JP2017038058A - Metal particle composition, conductor including the same, laminate, laminate wiring substrate, and electronic apparatus - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a metal particle composition capable of easily forming vias for electrically connecting conductors such as a wiring pattern through an insulation film, a conductor including the same, a laminate, a laminate wiring substrate, and an electronic apparatus.SOLUTION: The metal particle composition includes: (B) metal particles; (A) a fluorine-containing compound coupled to or adsorbed to the (B) metal particles; and (C) a solvent.SELECTED DRAWING: Figure 3

Description

  The present invention relates to a metal particle composition that can be used as an ink, a paste, or the like for forming a metal wiring, a conductor using the same, a laminated body, a laminated wiring board, and an electronic device.

In recent years, it has been studied to form a transistor array including a plurality of organic thin film transistors (organic TFTs) on a plastic substrate by a low-cost process and to apply it as a backplane for electronic paper, liquid crystal display, and the like.
In this organic thin film transistor manufacturing method, in order to differentiate it from conventional silicon TFTs, it is strongly possible to reduce the cost by patterning each component only by a printing process without performing a vacuum process or a photolithography technique. It is desired. In addition, electronic devices are being miniaturized, and many electronic devices are required to form fine circuits.

From such a background, a method for forming a via for electrically connecting conductors of a transistor array and a wiring pattern by using a printing method has been studied.
For example, after forming an insulating film on the substrate in a state of covering the wiring pattern provided on the substrate, a step of blowing a solvent that dissolves the insulating film by an inkjet method toward the insulating film on the wiring pattern, and a drying step By repeating the above, there has been proposed a method of forming via holes reaching these wiring patterns and filling the via holes with a conductive material (see, for example, Patent Document 1). In addition, a method has been proposed in which a via is directly formed in a special shape by an inkjet method on a wiring pattern provided on a substrate (see, for example, Patent Document 2).

JP 2012-204658 A Japanese Patent No. 5145687

According to the method described in Patent Document 1, it takes time to form a via hole with certainty by repeatedly performing the step of blowing the solvent to the same portion of the insulating film and repeating the above step and the drying step. There was a problem. In addition, although the diameter of the via hole formed by this method can be controlled to some extent by the volume of the solvent and the number of ejections, there is a problem that it is difficult to accurately control the diameter of the via hole.
In addition, the method described in Patent Document 2 has a problem that an effective conductive area cannot be obtained as the formed conductive portion becomes small because the protruding peripheral portion of the conductive portion is used.
Furthermore, these are devised only for the process for forming vias in the printing process, and there is a problem that the number of processes is complicated and the yield is lowered.

  An object of the present invention is to provide a metal particle composition capable of easily forming a via for electrically connecting conductors such as a wiring pattern via an insulating film, as well as a conductor using the same, a laminate, A multilayer wiring board and an electronic device are provided.

