TW202319124A - Method of forming film, method of manufacturing electronic device, and film forming apparatus - Google Patents

Abstract

Provided is a film formation method and an application thereof, the method comprising: a step for preparing a stepped substrate, which is a substrate having a step in the substrate thickness direction; and a film formation step for discharging an ink from an inkjet head to supply the ink onto at least the top surface of the step of the stepped substrate, blowing air on to the ink which has come into contact with the top surface of the step to form a film that covers at least the top surface and the side surfaces of the step.

Description

Film forming method, electronic device manufacturing method, and film forming apparatus

The present disclosure relates to a film forming method, an electronic element manufacturing method, and a film forming apparatus.

Various researches are being carried out on techniques for coating liquid on substrates with step differences (such as concave-convex patterns, electronic parts, etc.).

Patent Document 1 discloses the following coating device as a coating device capable of preventing uneven solution from being generated in a thin film formed by coating a solution on a substrate. The coating device disclosed in Patent Document 1 is a solution coating device that discharges the solution to the above-mentioned concave and convex portions of a substrate having a concave-convex pattern in which concave and convex portions are regularly formed on the upper surface by an inkjet method. And coating, the coating device of aforementioned solution has: a coating head having a plurality of nozzles arranged along a predetermined direction, and applying the dot-like solution to the substrate from the plurality of nozzles at a constant timing; a drive mechanism for relatively moving the above-mentioned substrate and the above-mentioned coating head; and The control means controls the relative movement of the substrate and the coating head by the drive mechanism so that each row of dot-shaped solutions ejected from the nozzles and coated on the substrate respectively straddles the upper surface of the substrate. Two or more of the protrusions adjacent to each other extend along the extending direction of the concave-convex pattern so that the relative movement direction is shifted by a predetermined angle with respect to the extending direction of the concave-convex pattern.

In Patent Document 2, as a sealant supply control method that provides a sealant supply control method that provides a sealant supply control method that provides a sealant supply control method that overlaps and coats a predetermined amount of sealant at a predetermined number of times without waiting for the penetration of the sealant, The following supply control methods are disclosed. The supply control method disclosed in Patent Document 2 is a sealant supply control method, which controls the relative movement of the coating head that discharges the sealant and the circuit board on which the electronic parts are mounted, between each electronic part and each of the above-mentioned circuit boards. The supply of the sealant that is repeatedly coated and overlapped several times, the supply control method of the aforementioned sealant is as follows: Divide the supply amount of sealant to be applied to one electronic part into the number of times of application corresponding to the viscosity of the sealant and the size of the electronic part, and set the divided amount of the sealant to increase with the number of times of application. The amount that increases and alternately increases and decreases is distributed during each coating, and is set and supplied to each coating head by controlling the variable discharge amount of the sealant from the coating head based on the discharge pressure of the coating head. The amount of sealant to be dispensed when applying.

[Patent Document 1] Japanese Patent No. 5244758 [Patent Document 2] Japanese Patent Application Laid-Open No. 11-47657

On a substrate having a step in the thickness direction of the substrate, that is, a substrate with a step, a film covering at least the top surface (that is, the upper surface) and side surfaces of the step may be formed by an inkjet method. As an example of the board|substrate with a step, the electronic board|substrate provided with the wiring board and the electronic component arrange|positioned on the wiring board is mentioned.

The inventors of the present invention have found that, in the formation of the above-mentioned film by the inkjet method, the thickness variation of the film from the top surface (that is, the upper surface) of the step to the side surface of the step sometimes becomes large.

As the case where the thickness variation of the film becomes large, specifically, for example, the following can be mentioned: The case where the thickness of the film on the sides of the step becomes too thin compared to the thickness of the film on the top surface of the step; The thickness of the film at the corner of the joint between the side surface and the top surface of the step is too thin compared with the thickness of the film on the top surface of the step.

An object of an aspect of the present disclosure is to provide a film forming method and a film forming apparatus, which form at least a top surface covered with a step on a substrate having a step in the thickness direction of the substrate, that is, a substrate with a step, by an inkjet method. In the case of the film on the side surface of the step, the variation in thickness of the film from the top surface of the step to the side surface of the step can be suppressed. The subject of another aspect of the present disclosure is to provide a method of manufacturing an electronic component, which uses an inkjet method to coat at least the top surface of the electronic component on the electronic substrate provided with the wiring substrate and the electronic components arranged on the wiring substrate. When the insulating layer and/or the conductive layer are formed in the region of the side surface of the electronic component to form an electronic element, the variation in the thickness of the insulating layer and/or conductive layer from the top surface of the electronic component to the side surface of the electronic component can be suppressed.

Specific means for solving the above-mentioned problems include the following aspects. <1> A method for forming a film, comprising: A process of preparing a substrate having a step in the thickness direction of the substrate, that is, a substrate with a step; and a film forming process of imparting ink to at least the top surface of the substrate with a step by ejecting ink from an inkjet head, and By blowing air to the ink applied to the top surface of the step, a film covering at least the top surface of the step and the side surfaces of the step is formed. <2> The method for forming a film according to <1>, wherein The wind speed is more than 1m/s and less than 30m/s. <3> The method for forming a film according to <1> or <2>, wherein The film forming process includes the step of recovering wind. <4> The method for forming a film according to any one of <1> to <3>, wherein The film forming process also includes a step of performing pinning exposure on the blown ink, The time from the start of the blowing of the wind to the start of the pinning exposure was 1 second or less. <5> The method for forming a film according to any one of <1> to <4>, wherein The film forming process further includes a step of performing pinning exposure on the ink applied to the top surface of the level difference before blowing the air. <6> The film forming method according to any one of <1> to <5>, wherein The wind blows from the blower, The direction of the wind includes a component of the direction opposite to the side where the inkjet head is arranged when viewed from the air blower. <7> The film forming method according to any one of <1> to <6>, wherein Ink application in the film formation process is performed while moving the step substrate and the inkjet head relatively, In ink applied to a substrate with a step difference, the dot resolution in the direction of relative movement is higher than that in the direction perpendicular to the direction of relative movement. <8> The method for forming a film according to any one of <1> to <7>, wherein Wind is a flow of inert gas, The ink is an active energy ray curable ink containing a polymerizable compound. <9> The method for forming a film according to any one of <1> to <8>, wherein The substrate with level difference includes a base substrate and components arranged on the base substrate, and there is a gap between the base substrate and the components. <10> The method for forming a film according to any one of <1> to <9>, wherein Before the film forming process, a partition wall forming process of forming a partition wall surrounding a region where a film is formed is also included by discharging ink from an inkjet head. <11> The method for forming a film according to any one of <1> to <10>, wherein Before the film forming process, a process of performing hydrophilic treatment on at least the region where the film is formed is also included. <12> A method of manufacturing an electronic device, comprising: Preparation of the manufacturing process of the electronic substrate, the aforementioned electronic substrate has a wiring substrate and electronic components arranged on the wiring substrate; and A process for obtaining electronic components by forming at least one of an insulating layer and a conductive layer on an electronic substrate, At least one of the insulating layer and the conductive layer is formed by the film forming method described in any one of <1> to <11>. <13> A film forming apparatus comprising: An inkjet nozzle for imparting ink onto the top surface of at least a step in a substrate having a step in the thickness direction of the substrate, that is, a substrate with a step; and The blower blows air to the ink on the top surface of the step difference, Relatively move the substrate with step difference and the inkjet nozzle, The inkjet nozzles and the blower are arranged in a direction of relative movement. <14> The film forming apparatus according to <13>, further comprising a wind recovery unit for recovering wind. <15> The film forming apparatus according to <13> or <14>, wherein The direction of the wind blown from the blower includes a component facing in the direction opposite to the side where the inkjet head is arranged when viewed from the blower. <16> The film forming apparatus according to any one of <13> to <15>, which includes two air blowers, Arrange inkjet nozzles between 2 air blowers, Relative movement is back and forth movement. <17> The film forming apparatus according to any one of <13> to <16>, wherein The air blower has a switch function for switching between an on state to start blowing of air and an off state to stop blowing of air. <18> The film forming apparatus according to any one of <13> to <17>, further comprising a pinning exposure machine for performing pinning exposure on the blown ink. <19> The film forming apparatus according to any one of <13> to <18>, further comprising a pinning exposure machine for performing pinning exposure on the ink applied to the top surface of the step and before blowing air. . [Invention effect]

According to an aspect of the present disclosure, a film forming method and a film forming device are provided, which form at least a top surface covered with a step on a substrate having a step in the thickness direction of the substrate, that is, a substrate with a step, by an inkjet method. In the case of the film on the side surface of the step, the variation in thickness of the film from the top surface of the step to the side surface of the step can be suppressed. According to another aspect of the present disclosure, it is possible to provide a method of manufacturing an electronic component, which uses an inkjet method to paint at least the top surface of the electronic component on the electronic substrate provided with the wiring substrate and the electronic components arranged on the wiring substrate. When the insulating layer and/or the conductive layer are formed in the region of the side surface of the electronic component to form an electronic element, the variation in the thickness of the insulating layer and/or conductive layer from the top surface of the electronic component to the side surface of the electronic component can be suppressed.

In this disclosure, the numerical range represented by "-" means the range which includes the numerical values described before and after "-" as a minimum value and a maximum value, respectively. In the numerical ranges described step by step in this disclosure, the upper limit or lower limit described in a certain numerical range may be replaced by the upper limit or lower limit of other numerical ranges described stepwise. In addition, in the numerical range described in this indication, the upper limit or the lower limit described in a certain numerical range may be substituted by the value shown in an Example.

In the present disclosure, when a plurality of substances corresponding to each component exist in the composition, unless otherwise specified, the amount of each component in the composition means the total amount of the plurality of substances present in the composition. In this disclosure, a combination of two or more preferable aspects is a more preferable aspect. In this disclosure, the term "process" not only includes an independent process, but also includes in this term as long as the desired purpose of the process is achieved even if it cannot be clearly distinguished from other processes.

〔How to form a film〕 Methods of forming films of the present disclosure include: The process of preparing a substrate with a step difference in the thickness direction of the substrate, that is, a substrate with a step difference (hereinafter also referred to as "substrate preparation process with a step difference"); and A film forming process, by discharging ink from an inkjet head, imparting ink to at least the top surface of a step in a substrate with a step, and blowing air against the ink liquid onto the top surface of the step, thereby forming at least The film covering the top surface of the step and the side of the step. The film forming method of the present disclosure may also include other processes as required.

According to the film forming method of the present disclosure, when the film covering at least the top surface of the step and the side surface of the step is formed on a substrate having a step in the thickness direction of the substrate, that is, a substrate with a step, by the ink-jet method, it is possible to suppress the difference from the step. The thickness deviation of the film on the top surface to the sides of the step. The reason for obtaining such an effect is considered to be that the wind blowing against the ink on the top surface of the level difference can wind a part of the ink on the top surface back to the side, whereby the film on the side surface of the level difference can be suppressed. The thinning of the thickness and/or the thickness of the film at the corner of the junction of the side surface and the top surface of the step.

There is no particular limitation on the apparatus for implementing the film forming method of the present disclosure. The film forming method of the present disclosure can be implemented, for example, by a film forming apparatus of the present disclosure described later.

<An embodiment of the film forming method> Hereinafter, one embodiment of the film forming method of the present disclosure will be described with reference to the drawings. However, the film forming method of the present disclosure is not limited to the following embodiments. In the following description, substantially the same elements (for example, parts or parts) are denoted by the same reference numerals, and overlapping descriptions may be omitted.

1A to 1D schematically show a process flow diagram of a film forming method according to an embodiment of the present disclosure. In the film forming method of the present embodiment, the stepped substrate 10 shown in FIG. 1A is prepared. The substrate with level difference 10 includes a flat base substrate 12 and a member 18 disposed on the base substrate 12 . In this embodiment, the end of the member 18 on the base substrate 12 corresponds to the “level difference” described in this disclosure, the side surface 18S of the end portion of the member 18 corresponds to the side surface of the step difference in this disclosure, and the top of the member 18 Face 18U corresponds to the top face of the step in this disclosure.

As shown in FIG. 1A and FIG. 1B, in this embodiment, the inkjet nozzle 24 is fixed, and the inkjet nozzle 24 is ejected from the inkjet nozzle 24 while the substrate 10 is facing the conveyor belt step difference in the conveying direction M1 (that is, while moving). ink26. Thereby, ink is imparted to region 26 comprising the top surface of member 18 . In the film formation process in this embodiment, the substrate with the step difference is moved while the inkjet head is fixed, but the inkjet head may be moved while the substrate with the step difference is fixed, or both the inkjet head and the substrate with the step difference may be moved. . In the film formation process in this embodiment, the ink is applied to the top surface of the straddling member 18 and the region outside the top surface (on the side surface of the member 18 and on the base substrate 12 ), but the ink application At least the top surface of the member 18 may be applied, or it may be provided only on the top surface of the member 18 .

As shown in FIG. 1B , in this embodiment, after the ink 26 is applied, the thickness of the ink 26 on the side 18S of the member 18 and the distance between the side 18S and the top surface 18U are compared with the thickness of the film on the top surface 18U. The thickness of the ink 26 on the corner portion 18C of the junction becomes thinner. Thereby, the thickness deviation of the film from the side surface 18S of the member 18 to the top surface 18U becomes large. An object of the film forming method of the present disclosure is to suppress this thickness variation.

As shown in FIG. 1C , in this embodiment, after ink 26 is applied, wind W1 is blown to ink 26 on top surface 18U. By the force of the wind W1, a part of the ink 26 on the central portion of the top surface 18U moves along the peripheral end portion of the top surface 18U, and further moves along the corner portion 18C and the side surface 18S. As a result, as shown in FIG. 1D , the thinning of the ink thickness on the corner portion 18C and the side surface 18S can be suppressed, and the thickness variation of the film 20 from the side surface 18S to the top surface 18U can be suppressed.

Next, each process in the film forming method of the present disclosure will be described.

＜Substrate preparation process with step difference＞ The film forming method of the present disclosure includes a stepwise substrate preparation process. The substrate with a step difference is a substrate having a step difference in the thickness direction of the substrate. The substrate preparation process with a step difference may be a process of simply preparing a substrate with a step difference manufactured in advance, or may be a process of manufacturing a substrate with a step difference.

An example of the stepped substrate is the stepped substrate 10 including the above-mentioned base substrate 12 and the member 18 arranged on the base substrate 12 . The member 18 may be a part (such as an electronic component) mounted on the base substrate 12 (such as a wiring substrate), or may be a patterned film (such as a metal patterned film, an insulating film, a photoresist patterned film) formed on the base substrate 12. wait).

As the board|substrate 10 with a step, the electronic board|substrate containing a wiring board and the electronic component arrange|positioned on a wiring board is mentioned. As the wiring board, a board on which wiring is formed, such as a printed wiring board, can be used. Examples of electronic components include semiconductor chips such as integrated circuits (IC; Integrated Circuit), capacitors, transistors, and the like. The wiring board may further include a ground electrode, ground wiring, a solder resist layer, and the like.

The substrate with step difference is not limited to the substrate with step difference formed by mounting components on the base substrate. It may be formed by etching and other processes on the base substrate. ), through holes, etc.).

The material of the base substrate in the stepped substrate is not particularly limited, and examples thereof include glass, ceramics, metal, and resin.

The substrate with step difference includes a base substrate and components disposed on the base substrate, and there may be a gap between the base substrate and the components. In the conventional film forming method without wind blowing, when there is a gap between the base substrate and the member, when the ink is applied to the region including the member, the ink enters the gap between the base substrate and the member , the thickness of the ink on the side surface of the member tends to be thinner. However, in the film forming method of the present disclosure, the ink on the top surface of the member can be wound back to the side surface by blowing air to the ink on the top surface of the member. In this way, when there is a gap between the base substrate and the member, it is easier to exert the effect of the present disclosure by blowing air to the ink on the top surface of the level difference.

FIG. 2 is a schematic side view of an example of a stepped substrate showing a state in which a gap exists between a base substrate and a member. The structure of the substrate 13 with a step difference shown in FIG. 2 is the following structure: in the substrate 10 with a step difference described above, by adding a plurality of connection members 16 between the base substrate 12 and the member 18, and on the base substrate 12 A gap 17 is provided with the component 18 . As the connecting member 16 , a connecting material (for example, solder balls, adhesive, etc.) for connecting the base substrate 12 and the member 18 may be mentioned.

＜Film Formation Process＞ The film forming method of the present disclosure includes a film forming process. The film forming process is a process of imparting the ink onto at least the top surface of the step in the substrate with the step by ejecting the ink from the inkjet head, and blowing air against the ink liquid on the top surface of the step, Thus, a film covering at least the top surface of the step and the side surfaces of the step is formed.

(impartment of ink) The ink is not particularly limited, and examples thereof include conductive inks and insulating inks described in the section of the manufacturing method of electronic components described later.

