Copper ink, electronic circuit board, and method for manufacturing electronic circuit board

Abstract

To provide a copper ink capable of producing a highly reliable circuit pattern with less short circuit by suppressing bleeding during copper ink printing on a substrate, and to provide an electronic circuit board using the same and a method for manufacturing the electronic circuit board.SOLUTION: There is provided a copper ink containing copper particles, in which a thixotropy index TI defined by a ratio (η1 / η10) of a viscosity η10 at a shear rate 1sec-1 to a viscosity η1 at a shear rate 10sec-1 is 7.5 or less, and a hysteresis area of shearing stress obtained by measuring dynamic viscoelasticity when a shear rate is increased from 0. 01sec-1 to 300sec-1 in 50 seconds, held at 300sec-1 for 50 seconds, and then decreased from 300sec-1 to 0. 01sec-1 in 50 seconds is 3000Pa·sec-1 or more.SELECTED DRAWING: Figure 7

Description

[Technical Field]

[0001] The present invention relates to a copper ink, an electronic circuit board, and a method for manufacturing an electronic circuit board, and more particularly to a copper ink that can be used in a screen printing method, an electronic circuit board using the same, and a method for manufacturing an electronic circuit board. [Background technology]

[0002] As electronic devices and information terminals become smaller and lighter, the electronic components used inside the devices are becoming smaller and smaller. This has led to a gradual decrease in the size of the wiring patterns inside the electronic components, as well as narrower widths of the wiring patterns and spacing between the wires.

[0003] Optical patterning, which involves exposure and etching processes, is a common method for forming high-resolution wiring patterns on electronic components. However, optical patterning has the drawback of excessive waste of materials such as photoresist, developer, and etching solution. Optical patterning also has the drawback of being difficult to improve process efficiency due to its complex process. Optical patterning also has the drawback of requiring the use of large-area masks, making it difficult to apply new designs to the production line within the shortest possible time.

[0004] In order to overcome the various drawbacks of optical patterning, a method for forming metal wiring by printing using ink has been developed as a method for directly applying a pattern to a substrate without a mask. One known printing method using ink is screen offset printing. This screen offset printing method involves printing a predetermined pattern by screen printing on the surface of a silicone blanket (a blanket made of silicone rubber), and then transferring the printed pattern to the substrate or film that is the intended printing target, thereby forming a pattern. Various inks that can be used for screen offset printing have been developed in the past (see, for example, Patent Documents 1 to 3). [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2017-069198 [Patent Document 2] Japanese Patent Publication No. 2020-009554 [Patent Document 3] Special Publication No. 2014-507510 Summary of the Invention [Problem to be solved by the invention]

[0006] In response to the recent demand for finer circuit patterns, there is a need to print copper ink on substrates with higher resolution than ever before. For example, if the copper ink bleeds on the substrate when it is applied, it can cause short circuits in the resulting circuit pattern. In particular, in the manufacture of electronic circuit boards with ultra-fine wiring with a line width of 20 μm or less, the characteristics of the copper ink used to print the wiring can affect the reliability of the electronic circuit board.

[0007] In view of the above problems, the present invention provides a copper ink that can suppress bleeding when printing copper ink onto a substrate and can produce a highly reliable circuit pattern with few short circuits, as well as an electronic circuit board and a method for manufacturing an electronic circuit board using the same. [Means for solving the problem]

[0008] In order to solve the above problems, according to one embodiment of the present invention, there is provided a copper ink containing copper particles, which is formed at a shear rate of 1 sec -1 Viscosity η1 at shear rate of 10sec -1 The thixotropy index TI (1 / 10), defined as the ratio of viscosity η10 at η1 / η10, is 7.5 or less, and the shear rate is 0.01 sec -1 300 seconds from -1 It is raised to 300 s in 50 s, held for 50 s, and then -1 to 0.01 seconds-1 The hysteresis area of ​​the shear stress measured by dynamic viscoelasticity measurement when the sample was lowered to 3000 Pa·sec in 50 seconds was -1 That's it, copper ink.

[0009] According to another embodiment of the present invention, there is provided an electronic circuit board comprising a wiring layer using the above-mentioned copper ink.

[0010] According to yet another embodiment of the present invention, there is provided a method for manufacturing an electronic circuit board, comprising: forming a copper ink film on a blanket by screen printing using a copper ink; transferring the copper ink film from the blanket onto a substrate; and firing the copper ink film transferred onto the substrate to form a circuit on the substrate. [Effects of the Invention]

[0011] According to the present invention, it is possible to provide a copper ink that can suppress bleeding when printing copper ink onto a substrate and can produce a highly reliable circuit pattern with few short circuits, as well as an electronic circuit board and a method for manufacturing an electronic circuit board using the same. [Brief explanation of the drawings]