According to the present invention, the following metal particle composition and the like are provided.
1. (B) metal particles;
(A) a fluorine-containing compound that binds to or adsorbs to (B) the metal particles;
(C) A metal particle composition comprising a solvent.
2. 2. The metal particle composition according to 1, which is a genus particle dispersion.
3. The (A) fluorine-containing compound is a fluorine-containing thiol compound, a fluorine-containing disulfide compound, a fluorine-containing amine compound, a fluorine-containing carboxylic acid compound, a fluorine-containing silane compound, a fluorine-containing nitrile compound, a fluorine-containing tellurium compound, or a fluorine-containing alkoxysilane compound. And the metal particle composition according to 1 or 2, wherein the metal particle composition is one or more selected from the group consisting of fluorine-containing selenium compounds.
4). The metal particle composition according to any one of 1 to 3, wherein the (A) fluorine-containing compound is a fluorine-containing thiol compound.
5). The solvent (C) is hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, isooctane, cyclohexane, cycloheptane, cyclooctane, benzene, toluene, xylene, trimethylbenzene, dodecyl. From benzene, isopropyl alcohol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, cyclohexanol, 1-methoxy-2-propanol, cyclohexanone, methyl isobutyl ketone The metal particle composition according to any one of 1 to 4, which is one or more selected from the group consisting of:
6). The metal particle composition according to any one of 1 to 5, wherein the solidified film dried and solidified has a surface energy of 60 mN / m or less.
7). The metal particle composition according to any one of 1 to 6, wherein the (A) fluorine-containing compound is bonded to or adsorbed to the surface of the (B) metal particle.
8). Content of said (A) fluorine-containing compound is 10 mass% or less with respect to the metal particle dispersion whole quantity, The metal particle composition in any one of 1-7 characterized by the above-mentioned.
9. Content of the said (C) solvent is 25 mass% or more and 82 mass% or less with respect to metal particle dispersion whole quantity, The metal particle composition in any one of 1-8 characterized by the above-mentioned.
10. The metal particles (B) are at least one selected from the group consisting of silver particles, copper particles, nickel particles, palladium particles, platinum particles, and gold particles. Metal particle composition.
11. (B) The metal particle composition according to any one of 1 to 10, wherein the metal particle is a silver particle.
12 Content of said (B) metal particle is 15 mass% or more and 70 mass% or less with respect to metal particle composition whole quantity, The metal particle composition in any one of 1-11 characterized by the above-mentioned.
13. A conductor comprising the metal particle composition according to any one of 1 to 12.
14 A substrate,
An electrode provided on the substrate;
A laminate comprising the conductor according to 13, which is formed on the electrode.
15. 15. The laminate according to 14, further comprising an insulating film formed on the substrate and the electrode and exposing a part of the conductor.
16. 16. The laminate according to 15, further comprising a conductive film formed on the insulating film and in contact with the exposed portion of the conductor.
17. A laminated wiring board comprising the laminate according to any one of 14 to 16.
18. An electronic apparatus comprising the laminated wiring board according to 18.17.
19. 19. The electronic device according to 18, which is a liquid crystal display, a television, a car navigation, a mobile phone, a game machine, a digital camera, a personal computer, a printer, an automobile, a robot, a light emitting diode illumination, or a wearable device.

  According to the present invention, a metal particle composition capable of easily forming a via for electrically connecting conductors such as a wiring pattern via an insulating film, as well as a conductor using the same, a laminate, A multilayer wiring board and an electronic device can be provided.

It is the schematic which shows the board | substrate (array) with a wiring pattern before via formation. It is the schematic which shows the array after forming a via | veer. It is the schematic which shows the array after forming the insulating film. It is IV-IV sectional drawing in FIG. It is the schematic which shows the array after forming the electrically conductive film. It is VI-VI sectional drawing in FIG.

[Metal particle composition]
The metal particle composition of the present invention comprises:
(B) metal particles;
(A) a fluorine-containing compound that binds to or adsorbs to (B) the metal particles;
(C) a solvent.
Here, the form of the “metal particle composition” may be not only a dispersion but also a paste or the like. When expressed in terms of viscosity, a form adapted to various printing methods from several mPa · s to several thousand Pa · s. Can be controlled by adjusting each composition ratio of the metal particle composition. In particular, a metal particle composition (hereinafter referred to as a dispersion) having a viscosity of about several mPa · s to several hundred mPa · s is preferable.
The printed body of the metal particle composition of the present invention (hereinafter sometimes simply referred to as the composition of the present invention) can exhibit both conductivity and liquid repellency. Therefore, for example, the printed body of the composition of the present invention can be used as a via for electrically connecting conductors. Specifically, even if an insulating material is applied onto a film obtained by drying and solidifying the printed body of the composition of the present invention, only the film portion obtained by drying and solidifying the printed body of the composition of the present invention will repel the insulating material. Can do. Thereby, the printed body of the composition of the present invention can be used as the via, and the via can be easily formed.

In the composition of the present invention, the surface energy of the solidified film dried and solidified is preferably 60 mN / m or less. On the other hand, if the surface energy of the dispersion exceeds 60 mN / m, the insulating film may also be covered on the solidified film obtained by drying and solidifying the printed material of the dispersion of the present invention.
The surface energy of the solidified film of the dispersion of the present invention is 20 mN / m or more and 40 mN / m from the viewpoint of using a low surface energy insulating film to improve film formation uniformity and suppressing spreading of the coating on the underlying conductor. It is particularly preferred that
The surface energy of the solidified film obtained by drying and solidifying the dispersion can be measured by a contact angle measurement method. Examples of means for adjusting the surface energy of the solidified film obtained by drying and solidifying the dispersion of the present invention include adjusting the type and amount of component (A), the temperature during drying, and the time during drying. .
Hereinafter, each component etc. which the composition of this invention contains are demonstrated.

