode that the electronic component was mounted in alignment with the position of the pattern formed on the board | substrate. FIG. 10 is an enlarged view within a chain line circle in FIG. 9. It is a schematic side view which shows a mode that a 1st liquid is made to land on a board | substrate by the 1st scan of a nozzle in other embodiment (2). It is a schematic side view which shows a mode that a 2nd liquid is made to land in the same position as the landing position of a 1st liquid by the 2nd scan of a nozzle in other embodiment (2). It is a flowchart which shows the flow of the process in this invention. It is a partial expanded sectional view of the film | membrane formed in other embodiment.

1. Printer device (inkjet type droplet discharge device)
6A ... 1st nozzle (one said droplet discharge nozzle)
6B ... second nozzle (the other droplet discharge nozzle)
10 ... Substrate (base material)
D1, D2 ... Droplet L1 ... First liquid L2 ... Second liquid

Claims (8)

A method of forming a composite metal oxide film on a substrate using an ink jet type droplet discharge device having a first nozzle and a second nozzle,
A first liquid discharging step of discharging a first liquid containing a metal salt constituting the composite metal oxide from the first nozzle and landing on the substrate;
The same position as the landing position of the first liquid in the first liquid discharging step by discharging a second liquid containing a precipitant that reacts with the metal constituting the composite metal oxide to form a coprecipitate from the second nozzle. A second liquid discharge step for landing on
Firing a coprecipitate formed by mixing the first liquid and the second liquid on the substrate, and forming a film of the composite metal oxide on the substrate;
A method for forming a composite metal oxide film. To claim 1, characterized in that it comprises a surface treatment step to increase the liquid repellency of the landing surface of the first liquid and the second liquid is landed in the substrate before the first liquid discharge step and the second liquid discharge step A method for forming a composite metal oxide film as described. Forming a composite metal oxide film according to claim 1 or claim 2 with the first liquid discharge step and the second liquid discharge step is characterized by being carried out simultaneously. Claims, characterized in that repeating the desired first liquid discharge process on the landing position, and after the second liquid discharge step, first liquid discharge step while changing the landing position, and the second liquid discharge step 4. The method for forming a composite metal oxide film according to any one of 1 to 3 . 2. The method of forming a composite metal oxide film according to claim 1 , wherein the composite metal oxide film is a piezoelectric film constituting a piezoelectric actuator. 2. The method of forming a composite metal oxide film according to claim 1 , wherein the composite metal oxide is lead zirconate titanate. The method for forming a composite metal oxide film according to claim 1 , wherein the second liquid includes a solution in which ammonium sulfate is dissolved in ammonia water. The method for forming a composite metal oxide film according to claim 1 , wherein the first liquid includes an aqueous block copolymer solution.

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