[0012] [Figure 1] FIG. 1 is an explanatory diagram illustrating the hysteresis area of ​​a copper ink according to an embodiment of the present invention, and is a graph showing the hysteresis area of ​​copper ink No. 1 of an example. [Figure 2] 1 is a graph showing a flow curve of copper ink No. 1. [Figure 3] This is a photograph of a linear pattern with a wiring line width of 20 μm printed on a PDMS blanket by screen offset printing using copper ink No. 1. [Figure 4] This is a photograph of a line pattern with a wiring line width of 20 μm printed on a PI substrate by screen offset printing using copper ink No. 1. [Figure 5]This is a photograph of a linear pattern with a wiring line width of 15 μm printed on a PDMS blanket by screen offset printing using copper ink No. 7. [Figure 6] This is a photograph of a linear pattern with a wiring line width of 20 μm printed on a PI substrate by screen offset printing using copper ink No. 6. [Figure 7] 1 is a graph showing the relationship between the thixotropy index TI (1 / 10) and the hysteresis area. [Figure 8] 10 is a graph showing the relationship between the viscosity η156 of the copper ink at a shear rate of 156 sec −1 and the hysteresis area. DETAILED DESCRIPTION OF THE INVENTION

[0013] (copper ink) An embodiment of the copper ink according to the present invention will be described in detail below. The copper ink according to the embodiment of the present invention is suitable for use in printing on a substrate. The copper ink is used in printing in which the copper ink is directly printed onto a substrate, such as screen printing through a mesh. Alternatively, as is known, for example, as a screen offset printing method, the copper ink according to the embodiment of the present invention is particularly suitable as a copper ink used in screen offset printing in which the copper ink is first printed onto the surface of a blanket in the form of a roll, plate, or block to form a copper ink film, and then the copper ink film is transferred from the blanket to a substrate.

[0014] <Thixotropy index> Thixotropy describes the property of a substance where the viscosity changes over time, and can be expressed by the thixotropy index (TI). TI is expressed as the ratio of viscosities at different shear rates. A substance with a TI close to 1 is called a Newtonian fluid. A TI of 1 or greater is considered to be more thixotropic, with a high viscosity in the low shear region (static state) and a low viscosity in the high shear region (flowing state). The copper ink according to this embodiment preferably has a TI that allows it to be fluid with low viscosity during printing (high shear region), making it possible to print.

[0015] Specifically, the copper ink according to this embodiment has a shear rate of 1 sec -1 Viscosity η1 at shear rate of 10sec -1 The TI(1 / 10), defined as the ratio (η1 / η10) of viscosity at the time of printing to viscosity at the time of printing, is 7.5 or less. If the TI(1 / 10) is higher than 7.5, bleeding may occur when printing a circuit pattern with a line and space (L / S) of 20 μm or less using screen offset printing, and the rate of short circuits (defect rate) may increase.

[0016] The lower limit of TI(1 / 10) is not particularly limited. However, a small TI(1 / 10) indicates that there is little difference between the low shear region (e.g., in a static state) and the high shear region (e.g., in a printed state). In order to provide a copper ink capable of accurately forming fine wiring with high connection reliability, it is preferable for the TI(1 / 10) to have a certain degree of fluidity in a printed state and a certain degree of viscosity in a static state. Therefore, it is more preferable that TI(1 / 10) be 1.5 or more, and even more preferable that it be 2.5 or more.

[0017] The TI (1 / 10) can be measured using a dynamic viscoelasticity measuring device (rheometer). In this embodiment, an Anton Paar rheometer (model number: MCR102) is used as the dynamic viscoelasticity measuring device, with the measurement section temperature set to 25°C, the measuring jig set to PP (parallel plate) 25, and the gap set to 0.5 mm. Using the dedicated software (RheoCompass ver1.20.471) provided with the dynamic viscoelasticity measuring device, the measurement mode was set to "flow curve measurement," and the shear rate was set to 0.01 to 1000 sec -1 The viscosity was measured in the range of 1 / 2 shear rate. -1 The viscosity at shear rate of 10sec -1 The TI (1 / 10) was calculated based on the viscosity at the time of measurement. The amount of copper ink used for measurement should be the amount that can fill the gap between the measurement jig and the device. Any copper ink that spills out from the measurement jig should be wiped off before measurement.

[0018] <Hysteresis area> Copper ink exhibits a slightly different stress-strain relationship when loaded and unloaded, resulting in a so-called hysteresis loop. Figure 1 shows an example of a hysteresis loop obtained when the shear rate is changed using the copper ink viscoelasticity measuring device according to this embodiment. When the shear rate is increased, the shear stress increases along the curve (upper curve) during loading (Figure 1). When the shear rate is decreased from an increased state, the shear stress decreases along the curve (lower curve) during unloading (Figure 1). The hysteresis area, which represents the area of ​​this hysteresis loop, indicates how long it takes for the shear stress to change with a change in shear rate. Therefore, the hysteresis area is one indicator of the time dependence of the viscosity of copper ink when the shear rate of the copper ink is increased and then decreased.