[(A) component]
The component (A) in the composition of the present invention is a fluorine-containing compound that binds to or adsorbs to metal particles. When the component (A) is bonded to or adsorbed on the surface of the metal particles as the component (B), the metal particles can be made liquid repellent. As a result, the solidified film of the printed body obtained from the composition of the present invention can exhibit both conductivity and liquid repellency.

  The fluorine-containing compound as component (A) is a fluorine-containing thiol compound, fluorine-containing disulfide compound, fluorine-containing amine compound, fluorine-containing carboxylic acid compound, fluorine-containing silane compound, fluorine-containing nitrile compound, fluorine-containing tellurium compound, fluorine-containing alkoxy. It is preferable that it is 1 or more types selected from the group which consists of a silane compound and a fluorine-containing selenium compound. Among these, it is more preferable that it is at least one selected from the group consisting of a fluorine-containing thiol compound, a fluorine-containing disulfide compound, a fluorine-containing amine compound, and a fluorine-containing carboxylic acid compound.

Such as fluorine in the thiol containing compound and a fluorine-containing disulfide compounds, thiol portion and sulfides portions respectively thiolate ion - surface to bind or adsorb the metal particles as ^(-S). Further, in the fluorine-containing amine compound, an amine unit are bonded to the surface of the metal particles or adsorbed as the amine (-NH _2), a fluorine-containing carboxylic acid compounds, portion carboxylic acid carboxylate anion - metals as ^(-COO) Bind or adsorb to the surface of the particles.
These fluorine-containing compounds can exist in a state of being bonded or adsorbed on the surface of the metal particles in the composition, and preferably all the fluorine-containing compounds in the composition are bonded to or adsorbed to the metal particles. Yes. However, the composition of the present invention may include metal particles composed of fluorine-containing compounds that are bonded to or adsorbed on the surfaces of the metal particles, and fluorine-containing compounds that are not bonded to or adsorbed to the metal particles. And metal particles to which no fluorine-containing compound is bound or adsorbed may be present.

  Examples of the fluorine-containing thiol compound include a fluorine-containing thiol compound having an aromatic ring and a thiol compound having a carbon chain having a fluorinated portion. Among these, a fluorine-containing thiol compound having an aromatic ring is preferable, a fluorine-containing thiol compound having 6 to 20 carbon atoms having an aromatic ring is more preferable, and a carbon number having 6 to 20 carbon atoms having a benzene ring is preferable from the surface modification property of metal particles. More preferred is a fluorine-containing thiol compound.

Specific examples of the fluorine-containing thiol compound include 4-trifluoromethylbenzenethiol, 3-trifluoromethylbenzenethiol, pentafluorobenzenethiol, 2,3,5,6-tetrafluorobenzenethiol, 2,3,5, 6-tetrafluoro-4- (trifluoromethyl) benzenethiol, 2,3,5,6-tetrafluoro-4-mercaptobenzoic acid methyl ester, 3,5-bistrifluoromethylbenzenethiol, 4-fluorobenzenethiol, And 11- (2,3,4,5,6-pentafluorobenzyloxy) -1-undecanethiol (the following chemical formula), 1H, 1H, 2H, 2H-perfluorodecanethiol, 1H, 1H, 2H, 2H- Examples include perfluorooctane thiol.
Among these, from the viewpoint of liquid repellency, pentafluorobenzenethiol, trifluoromethylbenzenethiol and / or 2,3,5,6-tetrafluoro-4- (trifluoromethyl) benzenethiol, compounds of the following formula, etc. Particularly preferred.