As a method for applying ink, known methods in inkjet recording can be appropriately applied. As the method of ejecting ink from the inkjet head, there are charge control method using electrostatic attraction to eject ink, slit spin coating method (pressure pulse method) using vibration pressure of piezoelectric element, converting electrical signal into sound beam Either of the acoustic inkjet method of irradiating ink and ejecting ink with radiation pressure, and the thermal inkjet (Bubble Jet (registered trademark)) method of heating ink to form bubbles and utilizing the generated pressure. As a method of ejecting ink from an inkjet head, the following inkjet recording method can be effectively used in particular: By the method described in Japanese Patent Laid-Open No. 54-59936, the ink subjected to the action of heat energy undergoes a rapid volume change, by Ink is ejected from the nozzle based on the force of this state change. Moreover, regarding the method of ejecting the ink from the inkjet head, the methods described in paragraphs 0093 to 0105 of JP-A-2003-306623 can also be referred to.

It is preferable to apply the ink in the film forming process while relatively moving the stepped substrate and the inkjet head. Thereby, ink can be efficiently applied to a desired area on the board|substrate with a step difference. In this case, the substrate with the step may be moved while the inkjet head is fixed, the inkjet head may be moved while the substrate with the step is fixed, or both the inkjet head and the substrate with the step may be moved.

In the case of applying the ink in the film formation process while moving the substrate with the step difference and the inkjet head relatively, the dot resolution in the direction of the relative movement is higher than that of the opposite in the ink applied to the substrate with the step difference The point resolution in the direction perpendicular to the moving direction is better. This makes it easy for the ink to settle on the corners of the steps intersecting (for example, perpendicular) to the direction of relative movement. As a result, it is easy to secure the amount of ink adhering to the side surfaces of the steps intersecting the direction. As a result, since the thickness of the ink on the side surface of the step is ensured, the variation in film thickness from the side surface of the step to the top surface is further suppressed.

3 is a schematic plan view schematically showing an example of an aspect in which the dot resolution in the direction of relative movement is higher than the dot resolution in the direction perpendicular to the direction of relative movement. Fig. 4 is a schematic side view schematically showing an example of how ink impinges on a corner of a member.

In an example shown in FIG. 3 , the stepped substrate 10 moves toward the conveyance direction M1 and a large number of ink dots D1 are formed on the entire member 18 and its surroundings on the stepped substrate 10 . In this example, the density (that is, the dot resolution) of the ink dot D1 in the direction parallel to the conveying direction M1 (that is, the direction of relative movement) is higher than that of the ink dot D1 in the direction perpendicular to the direction of relative movement. Density (ie, point resolution) is higher. More specifically, FIG. 3 shows a state where the dot resolution in the direction of relative movement is about twice the dot resolution in the direction perpendicular to the direction of relative movement.

When the dot resolution in the direction of relative movement is higher than that in the direction perpendicular to the direction of relative movement, as shown in FIG. 18C. As a result, the amount of ink adhering to the side surface 18S below the corner portion 18C can be ensured, and as a result, the thickness of the ink 26 on the side surface 18S of the step can be ensured, so that the transfer from the side surface 18S of the step to the top surface 18U can be further suppressed. The thickness deviation of the film.

(wind blowing) In the film forming process, a film covering at least the top surface of the step and the side surfaces of the step is formed by blowing air against the ink liquid on the top surface of the step. More specifically, as described above, by the force of the wind, part of the ink impregnated on the top surface moves to the corners and side surfaces, and as a result, the thickness of the ink at the corners and side surfaces is prevented from becoming thinner. Phenomenon.

In the case where the film forming process includes blowing wind to the ink attached to the top surface of the step on the substrate with steps, the wind speed of the wind is not particularly limited. From the viewpoint of effectively exerting the above effects, the wind speed is preferably 1m/s to 30m/s, more preferably 1m/s to less than 30m/s, and more preferably 1m/s to 25m/s. 2 m/s to 20 m/s is more preferable, and 5 m/s to 15 m/s is still more preferable.

In the case where the film forming process includes a step of blowing air against the ink liquidated on the top surface of the step on the substrate with the step, the direction of blowing the air against the ink liquidated on the top surface of the step is not particularly limited. From the viewpoint of effectively exerting the above effects, the direction of blowing air against the ink on the top surface of the level difference is preferably a direction with an elevation angle of 10° to 90°, and a direction with an elevation angle of 20° to 90° is more preferable. , the direction in which the elevation angle is 30° to 90° is more preferable.

In this disclosure, "the direction of the ink blowing wind B facing the liquid on the top surface of the step difference is the direction where the elevation angle becomes X°." It refers to the horizontal plane when looking up at the direction of the wind B coming from the position of the blowing wind B The angle of is X° (here, X° is an angle within a range from 0° to 90°). Fig. 5 is a schematic diagram showing an example of an elevation angle. The elevation angle in this example is the angle X° with respect to the horizontal plane when looking up at the direction where the wind comes from the position P1 where the wind blows indicated by symbol W1.

Moreover, it is preferable that the wind is the wind blown from the blower. As the blower, for example, a dryer, a hot air generator, a compressed air generator, a fan, a blower, etc. can be used. In addition, as a blower, the piping through which compressed air flows in the factory can be drawn back into the film forming apparatus and used.

It is preferable that the direction of the air blown from the blower includes a direction component opposite to the side where the inkjet head is arranged when viewed from the blower (for example, refer to FIG. 7B described later). Thereby, since the wind does not blow in the direction of the inkjet head, it is possible to further suppress the decrease in the discharge accuracy of the ink due to the influence of the wind.

In the film forming method of the present disclosure, the wind is not particularly limited, and any gas flow can be used. In the film forming method of the present disclosure, when the ink is an active energy ray-curable ink containing a polymerizable compound, the wind is preferably an inert gas flow. Thereby, the inhibition of polymerization due to oxygen can be suppressed (specifically, the phenomenon that the polymerization of the polymerizable compound in the active energy ray-curable ink is inhibited by oxygen), so the curability of the active energy ray-curable ink is improved. excellent. Examples of the inert gas include nitrogen, argon, helium and the like.

Also, it is preferable that the film forming process includes a step of recovering the wind blowing the ink. Thereby, the pressure rise in the apparatus (for example, an inkjet recording apparatus) which performs a film formation process can be suppressed further. In addition, satellite droplets and/or mist droplets discharged from the inkjet head and not attached to the substrate can be recovered. The recovery of wind can be carried out using, for example, a wind recovery device, an exhaust device, etc., which combine a fan and piping connected to the outside of the film forming apparatus. For example, in the above-mentioned wind recovery machine, a replaceable filter is arranged in front of the fan and replaced regularly, thereby preventing satellite droplets and/or mist droplets from spreading into the factory.

(Pinning Exposure) The film forming process may further include a step of performing pinning exposure (hereinafter, also referred to as “pinning exposure A”) to the blown ink. The cumulative exposure amount of the pinning exposure A is not particularly limited, but is, for example, 0.1 J/cm ² to 1000 J/cm ² . Since the fluidity of the ink can be suppressed by the pinning exposure A, the ink adhering to the side surface of the step can be suppressed from flowing down due to gravity. Therefore, the thickness deviation of the film from the side surface of the step to the top surface can be further suppressed. The cumulative exposure amount of the pinning exposure A is not particularly limited, but is, for example, 0.1 J/cm ² to 1000 J/cm ² . When the ink in the film formation process is the conductive layer forming ink described later, the cumulative exposure amount of the pinning exposure A with respect to the conductive layer forming ink is preferably 0.1 J/cm ² to 1000 J/cm ² , more preferably 1J/cm ² to 100J/cm ² . When the ink used in the film formation process is the insulating layer forming ink described later, the cumulative exposure amount of the pinning exposure A with respect to the insulating layer forming ink is preferably 0.1 J/cm ² to 100 J/cm ² , more preferably 0.1J/cm ² to 10J/cm ² .

The time from the start of the blowing of the wind to the start of the pinning exposure A is preferably 1 second or less. Thereby, it is possible to further suppress the thickness variation of the film from the side surface of the step to the top surface.

The film forming process may further include a step of performing pinning exposure (hereinafter, also referred to as “pinning exposure B”) on the ink provided on the top surface of the step and before blowing the air. Thereby, the viscosity of the ink on the top surface can be appropriately increased, so that the ink on the top surface can be further suppressed from excessively flowing down due to the blowing of the wind, and it is easy to appropriately leave the ink on the top surface after the blowing of the wind on the top surface. top surface. As a result, the effect of suppressing the thickness variation of the film from the side surface of the step to the top surface can be exhibited more effectively. The preferable range of the cumulative exposure amount of the pinning exposure B is the same as the preferable range of the cumulative exposure amount of the pinning exposure A.

In addition, the above-mentioned pinning exposure A (that is, the pinning exposure before the ink is blown with air) and the above-mentioned pinning exposure B (that is, the pinning exposure after the ink has been blown with air) are arbitrary operations. Therefore, in the film formation process, only one of the pinning exposure A and the pinning exposure B may be implemented, both of them may be implemented, and neither of them may be implemented.

(heating) The film forming process may include a step of heating the stepped substrate to which ink is imparted to a temperature of 100° C. or higher. Thereby, since the fluidity of ink can be suppressed by heating and drying of ink, it can suppress that the ink attached to the side surface of a level difference flows down by gravity. Therefore, the thickness deviation of the film from the side surface of the step to the top surface can be further suppressed.

The heating temperature of the substrate to which the ink step is imparted is preferably 250°C or lower, more preferably 50°C to 200°C, and more preferably 60°C to 180°C.

＜Partition wall forming process＞ In the film forming method of the present disclosure, prior to the film forming process, there may be mentioned a barrier wall forming process of forming barrier walls surrounding a region where a film is formed by discharging ink from an inkjet head. In this aspect, by the partition wall formed before the film formation process, it is possible to suppress the phenomenon that the ink in the film formation process flows out to the outside than the originally intended area and/or the ink in the film formation process goes back to the belt step difference The phenomenon that the film of the substrate is not formed on the surface.

6 is a schematic side view showing an example after the barrier rib forming process and before the film forming process when the film forming method of the present disclosure includes the barrier rib forming process. The example shown in FIG. 6 is the same as the example shown in FIG. 2 except that partition walls 19 are formed. Before the film formation process (that is, before the ink is applied), the aforementioned outflow and wrapping can be suppressed by providing the partition wall 19 surrounding the region where the film is formed.

The method for forming the partition wall is not particularly limited, but it is preferably formed by an inkjet method in the same manner as the film formation process from the viewpoint of productivity.

＜The process of implementing hydrophilization treatment＞ In the film forming method of the present disclosure, prior to the film forming process, a process of performing a hydrophilic treatment on at least a region where the film is formed may be included. As a result, ink adhesion to the side surfaces and corners of the step is improved, so that the thickness variation of the film from the side surface of the step to the top surface can be further suppressed.

Examples of the hydrophilic treatment include corona discharge treatment, ozone treatment, argon plasma treatment, acid plasma treatment, and the like.

＜Preheating process＞ In the film forming method of the present disclosure, it is preferable to include a process of heating the substrate with a step (in the present disclosure, also referred to as “preheating process”) before the film forming process. In this case, the ink is applied to the stepped substrate heated to the above-mentioned temperature in the film formation process.

According to the aspect including the preheating process, the fluidity of the ink can also be suppressed by heating and drying the ink, so that the ink adhering to the side surface of the step can be suppressed from flowing down due to gravity. Therefore, the thickness deviation of the film from the top surface of the step to the side surface can be further suppressed.

The heating temperature in the preheating process is more preferably from 20°C to 120°C, further preferably from 28°C to 80°C.

＜Film formation on the end surface of substrate with step difference＞ In the film forming method of the present disclosure, as described above, ink is applied to at least the top surface of the stepped substrate and air is blown to the applied ink, thereby forming a thickness that suppresses from the side surface of the step to the top surface. The film of deviation. At this time, the ink is also applied to the vicinity of the end of the substrate with a step difference, and the ink near the end is blown to return the ink to the end surface of the substrate with a step difference, whereby the end surface of the substrate with a step difference can be formed. membrane. Thereby, it is possible to form a film excellent in covering property on the end surface of the substrate with steps.

The apparatus for carrying out the above-mentioned film forming method of the present disclosure is not particularly limited, but the film forming apparatus of the present disclosure shown below is preferable.

〔Film forming device〕 The film forming apparatus of the present disclosure has: An inkjet nozzle for imparting ink onto the top surface of at least a step in a substrate having a step in the thickness direction of the substrate, that is, a substrate with a step; and The blower blows air to the ink on the top surface of the step difference, Relatively move the substrate with step difference and the inkjet nozzle, The inkjet nozzles and the blower are arranged in a direction of relative movement.

According to the film forming apparatus of the present disclosure, similarly to the film forming method of the present disclosure, it is possible to form a substrate having a step in the thickness direction of the substrate, that is, a substrate with a step, which suppresses thickness deviation from the top surface of the step to the side surface. film. The reason why such an effect is obtained is as described in the section of the film formation method of the present disclosure.

Hereinafter, preferred aspects of the film forming apparatus of the present disclosure will be described. The following aspects can be applied in appropriate combinations.

It is preferable that the film forming apparatus of the present disclosure further includes a wind recovery unit for recovering the above-mentioned wind. The effect by recovering wind and an example of a wind recovering device are as described in the section of the film forming method of the present disclosure.

It is preferable that the direction of the air blown from the blower includes a direction component opposite to the side where the inkjet head is arranged when viewed from the blower (for example, refer to FIG. 7B described later). Thereby, since the wind does not blow in the direction of the inkjet head, it is possible to further suppress the decrease in the discharge accuracy of the ink due to the influence of the wind.

FIG. 7A is a schematic plan view showing an example of the film forming apparatus of the present disclosure, and FIG. 7B is a side view of FIG. 7A . As shown in FIG. 7A and FIG. 7B , the film forming apparatus 300 of this example is equipped with a substrate conveying stage 212 for conveying the substrate 10 with a step difference, a conveying rail 210 for moving the substrate conveying stage 212, an inkjet nozzle 24, and an air blower 28. , a wind recycling machine 30 and a pinning exposure machine 32 . The inkjet head 24 , the air blower 28 , the air recovery unit 30 , and the pin exposure unit 32 are sequentially arranged upstream from the transport direction M1 (ie, the moving direction of the substrate transport stage 212 ).

In the formation of the film using the film forming apparatus 300, ink from the inkjet head 24, ink from the blower, etc. 28 wind blowing and pinning exposure by pinning exposure machine 32 . At this time, recovery of the wind by the wind recovery device 30 is appropriately performed. By blowing the air from the air blower 28 to the ink applied to the top surface of the step, it is possible to suppress the thickness deviation of the film from the side surface of the step to the top surface as described above. By the pinning exposure by the pinning exposure machine 32, as mentioned above, the thickness variation of the said film is suppressed further. By recovering the wind by the wind recovering device 30, it is possible to further suppress the pressure rise in the device as described above, and to recover satellite droplets and/or mist droplets of the ink.

As shown in FIG. 7B , in this example, the direction W1 of the wind blown from the air blower 28 includes a component W1X in the direction opposite to the side where the inkjet head 24 is arranged when viewed from the air blower 28 . Thereby, since the wind does not blow in the direction of the inkjet head 24, it is possible to further suppress the reduction of the discharge accuracy of the ink due to the influence of the wind.

As shown in Figure 7B, in this example, the reflection angle (hereinafter, also referred to simply as "reflection angle") of the direction of the wind recovered by the wind recovery device 30 relative to the top surface of the step difference is adjusted to be the same as that blown out from the blower 28. The incident angles of the wind direction W1 with respect to the top surface of the step (hereinafter also simply referred to as “incident angles”) are substantially the same.

Here, the incident angle of the wind blown from the air blower 28 toward the top surface of the step W1 corresponds to the aforementioned elevation angle (for example, refer to FIG. 5 ). The preferable range of the aforementioned incident angle is the same as the aforementioned preferable range of the elevation angle.

The aforementioned incident angle (that is, the elevation angle) is defined by the direction W1 of the wind blown from the air blower 28 , so the direction of progress of the wind inside the air blower may be any direction. Therefore, for example, the same effect as that of the film forming apparatus 300 in FIG. 7B can be exhibited in a modified example (film forming apparatus 300X) shown in FIG. 7C described below. FIG. 7C is a schematic cross-sectional view showing a modified example (film forming apparatus 300X) of the film forming apparatus 300 shown in FIG. 7B . As shown in FIG. 7C , in the inside of the air blower 28X (ie, the flow path) in the film forming apparatus 300X, the wind first goes downward in the direction of gravity, then bends halfway and is blown out from the air blower 28X. The incident angle ( FIG. 7C ) of the wind blown from the blower 28X toward W1 is about the same as the incident angle ( FIG. 7B ) of the wind blown from the blower 28 toward W1 . As shown in FIG. 7C , the wind is recovered by the wind recovery device 30X in the film forming apparatus 300X. The reflection angle of the wind at this time ( FIG. 7C ) is about the same as the reflection angle of the wind when the wind is recovered by the wind recovery device 30 ( FIG. 7B ). The wind recovered by the wind recovery unit 30X bends its traveling direction inside the wind recovery unit 30X (that is, the flow path), and then proceeds in the direction of gravity. The structure of the film forming apparatus 300X shown in FIG. 7C is the same as that of the film forming apparatus 300 shown in FIG. 7B except for the above-mentioned points. The same effect as that of the film forming apparatus 300 shown in FIG. 7B can also be exhibited by the film forming apparatus 300X shown in FIG. 7C .

It is preferable that the air blower 28 and the air blower 28X have a switch function for switching between an on state to start blowing of air and an off state to stop blowing of air. Thereby, the air can be blown selectively to the ink on the region including the top surface of the level difference. The opening and closing function can be realized, for example, by providing a louver at the blowing outlet of the blower.