[0019] A large hysteresis area indicates that the viscosity of the copper ink recovers slowly when the shear rate is increased and then decreased, i.e., when the viscosity of the copper ink changes from high to low and then back to high. In screen offset printing, a delay time is required after the circuit pattern is printed on the blanket before the transfer to the substrate begins. If the hysteresis area of ​​the copper ink is large, the viscosity of the circuit pattern gradually recovers during the time until the transfer begins. In other words, if the hysteresis area of ​​the copper ink is large, the unevenness (mesh marks) on the circuit pattern surface caused by the screen mesh are gradually alleviated and smoothed before the transfer begins. As a result, pressure is applied uniformly to the circuit pattern during transfer, reducing bleeding of the transferred circuit pattern, improving linearity, and suppressing contact (short circuit) between adjacent circuit patterns. Considering these characteristics, the copper ink of this embodiment has a hysteresis area of ​​3000 Pa·sec -1 Above 5000 Pa·sec -1 It is preferable that the temperature is 10,000 Pa·sec or higher. -1 It is even more preferable that the above is true.

[0020] On the other hand, if the hysteresis area is too large, the viscosity recovery of the copper ink is delayed until it is transferred to the substrate during screen offset printing, and the ink may be transferred while still at a low viscosity. As a result, the copper ink wiring may overlap with each other, making it difficult to form fine wiring. Therefore, the hysteresis area of ​​the copper ink should be, for example, 500,000 Pa·sec -1 Preferably it is less than 450,000 Pa·sec -1 or less, more preferably 350,000 Pa·sec -1 The following is the result.

[0021] The hysteresis area is measured using a dynamic viscoelasticity measuring device (rheometer). In this embodiment, an Anton Paar rheometer (model number: MCR102) is used as the dynamic viscoelasticity measuring device, with the measurement section temperature set to 25°C, the measuring jig set to PP (parallel plate) 25, and the gap set to 0.5 mm. Using the dedicated software (RheoCompass ver1.20.471) provided with the dynamic viscoelasticity measuring device, the measurement mode was set to "flow curve measurement (rise-hold-fall)" and a shear rate profile was set to calculate the hysteresis area of ​​the copper ink. The profile had a shear rate of 0.01 sec -1 300 seconds from -1 It takes 50 seconds to rise to 300 -1 After holding for 50 seconds, -1 to 0.01 seconds -1 The setting was such that the temperature would drop to 50 seconds. The hysteresis area was the value automatically output by the above-mentioned software (RheoCompass ver1.20.471). As with the TI mentioned above, the amount of copper ink used for measurement was an amount that could fill the gap between the measurement jig and the device, and any copper ink that spilled out of the measurement jig was wiped off before measurement.

[0022] <Viscosity η156> Shear rate 156sec -1 This roughly corresponds to the printing speed (squeegee speed) on the blanket using a screen mask in the Examples described later. If the viscosity of the copper ink during printing is low, for example, when a blanket made of polydimethylsiloxane (PDMS) is used as the blanket, the copper ink may sag during screen printing, making it difficult to form fine wiring.

[0023] Considering the above characteristics of the copper ink during printing, the viscosity η156 of the copper ink according to this embodiment is preferably 2.0 Pa·sec or more, more preferably 3.0 Pa·sec or more, and even more preferably 3.5 Pa·sec or more. On the other hand, if the viscosity of the copper ink during printing is high, it may be difficult to eject the ink cleanly from the screen, making it difficult to realize a fine wiring shape. In addition, the shear rate η156 sec -1 Another problem is that it is difficult to produce a copper ink having a viscosity η156 exceeding 15.0 Pa·sec. The viscosity η156 is preferably 15.0 Pa·sec or less, more preferably 13.0 Pa·sec or less, and even more preferably 12.0 Pa·sec or less.

[0024] In particular, copper ink that has little bleeding during printing and can improve the linearity of fine wiring patterns with L / S of 20 μm / 20 μm or less requires a viscosity η of 156 [Pa·sec] and a hysteresis area [Pa·sec]. -1 ] and Y represented by the following relational expression (1): Y<43000X-85000 (1) A copper ink that satisfies the above requirement is preferred. Here, the shear rate is 156 sec -1 The viscosity η156 at 156°C was measured using an Anton Paar rheometer (model: MCR102) as a dynamic viscoelasticity measuring device, with the measurement section temperature set to 25°C, the measuring jig set to PP25, and the gap set to 0.5 mm. Using the dedicated software (RheoCompass ver1.20.471) that came with the dynamic viscoelasticity measuring device, the measurement mode was set to "flow curve measurement," and the shear rate was set to 156 sec -1 The viscosity of the copper ink was measured in the same manner as in the TI described above, with the amount of copper ink used being an amount that could fill the gap between the measurement jig and the device, and any copper ink that spilled out of the measurement jig was wiped off before the measurement.

[0025] <Viscosity η1> Shear rate 1 sec -1The viscosity η1 in the shear rate 1 sec can be likened to the viscosity of copper ink in a stationary state. In particular, it is preferable for copper ink to have a certain degree of viscosity in a stationary state in order to suppress bleeding when printing copper ink onto a substrate during circuit pattern creation and to be able to create highly reliable circuit patterns with few short circuits. -1 The viscosity η1 at, for example, 10 sec -1 ~1000sec -1 It is preferable that the time is 20 seconds. -1 ~150sec -1 It is more preferable that:

[0026] (Copper ink composition) The copper ink according to this embodiment contains (a) copper particles, (b) a binder resin, (c) a solvent, and (d) an additive.