  Examples of the fluorine-containing disulfide compound include a fluorine-containing disulfide compound having an aromatic ring and a disulfide compound having a carbon chain having a fluorinated portion. Among these, a fluorine-containing disulfide compound having an aromatic ring is preferable, a fluorine-containing disulfide compound having 12 to 40 carbon atoms having an aromatic ring is more preferable, and a carbon number having 12 to 40 carbon atoms having a benzene ring is preferable. More preferred are fluorine-containing disulfide compounds.

  Specific examples of the fluorine-containing disulfide compound having 12 to 40 carbon atoms having an aromatic ring include compounds obtained by dimerizing the above-mentioned fluorine-containing thiol compound. From the viewpoint of liquid repellency, trifluoromethylbenzenethiol or 2 , 3,5,6-tetrafluoro-4- (trifluoromethyl) benzenethiol is a dimerized compound.

  Examples of the fluorine-containing amine compound include a fluorine-containing amine compound having an aromatic ring and an amine compound having a carbon chain having a fluorinated portion. Among these, the fluorine-containing amine compound which has an aromatic ring from the surface modification property of a metal particle is preferable, the C6-C20 fluorine-containing amine compound which has an aromatic ring is more preferable, and C6-C20 which has a benzene ring. More preferred are fluorine-containing amine compounds.

  Specific examples of the fluorine-containing amine compound include 2,3,4,5,6-pentafluoroaniline, 2,3,4,5-tetrafluoroaniline, 2,4,5-trifluorophenylamine, 4,5 -Difluoro-2-aminobenzotrifluoride, 2-amino-5,6-difluoro-benzotrifluoride, (3,4,5-trifluorophenyl)-(7-methoxymethyl- [1,4] -dioxano [ 2,3-g] quinazolin-4-yl) -amine, 4-fluoro-2- (trifluoromethyl) -aniline, 3,4-difluoroaniline, 2- (difluoromethyl) -4-fluoroaniline, 2, 2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctane-1-amine.

  Examples of the fluorine-containing carboxylic acid compound include a fluorine-containing carboxylic acid compound having an aromatic ring, a carboxylic acid compound having a carbon chain having a fluorinated portion, and the like. Among these, the fluorine-containing carboxylic acid compound having an aromatic ring is preferable from the surface modification property of the metal particles, the fluorine-containing carboxylic acid compound having 6 to 20 carbon atoms having an aromatic ring is more preferable, and the carbon number having 6 benzene rings. More preferred are -20 fluorine-containing carboxylic acid compounds.

  Specific examples of the fluorine-containing carboxylic acid compound include 2,3,4,5,6-pentafluorobenzoic acid, 2,3,4,6-tetrafluorobenzoic acid, 2,4,5-trifluorobenzoic acid, 2,3,4-trifluorobenzoic acid, 2-ethyl-tetrafluorobenzoic acid, 2-isopropyl-tetrafluorobenzoic acid, 3-cyclopropyl-2,4,5-trifluorobenzoic acid, 2-butyl-tetra Examples thereof include fluorobenzoic acid, undecafluorohexanoic acid, and nonadecafluorodecanoic acid.

The content of the component (A) is preferably 10% by mass or less and more preferably 5% by mass or less with respect to the total amount of the composition. If content of (A) component exists in the said range, the dispersibility of the metal particle in a composition will not be inhibited.
The lower limit of the content of the component (A) is not particularly limited, but is preferably 0.1% by mass or more from the viewpoint of liquid repellency of the printed material obtained from the composition of the present invention.

[Component (B)]
(B) The metal particle which is a component becomes the origin of electrical conductivity expression of the composition of this invention.
The metal particles are preferably metal particles having an average particle diameter of 10 nm to 1000 nm, and more preferably metal nanoparticles having an average particle diameter of 10 nm to 100 nm. The metal particles may include metal nanowires having a diameter of 50 nm or less.
The average particle size of the metal particles can be measured by observation with a transmission electron microscope (TEM). Specifically, in a visual field including about 50 particles, there is a method of measuring the projected area equivalent circle diameter of all the particles and calculating the average.
The metal particle which is the component (B) used in the composition of the present invention has a fluorine-containing compound bonded or adsorbed, and the fluorine-containing compound is not bonded or adsorbed. You may mix and use the metal particle which is not.