The film forming apparatus of the present disclosure is not limited to the example shown in FIGS. 7A to 7C . The direction W1 of the wind blown from the blower 28 and the direction of the wind recovered by the wind recovering device 30 are not limited to the above example from the viewpoint of the effect of forming a film that suppresses thickness variation from the top surface of the step to the side surface. . For example, the direction W1 of the wind blown from the blower 28 is downward in the direction of gravity, and the direction of the wind recovered by the wind recovery device 30 may be in the direction of gravity. Also, from the viewpoint of the effect of forming a film that can suppress thickness variation from the top surface of the step to the side surface, the arrangement of the air blower and the wind recovery device can be replaced. Also, from the viewpoint of the above effects, the wind recovery unit and the pinning exposure unit can be omitted.

FIG. 8A is a schematic plan view showing another example of the film forming apparatus (film forming apparatus 300A) of the present disclosure, and FIG. 8B is a side view of FIG. 8A . The film forming apparatus 300A shown in FIGS. 8A and 8B is an example of the following: Compared with the film forming apparatus 300 shown in FIGS. 7A and 7B , the direction W1 of the wind blown from the air blower 28 is changed downward in the direction of gravity. The direction of the wind recovered by the wind recovering device 30 changes along the direction of gravity. Also in the film forming apparatus 300A shown in FIGS. 8A and 8B , as in the film forming apparatus 300 shown in FIGS. 7A and 7B , from the transport direction M1 (that is, the moving direction of the substrate transport stage 212 ) On the upstream side, an inkjet nozzle 24 , a blower 28 , an air recovery unit 30 and a pinning exposure unit 32 are arranged in sequence.

FIG. 9A is a schematic plan view showing still another example of the film forming apparatus (film forming apparatus 300B) of the present disclosure, and FIG. 9B is a side view of FIG. 9A . The film forming apparatus 300B shown in FIGS. 9A and 9B is an example in which the positions of the air blower 28 and the wind recovering device 30 are replaced with those of the film forming apparatus 300A shown in FIGS. 8A and 8B . That is, in this modified example, the inkjet head 24, the air recovery unit 30, the air blower 28, and the pin exposure unit 32 are sequentially arranged from the upstream side of the transport direction M1 (that is, the moving direction of the substrate transport stage 212). . According to this film forming apparatus 300B, not only the wind from the air blower 28 but also fine ink droplets (ink mist droplets) carried along with the substrate 10 with the step difference before reaching the substrate 10 with the step difference can be recovered by the wind recovery unit 30 . Furthermore, similarly to the example shown in FIGS. 8A and 8B , by the air blower 28 , it is possible to form a film capable of suppressing variation in thickness from the side surface of the step to the top surface. In addition, since fine ink droplets can be collected by the air recovery unit 30 , it is possible to suppress scattering of the fine ink droplets by the wind from the air blower 28 .

FIG. 10A is a schematic plan view showing still another example of the film forming apparatus (film forming apparatus 300C) of the present disclosure, and FIG. 10B is a side view of FIG. 10A . The film forming apparatus 300C shown in FIGS. 10A and 10B is an example in which a pinning exposure machine 34 is added between the inkjet head 24 and the blower 28 relative to the film forming apparatus 300A shown in FIGS. 8A and 8B . In the film forming apparatus 300C, the inkjet head 24, the pinning exposure machine 34, the air blower 28, the wind recovering machine 30, and the nailer are sequentially arranged from the upstream side of the conveying direction M1 (that is, the moving direction of the substrate conveying stage 212). Bar exposure machine 32. According to the film forming apparatus 300C shown in FIG. 10A and FIG. 10B , the pinning exposure machine 34 can perform pinning exposure on the ink provided on the top surface and before blowing air. Thereby, the viscosity of the ink on the top surface can be appropriately increased, so that the ink on the top surface can be further suppressed from excessively flowing down due to the blowing of the wind, and it is easy to appropriately leave the ink on the top surface after the blowing of the wind on the top surface. top surface. As a result, the effect of suppressing the thickness variation of the film from the side surface of the step to the top surface can be exhibited more effectively.

In addition, the pinning exposure of the ink applied to the top surface and before blowing the air is performed using the film forming apparatus 300C. In addition, it can also be performed by reciprocating the substrate with a step and using the method shown in FIGS. 8A and 8B . The film forming apparatus 300A shown is used.

Also, from the viewpoint of the effect of suppressing the excessive flow of ink on the top surface due to the blowing of the wind, it is possible to perform the pinning exposure of the ink before the blowing of the wind and omit the pinning exposure of the ink after the blowing of the wind.

In addition, as shown below, in the example shown in FIG. 8A and FIG. 8B , it is possible to perform wind recovery even if the wind recovery device is omitted.

FIG. 11 is a schematic plan view showing another example of the film forming apparatus of the present disclosure. The film forming apparatus 301 shown in FIG. 11 is an apparatus that uses the film forming apparatus 300 as a base, omits the wind recovery device 30 , and provides a through hole 214 on the substrate conveying stage 213 instead. The through-hole 214 in this example is provided outside the region of the substrate transfer stage 213 connected to the substrate 10 with a step difference. In the film forming apparatus 301, the space in which the stepped substrate 10 is disposed is exhausted through the through-hole 214, whereby wind can be collected.

Fig. 12 is a schematic plan view showing still another example of the film forming apparatus of the present disclosure. The film forming device 302 shown in FIG. 12 is the following device: the film forming device 300 is used as the base, the wind recovery device 30 is omitted, and the through hole 216 is provided on the substrate conveying stage 215 instead, and then used as the substrate 10A with a step difference. Substrate with step difference having through hole 11. The through hole 216 in this example is a through hole in the substrate transfer stage 215 that is conveyed from the outside of the region connected to the stepped substrate 10A to the region connected to the stepped substrate 10A. The through hole 216 has the function of recovering wind and the function of attracting the substrate 10A with a step difference to the substrate transport stage 215 . In the film forming apparatus 302 , the space in which the stepped substrate 10A is arranged is exhausted through the through hole 11 of the stepped substrate 10A itself and the through hole 216 of the substrate transport stage 215 , thereby recovering air.

The film forming apparatus of the present disclosure is provided with two of the aforementioned air blowers, An inkjet nozzle is arranged between the above two air blowers, It is preferable that the relative movement between the substrate with the level difference and the inkjet nozzle is reciprocating. According to this aspect, ink application and wind blowing can be performed in both the forward movement and the backward movement, so the productivity of film formation is excellent.

13A is a schematic plan view showing an example of the film forming apparatus of the present disclosure having two air blowers, FIG. 13B is a side view of FIG. Side view in the opposite direction.

As shown in FIGS. 13A to 13C , the film forming apparatus 400 of this example is based on the film forming apparatus 300. The air blower 28B, the wind recovery machine 30B, and the pinning exposure machine 32B are sequentially arranged and added to the ink jetting direction M11. The one on the upstream side of the shower head 24 . The substrate conveyance stage 212 in the film forming apparatus 400 is movable (that is, reciprocating) in both the conveyance direction M11 (forward stroke) and the conveyance direction M11B (return stroke).

In the formation of the film using the film forming apparatus 400, similarly to the formation of the film using the film forming apparatus 300, the top surface of the stepped substrate 10 that is conveyed in the conveying direction M11 (forward) Ink application from the inkjet head 24 , air blowing from the air blower 28 , and pin exposure by the pin exposure machine 32 are performed sequentially in the region. At this time, recovery of the wind by the wind recovery device 30 is appropriately performed. During this period, none of the air blower 28B, the air recovery unit 30B, and the pinning exposure unit 32B are operated, and are set to an off state. In addition, in the substrate conveying stage 212 in the film forming apparatus 400, the ink from the inkjet head 24 is sequentially applied to the region including the top surface of the stepped substrate 10 conveyed in the conveying direction M11B (return). , the blowing of the wind from the air blower 28B, and the pinning exposure by the pinning exposure machine 32B. At this time, recovery of the wind by the wind recovery device 30B is appropriately performed. During this period, the air blower 28, the air recovery unit 30, and the pinning exposure unit 32 are not in operation, and are set to a closed state.

As an example different from the example shown in FIGS. 13A to 13C , at least one of the positions of the blower 28 and the wind recovery unit 30 and the position of the blower 28B and the wind recovery unit 30B may be replaced. 14A is a schematic top view showing another example of the film forming apparatus of the present disclosure having two air blowers, FIG. 14B is a side view of FIG. 14A , and FIG. 14C is a transfer direction of a substrate with a step difference relative to FIG. 14B. Side view when set to the opposite orientation. According to the film forming apparatus 400A shown in FIG. 14A to FIG. 14C , in the conveying direction M11 (outgoing stroke), the wind recovering device 30 not only recovers the wind from the air blower 28, but also recovers the substrate 10 that has not reached the belt step difference to be separated from the substrate 10. Tiny ink droplets (ink mist) carried by the substrate 10 with a step difference. Furthermore, as in the case of using the film forming apparatus 400 shown in FIGS. 13A to 13C , the blower 28 can form a film in which thickness variation from the side surface to the top surface of the step can be suppressed. In addition, since fine ink droplets can be collected by the air recovery unit 30 , it is possible to suppress scattering of the fine ink droplets by the wind from the air blower 28 . In addition, according to the above-mentioned modified example (film forming apparatus 400A), in the conveying direction M11B (return), the wind recovering device 30B not only recovers the wind from the air blower 28B, but also recovers the substrate 10 that has not reached the belt level difference and is different from the belt level difference. The tiny ink droplets (ink mist) carried by the substrate 10 together. Furthermore, similarly to the example shown in FIGS. 11A to 11C , by the blower 28B, it is possible to form a film capable of suppressing variation in thickness from the side surface of the step to the top surface. In addition, since fine ink droplets can be collected by the air recovery unit 30B, it is possible to suppress the scattering of the fine ink droplets by the wind from the air blower 28B.

The film forming method of the present disclosure and the film forming apparatus of the present disclosure described above can be applied to all applications as a method and an apparatus for forming a film on a substrate with a step difference by an inkjet method. The film formation method of this disclosure and the film formation apparatus of this disclosure can be applied to the manufacturing method of the electronic device of this disclosure mentioned later, for example.

[Manufacturing method of electronic device] The manufacturing method of the disclosed electronic component includes: Preparation of the manufacturing process of the electronic substrate, the aforementioned electronic substrate has a wiring substrate and electronic components arranged on the wiring substrate; and A process for obtaining electronic components by forming at least one of an insulating layer and a conductive layer on an electronic substrate, At least one of the insulating layer and the conductive layer is formed by the aforementioned film forming method of the present disclosure. The manufacturing method of the electronic device disclosed in the present disclosure may also include other processes as required.

The method of manufacturing an electronic device of the present disclosure includes the method of forming a film of the present disclosure described above. Therefore, the method of manufacturing an electronic device of the present disclosure can exhibit the same effects as those based on the method of forming a film of the present disclosure described above. Formation of at least one of the insulating layer and the conductive layer in the manufacturing method of the electronic device of the present disclosure can be performed by the aforementioned film forming apparatus of the present disclosure.

As mentioned above, The electronic substrate (that is, an electronic substrate including a wiring board and electronic components disposed on the wiring board) in the method of manufacturing an electronic component of the present disclosure corresponds to the "substrate with a step difference" in the film forming method of the present disclosure described above. ", The end of the electronic component on the wiring board, the side surface of the end of the electronic component, and the top surface of the electronic component in the method of manufacturing an electronic component of the present disclosure correspond to the “level difference” in the above-mentioned method of forming a film of the present disclosure. , "The side of the step difference" and "The top surface of the step difference".

＜An example of the manufacturing method of electronic components＞ Hereinafter, an example of the manufacturing method of the electronic device of the present disclosure will be described with reference to the drawings. However, the manufacturing method of the electronic device of the present disclosure is not limited to the following example. The manufacturing method of the electronic device disclosed herein includes: An electronic substrate preparation process for preparing an electronic substrate, the aforementioned electronic substrate includes: a wiring substrate having a mounting surface; a plurality of electronic components mounted on the mounting surface of the wiring substrate and a ground electrode, so as to surround at least one of the plurality of electronic components in a plan view Set up for the configuration of 1 electronic component; In the first process, an insulating protective layer covering at least one electronic component is formed in the grounding area surrounded by the grounding electrode; and In the second process, as a cured product of the ink for forming the electromagnetic wave shielding layer, an electromagnetic wave shielding layer that spans over the insulating protective layer and the ground electrode, is covered with the insulating protective layer and is electrically connected to the ground electrode is formed, At least one of the insulating protective layer and the electromagnetic wave shielding layer is formed by the above-mentioned film forming method of the present disclosure.

Here, the insulating protective layer is an example of an insulating layer, and the electromagnetic wave shielding layer is an example of a conductive layer.

15A is a schematic plan view of an electronic substrate prepared in the electronic substrate preparation process, and FIG. 15B is a cross-sectional view taken along line X-X in FIG. 15A. 16A is a schematic plan view of an electronic substrate on which an insulating protective layer is formed as an example of an insulating layer, and FIG. 16B is a cross-sectional view taken along line X-X in FIG. 16A. 17A is a schematic plan view of an electronic substrate (that is, the electronic component of this embodiment) formed with an electromagnetic wave shielding layer as an example of a conductive layer, and FIG. 17B is a cross-sectional view taken along line X-X in FIG. 17A.

-Electronic substrate preparation process- As shown in FIG. 15A and FIG. 15B , in the electronic substrate preparation process in this example, an electronic substrate 110 is prepared. The electronic substrate 110 has a wiring substrate 112 having a mounting surface, and a plurality of The electronic component 118 and the ground electrode 116 provided in an arrangement surrounding the plurality of electronic components 118 in plan view. Although not shown, each of the plurality of electronic components 118 is mounted on the mounting surface of the wiring board 112 via solder balls. There are slight gaps between the wiring board 112 and each of the plurality of electronic components 118 (see the aforementioned FIG. 2 ).

The electronic substrate preparation process may be a process of simply preparing the prefabricated electronic substrate 110 , or may be a process of manufacturing the electronic substrate 110 . As a method of manufacturing the electronic substrate 110 , for example, a known method of manufacturing an electronic substrate in which electronic components are mounted on a printed wiring board can be appropriately referred to.

As the wiring board 112, a board on which wiring is formed, such as a printed wiring board, can be used. The wiring board 112 may also include electrodes other than the ground electrode 116, a solder resist layer, and the like.

The ground electrode 116 is an electrode to which a ground (GND) potential is applied. In this example, the ground electrode 116 is arranged to surround a plurality of electronic components (electronic components 118 ). In other words, a plurality of electronic components (electronic components 118 ) are mounted in ground region 114A surrounded by ground electrode 116 .

As shown in FIG. 15A , the ground electrode 116 in this example is formed as a discontinuous pattern (specifically, a divided line pattern), but the ground electrode in the present disclosure is not limited to this example. For example, the ground electrodes in the present disclosure may be formed as a continuous pattern (ie, an undivided line pattern).

In addition, the ground electrode 116 in this example is formed as a ring-shaped pattern that completely circles around a plurality of electronic components (electronic components 118 ). However, the ground electrode 116 in the present disclosure is not limited to the ring pattern, and may be, for example, a pattern in which at least a part of the ring pattern is missing. From the viewpoint of further reducing the influence of electromagnetic waves from the outside on the plurality of electronic components (electronic component 118), it is preferable that the ground electrode 116 surrounds the area where the plurality of electronic components are arranged by half a circle or more, and surrounds more than 3/4 circle. for better.

Also, as shown in FIG. 15B , the ground electrode 116 in this example is formed to be buried in a part of the thickness direction of the ground electrode 116 with respect to the wiring board 112 , but the ground electrode in the present disclosure is not limited to this example. For example, the ground electrode in the present disclosure may be formed to be buried in the entire thickness direction of the ground electrode. In addition, the ground electrode in the present disclosure may be formed on the surface of the wiring substrate 112 without being buried in the wiring substrate 112 . Also, the ground electrode in the present disclosure may be formed as a pattern penetrating the wiring substrate 112 .

The plurality of electronic components 118 installed in the ground area 114A may be electronic components of the same design, or electronic components of different designs. In addition, the number of electronic components mounted in the ground area is not limited to a plurality, and may be only one. Examples of the electronic component 118 include semiconductor chips such as integrated circuits (IC; Integrated Circuit), capacitors, transistors, and the like.

The height of the electronic component (such as the electronic component 118 ) in this disclosure is preferably greater than 100 μm, more preferably greater than 200 μm, and further preferably greater than 300 μm. The height of the electronic component is preferably at most 2000 μm, more preferably at most 1000 μm.

The height of the ground electrode (such as the ground electrode 116 ) in the present disclosure is preferably greater than −10 μm, more preferably greater than 0 μm, and further preferably greater than 5 μm. The height of the ground electrode is preferably at most 100 μm, more preferably at most 50 μm, further preferably at most 30 μm.

-1st process- As shown in FIGS. 16A and 16B , in the first process, an insulating protective layer 122 covering the plurality of electronic components 118 mounted in the ground region 114A is formed.