[0027] (a) Copper particles Copper particles contain copper (Cu) and are often composed mostly of copper. The copper content of the copper particles, excluding copper oxide, is, for example, 98% by mass or more, and typically 99.5% by mass or more. The copper content of the copper particles can be confirmed and measured by X-ray diffraction (XRD).

[0028] The average particle diameter D50 of the copper particles can be, for example, 0.01 μm to 5.00 μm, preferably 0.05 μm to 1.00 μm, and more preferably 0.10 μm to 0.80 μm. The copper particles may be composed of a mixture of two or three types of copper particles with different average particle diameters D50. For example, copper particles having an average particle diameter D50 of 0.01 μm to 5.00 μm, copper particles having an average particle diameter D50 of 0.05 μm to 1.00 μm, and copper particles having an average particle diameter D50 of 0.10 μm to 0.80 μm may be mixed to form copper particles. The method for measuring the particle diameter D50 of copper particles will be described later.

[0029] The content of copper particles in the copper ink can be, for example, 60.0% to 90.0% by mass, preferably 65.0% to 85.0% by mass, and more preferably 70.0% to 80.0% by mass.

[0030] (b) Binder resin The binder resin is not particularly limited, but may include, for example, one or a mixture of two or more selected from the group consisting of copolymer polyester, polyester, ethyl cellulose, acrylic resin, and epoxy resin. Of these, the copper ink according to this embodiment preferably includes an acrylic resin.

[0031] Examples of acrylic resins include resins containing (meth)acrylate units, such as polymers or copolymers of acrylic monomers such as alkyl (meth)acrylic esters, (meth)acrylic acid, and (meth)acrylamide, as well as copolymers of the above acrylic monomers with monomers such as styrene and maleic anhydride.

[0032] Considering the various properties required for a copper ink capable of printing fine wiring with an L / S of 20 μm / 20 μm or less on a substrate with high precision, the weight-average molecular weight Mw of the resin is preferably 5,000 or more, more preferably 30,000 or more, and even more preferably 50,000 or more. Specifically, the weight-average molecular weight Mw of the resin is preferably 5,000 or more and 500,000 or less, more preferably 30,000 or more and 400,000 or less, and even more preferably 50,000 or more and 300,000 or less.

[0033] The content of the binder resin in the copper ink can be, for example, 1.0% by mass to 25.0% by mass, preferably 2.0% by mass to 22.0% by mass, and more preferably 5.0% by mass to 20.0% by mass.

[0034] When preparing copper ink, the binder resin may be used in the form of a solution by mixing it with a solvent, which will be described later. Considering the properties required for a copper ink that can print fine wiring on a substrate with high precision and little bleeding, the solids ratio of the binder resin in the binder solution can be adjusted to between 20.0% and 80.0% by mass, more preferably between 25.0% and 75.0% by mass, and even more preferably between 30.0% and 70.0% by mass.

[0035] Furthermore, the resin solids ratio of the binder resin to the copper particles in the copper ink [mass % vs Cu] is preferably 1.0 mass % to 15.0 mass %, more preferably 2.0 mass % to 10.0 mass %, and even more preferably 3.0 mass % to 8.0 mass %.

[0036] (c) Solvent The solvent mainly serves as a viscosity adjuster or diluent (solvent) to dissolve the binder resin and allow it to blend with the copper particles. The solvent is not particularly limited, but examples include terpenes such as terpineol and dihydroterpineol, ethers such as ethylene glycol butyl ether, diethylene glycol methyl ether, and diethylene glycol ethyl ether, and esters such as diethylene glycol monobutyl ether acetate, ethylene glycol ethyl ether acetate, diethylene glycol butyl ether acetate, ethyl lactate, butyl lactate, γ-butyrolactone, and propylene carbonate. These solvents can be used alone or in combination.

[0037] As described above, the solvent is contained in the binder resin so that the solids ratio of the binder resin is 20.0 mass % to 80.0 mass %, and in addition, in the preparation of the copper ink, a solvent may be further added to the mixture of copper particles, binder resin, and additives as a solvent for dissolving and blending the copper particles, binder resin, and additives with each other. The amount of solvent added together with the copper particles, binder resin, and additives when preparing the copper ink can be adjusted, for example, in the range of 0.5 mass % to 20.0 mass %, depending on the desired properties of the copper ink.

[0038] (d) Additives The additive is a substance added to improve the dispersibility or thixotropy of copper particles in the copper ink. Examples of additives that can be used to improve dispersibility include polyether phosphate esters or mixtures of higher fatty acids and amines. Examples of additives that can be used to improve thixotropy include polyolefins. The additive is diluted with the above-mentioned solvents as needed.