  Examples of the metal constituting the metal particles include silver, copper, nickel, palladium, platinum, and gold. As the metal particles, one of these metal particles may be used alone, or two or more metal particles may be used in combination. Among these, silver nanoparticles are particularly preferable from the viewpoint of conductor characteristics and ease of handling of the metal particle composition.

The metal particles may be used in the state of a metal particle dispersion dispersed in a dispersion medium during the production of a dispersion liquid (hereinafter sometimes referred to as the dispersion liquid of the present invention) which is a preferred form of the present invention. In this case, the dispersant may be bound to or adsorbed on the surface of the metal particles. When the dispersing agent is bonded to or adsorbed on the surface of the metal particles, the dispersing agent may be detached or remain as it is on the metal surface when mixed with the fluorine-containing compound. This differs depending on the type of dispersant and the coating amount of the dispersant.
The metal particles used in producing the composition of the present invention may be any of commercially available metal particle dispersions, solid metal particles, and metal particle dispersions in which the dispersant is component (A).

  The content of the component (B) is preferably 15% by mass or more and 70% by mass or less, and more preferably 20% by mass or more and 50% by mass or less with respect to the total amount of the composition. If content of (B) component exists in the said range, a conductive via can be formed more efficiently.

[Component (C)]
Examples of the solvent as component (C) include long-chain alkanes such as hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, and isooctane; cyclohexane, cycloheptane, cyclooctane, and the like. Cyclic alkanes; aromatic hydrocarbons such as benzene, toluene, xylene, trimethylbenzene, dodecylbenzene; isopropyl alcohol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecane Alcohols such as diol, cyclohexanol and 1-methoxy-2-propanol; ketones such as cyclohexanone and methyl isobutyl ketone can be used. Since these solvents have a relatively low viscosity, they are suitable for printing solutions that use low viscosity inks, such as ink solutions for ink jet printing.
These solvents may be used alone or in a combination of two or more.

Of these solvents, a solvent having a boiling point in the range of 180 ° C to 300 ° C is preferable. When the boiling point is high, a change in the composition ratio of the composition due to evaporation can be prevented. On the other hand, if the boiling point is too high, the temperature required for solidification after printing becomes high.
The solvent preferably contains at least one selected from the above long-chain alkanes, and more preferably contains at least one selected from long-chain alkanes having a boiling point in the range of 180 ° C to 300 ° C.
Preferred solvents include undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane and the like.

  The content of the component (C) is preferably 25% by mass or more and 82% by mass or less, and more preferably 50% by mass or more and 80% by mass or less with respect to the total amount of the composition. If content of (C) component exists in the said range, the composition of this invention can be apply | coated appropriately.

[Other ingredients]
The composition of the present invention may contain (A) a fluorine-containing compound that binds to or adsorbs to metal particles, (B) metal particles, and (C) a solvent, and may further contain optional components.
Examples of the optional component include a dispersant that stabilizes the dispersion of the present invention.

[Method for producing metal particle composition]
The metal particle composition of this invention can be manufactured by mixing each component mentioned above, for example. The mixing method is not particularly limited, and examples thereof include a method of mixing using a mixer such as a mechanical stirrer, a magnetic stirrer, an ultrasonic disperser, a planetary mill, a ball mill, or a three roll.

[Via formation method]
The printed material obtained from the composition of the present invention functions as a conductor having both conductivity and liquid repellency. The (A) fluorine-containing compound that binds to or adsorbs to the metal particles and (B) the conductor containing the metal particles are preferably used as a via for electrically connecting conductors such as wiring patterns. Can do.
More specifically, the laminate of the present invention including the conductor includes a substrate, an electrode provided on the substrate, and a conductor formed on the electrode. The laminate of the present invention preferably further comprises an insulating film formed on the substrate and the electrode and exposing a part of the conductor, more preferably a conductive film formed on the insulating film and in contact with the exposed part of the conductor. Further comprising a membrane.
Hereinafter, an embodiment of via formation using the dispersion of the present invention will be described with reference to the drawings.