The insulating protection layer 122 is formed in the ground area 114A and spans over the plurality of electronic components 118 and the surrounding areas of the plurality of electronic components 118 . The function of the insulating protective layer is, for example, the function of protecting electronic components and the function of inhibiting short circuit between electronic components and other conductive components (such as electromagnetic wave shielding layer).

In the first process of this example, the insulating protective layer 122 can be formed using, for example, an insulating layer forming ink. The ink for forming an insulating layer is, for example, an active energy ray curable ink. The formation of the insulating protective layer 122 can be applied to the above-mentioned film production method of the present disclosure. Thereby, the insulating protective layer 122 which suppresses the thickness variation from the side surface to the top surface of the electronic component 118 can be formed.

-Second process- As shown in FIG. 17A and FIG. 17B , in the second process, at least a part of the insulating protection layer 122 and the ground electrode 116 are formed using the ink for forming the electromagnetic wave shielding layer as the ink for forming the conductive layer and covered with an insulating protection layer. Layer 122 and the electromagnetic wave shielding layer 130 (that is, a conductive layer) are cured products of ink for forming an electromagnetic wave shielding layer that is electrically connected to the ground electrode 116 . Thereby, the electronic component 100 was obtained. The electromagnetic wave shielding layer 130 is formed by applying ink for forming an electromagnetic wave shielding layer into the ground region 114A and curing it. The preferable range of the ink for forming an electromagnetic wave shielding layer and the formation method of an electromagnetic wave shielding layer will be mentioned later.

The electromagnetic wave shielding layer is a layer for reducing the influence of electromagnetic waves on electronic components by shielding electromagnetic waves irradiated to electronic components. In this disclosure, the performance of the electromagnetic wave shielding layer is also referred to as "electromagnetic wave shielding property". The electromagnetic wave shielding property of the electromagnetic wave shielding layer functions when the electromagnetic wave shielding layer is arranged on the electronic component through the insulating protective layer. In addition, the electromagnetic wave shielding property of the electromagnetic wave shielding layer functions by giving a ground (GND) potential to the electromagnetic wave shielding layer. Therefore, as a prerequisite for the electromagnetic wave shielding layer, the electromagnetic wave shielding layer has conductivity.

The formation of the electromagnetic wave shielding layer 130 can also be applied to the above-mentioned manufacturing method of the disclosed film. Thereby, the electromagnetic wave shielding layer 130 which suppresses the thickness variation from the side surface to the top surface of the electronic component 118 can be formed via the insulating protective layer 122 .

Next, comparison of the ink for forming a conductive layer (such as ink for forming an electromagnetic wave shielding layer), the method for forming an electromagnetic wave shielding layer, the ink for forming an insulating layer (for example, ink for forming an insulating protective layer) and the method for forming an insulating protective layer A good example will be explained.

＜Ink for forming conductive layer＞ As inks for forming conductive layers (such as inks for forming electromagnetic wave shielding layers), inks containing metal particles (hereinafter also referred to as "metal particle inks"), inks containing metal complexes (hereinafter also referred to as "metal complexes") Compound inks") or inks containing metal salts (hereinafter, also referred to as "metal salt inks") are preferred, and metal salt inks or metal complex inks are more preferred.

(Metallic Particle Ink) Metal particle ink is, for example, an ink composition in which metal particles are dispersed in a dispersion medium.

-Metal particles- As a metal which comprises a metal particle, the particle|grains of a base metal and a noble metal are mentioned, for example. Examples of base metals include nickel, titanium, cobalt, copper, chromium, manganese, iron, zirconium, tin, tungsten, molybdenum, and vanadium. Examples of noble metals include gold, silver, platinum, palladium, iridium, osmium, ruthenium, rhodium, rhenium, and alloys containing these metals. Among them, it is preferable that the metal constituting the metal particles contains at least one selected from the group consisting of silver, gold, platinum, nickel, palladium, and copper, and more preferably contains silver, from the viewpoint of electromagnetic wave shielding properties.

The average particle size of the metal particles is not particularly limited, but is preferably from 10 nm to 500 nm, more preferably from 10 nm to 200 nm. When the average particle diameter is within the above range, the calcining temperature of the metal particles is lowered, and the process suitability for forming the electromagnetic wave shielding layer is improved. In particular, when the metal particle ink is applied by a spray coating method or an inkjet recording method, there is a tendency to improve dischargeability, pattern formability, and uniformity of film thickness of the electromagnetic wave shielding layer. The average particle diameter referred to here means the average value of the primary particle diameters (average primary particle diameter) of the metal particles.

The average particle size of the metal particles is measured by the laser diffraction/scattering method. The average particle diameter of the metal particles is, for example, a value calculated as the average value of the three measurements of the 50% volume cumulative diameter (D50) measured three times, and a laser diffraction/scattering type particle size distribution measuring device (product name " LA-960", manufactured by HORIBA, Ltd.) for measurement.

In addition, the metal particle ink may contain metal particles having an average particle diameter of 500 nm or more as needed. When metal particles having an average particle diameter of 500 nm or more are contained, the electromagnetic wave shielding layer can be bonded by lowering the melting point of the nm-sized metal particles around the μm-sized metal particles.

In the metal particle ink, the content of the metal particles is preferably 10% by mass to 90% by mass, more preferably 20% by mass to 50% by mass, based on the total amount of the metal particle ink. When the content of the metal particles is 10% by mass or more, the surface resistivity is further reduced. When the content of the metal particles is 90% by mass or less, the discharge property is improved when the metal particle ink is provided using the inkjet recording method.

In addition to the metal particles, the metal particle ink may contain, for example, a dispersant, a resin, a dispersion medium, a thickener, and a surface tension regulator.

-Dispersant- The metal particle ink may contain a dispersant attached to at least a part of the surface of the metal particle. The dispersant substantially constitutes metal colloid particles together with the metal particles. The dispersant has the function of coating the metal particles to improve the dispersibility of the metal particles and prevent aggregation. The dispersant is preferably an organic compound capable of forming metal colloid particles. From the viewpoint of electromagnetic shielding property and dispersion stability, the dispersant is preferably an amine, carboxylic acid, alcohol or resin dispersant.

The dispersant contained in the metal particle ink may be one type, or two or more types.

Examples of the amine include saturated or unsaturated aliphatic amines. Among them, the amine is preferably an aliphatic amine having 4 to 8 carbon atoms. The aliphatic amine having 4 to 8 carbon atoms may be linear or branched, and may have a ring structure.

Examples of aliphatic amines include butylamine, n-pentylamine, isopentylamine, hexylamine, 2-ethylhexylamine, and octylamine.

Examples of the amine having an alicyclic structure include cycloalkylamines such as cyclopentylamine and cyclohexylamine.

Aniline is mentioned as an aromatic amine.

Amines may have functional groups other than amine groups. As a functional group other than an amino group, a hydroxyl group, a carboxyl group, an alkoxy group, a carbonyl group, an ester group, and a mercapto group are mentioned, for example.

Examples of the carboxylic acid include formic acid, oxalic acid, acetic acid, caproic acid, acrylic acid, octanoic acid, oleic acid, thiocyanic acid, ricinoleic acid, gallic acid and salicylic acid. The carboxyl group that is part of the carboxylic acid can form salts with metal ions. The metal ion which forms a salt may be 1 type, and may be 2 or more types.

Carboxylic acids may have functional groups other than carboxyl. As a functional group other than a carboxyl group, an amino group, a hydroxyl group, an alkoxy group, a carbonyl group, an ester group, and a mercapto group are mentioned, for example.

Examples of the alcohol include terpene-based alcohol, allyl alcohol, and oleyl alcohol. Alcohol easily coordinates to the surface of the metal particles and can suppress the aggregation of the metal particles.

As a resin dispersing agent, the dispersing agent which has a nonionic group as a hydrophilic group and can be dissolved uniformly in a solvent is mentioned, for example. Examples of resin dispersants include polyvinylpyrrolidone, polyethylene glycol, polyethylene glycol-polypropylene glycol copolymers, polyvinyl alcohol, polyallylamine, and polyvinyl alcohol-polyvinyl acetate copolymers. . In the molecular weight of the resin dispersant, the weight average molecular weight is preferably 1,000 to 50,000, more preferably 1,000 to 30,000.

In the metal particle ink, the content of the dispersant is preferably 0.5% by mass to 50% by mass, more preferably 1% by mass to 30% by mass, based on the total amount of the metal particle ink.

-Dispersion medium- It is preferable that the metal particle ink contains a dispersion medium. The type of dispersion medium is not particularly limited, and examples thereof include hydrocarbons, alcohols, and water.

The dispersion medium contained in the metal particle ink may be one type, or two or more types. It is preferable that the dispersion medium contained in the metal particle ink is volatile. The boiling point of the dispersion medium is preferably from 50°C to 250°C, more preferably from 70°C to 220°C, and still more preferably from 80°C to 200°C. When the boiling point of the dispersion medium is 50° C. to 250° C., it tends to be possible to achieve both stability and sinterability of the metal particle ink.

Examples of hydrocarbons include aliphatic hydrocarbons and aromatic hydrocarbons.

Examples of aliphatic hydrocarbons include tetradecane, octadecane, heptamethylnonane, tetramethylpentadecane, hexane, heptane, octane, nonane, decane, tridecane, methane Saturated or unsaturated aliphatic hydrocarbons such as pentane, normal alkanes, and isoalkanes.

Examples of aromatic hydrocarbons include toluene and xylene.

As alcohol, aliphatic alcohol and alicyclic alcohol are mentioned. When alcohol is used as the dispersion medium, the dispersant is preferably amine or carboxylic acid.

Examples of aliphatic alcohols include heptanol, octanol (for example, 1-octanol, 2-octanol, 3-octanol, etc.), decyl alcohol (for example, 1-decyl alcohol, etc.), lauryl alcohol, Tetradecyl alcohol, cetyl alcohol, 2-ethyl-1-hexanol, stearyl alcohol, cetyl alcohol, oleyl alcohol, etc. can contain ether bond carbon number 6 in the saturated or unsaturated chain ~20 aliphatic alcohols.

Examples of alicyclic alcohols include cycloalkanols such as cyclohexanol; terpineols (including α, β, γ isomers or any mixture thereof), and terpene alcohols such as dihydroxyterpineol; Dihydroxyterpineol, myrtenol, suberyl alcohol, menthol, carveol, perillyl alcohol, pinocarveol, suberyl alcohol, and verbenol.

The dispersion medium may be water. From the viewpoint of adjusting physical properties such as viscosity, surface tension, and volatility, the dispersion medium may be a mixed solvent of water and other solvents. The other solvent mixed with water is preferably alcohol. The alcohol used in combination with water is preferably an alcohol with a boiling point of 130° C. or lower that can be mixed with water. Examples of the alcohol include 1-propanol, 2-propanol, 1-butanol, 2-butanol, tertiary butanol, 1-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl Ether, Ethylene Glycol Monopropyl Ether and Propylene Glycol Monomethyl Ether.

In the metal particle ink, the content of the dispersion medium is preferably 1% by mass to 50% by mass relative to the total amount of the metal particle ink. If the content of the dispersion medium is 1% by mass to 50% by mass, sufficient conductivity can be obtained as an ink for forming an electromagnetic wave shielding layer. The content of the dispersion medium is more preferably 10% by mass to 45% by mass, and more preferably 20% by mass to 40% by mass.

-resin- Metal particle ink may contain resin. Examples of the resin include polyester, polyurethane, melamine resin, acrylic resin, styrene resin, polyether and terpene resin.

The resin contained in the metal particle ink may be one type, or two or more types.

In the metal particle ink, the resin content is preferably 0.1% by mass to 5% by mass relative to the total amount of the metal particle ink.

-Tackifier- Metal particle inks may contain tackifiers. Examples of thickeners include clay minerals such as clay, bentonite, and lithium bentonite; methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and hydroxypropylmethylcellulose. Cellulose derivatives such as cellulose; and polysaccharides such as xanthan gum and guar gum.

The thickener contained in the metal particle ink may be one type, or two or more types.

In the metal particle ink, the content of the thickener is preferably 0.1% by mass to 5% by mass relative to the total amount of the metal particle ink.

-Surfactant- The metal particle ink may contain a surfactant. When a surfactant is contained in the metal particle ink, it is easy to form a uniform electromagnetic wave shielding layer.

The surfactant may be any of anionic surfactants, cationic surfactants, and nonionic surfactants. Among them, the surfactant is preferably a fluorine-based surfactant from the viewpoint of being able to adjust the surface tension with a small amount of content. Also, the surfactant is preferably a compound having a boiling point exceeding 250°C.

The viscosity of the metal particle ink is not particularly limited, and may be 0.01Pa･s to 5000Pa･s, preferably 0.1Pa･s to 100Pa･s. In the case of applying metal particle ink by spraying method or inkjet recording method, the viscosity of metal particle ink is preferably 1mPa･s～100mPa･s, more preferably 2mPa･s～50mPa･s, 3mPa･s～30mPa ･s is more preferable.

The viscosity of the metal particle ink is a value measured at 25° C. using a viscometer. The viscosity is measured using, for example, a VISCOMETER TV-22 viscometer (manufactured by TOKI SANGYO CO., LTD.).

The surface tension of the metal particle ink is not particularly limited, but is preferably 20 mN/m to 45 mN/m, more preferably 25 mN/m to 40 mN/m. The surface tension is a value measured at 25° C. using a surface tensiometer.

The surface tension of the metal particle ink is measured using, for example, DY-700 (manufactured by Kyowa Interface Science Co., Ltd.).

-Manufacturing method of metal particles- Metal particles may be commercially available or may be produced by a known method. As a manufacturing method of a metal particle, a wet reduction method, a gas phase method, and a plasma method are mentioned, for example. A preferable method for producing metal particles is a wet reduction method capable of producing metal particles with an average particle diameter of 200 nm or less such that the particle diameter distribution is narrowed. The production method of metal particles based on the wet reduction method includes, for example, a method including the following process: a mixed metal salt and a reducing agent described in Japanese Patent Laid-Open No. 2017-37761, International Publication No. 2014-57633, etc. combining the reaction solution and heating the complexing reaction solution to reduce metal ions in the complexing reaction solution to obtain a slurry of metal nanoparticles.

In producing the metal particle ink, heat treatment may be performed in order to adjust the content of each component contained in the metal particle ink within a predetermined range. The heat treatment may be performed under reduced pressure or under normal pressure. Moreover, when carrying out under normal pressure, it may carry out in air|atmosphere, and may carry out in an inert gas atmosphere.

(metal complex ink) The metal complex ink is, for example, an ink composition in which a metal complex is dissolved in a solvent.

-Metal complexes- Examples of the metal constituting the metal complex include silver, copper, gold, aluminum, magnesium, tungsten, molybdenum, zinc, nickel, iron, platinum, tin, copper and lead. Among them, from the viewpoint of electromagnetic shielding properties, it is preferable that the metal constituting the metal complex contains at least one selected from the group consisting of silver, gold, platinum, nickel, palladium, and copper, and it is more preferable that it contains silver.

The content of the metal contained in the metal complex ink is preferably 1% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, based on the total amount of the metal complex ink, in terms of metal elements. 7 mass % - 20 mass % are still more preferable.

A metal complex is obtained, for example, by reacting a metal salt with a complexing agent. As a method for producing a metal complex, for example, a method of adding a metal salt and a complexing agent to an organic solvent and stirring for a predetermined time is mentioned. The stirring method is not particularly limited, and can be appropriately selected from known methods such as a method of stirring using a stirrer, a stirring blade, or a mixer, and a method of applying ultrasonic waves.

Examples of metal salts include metal oxides, thiocitrates, sulfides, chlorides, cyanides, cyanates, carbonates, acetates, nitrates, nitrites, sulfates, phosphates, peroxides, Chlorates, tetrafluoroborates, acetylacetonate complex salts and carboxylates.

Examples of complexing agents include amines, ammonium carbamate-based compounds, ammonium carbonate-based compounds, ammonium bicarbonate compounds, and carboxylic acids. Among them, from the viewpoint of electromagnetic wave shielding properties and the stability of the metal complex, the complexing agent is selected from the group consisting of ammonium carbamate compounds, ammonium carbonate compounds, amines, and carboxylic acids with 8 to 20 carbon atoms. At least one of them is preferred.

The metal complex has a structure derived from a complexing agent and has a structure derived from at least one selected from the group consisting of ammonium carbamate compounds, ammonium carbonate compounds, amines, and carboxylic acids with 8 to 20 carbon atoms Metal complexes are preferred.

Examples of the amine of the complexing agent include ammonia, primary amines, secondary amines, tertiary amines, and polyamines.

Examples of primary amines having a linear alkyl group include methylamine, ethylamine, 1-propylamine, n-butylamine, n-pentylamine, n-hexylamine, heptylamine, and octylamine. , nonylamine, n-decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine and octadecylamine.

Examples of the primary amine having a branched alkyl group include isopropylamine, secondary butylamine, tertiary butylamine, isopentylamine, 2-ethylhexylamine, and tertiary octylamine.

As a primary amine which has an alicyclic structure, cyclohexylamine and dicyclohexylamine are mentioned, for example.

Examples of primary amines having a hydroxyalkyl group include ethanolamine, diethanolamine, triethanolamine, N-methylethanolamine, propanolamine, isopropanolamine, dipropanolamine, diisopropanolamine, and tripranolamine. amine and triisopropanolamine.