[0039] Considering the properties required of a copper ink that can print fine wiring on a substrate with high precision and little bleeding, the additive ratio to copper particles in the copper ink [mass % vs Cu] is preferably 10.0 mass % or less, more preferably 5.0 mass % or less, and even more preferably 3.0 mass % or less.

[0040] In addition to the materials described above, various additives may be added to improve the stability and printability of the ink. For example, a leveling agent, a viscosity modifier, a rheology control agent, an antifoaming agent, an anti-sagging agent, etc. Rheology control agents are used to control the rheology of the copper ink to prevent settling during storage of the copper ink, prevent sagging of printed matter, and improve ease of application.

[0041] (Method of manufacturing copper ink) Copper particles, a binder resin, a solvent, and an additive are prepared, mixed, and then kneaded to produce a copper ink.

[0042] The order in which the copper particles, binder resin, solvent, and additives are mixed together is not limited. For example, the additives may be mixed with the solvent, or in some cases, the additives may be mixed with the solvent beforehand, and then mixed with the copper particles and binder resin. The binder resin may be mixed with the solvent beforehand, and then mixed with the copper particles and additives. The copper particles used in the production of copper ink may be purchased or otherwise obtained. Alternatively, copper particles having predetermined properties may be prepared in advance by a liquid phase method such as a known chemical reduction method or disproportionation method.

[0043] According to this embodiment, by preparing appropriate copper particles, binder resin, solvent, and additives in appropriate ratios, bleeding when printing copper ink onto a substrate can be suppressed, thereby obtaining a copper ink that can produce highly reliable circuit patterns with few short circuits.

[0044] (Electronic circuit board and method of manufacturing the electronic circuit board) An electronic circuit board having a wiring layer formed using the copper ink according to this embodiment can be manufactured by a screen printing method, more preferably a screen offset printing method, using the copper ink. The method for manufacturing the electronic circuit board is not particularly limited. For example, when using screen offset printing as the method for manufacturing the electronic circuit board, a copper ink film is formed on a blanket using the copper ink. The copper ink film is then transferred from the blanket to a substrate. Furthermore, the copper ink film transferred to the substrate is fired to form a circuit on the substrate, thereby obtaining an electronic circuit board having a wiring layer using the copper ink according to this embodiment.

[0045] The substrate is preferably a polyimide substrate. The blanket is preferably made of polydimethylsiloxane (PDMS). In a method for manufacturing an electronic circuit board using screen offset printing, for example, a screen mask is used in which a pattern plate made of Ni or the like on which a predetermined wiring pattern is formed is attached to a screen mesh. The number of meshes per inch of the screen mesh can be, for example, 400 to 900. The thickness of the screen mesh can be, for example, 15 μm to 42 μm.

[0046] Copper ink is placed on a screen mask, coated with a doctor blade, and then squeegeeed onto a blanket to form a copper ink film on the blanket. Urethane squeegee rubber or the like can be used as the squeegee. The squeegee speed is not limited to the following. To accurately print fine wiring with an L / S of 20 μm / 20 μm or less, the speed is set to, for example, 5 mm / s to 50 mm / s. The squeegee pressure can be set to, for example, 0.5 mm to 3.0 mm, and the clearance can be set to, for example, 0.1 mm to 1.0 mm.

[0047] The copper ink film printed on the blanket is then transferred onto a substrate. The transfer conditions can be, for example, a transfer speed of 5 mm / s to 50 mm / s, a push-in amount of 50 μm to 400 μm, and a delay time of 0 to 60 seconds. The copper ink film transferred onto the substrate is then baked in an inert gas atmosphere at 200°C to 400°C for 10 to 60 minutes, thereby forming a circuit on the substrate. The delay time refers to the time from when a predetermined amount of copper ink (one cycle of copper ink) has finished being printed on the blanket until the transfer of the copper ink to the substrate begins. [Example]

[0048] Examples of the present invention will be described below together with comparative examples. These examples are provided for a better understanding of the present invention and its advantages, and are not intended to limit the present invention.

[0049] (Preparation of copper ink) Copper particles A to D, binder resins E to K, additives L to N, and solvents O to S were weighed into a 100 mL container to achieve the mixing ratios shown in Tables 1 and 2. The mixture was stirred at 2000 rpm for 1 minute using a rotation-revolution mixer (Awatori Taro, ARE-310, manufactured by Thinky Corporation) and then degassed at 2000 rpm for 1 minute. The degassed mixture was passed through a three-roll mill (80E, manufactured by EXAT Co., Ltd.) 10 times with a roll gap of 5 μm and a roll rotation speed of 130 rpm, yielding copper inks Nos. 1 to 19, 22 to 24, 26 to 27, 29, and 30.