FIG. 1 is a schematic view showing a substrate (array) with a wiring pattern before via formation.
As shown in FIG. 1, an array 3 having a wiring pattern 2 made of metal electrodes on a substrate 1 is prepared. The wiring pattern 2 can be provided by a known method.
As the substrate, a glass substrate, a plastic film (for example, polyethylene terephthalate (PET), polyethersulfone (PES), polycarbonate (PC)) or the like can be used. The material of the metal electrode is not particularly limited as long as it is a conductive material, and a known material can be used. For example, the same material as that of the above metal particles can be used.

Next, as shown in FIG. 2, the via 4 is formed by applying the metal particle dispersion of the present invention to a desired location on the surface of the wiring pattern 2.
Examples of the method for applying the dispersion include an inkjet printing method and a screen printing method, and an inkjet printing method capable of flexible alignment is preferable. According to the inkjet printing method, the diameter of the via 4 can be made substantially the same as the diameter of the coating pattern of the metal particle dispersion. Therefore, the diameter of the via 4 can be easily controlled to a desired value by adjusting the coating amount of the dispersion liquid. Here, the via 4 is formed with a diameter of 20 μm or more and 200 μm or less, for example.
As conditions for applying the dispersion liquid and drying to form a solidified film, a temperature of 50 ° C. to 250 ° C. for 3 minutes to 1 hour is preferable. When the heating temperature is too low, it is not dried, and when it is too high, it is necessary to use a member having high heat resistance as the peripheral member, and therefore it is particularly preferably 100 ° C. to 180 ° C. The shorter the time, the better. However, if it is too short, it will not dry sufficiently and the conductivity will be low, so 10 to 30 minutes is particularly preferred.

Next, as shown in FIG. 3, an insulating film 5 is formed on the array 3 after the vias 4 are formed using an insulating material by a spin coat method or the like. The insulating material is not particularly limited as long as it has electrical insulating properties and can be formed as a thin film, and known materials can be used.
At this time, the via 4 repels the insulating material due to the liquid repellency of the via 4 formed using the dispersion liquid of the present invention, so that the protruding portion of the convex via 4 is exposed without being covered with the insulating film 5 ( (See FIG. 4). When the dispersion of the present invention is used for forming the via, there is no need to expose the via portion covered with the insulating film, and the via 4 that can electrically connect the wiring pattern 2 and the conductive film 6 described later is formed. It becomes possible to form.

  Then, as shown in FIG. 5, a conductive film 6 is formed on the array 3 after forming the insulating film 5 using a conductive material by a screen printing method or the like. Thereby, since the protrusion part of the via 4 and the conductive film 6 are in contact with each other, the wiring pattern 2 and the conductive film 6 are brought into conduction, and the electrode can be taken out (see FIG. 6). In addition, as a conductive material, if it is a material which has electroconductivity, it will not specifically limit, A well-known thing can be used. For example, the same material as the metal electrode can be used.

  The solidified film of the printed body obtained with the composition of the present invention has conductivity and liquid repellency. Therefore, for example, as described above, after forming a via using the composition, when an insulating material is applied in the next step, the insulating material in the via forming portion is repelled due to the liquid repellency of the via. It is not covered with an insulating film. Via the exposed via that is not covered with the insulating film, the conductivity of the via can connect the electrode formed on the insulating film and the electrode under the insulating film. As a result, patterning formation of the interlayer insulating film becomes unnecessary, and the via formation process can be greatly reduced, so that productivity can be improved. Further, since the via can be formed by an ink jet printing method, the via can be formed with high accuracy.

The laminated body in which two electrodes are conducted through vias obtained by the above-described via formation method is, for example, a semiconductor element, a touch panel sensor, an RF-ID (Radio Frequency Identification), an organic electroluminescence element, a laminated wiring board (flexible). It can be used for printed circuit boards (FPC) and rigid printed circuit boards.
Further, the laminated wiring board can be used for electronic devices such as liquid crystal displays, televisions, car navigation systems, mobile phones, game machines, digital cameras, personal computers, printers, automobiles, robots, and light-emitting diodes.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by the following examples.

Example 1
(1) Preparation of metal particle dispersion liquid Silver nanocolloid dispersion liquid (dispersion medium: tetradecane), pentafluorobenzenethiol and dodecane having an average particle diameter of 40 nm, silver nanocolloid: pentafluorobenzenethiol: solvent (dodecane + tetradecane) The metal particle dispersion 1 was produced by mixing so that the mass ratio was 32: 4: 64.