Examples of primary amines having an aromatic ring include benzylamine, N,N-dimethylbenzylamine, phenylamine, diphenylamine, triphenylamine, aniline, N,N-dimethylaniline, N, N-dimethyl-p-toluidine, 4-aminopyridine and 4-dimethylaminopyridine.

Examples of secondary amines include dimethylamine, diethylamine, dipropylamine, dibutylamine, diphenylamine, dicyclopentylamine and methylbutylamine.

Examples of tertiary amines include trimethylamine, triethylamine, tripropylamine and triphenylamine.

Examples of polyamines include ethylenediamine, 1,3-diaminopropane, diethylenetriamine, triethylenetetramine, tetramethylenepentamine, hexamethylenediamine, tetraethylene Pentamines and combinations thereof.

The amine is preferably an alkylamine, more preferably an alkylamine having 3 to 10 carbon atoms, and even more preferably a primary alkylamine having 4 to 10 carbon atoms.

The amines constituting the metal complex may be one type, or two or more types.

When reacting the metal salt and the amine, the ratio of the molar amount of the amine to the molar amount of the metal salt is preferably 1 to 15 times, more preferably 1.5 to 6 times. When the above-mentioned ratio is within the above-mentioned range, the complex formation reaction is completed and a transparent solution is obtained.

Ammonium carbamate-based compounds as complexing agents include ammonium carbamate, methylammonium methyl carbamate, ethylammonium ethyl carbamate, 1-propylammonium 1-propyl Urethane, Isopropyl Ammonium Isopropyl Urethane, Butyl Ammonium Butyl Urethane, Isobutyl Ammonium Isobutyl Urethane, Amyl Ammonium Amyl Amino Formate, Hexylammonium Hexyl Carbamate, Heptyl Ammonium Heptyl Carbamate, Octyl Ammonium Octyl Carbamate, 2-Ethylhexyl Ammonium 2-Ethylhexyl Carbamate ester, nonyl ammonium nonyl carbamate, and decyl ammonium decyl carbamate.

Ammonium carbonate-based compounds as complexing agents include ammonium carbonate, methylammonium carbonate, ethylammonium carbonate, 1-propylammonium carbonate, isopropylammonium carbonate, butylammonium carbonate, isobutylammonium carbonate, Ammonium carbonate, pentylammonium carbonate, hexylammonium carbonate, heptylammonium carbonate, octylammonium carbonate, 2-ethylhexylammonium carbonate, nonylammonium carbonate, and decylammonium carbonate.

Ammonium bicarbonate-based compounds as complexing agents include ammonium bicarbonate, methylammonium bicarbonate, ethylammonium bicarbonate, 1-propylammonium bicarbonate, isopropylammonium bicarbonate, Butylammonium bicarbonate, Isobutylammonium bicarbonate, Amylammonium bicarbonate, Hexylammonium bicarbonate, Heptylammonium bicarbonate, Octylammonium bicarbonate, 2-Ethylhexylammonium bicarbonate Salt, nonyl ammonium bicarbonate and decyl ammonium bicarbonate.

When the metal salt is reacted with an ammonium carbamate compound, ammonium carbonate compound or ammonium bicarbonate compound, the molar amount of the ammonium carbamate compound, ammonium carbonate compound or ammonium bicarbonate relative to the metal salt The molar ratio of the hydrogen salt-based compound is preferably 0.01 to 1, more preferably 0.05 to 0.6.

Examples of carboxylic acids that are complexing agents include caproic acid, octanoic acid, nonanoic acid, 2-ethylhexanoic acid, capric acid, neodecanoic acid, undecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid Acid, Hexadecenoic Acid, Oleic Acid, Linoleic Acid and Linolenic Acid. Among them, the carboxylic acid is preferably a carboxylic acid having 8 to 20 carbon atoms, and more preferably a carboxylic acid having 10 to 16 carbon atoms.

In the metal complex ink, the content of the metal complex is preferably 10% by mass to 90% by mass, more preferably 10% by mass to 40% by mass, based on the total amount of the metal complex ink. When the content of the metal complex is 10% by mass or more, the surface resistivity will further decrease. When the content of the metal complex is 90% by mass or less, the discharge property will be improved when the metal particle ink is provided using the inkjet recording method.

-Solvent- It is preferable that the metal complex ink contains a solvent. The solvent is not particularly limited as long as it can dissolve components contained in the metal complex ink such as the metal complex. From the viewpoint of ease of manufacture, the boiling point of the solvent is preferably from 30°C to 300°C, more preferably from 50°C to 200°C, and more preferably from 50°C to 150°C.

In the metal complex ink, the content of the solvent is 0.01mmol/g to 3.6mmol/g relative to the concentration of the metal ion of the metal complex (the amount of metal that exists as a free ion relative to 1g of the metal complex) Preferably, 0.05mmol/g～2mmol/g is more preferred. When the concentration of the metal ions is within the above range, the metal complex ink has excellent fluidity and can obtain electromagnetic wave shielding properties.

Examples of solvents include hydrocarbons, cyclic hydrocarbons, aromatic hydrocarbons, urethanes, olefins, amides, ethers, esters, alcohols, mercaptans, thioethers, phosphines, and water. The solvent contained in the metal complex ink may be only one type, or may be two or more types.

The hydrocarbon is preferably a linear or branched hydrocarbon having 6 to 20 carbon atoms. Examples of hydrocarbons include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, Octane, nonadecane and eicosane.

The cyclic hydrocarbon is preferably a cyclic hydrocarbon having 6 to 20 carbon atoms. As cyclic hydrocarbons, for example, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, and decahydronaphthalene can be contained.

Examples of aromatic hydrocarbons include benzene, toluene, xylene and tetralin.

The ether may be any of linear ethers, branched ethers, and cyclic ethers. Examples of ethers include diethyl ether, dipropyl ether, dibutyl ether, methyl-tertiary butyl ether, tetrahydrofuran, tetrahydropyran, dihydroxypyran, and 1,4-dioxane.

Alcohol may be any one of primary alcohol, secondary alcohol and tertiary alcohol.

Examples of the alcohol include ethanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-octanol, 2-octanol, 3-octanol, tetrahydrofurfuryl alcohol, cyclopentanol, terpineol, decanol, Isodecyl Alcohol, Lauryl Alcohol, Isolauryl Alcohol, Myristyl Alcohol, Isomyristyl Alcohol, Cetyl Alcohol (Cetanol), Isocetyl Alcohol, Stearyl Alcohol, Isostearyl Alcohol, Oleyl Alcohol, Isostearyl Alcohol Alcohol, Linolenyl Alcohol, Isolinalyl Alcohol, Palmityl Alcohol, Isopalmityl Alcohol, Eicosyl Alcohol and Iso-Eicosyl Alcohol.

As a ketone, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are mentioned, for example.

Examples of esters include methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, secondary butyl acetate, methoxybutyl acetate, ethylene glycol monomethyl ether acetic acid Ester, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol Alcohol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether Acetate, Dipropylene Glycol Monobutyl Ether Acetate and 3-Methoxybutyl Acetate.

-reducing agent- Metal complex inks may contain reducing agents. When the metal complex ink contains a reducing agent, the reduction from the metal complex to metal is promoted.

Examples of reducing agents include boron hydride metal salts, aluminum hydride salts, amines, alcohols, organic acids, reducing sugars, sugar alcohols, sodium sulfite, hydrazine compounds, dextrin, hydroquinone, hydroxylamine, ethylene glycol, glutathione Peptides and oxime compounds.

The reducing agent may be an oxime compound described in JP 2014-516463 A. Examples of oxime compounds include acetone oxime, cyclohexanone oxime, 2-butanone oxime, 2,3-butanedione monoxime, dimethylglyoxaldioxime, methylacetyloxyacetic acid Ester monoxime, methylpyruvate monoxime, benzaldehyde oxime, 1-indanone oxime, 2-adamantanone oxime, 2-methylbenzylamine oxime, 3-methylbenzylamide oxime, 4-methylbenzylamine oxime Benzylamide oxime, 3-aminobenzylamide oxime, 4-aminobenzylamide oxime, acetophenone oxime, benzylamide oxime and tertiary butyl acetophenone oxime.

The reducing agent contained in the metal complex ink may be one type, or two or more types.

In the metal complex ink, the content of the reducing agent is not particularly limited, but it is preferably 0.1% by mass to 20% by mass, more preferably 0.3% by mass to 10% by mass, relative to the total amount of the metal complex ink, 1% by mass to 5% by mass is further more preferable.

-resin- The metal complex ink may contain a resin. When a resin is contained in the metal complex ink, the adhesion between the metal complex ink and the base material is improved.

Examples of the resin include polyester, polyethylene, polypropylene, polyacetal, polyolefin, polycarbonate, polyamide, fluororesin, silicone resin, ethyl cellulose, hydroxyethyl cellulose, rosin , acrylic resin, polyvinyl chloride, polysulfone, polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl-based resin, polyacrylonitrile, polysulfide, polyamideimide, polyether, polyarylate, poly Ether ether ketone, polyurethane, epoxy resin, vinyl ester resin, phenolic resin, melamine resin and urea resin.

The resin contained in the metal complex ink may be one type, or two or more types.

-additive- Metal complex inks may also contain inorganic oxides such as inorganic salts, organic salts, and silicon dioxide; surface regulators, wetting agents, crosslinking agents, antioxidants, rust inhibitors, Heat-resistant stabilizers, surfactants, plasticizers, hardeners, tackifiers, silane coupling agents and other additives. In the metal complex ink, the total content of the additives is preferably 20% by mass or less with respect to the total amount of the metal complex ink.

The viscosity of the metal complex ink is not particularly limited, and may be 0.01Pa･s to 5000Pa･s, preferably 0.1Pa･s to 100Pa･s. In the case of applying the metal complex ink by spraying method or inkjet recording method, the viscosity of the metal complex ink is preferably 1mPa･s～100mPa･s, more preferably 2mPa･s～50mPa･s, and 3mPa ･s～30mPa･s is more preferable.

The viscosity of the metal complex ink is a value measured at 25° C. using a viscometer. The viscosity is measured using, for example, a VISCOMETER TV-22 viscometer (manufactured by TOKI SANGYO CO., LTD.).

The surface tension of the metal complex ink is not particularly limited, but is preferably 20 mN/m to 45 mN/m, more preferably 25 mN/m to 35 mN/m. The surface tension is a value measured at 25° C. using a surface tensiometer.

The surface tension of the metal complex ink is measured using, for example, DY-700 (manufactured by Kyowa Interface Science Co., Ltd.).

(metal salt ink) The metal salt ink is, for example, an ink composition in which a metal salt is dissolved in a solvent.

-Metal salt- Examples of the metal constituting the metal salt include silver, copper, gold, aluminum, magnesium, tungsten, molybdenum, zinc, nickel, iron, platinum, tin, copper and lead. Among them, it is preferable that the metal constituting the metal salt contains at least one selected from the group consisting of silver, gold, platinum, nickel, palladium, and copper, and more preferably contains silver, from the viewpoint of electromagnetic shielding properties.

The content of the metal contained in the metal salt ink is preferably 1% by mass to 40% by mass, more preferably 5% by mass to 30% by mass, and 7% by mass to the total amount of the metal salt ink, in terms of metal elements. 20 mass % is more preferable.

In the metal salt ink, the content of the metal salt is preferably 10% by mass to 90% by mass, more preferably 10% by mass to 40% by mass, based on the total amount of the metal salt ink. When the content of the metal salt is 10% by mass or more, the surface resistivity is further reduced. When the content of the metal salt is 90% by mass or less, the discharge property is improved when the metal particle ink is applied by a spray coating method or an inkjet recording method.

Examples of metal salts include metal benzoate, halide, carbonate, citrate, iodate, nitrite, nitrate, acetate, phosphate, sulfate, sulfide, trifluoro Acetates and carboxylates. In addition, salt can combine 2 or more types.

From the viewpoint of electromagnetic shielding properties and storage stability, the metal salt is preferably a metal carboxylate. The carboxylic acid forming the carboxylate is preferably at least one selected from the group consisting of formic acid and carboxylic acids with 1 to 30 carbons, more preferably carboxylic acids with 8 to 20 carbons, and 8 to 20 carbons The fatty acid is further preferred. The fatty acid may be linear or branched, and may have a substituent.

Examples of straight-chain fatty acids include acetic acid, propionic acid, butyric acid, valeric acid, pentanoic acid, hexanoic acid, heptanoic acid, behenic acid, Oleic Acid, Octanoic Acid, Nonanoic Acid, Decanoic Acid, Caproic Acid, Enanthic Acid, Caprylic Acid, Pelargonic Acid, Capric acid and undecanoic acid.

Examples of branched fatty acids include isobutyric acid, isovaleric acid, ethylhexanoic acid, neodecanoic acid, pivalic acid, 2-methylpentanoic acid, 3-methylpentanoic acid, and 4-methylpentanoic acid. , 2,2-dimethyl butyric acid, 2,3-dimethyl butyric acid, 3,3-dimethyl butyric acid and 2-ethyl butyric acid.

Examples of carboxylic acids having substituents include hexafluoroacetylpyruvate, hydroangelic acid, 3-hydroxybutyrate, 2-methyl-3-hydroxybutyrate, 3-methoxybutyrate, acetone Dicarboxylic acid, 3-hydroxyglutaric acid, 2-methyl-3-hydroxyglutaric acid and 2,2,4,4-hydroxyglutaric acid.

The metal salt may be a commercial item or may be produced by a known method. Silver salt is produced by the following method, for example.

First, a silver compound (for example, silver acetate) serving as a silver supply source and formic acid or a fatty acid having 1 to 30 carbon atoms in an amount equivalent to the molar equivalent of the silver compound are added to an organic solvent such as ethanol. Use an ultrasonic mixer to stir for a specified time, wash with ethanol and decant the resulting precipitate. These processes can all be carried out at room temperature (25°C). The mixing ratio of the silver compound to formic acid or the fatty acid having 1 to 30 carbon atoms is preferably 1:2 to 2:1, more preferably 1:1, in terms of molar ratio.

-Solvent- It is preferable that the metal salt ink contains a solvent. The type of solvent is not particularly limited as long as it can dissolve the metal salt contained in the metal salt ink. From the viewpoint of ease of manufacture, the boiling point of the solvent is preferably from 30°C to 300°C, more preferably from 50°C to 300°C, and more preferably from 50°C to 250°C.

In the metal salt ink, the content of the solvent relative to the concentration of the metal ion of the metal salt (relative to the amount of metal present as free ions in 1 g of the metal salt) is preferably 0.01mmol/g to 3.6mmol/g, and 0.05mmol/g g～2.6mmol/g is more preferable. When the concentration of the metal ion is within the above range, the metal salt ink has excellent fluidity and can obtain electromagnetic wave shielding properties.

Examples of solvents include hydrocarbons, cyclic hydrocarbons, aromatic hydrocarbons, urethanes, olefins, amides, ethers, esters, alcohols, mercaptans, thioethers, phosphines, and water. The solvent contained in the metal salt ink may be only one kind, or may be two or more kinds.

The solvent preferably contains aromatic hydrocarbons. Examples of aromatic hydrocarbons include benzene, toluene, xylene, ethylbenzene, propylbenzene, cumene, butylbenzene, isobutylbenzene, tertiary butylbenzene, trimethylbenzene, pentylbenzene, Benzene, Hexylbenzene, Tetralin, Benzyl Alcohol, Phenol, Cresol, Methyl Benzoate, Ethyl Benzoate, Propyl Benzoate and Butyl Benzoate. From the viewpoint of compatibility with other components, the number of aromatic rings in the aromatic hydrocarbon is preferably 1 or 2, more preferably 1. From the viewpoint of ease of production, the boiling point of the aromatic hydrocarbon is preferably from 50°C to 300°C, more preferably from 60°C to 250°C, and more preferably from 80°C to 200°C.

The solvent may contain aromatic hydrocarbons and hydrocarbons other than aromatic hydrocarbons. Examples of hydrocarbons other than aromatic hydrocarbons include straight-chain hydrocarbons having 6 to 20 carbon atoms, branched-chain hydrocarbons having 6 to 20 carbon atoms, and alicyclic hydrocarbons having 6 to 20 carbon atoms. Examples of hydrocarbons other than aromatic hydrocarbons include pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane , hexadecane, octadecane, nonadecane, decahydronaphthalene, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, decene, terpene compounds and eicosane. Hydrocarbons other than aromatic hydrocarbons preferably contain unsaturated bonds. Examples of hydrocarbons other than unsaturated bond-containing aromatic hydrocarbons include terpene compounds. Terpene compounds can be classified into semiterpene, monoterpene, sesquiterpene, diterpene, sesterterpene, triterpene, etc. according to the number of isoprene units constituting the terpene compound. Terpenes, sesquarterpenes, and tetraterpenes. The terpene-based compound used as the solvent may be any of the above, but monoterpene is preferred. Examples of monoterpenes include pinene (α-pinene, β-pinene), terpineol (α-terpineol, β-terpineol, γ-terpineol), myrcene, Limonene, limonene (d-limonene, l-limonene, dipentene), radiphenene (α-radiphenene, β-radiphenene), alleroradine, phellandrene (α-phellandrene, β-phellandrene), terpinene (α-terpinene, γ-terpinene), terpinolene (α-terpinolene, β-terpinolene, γ-terpinolene, delta-terpinolene), 1,8-cineole, 1,4-cineole, sabinene, p-diene, carene (delta-3-carene). The monoterpene is preferably a cyclic monoterpene, more preferably pinene, terpineol or carene.