[0050] (copper particles) Average particle size D 50 Copper particles A and B with an average particle size of 0.18 μm and average particle size D 50 Copper particles C with an average particle size of 0.15 μm and average particle size D 50Copper particles D with a diameter of 0.77 μm were prepared. The average particle size D50 of copper particles A to D was determined by measuring the particle size of each copper particle using a laser diffraction / scattering particle size distribution analyzer. The particle size D50 was determined based on JIS Z8825 (2013) and refers to the particle size at which the cumulative volume-based frequency of each copper particle in the resulting particle size histogram (particle size distribution graph) reaches 50%. Specifically, 1 g of copper slurry was added to 10 mL of 2-propanol and subjected to ultrasonic irradiation for 10 minutes (ultrasonic cleaner US-3KS, 120 W, 38 kHz, manufactured by SND Corporation). 5 mL of the resulting dispersion was mixed with 15 mL of hexasodium metaphosphate aqueous solution and ultrasonicated for 20 minutes to obtain the dispersion for measurement. The hexasodium metaphosphate aqueous solution was prepared by dissolving 10 g of hexasodium metaphosphate manufactured by Junsei Chemical Co., Ltd. in 5 L of water. The laser diffraction / scattering particle size distribution measuring device used for the measurement was a Malvern MASTERSIZER 3000, and the measurement was carried out at a temperature of 40°C, with a stirrer at 2000 rpm and irradiated with 12 W of 40 kHz ultrasound.

[0051] (binder resin) The following binder resins were used as binder resins E to K. Binder resin E: ER2300 (acrylic resin 30.0% by mass, terpineol 70.0% by mass, weight average molecular weight 200,000), manufactured by Kusumoto Chemical Co., Ltd. Binder resin F: ER2602 (acrylic resin 70.0% by mass, butyl carbitol acetate (BCA) 30.0% by mass, weight average molecular weight 5,000), manufactured by Kusumoto Chemical Co., Ltd. Binder resin G: KFA2000 (acrylic resin 35.0% by mass, terpineol 65.0% by mass, weight average molecular weight 250,000), manufactured by GOO Chemical Industry Co., Ltd. Binder resin H: S-LEC ASM-3010 (acrylic resin 35.0% by mass, terpineol 65.0% by mass, weight average molecular weight 50,000) manufactured by Sekisui Chemical Co., Ltd. Binder resin I: S-LEC ASM-3010 (acrylic resin 48.0% by mass, terpineol 52.0% by mass, weight average molecular weight 50,000), manufactured by Sekisui Chemical Co., Ltd. Binder resin J: M4200 (acrylic resin 35.0% by mass, terpineol 65.0% by mass, weight average molecular weight 200,000), manufactured by Soken Chemical Co., Ltd. Binder resin K: M4210 (acrylic resin 30.0% by mass, dihydroterpineol 70.0% by mass, weight average molecular weight 20,000), manufactured by Soken Chemical Co., Ltd.

[0052] (additives) As additives L to N, the following dispersants or thixotropic agents were used. Dispersant L: ED-152 (polyether phosphate ester) manufactured by Kusumoto Chemical Co., Ltd. Dispersant M: ED-120 (a mixture of higher fatty acids and amines) manufactured by Kusumoto Chemicals Co., Ltd. Thixotropic agent N: ET4010 (polyolefin) manufactured by Kusumoto Chemicals Co., Ltd.

[0053] (solvent) The following solvents were used as solvents O to S. Solvent O: Terpineol (specific gravity 0.934, boiling point 213°C) Solvent P: γ-butyrolactone (specific gravity 1.13, boiling point 204°C) Solvent Q: Ethylene glycol (specific gravity 1.11, boiling point 197°C) Solvent R: Ethylene glycol monobutyl ether (specific gravity 0.902, boiling point 171°C) Solvent S: Propylene carbonate (specific gravity 1.2, boiling point 240°C)

[0054] Tables 1 and 2 show the mixing ratios of copper particles A to D, binder resins E to K, additives L to N, and solvents O to S for copper inks No. 1 to 19, 22 to 24, 26 to 27, 29, and 30 used in the preparation of the copper inks. While the total of copper particles, binder resin, additives, and solvents equals 100%, some inks in Tables 1 and 2 do not add up to 100% due to rounding to the nearest tenth. In Tables 1 and 2, "Copper Particle Content" refers to the copper particle content (mass %) in the prepared copper ink. "Resin Solids Ratio" refers to the ratio of the resin solids of the binder resin to the mass of copper particles in the copper ink (mass % vs. Cu). "Additive Ratio" refers to the ratio of additives to copper particles in the copper ink (mass % vs. Cu).

[0055] [Table 1]

[0056] [Table 2]

[0057] The evaluation results of the obtained copper inks Nos. 1 to 19, 22 to 24, 26 to 27, 29, and 30 are shown in Tables 3 and 4.

[0058] [Table 3]

[0059] [Table 4]

[0060] The copper ink was evaluated using the following measuring equipment and conditions. Conditions not specified were the same as those described above. Dynamic viscoelasticity measuring device: Anton Paar rheometer (model number: MCR102) Temperature of the device's measuring section: 25°C Measurement jig: PP25 (parallel plate) Gap: 0.5 [mm]

[0061] <Measurement of Viscosity and Thixotropy Index> Using the above dynamic viscoelasticity measuring device, by setting the measurement mode to "flow curve measurement", the viscosity η [Pa·sec] and TI at each shear rate [sec -1 in Table 3 were obtained. In the flow curve measurement, the shear rate of the copper ink was measured from 0.01 sec -1 to 1000 sec -1 while changing the viscosity η. Figure 2 shows an example of the flow curve of Copper Ink No. 1.