(2) Manufacture of laminated body On the glass substrate, the wiring pattern which consists of a silver electrode was provided by flexographic printing, and the array was produced.
Next, vias were formed by printing the prepared metal particle dispersion 1 on a desired portion of the surface of the wiring pattern by an ink jet printing method. The formed via was heat-treated at 150 ° C. for 20 minutes. As a result of measuring the cross-sectional shape of the via with a stylus profilometer, the central portion of the upper portion was a gentle convex shape, but was almost flat.
Subsequently, ANL1 (trade name) manufactured by Kaneka was spin-coated on the substrate after via formation to form an insulating film. As a result, an insulating film having a thickness of 500 nm was obtained. Moreover, it was confirmed with an optical microscope that the upper part of the via formed by the ink jet printing method was not covered with an insulating film.
The surface energy of the via was 26 mN / m based on the result of measuring the contact angle measurement method after forming the same ink on a glass substrate by drop casting.

Example 2
(1) Preparation of metal particle dispersion A silver nanocolloid dispersion liquid (dispersion medium: tetradecane) having an average particle diameter of 40 nm, pentafluorobenzenethiol, and tetradecane are mixed with silver nanocolloid: pentafluorobenzenethiol: tetradecane = 32: 0. It mixed so that it might become mass ratio of 3: 67.7, and the metal particle dispersion liquid 2 was manufactured.

(2) Manufacture of laminated body On the glass substrate, the wiring pattern which consists of a silver electrode was provided by flexographic printing, and the array was produced.
Next, vias were formed by printing the prepared metal particle dispersion 2 on a desired portion of the surface of the wiring pattern by an inkjet printing method. The formed via was heat-treated at 150 ° C. for 20 minutes. Further, the cross-sectional shape of the via was measured with a stylus profilometer, and as a result, the upper center portion was a gentle convex shape, but was almost flat.
Next, an ANL1 manufactured by Kaneka was spin-coated on the substrate after via formation to form an insulating film. As a result, an insulating film having a thickness of 500 nm was obtained. Moreover, it was confirmed with an optical microscope that the upper part of the via formed by the ink jet printing method was not covered with an insulating film. The surface energy of the via was 56 mN / m based on the result of measuring the contact angle measurement method after forming the same ink on a glass substrate by drop casting.

Comparative Example 1
(1) Preparation of Metal Particle Dispersion A silver nanocolloid dispersion (dispersion medium: tetradecane) having an average particle diameter of 40 nm and dodecane have a mass ratio of silver nanocolloid: solvent (dodecane + tetradecane) = 32: 68. To obtain a metal particle dispersion 3.

(2) Manufacture of laminated body On the glass substrate, the wiring pattern which consists of a silver electrode was provided by flexographic printing, and the array was produced.
Next, vias were formed by printing the metal particle dispersion 3 on a desired portion of the surface of the wiring pattern by an inkjet printing method. The formed via was heat-treated at 150 ° C. for 20 minutes. Further, the cross-sectional shape of the via was measured with a stylus profilometer, and as a result, the upper center portion was a gentle convex shape, but was almost flat.
Subsequently, an insulating film was formed on the substrate after via formation by spin coating using ANL1 manufactured by Kaneka. As a result, an insulating film having a thickness of 500 nm was obtained. In addition, the upper part of the via formed by the ink jet printing method is covered with an insulating film. The surface energy of the via was 73 mN / m based on the result of measuring the contact angle measurement method by depositing the same ink on a glass substrate by drop casting.

Comparative Example 2
(1) Preparation of metal particle dispersion liquid Silver nanocolloid dispersion liquid (dispersion medium: tetradecane) having an average particle diameter of 40 nm and tetradecane are mixed so as to have a mass ratio of silver nanocolloid: tetradecane = 32: 68, Metal particle dispersion 4 was produced.