The ether may be any of linear ethers, branched ethers, and cyclic ethers. Examples of ethers include diethyl ether, dipropyl ether, dibutyl ether, methyl-tertiary butyl ether, tetrahydrofuran, tetrahydropyran, dihydroxypyran, and 1,4-dioxane.

Alcohol may be any one of primary alcohol, secondary alcohol and tertiary alcohol.

Examples of the alcohol include ethanol, 1-propanol, 2-propanol, 1-methoxy-2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-octanol, 2-octanol, 3-octanol, tetrahydrofurfuryl alcohol, cyclopentanol, terpineol, decanol, Isodecyl Alcohol, Lauryl Alcohol, Isolauryl Alcohol, Myristyl Alcohol, Isomyristyl Alcohol, Cetyl Alcohol (Cetanol), Isocetyl Alcohol, Stearyl Alcohol, Isostearyl Alcohol, Oleyl Alcohol, Isostearyl Alcohol Alcohol, Linolenyl Alcohol, Isolinalyl Alcohol, Palmityl Alcohol, Isopalmityl Alcohol, Eicosyl Alcohol and Iso-Eicosyl Alcohol.

As a ketone, acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone are mentioned, for example.

Examples of esters include methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, secondary butyl acetate, methoxybutyl acetate, ethylene glycol monomethyl ether acetic acid Ester, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol Alcohol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether Acetate, Dipropylene Glycol Monobutyl Ether Acetate and 3-Methoxybutyl Acetate.

The viscosity of the metal salt ink is not particularly limited, and may be 0.01Pa･s to 5000Pa･s, preferably 0.1Pa･s to 100Pa･s. In the case of applying metal salt ink by spraying method or inkjet recording method, the viscosity of metal salt ink is preferably 1mPa･s～100mPa･s, more preferably 2mPa･s～50mPa･s, 3mPa･s～30mPa ･s is more preferable.

The viscosity of the metal salt ink is a value measured at 25°C using a viscometer. The viscosity is measured using, for example, a VISCOMETER TV-22 viscometer (manufactured by TOKI SANGYO CO., LTD.).

The surface tension of the metal salt ink is not particularly limited, but is preferably 20 mN/m to 45 mN/m, more preferably 25 mN/m to 35 mN/m. The surface tension is a value measured at 25° C. using a surface tensiometer.

The surface tension of the metal salt ink is measured, for example, using DY-700 (manufactured by Kyowa Interface Science Co., Ltd.).

The ink for forming an electromagnetic wave shielding layer preferably contains a metal complex or a metal salt. The metal complex is a metal complex having a structure derived from at least one selected from the group consisting of ammonium carbamate compounds, ammonium carbonate compounds, amines, and carboxylic acids with 8 to 20 carbon atoms. good. The metal salt is preferably a metal carboxylate.

<Formation method of electromagnetic wave shielding layer> In the second process, the electromagnetic wave shielding layer forming ink is applied to the ground area on the electronic substrate, the electromagnetic wave shielding layer forming ink applied on the top surface of the electronic component is blown with air, and the electromagnetic wave shielding layer is formed by blowing air It is preferable to form the electromagnetic wave shielding layer by heating the ink (for example, calcination described later) and/or curing it by ultraviolet irradiation.

Ultraviolet radiation to cure inks as described herein is sometimes referred to in this disclosure as "the present exposure."

In the second process, separately from the opportunistic heating and/or the curing of the present exposure, the aforementioned pinning can be implemented in at least one of the time sequences before and after the wind blowing of the ink on the top surface of the electronic part exposure.

(Applying method of ink for forming electromagnetic wave shielding layer) As a method of applying the ink for forming an electromagnetic wave shielding layer, an inkjet recording method, a dispenser method, or a spraying method is preferable, and an inkjet recording method is particularly preferable. The preferred aspect of the inkjet recording method is as described in the section of "film formation process".

The temperature of the electronic substrate when applying the ink for forming an electromagnetic wave shielding layer is preferably 20°C to 120°C, more preferably 28°C to 80°C.

From the viewpoint of electromagnetic wave shielding properties, the thickness of the entire electromagnetic wave shielding layer is preferably 0.1 μm to 30 μm, more preferably 0.3 μm to 15 μm.

The thickness of the entire electromagnetic shielding layer was measured using a laser microscope (product name "VK-X1000", manufactured by KEYENCE Corporation).

The average thickness per layer of the electromagnetic wave shielding layer is obtained by dividing the thickness of the entire electromagnetic wave shielding layer by the number of times the electromagnetic wave shielding layer is formed (that is, the number of times the ink for forming the electromagnetic wave shielding layer is applied).

In the second process, the average thickness per layer of the electromagnetic wave shielding layer is preferably 1.5 μm or less, more preferably 1.2 μm or less.

When the average thickness per layer of an electromagnetic wave shielding layer is 1.5 micrometers or less, electromagnetic wave shielding property will improve further.

(calcination process) The second process may include a firing process of forming the electromagnetic wave shielding layer by firing the electromagnetic wave shielding layer forming ink applied on the electronic substrate to cure the electromagnetic wave shielding layer forming ink.

The calcination temperature is preferably 250°C or lower, more preferably 50°C to 200°C, and even more preferably 60°C to 180°C. Also, the calcination time is preferably 1 minute to 120 minutes, more preferably 1 minute to 40 minutes. If the calcination temperature and calcination time are within the above-mentioned ranges, the influence of deformation of the base material due to heat, etc. can be reduced.

＜Inks for Insulation Layer Formation＞ The ink for forming an insulating layer (for example, the ink for forming an insulating protective layer) is preferably an active energy ray curable ink. The ink for forming an insulating layer as an active energy ray curable ink preferably contains a polymerizable monomer and a polymerization initiator.

(polymerizable monomer) The polymerizable monomer system refers to a monomer having at least one polymerizable group in one molecule. The polymerizable group in the polymerizable monomer may be a cation polymerizable group or a radical polymerizable group, but it is preferably a radical polymerizable group from the viewpoint of curability. Also, from the viewpoint of curability, it is preferable that the radical polymerizable group is an ethylenically unsaturated group.

In this disclosure, a monomer refers to a compound with a molecular weight of 1000 or less. The molecular weight can be calculated from the types and numbers of atoms constituting the compound.

The polymerizable monomer may be a monofunctional polymerizable monomer having one polymerizable group, or may be a polyfunctional polymerizable monomer having two or more polymerizable groups.

The monofunctional polymerizable monomer is not particularly limited as long as it has one polymerizable group. From the viewpoint of curability, the monofunctional polymerizable monomer is preferably a monofunctional radical polymerizable monomer, more preferably a monofunctional ethylenically unsaturated monomer.

Examples of monofunctional ethylenically unsaturated monomers include monofunctional (meth)acrylates, monofunctional (meth)acrylamides, monofunctional aromatic vinyl compounds, monofunctional vinyl ethers, and monofunctional N- vinyl compound.

Examples of monofunctional (meth)acrylates include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, (meth)acrylate ) hexyl acrylate, 2-ethylhexyl (meth) acrylate, tertiary octyl (meth) acrylate, isoamyl (meth) acrylate, decyl (meth) acrylate, iso(meth) acrylate Decyl ester, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, cyclohexyl (meth)acrylate, 4-n-butyl (meth)acrylate Cyclohexyl (meth)acrylate, 4-tertiary butylcyclohexyl (meth)acrylate, camphenyl (meth)acrylate, isocamphoryl (meth)acrylate, 2-ethylhexyl diacrylate (meth)acrylate Glycol esters, butoxyethyl (meth)acrylate, 2-chloroethyl (meth)acrylate, 4-bromobutyl (meth)acrylate, cyanoethyl (meth)acrylate, (meth)acrylate base) benzyl acrylate, butoxymethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-(2-methoxyethoxy)ethyl (meth)acrylate, 2-(2-Butoxyethoxy)ethyl (meth)acrylate, 2,2,2-tetrafluoroethyl (meth)acrylate, 1H,1H,2H,2H-peroxide (meth)acrylate Fluorodecanyl, 4-butylphenyl (meth)acrylate, phenyl (meth)acrylate, 2,4,5-tetramethylphenyl (meth)acrylate, 4-chlorobenzene (meth)acrylate ester, 2-phenoxymethyl (meth)acrylate, 2-phenoxyethyl (meth)acrylate, glycidyl (meth)acrylate, glycidoxybutyl (meth)acrylate , Glycidoxyethyl (meth)acrylate, Glycidoxypropyl (meth)acrylate, Tetrahydrofurfuryl (meth)acrylate, 2-Hydroxyethyl (meth)acrylate, (meth) base) 3-hydroxypropyl acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxy (meth)acrylate Butyl ester, cyclic trimethylolpropane formal (meth)acrylate, phenylglycidyl ether (meth)acrylate, dimethylaminoethyl (meth)acrylate, (meth) Diethylaminoethyl acrylate, Dimethylaminopropyl (meth)acrylate, Diethylaminopropyl (meth)acrylate, Trimethoxyallylpropyl (meth)acrylate, ( Trimethylsilylpropyl methacrylate, polyethylene oxide monomethyl ether (meth)acrylate, polyethylene oxide (meth)acrylate, polyethylene oxide (meth)acrylate Monoalkyl ether ester, Dipropylene glycol (meth)acrylate, Polypropylene oxide monoalkyl ether (meth)acrylate, 2-Methacryloxyethylsuccinate, 2-Methacrylic acid Acyloxyhexahydrophthalate, 2-methacryloxyethyl-2-hydroxypropylphthalate, ethoxydiethylene glycol (meth)acrylate, ( Butoxydiethylene glycol methacrylate, trifluoroethyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate Ester, ethylene oxide (EO) modified phenol (meth)acrylate, EO modified cresol (meth)acrylate, EO modified nonylphenol (meth)acrylate, propylene oxide (PO) Modified nonylphenol (meth)acrylate, (meth)acrylate EO modified-2-ethylhexyl, dicyclopentenyl (meth)acrylate, (meth)acrylate dicyclopentenyl oxide ethyl ethyl ester, dicyclopentyl (meth)acrylate, (3-ethyl-3-oxetanylmethyl)(meth)acrylate, phenoxyethylene glycol (meth)acrylate, (meth)acrylate base) 2-carboxyethyl acrylate and 2-(meth)acryloxyethyl succinate.

Among them, from the viewpoint of improving heat resistance, the monofunctional (meth)acrylate is preferably a monofunctional (meth)acrylate having an aromatic ring or an aliphatic ring, and isocamphoryl (meth)acrylate, ( 4-tertiary butylcyclohexyl meth)acrylate, dicyclopentenyl (meth)acrylate, or dicyclopentyl (meth)acrylate are more preferable.

Examples of monofunctional (meth)acrylamide include (meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl N-butyl(meth)acrylamide, N-butyl(meth)acrylamide, N-tertiary butyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide , N-isopropyl(meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl( Meth)acrylamide and (meth)acryloylpermaline.

Examples of monofunctional aromatic vinyl compounds include styrene, dimethylstyrene, trimethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxy Styrene, chlorostyrene, dichlorostyrene, bromostyrene, methyl vinyl benzoate, 3-methylstyrene, 4-methylstyrene, 3-ethylstyrene, 4-ethylstyrene , 3-propylstyrene, 4-propylstyrene, 3-butylstyrene, 4-butylstyrene, 3-hexylstyrene, 4-hexylstyrene, 3-octylstyrene, 4- Octylstyrene, 3-(2-ethylhexyl)styrene, 4-(2-ethylhexyl)styrene, allylstyrene, isopropenylstyrene, butylenestyrene, octenylbenzene Ethylene, 4-tertiary butoxycarbonylstyrene and 4-tertiary butoxystyrene.

Examples of monofunctional vinyl ethers include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, tertiary butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonylethylene ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4-methylcyclohexyl methyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentyl ethyl ether Base vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, Methoxypolyethylene glycol vinyl ether, tetrahydrofurfuryl vinyl ether, 2-hydroxyethyl vinyl ether, 2-hydroxypropyl vinyl ether, 4-hydroxybutyl vinyl ether, 4-hydroxymethylcyclohexylmethylethylene ether, diethylene glycol monovinyl ether, polyethylene glycol vinyl ether, chloroethyl vinyl ether, chlorobutyl vinyl ether, chloroethoxyethyl vinyl ether, phenylethyl vinyl ether and phenoxy polyethylene Glycol vinyl ether.

Examples of monofunctional N-vinyl compounds include N-vinyl-ε-caprolactam and N-vinylpyrrolidone.

The polyfunctional polymerizable monomer is not particularly limited as long as it is a monomer having two or more polymerizable groups. From the viewpoint of curability, the polyfunctional polymerizable monomer is preferably a polyfunctional radical polymerizable monomer, more preferably a polyfunctional ethylenically unsaturated monomer.

Examples of polyfunctional ethylenically unsaturated monomers include polyfunctional (meth)acrylate compounds and polyfunctional vinyl ethers.

Examples of polyfunctional (meth)acrylates include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, poly Ethylene Glycol Di(meth)acrylate, Propylene Glycol Di(meth)acrylate, Dipropylene Glycol Di(meth)acrylate, Tripropylene Glycol Di(meth)acrylate, Polypropylene Glycol Di(meth)acrylate, Butanediol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di( Meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, heptanediol di(meth)acrylate, EO modification Neopentyl glycol di(meth)acrylate, PO modified neopentyl glycol di(meth)acrylate, EO modified hexanediol di(meth)acrylate, PO modified hexanediol di(meth)acrylate Meth)acrylate, Octanediol Di(meth)acrylate, Nonanediol Di(meth)acrylate, Decanediol Di(meth)acrylate, Dodecanediol Di(meth)acrylate, Dodecanediol Di(meth)acrylate base) acrylate, glycerol di(meth)acrylate, neopentylthritol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diepoxy Propyl ether di(meth)acrylate, Tricyclodecane dimethanol di(meth)acrylate, Trimethylolethane tri(meth)acrylate, Trimethylolpropane tri(meth)acrylate ester, trimethylolpropane EO addition tri(meth)acrylate, neopentylthritol tri(meth)acrylate, neopentylthritol tetra(meth)acrylate, dipenteoerythritol tetra(meth)acrylate base) acrylate, diperythritol penta(meth)acrylate, diperythritol hexa(meth)acrylate, tri(meth)acryloxyethoxytrimethylolpropane, glycerin Polyglycidyl ether poly(meth)acrylate and tris(2-acryloxyethyl)isocyanurate.

Examples of polyfunctional vinyl ethers include 1,4-butanediol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, polyethylene glycol divinyl ether, and polyethylene glycol divinyl ether. Ether, propylene glycol divinyl ether, butanediol divinyl ether, hexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, bisphenol A alkylene oxide divinyl ether, bisphenol F alkylene oxide Divinyl ether, trimethylolethane trivinyl ether, trimethylolpropane trivinyl ether, ditrimethylolpropane tetravinyl ether, glycerin trivinyl ether, neopentylthritol tetravinyl ether, dineopentyl tetra Alcohol Pentavinyl Ether, Dineopentyl Rityl Hexaethylene Ether, EO Added Trimethylolpropane Trivinyl Ether, PO Added Trimethylolpropane Trivinyl Ether, EO Added Ditrimethylolpropane Tetravinyl Ether , PO addition of two trimethylolpropane tetraethylene ether, EO addition of neopentylthritol tetraethylene ether, PO addition of neopentylthritol tetraethylene ether, EO addition of dineopentylthritol hexaethylene ether and PO addition into two new pentaerythritol hexaethylene ether.

Among them, the polyfunctional polymerizable monomer is preferably a monomer having 3 to 11 carbon atoms in a portion other than the (meth)acryl group from the viewpoint of curability. As a monomer having 3 to 11 carbon atoms other than the (meth)acryl group, specifically, 1,6-hexanediol di(meth)acrylate, dipropylene glycol di(meth)acrylic acid ester, PO modified neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate Acrylate, polyethylene glycol di(meth)acrylate (EO chain n=4) or 1,10-decanediol di(meth)acrylate is more preferred.

The content of the polymerizable monomer is preferably 10% by mass to 98% by mass, more preferably 50% by mass to 98% by mass, based on the total amount of the ink for forming an insulating protective layer.

(polymerization initiator) Examples of the polymerization initiator contained in the ink for forming an insulating layer include oxime compounds, alkylphenone compounds, acylphosphine compounds, aromatic onium salt compounds, organic peroxides, sulfur compounds, hexaaryl Biimidazole compounds, borate compounds, acridium compounds, titanocene compounds, active ester compounds, compounds with carbon-halogen bonds, and alkylamines.

Among them, from the viewpoint of further improving the conductivity, the polymerization initiator contained in the ink for forming an insulating layer is at least one selected from the group consisting of oxime compounds, alkylphenone compounds, and titanocene compounds. Preferably, an alkylphenone compound is more preferable, and at least one selected from the group consisting of an α-aminoalkylphenone compound and a benzyl ketal alkylphenone is still more preferable.

The content of the polymerization initiator is preferably 0.5% by mass to 20% by mass, more preferably 2% by mass to 10% by mass, based on the total amount of the insulating layer forming ink.