[0062] <Measurement of Hysteresis Area> Performed using a dynamic viscoelasticity measuring device (rheometer). In this embodiment, a rheometer (model number: MCR102) manufactured by Anton Paar was used as the dynamic viscoelasticity measuring device, with the measurement unit temperature: 25°C, the measurement jig: PP (parallel plate) 25, and the gap: 0.5 mm. Using the dedicated software (RheoCompass ver1.20.471) attached to the dynamic viscoelasticity measuring device, the measurement mode was set to "flow curve measurement", and a shear rate profile for calculating the hysteresis area of the copper ink was set. The profile was set to increase the shear rate from 0.01 sec -1 to 300 sec -1 in 50 seconds, hold at 300 sec -1 for 50 seconds, and then decrease from 300 sec -1 to 0.01 sec -1 in 50 seconds. Figure 1 shows an example of the hysteresis area of Copper Ink No. 1.

[0063] <Evaluation of Defect Rate during Printing on PDMS Blanket or PI Substrate> Screen offset printing was performed using Copper Inks No. 1 to 19, 22 to 24, 26 to 27, 29, and 30, and their printability was confirmed. Here, a commercially available printing device (manufactured by Minogroup Co., Ltd., model number SO-1010) was used.

[0064] The substrate used for printing was a PI substrate (Apical, polyimide substrate, manufactured by Kaneka Corporation), and the blanket was the aforementioned polydimethylsiloxane (PDMS) blanket roll (Fujikura Composites, Type: #700-STD). A 32 cm x 32 cm screen mask with a linear pattern of 20 μm / 20 μm, 15 μm / 15 μm, and 10 μm / 10 μm, formed over a 2 cm x 2 cm area, was used. A Ni pattern plate was used as the mask, and this was attached to the screen mesh by electroplating. The mesh count per inch was 500, the mesh material was stainless steel, the mesh diameter was 13 μm, and the total thickness was 31 μm. For screen offset printing, copper ink was placed on the screen, coated (filled) with a doctor blade, and then squeegeeed onto the blanket. The printing conditions were as described above.

[0065] The copper ink circuit patterns printed on the substrate were observed using an optical microscope, and images were obtained. Examples of the obtained images are shown in Figures 3 to 6. Each copper ink was used for five printing runs, and images of an arbitrary region of each resulting wiring pattern were obtained. The percentage of straight lines in which adjacent straight lines were connected horizontally among the total number of straight lines present in the five acquired images was used as the "defect rate," and the average defect rate was calculated. When printing onto the PDMS blanket, a defect rate of 5% or less was evaluated as "good," a defect rate of more than 5% was evaluated as "fair," and printability was evaluated as "unprintable." When printing onto the PI substrate, a defect rate of 7% or less was evaluated as "good," a defect rate of more than 7% was evaluated as "fair," and transferability was evaluated as "unprintable." In this evaluation, "unprintable" refers to cases where printing onto the PDMS blanket using copper ink was not possible. "Transferability" refers to both cases where printing onto the PDMS blanket was possible but printing from the PDMS blanket to the polyimide substrate was not possible, and cases where printing onto the PDMS blanket was not possible.

[0066] Figure 3 shows an image after printing on a blanket so that the L / S is 20 μm / 20 μm using Copper Ink No. 1 (Example). Figure 4 shows an image after transferring from the blanket to a PI substrate so that the L / S is 20 μm / 20 μm using Copper Ink No. 1 (Example). In the examples shown in Figures 3 and 4, there are no cases where adjacent straight lines are connected to each other. Therefore, the defect rate is 0% in both cases. In Figure 3, although some disconnections in the same line are confirmed instead of short circuits where adjacent lines are connected horizontally, such disconnections are highly influenced by the printing conditions of the ink, so they are excluded from the evaluation target of the defect rate. Figure 5 is a photograph after transferring to a blanket so that the L / S is 15 μm / 15 μm using Copper Ink No. 7 (Example). In this example, among 160 straight lines, it was confirmed that adjacent straight line patterns are connected horizontally in 20 straight lines, so the defect rate is (20 / 160)×100 = 12.5%, and the evaluation is Δ. Figure 6 is a photograph after printing on a PI substrate so that the L / S is 20 μm / 20 μm using Copper Ink No. 6 (Comparative Example). In this example, although printing was successful, the evaluation is Δ, but since all lines are connected horizontally, the defect rate is 100%.