(2) Manufacture of laminated body On the glass substrate, the wiring pattern which consists of a silver electrode was provided by flexographic printing, and the array was produced.
Next, vias were formed by printing the metal particle dispersion 4 on a desired portion of the surface of the wiring pattern by an ink jet printing method. The formed via was heat-treated at 150 ° C. for 20 minutes. Further, the cross-sectional shape of the via was measured with a stylus profilometer, and as a result, the upper center portion was a gentle convex shape, but was almost flat.
Subsequently, an insulating film was formed on the substrate after via formation by spin coating using ANL1 manufactured by Kaneka. As a result, an insulating film having a thickness of 500 nm was obtained. In addition, the upper part of the via formed by the ink jet printing method is covered with an insulating film. The surface energy of the via was 73 mN / m based on the result of measuring the contact angle measurement method by depositing the same ink on a glass substrate by drop casting.

  The present invention can be used for forming a via for electrically connecting conductors in a transistor array.

DESCRIPTION OF SYMBOLS 1 Substrate 2 Wiring pattern 3 Array 4 Via 5 Insulating film 6 Conductive film

Claims (19)

(B) metal particles;
(A) a fluorine-containing compound that binds to or adsorbs to (B) the metal particles;
(C) A metal particle composition comprising a solvent.   The metal particle composition according to claim 1, which is a metal particle dispersion.   The (A) fluorine-containing compound is a fluorine-containing thiol compound, a fluorine-containing disulfide compound, a fluorine-containing amine compound, a fluorine-containing carboxylic acid compound, a fluorine-containing silane compound, a fluorine-containing nitrile compound, a fluorine-containing tellurium compound, or a fluorine-containing alkoxysilane compound. The metal particle composition according to claim 1, wherein the metal particle composition is one or more selected from the group consisting of fluorine-containing selenium compounds.   The metal particle composition according to any one of claims 1 to 3, wherein the (A) fluorine-containing compound is a fluorine-containing thiol compound.   The solvent (C) is hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, isooctane, cyclohexane, cycloheptane, cyclooctane, benzene, toluene, xylene, trimethylbenzene, dodecyl. From benzene, isopropyl alcohol, hexanol, heptanol, octanol, nonanol, decanol, undecanol, dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, cyclohexanol, 1-methoxy-2-propanol, cyclohexanone, methyl isobutyl ketone The metal particle composition according to any one of claims 1 to 4, wherein the metal particle composition is at least one selected from the group consisting of:   The metal particle composition according to any one of claims 1 to 5, wherein the solidified film dried and solidified has a surface energy of 60 mN / m or less.   The metal particle composition according to any one of claims 1 to 6, wherein the (A) fluorine-containing compound is bonded to or adsorbed on the surface of the (B) metal particle. object.   Content of the said (A) fluorine-containing compound is 10 mass% or less with respect to the metal particle dispersion liquid whole quantity, The metal particle composition as described in any one of Claims 1-7 characterized by the above-mentioned.   The metal particle composition according to any one of claims 1 to 8, wherein the content of the solvent (C) is 25% by mass or more and 82% by mass or less with respect to the total amount of the metal particle dispersion. .   The metal particles (B) are at least one selected from the group consisting of silver particles, copper particles, nickel particles, palladium particles, platinum particles and gold particles. The metal particle composition according to one item.   The said (B) metal particle is silver particle, The metal particle composition as described in any one of Claims 1-10 characterized by the above-mentioned.   12. The metal particle composition according to claim 1, wherein the content of the metal particles (B) is 15% by mass to 70% by mass with respect to the total amount of the metal particle composition. object.   The conductor which consists of a metal particle composition as described in any one of Claims 1-12. A substrate,
An electrode provided on the substrate;
A laminate comprising: the conductor according to claim 13 formed on the electrode.   The laminate according to claim 14, further comprising an insulating film formed on the substrate and the electrode and exposing a part of the conductor.   The laminate according to claim 15, further comprising a conductive film formed on the insulating film and in contact with the exposed portion of the conductor.   A laminated wiring board comprising the laminate according to any one of claims 14 to 16.   An electronic apparatus comprising the laminated wiring board according to claim 17.   The electronic device according to claim 18, which is a liquid crystal display, a television, a car navigation, a mobile phone, a game machine, a digital camera, a personal computer, a printer, an automobile, a robot, a light emitting diode illumination, or a wearable device.

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