The ink for forming an insulating protective layer may contain other components than the polymerization initiator and the polymerizable monomer. Examples of other components include chain transfer agents, polymerization inhibitors, sensitizers, surfactants, and additives.

(chain transfer agent) The ink for forming an insulating layer may contain at least one chain transfer agent. From the viewpoint of improving the reactivity of the photopolymerization reaction, the chain transfer agent is preferably a polyfunctional mercaptan.

Examples of polyfunctional thiols include aliphatic thiols such as hexane-1,6-dithiol, decane-1,10-dithiol, dimercaptodiethyl ether, and dimercaptodiethylsulfide. Aromatic thiols such as xylene dithiol, 4,4′-dimercaptodiphenyl sulfide, 1,4-benzenedithiol, etc.; Ethylene glycol bis(thioglycolate), Polyethylene glycol bis(thioglycolate), Propylene glycol bis(thioglycolate), Glycerol tri(thioglycolate), Trimethylolethane tri(mercapto acetate), trimethylolpropane tri(thioglycolate), neopentylthritol tetrakis(thioglycolate), diperythritol hexa(thioglycolate) and other polyol poly(thioglycolate) ester); Ethylene Glycol Bis(3-Mercaptopropionate), Polyethylene Glycol Bis(3-Mercaptopropionate), Propylene Glycol Bis(3-Mercaptopropionate), Glycerol Tris(3-Mercaptopropionate), Tris Methylolethane Tris(Mercaptopropionate), Trimethylolpropane Tris(3-Mercaptopropionate), Neopentylthritol Tetrakis(3-Mercaptopropionate), Dineopentylthritol Hexa(3 -mercaptopropionate) and other polyol poly(3-mercaptopropionate); and 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutoxyethyl)-1,3,5-tris-2,4,6( 1H,3H,5H)-trione, neopentylthritol tetrakis(3-mercaptobutyrate) and other poly(mercaptobutyrate).

(polymerization inhibitor) The ink for forming an insulating layer may contain at least one polymerization inhibitor. Examples of polymerization inhibitors include p-methoxyphenol, quinones (for example, hydroquinone, benzoquinone, methoxybenzoquinone, etc.), phenanthrene, catechols, alkylphenols (for example, di butylated hydroxytoluene (BHT) etc.), alkyl bisphenols, zinc dimethyldithiocarbamate, copper dimethyldithiocarbamate, copper dibutyldithiocarbamate, water Copper sylate, thiodipropionates, mercaptobenzimidazoles, phosphorous acid, 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO), 2,2,6,6 -Tetramethyl-4-hydroxypiperidin-1-oxyl (TEMPOL) and tris(N-nitroso-N-phenylhydroxylamine) aluminum salt (alias: Cupferron Al).

Wherein, the polymerization inhibitor is at least one selected from p-methoxyphenol, catechols, quinones, alkylphenols, TEMPO, TEMPOL and tris(N-nitroso-N-phenylhydroxylamine) aluminum salt One is preferred, and at least one selected from p-methoxyphenol, hydroquinone, benzoquinone, BHT, TEMPO, TEMPOL and tris(N-nitroso-N-phenylhydroxylamine) aluminum salt is more preferred .

When the ink for forming an insulating layer contains a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01% by mass to 2.0% by mass, and preferably 0.02% by mass to 1.0% by mass, based on the total amount of the ink for forming an insulating protective layer. More preferably, 0.03% by mass to 0.5% by mass is particularly preferred.

(sensitizer) The ink for forming an insulating layer may contain at least one sensitizer.

As sensitizers, for example, polynuclear aromatic compounds (for example, pyrene, perylene, triphenylene, and 2-ethyl-9,10-dimethoxyanthracene), galaxies (for example, fluorescent yellow, eosin, erythroxin, rose bengal B and rose bengal), cyanine compounds (such as thiacarbocyanine and oxacarbocyanine), merocyanine compounds (such as merocyanine and carbocyanines), thiamines (e.g., thionine, methylene blue, and toluidine blue), acridines (e.g., acridine orange, chloroflavin, and acriflavine), anthraquinones (e.g., anthraquinone), squarylium-based compounds (for example, squaraine), coumarin-based compounds (for example, 7-diethylamino-4-methylcoumarin), thioxanthone-based compounds (for example, isopropylthioxanthone) and thioxanthone-based compounds (e.g., thioxanthone). Among them, the sensitizer is preferably a thioxanthone compound.

When the ink for forming an insulating layer contains a sensitizer, the content of the sensitizer is not particularly limited, but it is preferably 1.0% by mass to 15.0% by mass relative to the total amount of ink for forming an insulating protective layer, and 1.5% by mass % to 5.0% by mass is more preferable.

(surfactant) The ink for forming an insulating layer may contain at least one surfactant.

Examples of the surfactant include those described in JP-A-62-173463 and JP-A-62-183457. In addition, examples of surfactants include anionic surfactants such as dialkyl sulfosuccinates, alkylnaphthalene sulfonates, and fatty acid salts; polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl Nonionic surfactants such as ethers, acetylene glycols, polyethylene oxide/polyoxypropylene capped copolymers; and cationic surfactants such as alkylamine salts and quaternary ammonium salts. In addition, the surfactant may be a fluorine-based surfactant or a polysiloxane-based surfactant.

When the ink for forming an insulating layer contains a surfactant, the content of the surfactant is preferably 0.5% by mass or less, more preferably 0.1% by mass or less, based on the total amount of the ink for forming an insulating layer. The lower limit of the content of the surfactant is not particularly limited.

If the content of the surfactant is 0.5% by mass or less, the ink for insulating layer formation will hardly spread after the ink for forming an insulating layer is applied. Therefore, the outflow of the ink for insulating layer formation is suppressed, and electromagnetic wave shielding property improves.

(Organic solvents) The ink for forming an insulating layer may contain at least one type of organic solvent.

Examples of organic solvents include ethylene glycol monoethyl ether, diethylene glycol monoethyl ether, triethylene glycol monomethyl ether, propylene glycol monomethyl ether (PGME), dipropylene glycol monomethyl ether, tripropylene glycol monomethyl ether, etc. ( Poly)alkylene glycol monoalkyl ethers; Ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol diethyl ether, tetraethylene glycol dimethyl ether and other (poly)alkylene glycol dialkyl ethers; (Poly)alkylene glycol acetates such as diethylene glycol acetate; Ethylene glycol diacetate, propylene glycol diacetate and other (poly)alkylene glycol diacetates; Ethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate and other (poly)alkylene glycol monoalkyl ether acetates, methyl ethyl ketone, cyclohexanone and other ketones; Lactones such as γ-butyrolactone; Ethyl acetate, propyl acetate, butyl acetate, 3-methoxybutyl acetate (MBA), methyl propionate, ethyl propionate and other esters; Cyclic ethers such as tetrahydrofuran and dioxane; and Amides such as dimethylformamide and dimethylacetamide.

When the ink for forming an insulating layer contains an organic solvent, the content of the organic solvent is preferably 70% by mass or less, more preferably 50% by mass or less, based on the total amount of the ink for forming an insulating layer. The lower limit of the content of the organic solvent is not particularly limited.

(additive) The ink for forming an insulating layer may contain additives such as a co-sensitizer, an ultraviolet absorber, an antioxidant, an anti-fading agent, and a basic compound as necessary.

(physical properties) The pH of the ink for forming an insulating layer is preferably from 7 to 10, more preferably from 7.5 to 9.5, from the viewpoint of improving discharge stability when imparted by an inkjet recording method. The pH is measured at 25° C. using a pH meter, for example, a pH meter manufactured by DKK-TOA Corporation (model “HM-31”).

The viscosity of the ink for forming an insulating layer is preferably 0.5 mPa･s to 60 mPa･s, more preferably 2 mPa･s to 40 mPa･s. The viscosity is measured at 25° C. using a viscometer, for example, a TV-22 viscometer manufactured by TOKI SANGYO CO., LTD.

The surface tension of the ink for insulating layer formation is preferably 60 mN/m or less, more preferably 20 mN/m to 50 mN/m, and still more preferably 25 mN/m to 45 mN/m. The surface tension is measured at 25° C. using a surface tensiometer such as an automatic surface tensiometer manufactured by Kyowa Interface Science Co., Ltd. (product name “CBVP-Z”) and measured by a plate method.

＜Method for forming an insulating protective layer＞ In the first process, it is preferable to apply the ink for forming an insulating layer on the electronic base material using an inkjet recording method, a dispenser coating method, or a spray coating method, and to apply the insulating layer on the top surface of the electronic component. The layer-forming ink is blown with air, and then the blown insulating layer-forming ink is cured to form an insulating protective layer.

Among the methods of applying the ink for insulating layer formation, the inkjet recording method is preferable from the viewpoint that a small amount can be dropped and the thickness of the ink film formed by one application can be reduced. The details of the inkjet recording method are as described above.

The method of hardening the ink for forming an insulating layer is not particularly limited, for example, a method of irradiating active energy rays to the ink for forming an insulating layer provided on a base material (for example, this exposure).

Examples of active energy rays include ultraviolet rays, visible rays, and electron beams, and among them, ultraviolet rays (hereinafter also referred to as "UV") are preferable.

The peak wavelength of ultraviolet rays is preferably from 200 nm to 405 nm, more preferably from 250 nm to 400 nm, and still more preferably from 300 nm to 400 nm.

The exposure dose in the irradiation of active energy rays is preferably 100 mJ/cm ² to 5000 mJ/cm ² , more preferably 300 mJ/cm ² to 1500 mJ/cm ² .

As a light source for ultraviolet irradiation, mercury lamps, gas lasers, and solid lasers are mainly used, and mercury lamps, metal halide lamps, and ultraviolet fluorescent lamps are widely known. In addition, UV-LEDs (light emitting diodes) and UV-LDs (laser diodes) are small, have a long life, high efficiency, and low cost, and are expected to be used as light sources for ultraviolet irradiation. Among them, the light source for ultraviolet irradiation is preferably metal halide lamp, high-pressure mercury lamp, medium-pressure mercury lamp, low-pressure mercury lamp or UV-LED.

In the process of obtaining an insulating protective layer, in order to obtain an insulating protective layer of a desired thickness, it is preferable to repeat the process of applying insulating ink and irradiating active energy rays two or more times.

The thickness of the insulating protective layer is preferably from 5 μm to 5000 μm, more preferably from 10 μm to 2000 μm.

In the first process, separately from the irradiation of active energy rays (for example, this exposure), the above-mentioned nailing can be performed in at least one of the timings before and after the wind blowing of the ink on the top surface of the electronic component. exposure. [Example]

Hereinafter, although the Example of this indication is shown, this indication is not limited to the following Example.

[Example 1] <Preparation of ink for conductive layer formation> 40 g of silver neodecanoate was added to a 200 mL 3-necked flask. Next, 30.0 g of trimethylbenzene and 30.0 g of terpineol were added and stirred to obtain a silver salt-containing solution. This solution was filtered using a PTFE (polytetrafluoroethylene) membrane filter with a pore size of 0.45 μm to obtain an ink for forming a conductive layer.

＜Preparation of electronic board＞ A wiring board with electronic parts is prepared. In the wiring board with electronic parts, the wiring board and the electronic parts are connected by a plurality of solder balls, and there are minute gaps between the electronic parts and the wiring board and between the plurality of solder balls. Using a dispenser from Musashi engineering. Inc., Zymet's Underfill material was filled in the gap, and then left to stand in a constant temperature oven for 20 minutes, thereby filling the gap. Through the above, an electronic substrate having the same structure as the electronic substrate 110 shown in FIGS. 15A and 15B (that is, an electronic substrate as a substrate with steps) is prepared. Each dimension in the prepared electronic substrate is as follows.

Width of ground electrode: 600 μm The height of the ground electrode (the height of the protruding part on the wiring board): 25μm Area surrounded by ground electrodes (ground area): 10.65mm×10.65mm Size and shape of electronic parts: rectangular shape of 10.00mm×10.00mm Height of electronic parts (height from the surface of the wiring board to the top surface of the electronic parts): 500 μm Distance between electronic parts and ground electrode: 50μm

<Formation of the conductive layer> An inkjet recording apparatus equipped with the following single-pass method was prepared: a stage on which a substrate (for example, the above-mentioned electronic substrate) is placed; a conveyor for conveying the stage; an inkjet head arranged in a row of nozzles 1200dpi (dot per inch) perpendicular to the conveying direction of the stage; a dryer; and a 385nm LED light source (13W/cm ² , manufactured by KYOCERA Corporation) as a pinning light source. Here, an inkjet, a dryer, and a pinning light source are arranged in this order from the upstream side in the transport direction of the stage.

An electronic substrate was fixed on the stage in the above inkjet recording device with an adhesive tape. At this time, the electronic substrate is fixed on the stage so that one of the four sides of the electronic components on the electronic substrate is parallel to the nozzle array of the inkjet head. The ink for forming a conductive layer is loaded on the inkjet recording device, and the ink for forming a conductive layer is applied to the electronic substrate while conveying the electronic substrate. In the application of the conductive layer forming ink, the resolution (dpi) in the direction perpendicular to the relative movement direction and the resolution (dpi) in the relative movement direction were adjusted to the values shown in Table 1, respectively. The application area of the ink for forming the conductive layer includes the electronic component (10.00mm × 10.00mm rectangular area), and 0.20mm is exposed from each of the four sides of the electronic component, and it is made into a rectangular shape of 10.40mm × 10.40mm area. The application of the above conductive layer forming ink was repeated three times.

Using a dryer, blow the air at a temperature of 23° C. and a wind speed of 3 m/s in the direction shown below to the conductive layer-forming ink applied on the top surface of the electronic component in the electronic substrate. The direction of the blown air is set to a direction in which the elevation angle becomes 90° from the center above the top surface of the electronic component. The time from the end of the application of the ink for forming a conductive layer to the start of blowing of the wind was adjusted to 0.44 seconds. Next, pinning exposure was performed on the blown ink with a 385 nm LED light source (13 W/cm ² , manufactured by KYOCERA Corporation). The exposure amount of the pinning exposure was set to 5 J/cm ² . The time from the end of blowing the ink for forming a conductive layer to the start of the pinning exposure was adjusted to 0.44 seconds.

After the above-mentioned pinning exposure, the ink for forming a conductive layer to which heat was applied on the electronic substrate was heated (that is, fired) at 150° C. for 20 minutes to obtain a conductive layer serving as an electromagnetic wave shielding layer. Through the above, the electronic device of Example 1 was obtained.

＜Evaluation＞ The following evaluations were implemented about the obtained electronic component. The results are shown in Table 1.

(thickness of conductive layer) The thickness of the conductive layer was measured based on an optical microscope photograph of a cross-section of the electronic component. As the thickness of the conductive layer, were measured as follows: the thickness of the conductive layer on the top surface of the electronic component; the thickness of the conductive layer on the sides of the electronic component; and The thickness of the conductive layer on the corner between the top surface and the side surface of the electronic component. Based on the measurement results, the average value of the thickness and the deviation of the thickness were obtained.

(Scattering of ink in the area where the conductive layer is not formed) Scattering of the ink in the conductive layer non-formation region was evaluated as follows. Using an optical microscope (200X), observe three locations at a predetermined distance from the edge of the electronic component to each side, and confirm the presence or absence of scattering of the conductive ink. Based on the obtained results, ink scattering in the conductive layer non-formation region was evaluated according to the following evaluation criteria. In the following evaluation criteria, the most excellent level of ink scattering suppression performance in the conductive layer non-formation region was "5".

-Evaluation Criteria for Scattering of Ink in the Conductive Layer Non-Formation Area- 5: Scattering is not observed from the edge to a region of 300 μm or more and less than 500 μm, and also no scattering is observed from the edge to a region of 500 μm or more. 4: Scattering was observed from the edge to a region of 300 μm or more and less than 500 μm, but no scattering was observed from the edge to a region of 500 μm or more. 3: Scattering was observed from the edge to a region of 500 μm or more and less than 600 μm, but no scattering was observed from the edge to a region of 600 μm or more. 2: Scattering was observed from the edge to a portion of 600 μm or more and less than 1000 μm, but no scattering was observed from the edge to a region of 1000 μm or more. 1: Scattering is observed from the edge to a region of 1000 μm or more.

(Electromagnetic wave shielding performance) Using WM7400 (manufactured by MORITA TECH CO., LTD.), the electromagnetic wave leakage was measured in the range up to 3 GHz, and the electromagnetic wave shielding performance of the conductive layer (electromagnetic wave shielding layer) was evaluated according to the following evaluation criteria. In the following evaluation criteria, the most excellent level of electromagnetic wave shielding performance was "5".

-Evaluation criteria for electromagnetic wave shielding performance- 5: Less than 20dB 4: More than 20dB and less than 30dB 3: More than 30dB and less than 50dB 2: More than 50dB and less than 70dB 1: Above 70dB

(Amount of Ink Outflow (μm ³ ) in a Region Where a Conductive Layer Is Not Formed) The amount of ink outflow (μm ³ ) in a region where a conductive layer is not formed was measured.

[Example 2] In the application (three times) of the ink for forming a conductive layer, the same operation as in Example 1 was performed except that the resolution (dpi) in the relative movement direction was changed to that shown in Table 1. The results are shown in Table 1.