[0067] (Evaluation) <Relationship between TI(1 / 10) and Hysteresis Area> In Table 3, TI(1 / 10) is 7.5 or less and the hysteresis area is 3000 Pa·sec -1For the above-mentioned copper inks Nos. 1, 2, 3, 11, 14, 18, 5, 13, 16, 27, 10, 23, 24, 15, 26, 7, and 12, when creating linear patterns with an L / S of 20 μm / 20 μm, the defect rate was kept below 5% for both the PDMS blanket and the PI substrate. For copper inks Nos. 29 and 30, linear patterns with an L / S of 15 μm / 15 μm were not created, and linear patterns transferred from the PDMS blanket to the PI substrate were evaluated. For copper inks Nos. 29 and 30, the defect rate for printing on the PI substrate was kept below 5% even when the L / S was 15 μm / 15 μm. These results suggest that even when copper ink Nos. 29 and 30 are used to print wiring patterns with a 15 μm / 15 μm L / S on a PDMS blanket, the defect rate is likely to be 5% or less. Figure 7 is a graph showing the relationship between TI and hysteresis area for copper inks Nos. 1-7, 9-19, 22-24, 26-27, 29, and 30. Note that copper ink No. 8 has a hysteresis area of ​​0 Pa·sec. -1 Therefore, it is not shown in Figure 7. When the TI (1 / 10) and hysteresis area of ​​the copper inks according to this embodiment are within the ranges, a highly reliable circuit pattern with a low defect rate and few short circuits can be produced when producing a linear pattern with an L / S of 20 µm / 20 µm.

[0068] <Relationship between viscosity η156 (X) and hysteresis area (Y)> Figure 8 shows the shear rate of 156 sec -18 is a graph showing the relationship between the viscosity η156 of copper ink and the hysteresis area in FIG. 8 . The copper inks located to the left of the line Y=43000X-85000 shown in FIG. 8 do not satisfy the above-mentioned relational expression (1). As can be seen from FIG. 8 , although copper ink No. 27 is an example copper ink, it does not satisfy the relational expression (1). Copper inks No. 14 and No. 26 have TI (1 / 10) values ​​relatively close to the TI (1 / 10) of copper ink No. 27. Of these, copper ink No. 14 has the hysteresis area closest to that of copper ink No. 27. Therefore, when viewed from the perspectives of TI (1 / 10) and hysteresis area, copper ink No. 27 and copper ink No. 14 can be said to be somewhat similar. However, copper ink No. 14, which satisfies the relational expression (1), had better transferability to the PI substrate than copper ink No. 27, which did not satisfy the relational expression (1).

Claims

1. A copper ink comprising copper particles, Shear rate 1 sec -1 Viscosity η1 at shear rate of 10 sec -1 a thixotropy index TI (1 / 10) defined as the ratio of viscosity η10 at 1000 kJ / η10 (η1 / η10) to viscosity η10 at 1000 kJ / η10 is 7.5 or less; Shear rate: 0.01 sec -1 From 300 seconds -1 It takes 50 seconds to rise to 300 seconds. -1 After holding for 50 seconds, -1 From 0.01 seconds -1 The hysteresis area of ​​the shear stress measured by dynamic viscoelasticity measurement when the shear stress was lowered to 3000 Pa·sec in 50 seconds -1 That's it, copper ink.

2. Shear rate 156 sec -1 The viscosity η156 [Pa sec] is 2.0 Pa sec or more, X represented by the viscosity η156 and the hysteresis area [Pa sec -1 and Y represented by the following relational formula (1): Y<43000X-85000...(1) The copper ink of claim 1 , wherein

3. 2. The copper ink of claim 1, wherein the thixotropy index TI(1 / 10) is 1.5 or more.

4. The copper ink according to claim 2 , wherein the viscosity η156 is 15.0 Pa·sec or less.

5. The hysteresis area is 500,000 Pa·sec -1 2. The copper ink of claim 1, wherein:

6. The copper ink according to claim 1, which is a copper ink used in screen offset printing.

7. 7. The copper ink according to claim 6, which is a copper ink for printing using a blanket made of polydimethylsiloxane.

8. 8. The copper ink of claim 7, which is a copper ink for printing on a polyimide substrate.

9. The copper ink according to any one of claims 1 to 8, comprising the copper particles, a binder resin, a solvent, and an additive.

10. The copper ink according to claim 9, wherein the copper particles have an average particle size (D50) of 0.01 μm to 5.00 μm.

11. The copper ink according to claim 9 , wherein the binder resin comprises at least one selected from the group consisting of copolymer polyester, polyester, ethyl cellulose, acrylic resin, and epoxy resin.

12. The copper ink of claim 9 , wherein the solvent comprises at least one selected from the group consisting of terpenes, ethers, and esters.

13. 10. The copper ink according to claim 9, wherein the resin solid content ratio of the binder resin to the copper particles is 1.0% by mass to 15.0% by mass.

14. An electronic circuit board comprising a wiring layer using the copper ink according to any one of claims 1 to 8.

15. forming a copper ink film on a blanket by a screen printing method using the copper ink according to any one of claims 1 to 8; transferring the copper ink film from the blanket onto a substrate; Firing the copper ink film transferred onto the substrate to form a circuit on the substrate. A method for manufacturing an electronic circuit board, comprising:

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