[Embodiments 3 to 7] The operation similar to Example 2 was performed except having changed the wind speed of the wind which blows the ink for conductive layer formation to what is shown in Table 1. The results are shown in Table 1.

[Example 8] The same operation as in Example 2 was performed except that the air was recovered using an exhaust pipe and a fan. The results are shown in Table 1.

[Example 9] The same operation as in Example 8 was performed except that the direction of the blown air was changed to a direction in which the elevation angle was 30° (see FIG. 5 and FIG. 7B ). The results are shown in Table 1. In more detail, the direction of the blown air is the same as the example shown in FIG. 7B. In more detail, the direction of the air blown from the dryer includes the direction opposite to the side where the inkjet head is arranged when viewed from the dryer. oriented components.

[Example 10] In addition to changing the pinning exposure timing of the ink applied to the electronic substrate from after blowing the ink to before blowing the ink by replacing the arrangement of the pinning light source and the dryer, Same operation as in Example 8.

[Example 11] The operation similar to Example 10 was performed except having changed the wind speed of the wind which blows the ink for conductive layer formation to what is shown in Table 1. The results are shown in Table 1.

[Comparative Example 1] The same operation as in Example 2 was performed except that the wind blowing to the ink for conductive layer formation was not performed. The results are shown in Table 1.

[Table 1] Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Comparative example 1 Ink application conditions for conductive layer formation Resolution in the direction orthogonal to the direction of relative movement (dpi) 1200 1200 1200 1200 1200 1200 1200 1200 1200 1200 1200 1200 Resolution relative to the direction of movement (dpi) 1200 2400 2400 2400 2400 2400 2400 2400 2400 2400 2400 2400 Presence and speed of wind blowing with respect to the conductive layer-forming ink impregnated on the top surface of electronic components There is 3m/s There is 3m/s 1m/s There is 5m/s 10m/s 15m/s There is 25m/s There is 3m/s There is 3m/s There is 3m/s There is 5m/s none wind elevation 90° 90° 90° 90° 90° 90° 90° 90° 30° 90° 90° - With or without pinning exposure Yes (after the wind blows) Yes (after the wind blows) Yes (after the wind blows) Yes (after the wind blows) Yes (after the wind blows) Yes (after the wind blows) Yes (after the wind blows) Yes (after the wind blows) Yes (after the wind blows) Yes (before the wind blows) Yes (before the wind blows) have wind recovery none none none none none none none have have have have none Conductive layer thickness (μm) top surface of electronic components 2.00 3.00 3.05 3.00 3.00 2.95 2.95 3.00 3.00 3.00 3.00 3.00 on the side of the electronics 1.40 2.80 2.80 2.80 2.80 2.80 2.80 2.80 2.80 2.80 2.80 1.20 On the corner between the top surface and the side surface of the electronic component 0.60 2.60 2.40 2.60 2.60 2.53 2.52 2.60 2.60 2.65 2.65 0.50 The average value of the thickness of the conductive layer 1.33 2.80 2.75 2.80 2.80 2.76 2.76 2.80 2.80 2.82 2.82 1.57 Variation in the thickness of the conductive layer 0.70 0.20 0.33 0.20 0.20 0.21 0.22 0.20 0.20 0.18 0.18 1.29 Scattering of ink in the area where the conductive layer is not formed 4 4 4 4 4 4 3 5 5 5 5 4 Electromagnetic wave shielding performance 3 4 4 5 5 5 5 5 5 5 5 1 Outflow of ink in the conductive layer non-formation area (μm ³ ) 180 200 190 220 250 300 350 180 180 160 160 150

As shown in Table 1, in Examples 1 to 11 in which wind blowing was carried out against the conductive layer-forming ink impinged on the top surface of the electronic component, compared with Comparative Example 1 in which the above-mentioned wind blowing was not carried out , the thickness deviation of the conductive layer (ie, film) from the side surface to the top surface of the electronic part can be suppressed.

As can be seen from a comparison between Example 2 and Example 8, when the wind is collected (Example 8), scattering of ink in the conductive layer non-formation region can be further suppressed.

From the comparison between Example 1 and Example 2, it can be seen that in the case where the point resolution in the direction of relative movement is higher than that in the direction perpendicular to the direction of relative movement (Example 2), the electronic The deviation in thickness of the conductive layer (ie, film) from the sides of the part to the top surface.

[Examples 101 to 111, Comparative Example 101] Electronic components of Examples 101 to 111 and Comparative Example 101 were obtained in the same manner as Examples 1 to 11 and Comparative Example 1 except for the following points. For the obtained electronic component, the thickness of the insulating layer and the scattering of the ink for forming an insulating layer were evaluated in the same manner as the evaluation of the thickness of the conductive layer and the scattering of the ink for forming a conductive layer in Example 1. The results are shown in Table 2.

-Changes to Examples 1 to 11 and Comparative Example 1- ･The ink for forming an insulating layer was applied (once) instead of the ink for forming a conductive layer (three times), and an insulating layer was formed instead of a conductive layer. . ･Calcination after wind blowing is changed to UV (ultraviolet) irradiation as this exposure. Irradiation of ultraviolet rays as this exposure was performed using an ultraviolet irradiation device (product name "385nm LED light source (13W/cm ² , manufactured by KYOCERA Corporation)). The exposure amount as this exposure was set to 0.8J/cm ² . The time from the start of the blowing of the ink wind to the start of the irradiation of the active energy ray was adjusted to 0.44 seconds.･In Examples 101 to 111, the above-mentioned present exposure was performed without performing the pinning exposure after the blowing of the wind.

-Preparation of ink for insulating layer- Add to a 300mL resin beaker 2-(Dimethylamino)-2-(4-methylbenzyl)-1-(4-?olinylphenyl)-butan-1-one (product name "Omnirad 379", manufactured by IGM Resins B.V.) 4.0g, 2-isopropylthioxanthone (product name "SPEEDCURE ITX" manufactured by LAMBSON; hereinafter also referred to as "ITX") as a sensitizer 2.0 g, 30.0 g of isocamphene acrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation; hereinafter also referred to as "IBOA") as monofunctional acrylate X1 (that is, a monofunctional acrylate having a molecular weight of 200 or more and having a ring structure), 15.0 g of cyclic trimethylolpropane formal monoacrylate as monofunctional acrylate X2 (manufactured by OSAKA ORGANIC CHEMICAL INDUSTRY LTD., VISCOAT #200, hereinafter also referred to as "CTFA"), 20.0 g of N-vinylcaprolactam (hereinafter also referred to as "NVC") as a monofunctional monomer, 10.0 g of 1,6-hexanediol diacrylate (hereinafter also referred to as “1,6-HDDA”) as a bifunctional monomer, 10.0 g of alkoxylated hexanediol diacrylate (manufactured by Sartomer Company, Inc., CD561) as a bifunctional monomer, and 9.0 g of trimethylolpropane triacrylate (manufactured by FUJIFILM Wako Pure Chemical Corporation; hereinafter also referred to as "TMPTA") as a trifunctional monomer, Using a mixer (product name "L4R", manufactured by Silverson Nippon Limited), it was stirred at 25° C. for 20 minutes at 5,000 revolutions/minute to obtain an ink for an insulating layer.

[Table 2] Example 101 Example 102 Example 103 Example 104 Example 105 Example 106 Example 107 Example 108 Example 109 Example 110 Example 111 Comparative Example 101 Ink application conditions for insulating layer formation Resolution in the direction orthogonal to the direction of relative movement (dpi) 1200 1200 1200 1200 1200 1200 1200 1200 1200 1200 1200 1200 Resolution relative to the direction of movement (dpi) 1200 2400 2400 2400 2400 2400 2400 2400 2400 2400 2400 2400 The presence or absence of wind blowing and the wind speed of the insulating layer-forming ink impregnated on the top surface of the electronic component There is 3m/s There is 3m/s 1m/s There is 3m/s There is 5m/s 10m/s 15m/s There is 3m/s There is 3m/s There is 5m/s 10m/s none wind elevation 90° 90° 90° 90° 90° 90° 90° 90° 30° 90° 90° 90° With or without pinning exposure none none none none none none none none none Yes (before the wind blows) Yes (before the wind blows) none wind recovery none none none none none none none have have none none none Thickness of insulating layer (μm) top surface of electronic components 1.30 2.00 2.30 2.10 2.10 2.10 2.00 2.10 2.10 2.10 2.10 3.00 on the side of the electronics 0.70 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 1.00 On the corner between the top surface and the side surface of the electronic component 0.60 1.80 1.80 1.80 1.80 1.80 1.70 1.80 1.80 1.85 1.85 0.50 The average thickness of the insulating layer 0.87 1.93 2.03 1.97 1.97 1.97 1.90 1.97 1.97 1.98 1.98 1.50 Variation in the thickness of the insulating layer 0.38 0.12 0.25 0.15 0.15 0.15 0.17 0.15 0.15 0.13 0.13 1.32 Scattering of ink in the non-forming area of the insulating layer 4 4 4 4 4 3 3 5 5 4 3 4

As shown in Table 2, in Examples 101 to 111 in which wind blowing was carried out against the ink for forming an insulating layer on the top surface of an electronic component, compared with Comparative Example 101 in which the wind blowing was not performed, The thickness deviation of the insulating layer (that is, the film) from the side surface to the top surface of the electronic part can be suppressed.

10, 10A, 13: Substrate with step difference 12: Base substrate 16: Connecting components 17: Gap 18: Component 18C: Corner 18S: side 18U: top surface 19: next door 20: Membrane 24: Inkjet nozzle 26: Ink 28, 28B, 28X: blower 30, 30B, 30X: wind recovery machine 32, 32B, 34: pinning exposure machine 100: Electronic components 110: Electronic substrate 112: Wiring substrate 118:Electronic parts 114A: Grounded area 116: Ground electrode 122: insulating protective layer 130: Electromagnetic wave shielding layer 210: conveyor track 212, 213, 215: substrate conveying stage 11, 214, 216: through holes 300, 300X, 300A, 300B, 300C, 301, 302, 400, 400A: film forming device D1: ink dot M1, M11, M11B: The conveying direction of the substrate with step difference P1: The position where the wind blows W1: wind W1X: Components facing opposite to the side where the inkjet head is arranged when viewed from the blower X°: elevation angle

FIG. 1A schematically shows a process flow diagram of a film forming method according to an embodiment of the present disclosure. FIG. 1B schematically shows a process flow diagram of a film forming method according to an embodiment of the present disclosure. FIG. 1C schematically shows a process flow diagram of a film forming method according to an embodiment of the present disclosure. FIG. 1D schematically shows a process flow diagram of a film forming method according to an embodiment of the present disclosure. FIG. 2 is a schematic side view of an example of a stepped substrate showing a state in which a gap exists between a base substrate and a member. 3 is a schematic plan view schematically showing an example of an aspect in which the dot resolution in the direction of relative movement is higher than the dot resolution in the direction perpendicular to the direction of relative movement in the present disclosure. Fig. 4 is a schematic side view schematically showing an example of how ink impinges on corners of members in the present disclosure. FIG. 5 is a schematic diagram showing an example of an elevation angle in the present disclosure. 6 is a schematic side view showing an example after the barrier rib forming process and before the film forming process when the film forming method of the present disclosure includes the barrier rib forming process. FIG. 7A is a schematic plan view showing an example of the film forming apparatus of the present disclosure. Fig. 7B is a side view of Fig. 7A. Fig. 7C is a schematic cross-sectional view showing a modified example of the film forming apparatus shown in Fig. 7B. FIG. 8A is a schematic plan view showing another example of the film forming apparatus of the present disclosure. Fig. 8B is a side view of Fig. 8A. FIG. 9A is a schematic plan view showing still another example of the film forming apparatus of the present disclosure. Fig. 9B is a side view of Fig. 9A. Fig. 10A is a schematic plan view showing still another example of the film forming apparatus of the present disclosure. Figure 10B is a side view of Figure 10A. Fig. 11 is a schematic plan view showing still another example of the film forming apparatus of the present disclosure. Fig. 12 is a schematic plan view showing still another example of the film forming apparatus of the present disclosure. FIG. 13A is a schematic plan view showing an example of the film forming apparatus of the present disclosure including two air blowers. Figure 13B is a side view of Figure 13A. FIG. 13C is a side view when the conveying direction of the substrate with a step is reversed from FIG. 13B . FIG. 14A is a schematic plan view showing an example of the film forming apparatus of the present disclosure including two air blowers. Figure 14B is a side view of Figure 14A. FIG. 14C is a side view when the conveyance direction of the substrate with a step is reversed from FIG. 14B . 15A is a schematic plan view of an electronic substrate prepared in a preparation process in the method of manufacturing an electronic component according to the embodiment of the present disclosure. Fig. 15B is a sectional view taken along line X-X in Fig. 15A. 16A is a schematic plan view of an electronic substrate on which an insulating protective layer is formed in a first process in the method of manufacturing an electronic component according to the embodiment of the present disclosure. Fig. 16B is a sectional view taken along line X-X in Fig. 16A. 17A is a schematic plan view of an electronic substrate on which an electromagnetic wave shielding layer is formed in the second process of the method of manufacturing an electronic component according to an embodiment of the present disclosure (that is, the electronic component according to an embodiment of the present disclosure). Fig. 17B is a sectional view taken along line X-X in Fig. 17A.

none.

Claims (19)

A method for forming a film, comprising: The process of preparing a substrate having a step difference in the thickness direction of the substrate, that is, a substrate with a step difference; and A film forming process, by discharging ink from an inkjet head, imparting the ink on at least the top surface of the step in the substrate with the step, and blowing the ink applied to the top surface of the step , thereby forming a film covering at least the top surface of the aforementioned step and the side surfaces of the aforementioned step. The method for forming a film as claimed in item 1, wherein The wind speed of the aforementioned wind is 1 m/s or more and less than 30 m/s. The method for forming a film according to claim 1 or claim 2, wherein The aforementioned film forming process includes the step of recovering the aforementioned wind. The method for forming a film according to claim 1 or claim 2, wherein The aforementioned film forming process further includes the step of performing pinning exposure on the aforementioned ink that has been blown with the aforementioned wind, The time from the start of the wind blowing to the start of the pinning exposure is 1 second or less. The method for forming a film according to claim 1 or claim 2, wherein The film forming process further includes a step of performing pinning exposure on the ink applied to the top surface of the step before blowing the wind. The method for forming a film according to claim 1 or claim 2, wherein The aforementioned wind blows out from the blower, The direction of the wind includes a component of a direction opposite to the side where the inkjet head is arranged when viewed from the blower. The method for forming a film according to claim 1 or claim 2, wherein The ink application in the film forming process is performed while relatively moving the step substrate and the inkjet head, In the ink applied to the stepped substrate, the dot resolution in the direction of the relative movement is higher than the dot resolution in the direction perpendicular to the direction of the relative movement. The method for forming a film according to claim 1 or claim 2, wherein The aforementioned wind is the flow of inert gas, The aforementioned ink is an active energy ray curable ink containing a polymerizable compound. The method for forming a film according to claim 1 or claim 2, wherein The aforementioned substrate with step difference includes a base substrate and components arranged on the base substrate, and there is a gap between the aforementioned base substrate and the aforementioned components. The method for forming a film according to any one of claim 1 or claim 2, wherein Before the aforementioned film forming process, a barrier rib forming process of forming barrier ribs surrounding the region where the aforementioned film is formed is also included by discharging ink from an inkjet head. The method for forming a film according to claim 1 or claim 2, wherein Before the above-mentioned film forming process, a process of performing hydrophilic treatment on at least the region where the above-mentioned film is formed is also included. A method of manufacturing an electronic device, comprising: Preparation of the manufacturing process of the electronic substrate, the aforementioned electronic substrate has a wiring substrate and electronic components arranged on the aforementioned wiring substrate; and A process of forming at least one of an insulating layer and a conductive layer on the aforementioned electronic substrate to obtain an electronic component, At least one of the insulating layer and the conductive layer is formed by the film forming method according to any one of claim 1 to claim 11. A film forming device comprising: An inkjet nozzle for imparting ink onto the top surface of at least the aforementioned step in a substrate having a step in the thickness direction of the substrate, that is, a substrate with a step; and The air blower blows air to the aforementioned ink applied to the top surface of the aforementioned step difference, Relatively moving the aforementioned substrate with step difference and the aforementioned inkjet nozzle, The aforementioned inkjet nozzles and the aforementioned blower are arranged in the aforementioned direction of relative movement. The film forming apparatus according to claim 13, further comprising a wind recovering device for recovering the wind. The method for forming a film according to claim 13 or claim 14, wherein The direction of the wind blown from the blower includes a component facing opposite to the side where the inkjet head is arranged when viewed from the blower. The film forming apparatus according to claim 13 or claim 14, which includes two of the blowers, The aforementioned inkjet nozzle is arranged between the aforementioned 2 aforementioned air blowers, The aforementioned relative movement is back and forth movement. The film forming apparatus according to claim 13 or claim 14, wherein The air blower has a switch function for switching between an on state to start blowing of air and an off state to stop blowing of air. The film forming apparatus according to claim 13 or claim 14, further comprising a pinning exposure machine for performing pinning exposure on the ink to which the wind is blown. The film forming apparatus according to claim 13 or claim 14, further comprising a pinning exposure machine for performing pinning exposure on the ink applied to the top surface of the step before blowing the wind.

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